From 50e4b5cc577402263e2b7065294ecb7d95d7b3da Mon Sep 17 00:00:00 2001 From: GitHub Action Date: Tue, 19 Nov 2024 09:25:17 +0000 Subject: [PATCH] ci: Automated update Tue Nov 19 09:25:17 UTC 2024 --- AdvMater.xml | 7332 +++++++++++++++++++++++----------------------- advmater_old.csv | 14 + ejoc.xml | 56 +- ejoc_old.csv | 2 + 4 files changed, 3704 insertions(+), 3700 deletions(-) diff --git a/AdvMater.xml b/AdvMater.xml index 63e8a2bc..22fcfa4e 100644 --- a/AdvMater.xml +++ b/AdvMater.xml @@ -6,8 +6,8 @@ en-US © Wiley-VCH GmbH, Weinheim wileyonlinelibrary@wiley.com (Wiley Online Library) - Mon, 18 Nov 2024 08:51:02 +0000 - Mon, 18 Nov 2024 08:51:02 +0000 + Tue, 19 Nov 2024 08:22:02 +0000 + Tue, 19 Nov 2024 08:22:02 +0000 Atypon® Literatum™ https://validator.w3.org/feed/docs/rss2.html 10080 @@ -21,17 +21,17 @@ https://onlinelibrary.wiley.com/journal/15214095 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409971 - Sun, 17 Nov 2024 23:58:21 -0800 - 2024-11-17T11:58:21-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202401504 + Tue, 19 Nov 2024 00:19:41 -0800 + 2024-11-19T12:19:41-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202409971 - Managing Solvent Complexes to Amplify Ripening Process by Covalent Interaction Driving Force Under External Field for Perovskite Photovoltaic + 10.1002/adma.202401504 + Rational Design of Advanced Gene Delivery Carriers: Macrophage Phenotype Matters Advanced Materials, EarlyView. -Liquid crystal molecule is utilized to promote the movement of solvent complexes under external field, thus amplifying ripening process and optimizing the buried interface. Based on this, the efficiency of device reaches 25.24%, and it still maintains 75% of the original efficiency after 1400 h in a damp heat test. +Herein, it is first revealed that M2 phenotype macrophages with lowered mammalian target of rapamycin complex 1 (mTORC1) levels are harder to transfect than M1 phenotype (A). To enhance the transfection efficiency in M2 phenotype macrophages, chloroquine is applied to shift M2 to M1 phenotype. This strategy is translated to functional nucleic acid transfection in M2 phenotype macrophages upon bacteria immune evasion (B). @@ -41,46 +41,45 @@ Liquid crystal molecule is utilized to promote the movement of solvent complexes Abstract -Up to now, post‐annealing is most commonly used to post treat the perovskite film to accelerate the ripening process. Nonetheless, the top‐down crystallization mechanism impedes the efficient desolvation of solvent complexes. Thus, residual solvent complexes tend to accumulate at the bottom of the film during the ripening process and deteriorate the device. Here, a new strategy with unique concept is promoted to amplify ripening process of perovskite film, in which a nematic thermotropic liquid crystal (LC) molecular is introduced to facilitate the conversion of solvent complexes by utilizing the liquid crystalline behavior under external field. Upon the concurrent application of thermal and force fields, the covalent interaction between LC and solvent complexes generates a driving force, which promotes upward migration of solvent complexes, thereby facilitating their engagement in the ripening process. In addition, the driving force under external fields assists the flattening of grain boundary grooves. Therefore, film quality is improved efficiently with amplified ripening process and adequately handled buried interface. Based on the positive effects, the devices achieve a champion efficiency of 25.24%, and sustained ≈75% of its initial efficiency level even after undergoing a damp heat test (85 °C/85% RH) for 1400 h. +Nucleic acid delivery in hard‐to‐transfect macrophages have attracted increasing attention in diverse applications such as defence against bacterial infection. Regulated by microenvironments in specific applications, macrophages have a heterogenous nature and exist in different phenotypes with diverse functions, e.g., pro‐inflammatory and anti‐inflammatory. However, it is not clear whether macrophage phenotype affects nucleic acid delivery, and which one is harder to transfect, and the design of nucleic acid carriers in harder‐to‐transfect macrophage phenotypes is largely unexplored. Herein, it is first revealed that nucleic acid delivery efficacy in macrophages is influenced by phenotype: IL‐4‐treated “M2‐like” macrophages with suppressed mammalian target of rapamycin complex 1 (mTORC1) levels are harder‐to‐transfect than “M1‐like” macrophages for mRNA and DNA. This knowledge is then translated to the purpose‐design of gene delivery carriers for harder‐to‐transfect M2 phenotype macrophages dominant upon bacteria immune evasion. By loading chloroquine in tetrasulfide bond‐containing organosilica nanoparticles, the resultant composite promotes macrophage M2 polarization to M1 and increases mTORC1 levels for enhanced translation. The design is demonstrated in vitro and in vivo for pathogenic Escherichia coli (E. coli) and methicillin‐resistant Staphylococcus aureus (MRSA) infections. It is expected that the findings may provide new knowledge and gene delivery solutions in other applications where the M2 phenotype macrophage is dominant. - <img src="https://onlinelibrary.wiley.com/cms/asset/e09be2ff-dc40-43b0-a831-6f08ead0e654/adma202409971-gra-0001-m.png" - alt="Managing Solvent Complexes to Amplify Ripening Process by Covalent Interaction Driving Force Under External Field for Perovskite Photovoltaic"/> -<p>Liquid crystal molecule is utilized to promote the movement of solvent complexes under external field, thus amplifying ripening process and optimizing the buried interface. Based on this, the efficiency of device reaches 25.24%, and it still maintains 75% of the original efficiency after 1400 h in a damp heat test. + <img src="https://onlinelibrary.wiley.com/cms/asset/4f12a987-8093-4ab5-9657-5318302387ac/adma202401504-gra-0001-m.png" + alt="Rational Design of Advanced Gene Delivery Carriers: Macrophage Phenotype Matters"/> +<p>Herein, it is first revealed that M2 phenotype macrophages with lowered mammalian target of rapamycin complex 1 (mTORC1) levels are harder to transfect than M1 phenotype (A). To enhance the transfection efficiency in M2 phenotype macrophages, chloroquine is applied to shift M2 to M1 phenotype. This strategy is translated to functional nucleic acid transfection in M2 phenotype macrophages upon bacteria immune evasion (B). </p> <br/> <h2>Abstract</h2> -<p>Up to now, post-annealing is most commonly used to post treat the perovskite film to accelerate the ripening process. Nonetheless, the top-down crystallization mechanism impedes the efficient desolvation of solvent complexes. Thus, residual solvent complexes tend to accumulate at the bottom of the film during the ripening process and deteriorate the device. Here, a new strategy with unique concept is promoted to amplify ripening process of perovskite film, in which a nematic thermotropic liquid crystal (LC) molecular is introduced to facilitate the conversion of solvent complexes by utilizing the liquid crystalline behavior under external field. Upon the concurrent application of thermal and force fields, the covalent interaction between LC and solvent complexes generates a driving force, which promotes upward migration of solvent complexes, thereby facilitating their engagement in the ripening process. In addition, the driving force under external fields assists the flattening of grain boundary grooves. Therefore, film quality is improved efficiently with amplified ripening process and adequately handled buried interface. Based on the positive effects, the devices achieve a champion efficiency of 25.24%, and sustained ≈75% of its initial efficiency level even after undergoing a damp heat test (85 °C/85% RH) for 1400 h.</p> +<p>Nucleic acid delivery in hard-to-transfect macrophages have attracted increasing attention in diverse applications such as defence against bacterial infection. Regulated by microenvironments in specific applications, macrophages have a heterogenous nature and exist in different phenotypes with diverse functions, e.g., pro-inflammatory and anti-inflammatory. However, it is not clear whether macrophage phenotype affects nucleic acid delivery, and which one is harder to transfect, and the design of nucleic acid carriers in harder-to-transfect macrophage phenotypes is largely unexplored. Herein, it is first revealed that nucleic acid delivery efficacy in macrophages is influenced by phenotype: IL-4-treated “M2-like” macrophages with suppressed mammalian target of rapamycin complex 1 (mTORC1) levels are harder-to-transfect than “M1-like” macrophages for mRNA and DNA. This knowledge is then translated to the purpose-design of gene delivery carriers for harder-to-transfect M2 phenotype macrophages dominant upon bacteria immune evasion. By loading chloroquine in tetrasulfide bond-containing organosilica nanoparticles, the resultant composite promotes macrophage M2 polarization to M1 and increases mTORC1 levels for enhanced translation. The design is demonstrated in vitro and in vivo for pathogenic <i>Escherichia coli</i> (<i>E. coli</i>) and methicillin-resistant <i>Staphylococcus aureus</i> (MRSA) infections. It is expected that the findings may provide new knowledge and gene delivery solutions in other applications where the M2 phenotype macrophage is dominant.</p> -Jiajie Hong, -Zhi Xing, -Dengxue Li, -Biao Hu, -Kaiqin Xu, -Xiaotian Hu, -Ting Hu, -Yiwang Chen +Yue Wang, +Yining Yao, +Yue Zhang, +Yingjie Yu, +Jiangqi Luo, +Matthew J. Sweet, +Chengzhong Yu Research Article - Managing Solvent Complexes to Amplify Ripening Process by Covalent Interaction Driving Force Under External Field for Perovskite Photovoltaic - 10.1002/adma.202409971 + Rational Design of Advanced Gene Delivery Carriers: Macrophage Phenotype Matters + 10.1002/adma.202401504 Advanced Materials - 10.1002/adma.202409971 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409971 + 10.1002/adma.202401504 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202401504 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412185 - Sun, 17 Nov 2024 21:26:07 -0800 - 2024-11-17T09:26:07-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413270 + Tue, 19 Nov 2024 00:18:52 -0800 + 2024-11-19T12:18:52-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412185 - Poly(Lactic Acid): Recent Stereochemical Advances and New Materials Engineering + 10.1002/adma.202413270 + Balanced Miscibility and Crystallinity by 2D Acceptors Enabled Halogen‐Free Solvent‐Processed Organic Solar Cells to Achieve 19.28% Efficiency Advanced Materials, EarlyView. -Poly(lactic acid) (PLA) is a representative biobased and biodegradable polyester among sustainable materials. This review covers the basic structural variety of PLA, current states of stereocontrolled synthesis as well as the relationships between the structures and properties. Moreover, state‐of‐the‐art examples of high‐performance PLA‐based materials within an array of applications (packaging, fibers textiles, biomedicine, healthcare, and electronic devices) are highlighted. +Linear and branch side chains on chemical structures lead to the unique crystal structures of the elliptical and rectangular frameworks, respectively. The difference in intermolecular interaction significantly impacts the self‐aggregation tendency and compatibility with a guest acceptor. It found that excessive crystallinity with great self‐aggregation negatively affected molecular packing, while a moderate crystalline collaborated well with the guest acceptor and achieved a state‐of‐the‐art efficiency of 19.28% based on scalable and stable halogen‐free solvent‐processed organic solar cells. @@ -90,42 +89,50 @@ Poly(lactic acid) (PLA) is a representative biobased and biodegradable polyester Abstract -Poly(lactic acid) (PLA) is a representative biobased and biodegradable aliphatic polyester and a front‐runner among sustainable materials. As a semicrystalline thermoplastic, PLA exhibits excellent mechanical and physical properties, attracting considerable attention in commodity and medical fields. Stereochemistry is a key factor affecting PLA's properties, and to this end, the engineering of PLA's microstructure for tailored material properties has been an active area of research over the decade. This Review first covers the basic structural variety of PLA. A perspective on the current states of stereocontrolled synthesis as well as the relationships between the structures and properties of PLA stereosequences are included, with an emphasis on record regularity and properties. At last, state‐of‐the‐art examples of high‐performance PLA‐based materials within an array of applications are given, including packaging, fibers, and textiles, healthcare and electronic devices. Among various stereo‐regular sequences of PLA, poly(L‐lactic acid) (PLLA) is the most prominent category and has myriad unique properties and applications. In this regard, cutting‐edge applications of PLLA are mainly overviewed in this review. At the same time, new materials developed based on other PLA stereosequences are highlighted, which holds the potential to a wide variety of PLA‐based sustainable materials. +Two highly crystalline 2D acceptors, ATIC‐C11 and ATIC‐BO, with acenaphthene‐expanded quinoxaline central cores, have been demonstrated with very different characteristics in ternary organic solar cells (OSCs). The difference in side chains induces their distinctive molecular packing mode and unique crystal structure, in which ATIC‐C11 displays a 3D structure with an elliptical framework, and ATIC‐BO gives a rectangular framework. Their high crystallinity contributes to organized molecular packing in ternary devices, thus low energetic disorder and suppressed energy loss. Through the analysis of morphology and carrier kinetics, it is found that ATIC‐BO's strong self‐aggregation and immiscibility induce large aggregates and severely impede charge transfer (CT) and dissociation. Conversely, ATIC‐C11's suitable crystallinity and compatibility positively regulate the crystalline kinetics during film formation, thus forming much‐ordered molecular packing and favorable phase separation size in blend films. As a result, ATIC‐C11‐based ternary devices achieve a high efficiency of 19.28% with potential in scalability and stability, which is the top‐ranking efficiency among nonhalogenated solvent‐processed OSCs. This work not only displays highly efficient and stable halogen‐free solvent‐processed organic photovoltaics (OPVs), but also offers a new thought for material design and selection rule on the third component in highly efficient ternary OSCs. - <img src="https://onlinelibrary.wiley.com/cms/asset/1253b2be-0c2f-4573-a14a-700148a1331d/adma202412185-gra-0001-m.png" - alt="Poly(Lactic Acid): Recent Stereochemical Advances and New Materials Engineering"/> -<p>Poly(lactic acid) (PLA) is a representative biobased and biodegradable polyester among sustainable materials. This review covers the basic structural variety of PLA, current states of stereocontrolled synthesis as well as the relationships between the structures and properties. Moreover, state-of-the-art examples of high-performance PLA-based materials within an array of applications (packaging, fibers textiles, biomedicine, healthcare, and electronic devices) are highlighted. + <img src="https://onlinelibrary.wiley.com/cms/asset/811a9a5d-17fd-4917-a6b6-d9cbc27db6ce/adma202413270-gra-0001-m.png" + alt="Balanced Miscibility and Crystallinity by 2D Acceptors Enabled Halogen-Free Solvent-Processed Organic Solar Cells to Achieve 19.28% Efficiency"/> +<p>Linear and branch side chains on chemical structures lead to the unique crystal structures of the elliptical and rectangular frameworks, respectively. The difference in intermolecular interaction significantly impacts the self-aggregation tendency and compatibility with a guest acceptor. It found that excessive crystallinity with great self-aggregation negatively affected molecular packing, while a moderate crystalline collaborated well with the guest acceptor and achieved a state-of-the-art efficiency of 19.28% based on scalable and stable halogen-free solvent-processed organic solar cells. </p> <br/> <h2>Abstract</h2> -<p>Poly(lactic acid) (PLA) is a representative biobased and biodegradable aliphatic polyester and a front-runner among sustainable materials. As a semicrystalline thermoplastic, PLA exhibits excellent mechanical and physical properties, attracting considerable attention in commodity and medical fields. Stereochemistry is a key factor affecting PLA's properties, and to this end, the engineering of PLA's microstructure for tailored material properties has been an active area of research over the decade. This Review first covers the basic structural variety of PLA. A perspective on the current states of stereocontrolled synthesis as well as the relationships between the structures and properties of PLA stereosequences are included, with an emphasis on record regularity and properties. At last, state-of-the-art examples of high-performance PLA-based materials within an array of applications are given, including packaging, fibers, and textiles, healthcare and electronic devices. Among various stereo-regular sequences of PLA, poly(L-lactic acid) (PLLA) is the most prominent category and has myriad unique properties and applications. In this regard, cutting-edge applications of PLLA are mainly overviewed in this review. At the same time, new materials developed based on other PLA stereosequences are highlighted, which holds the potential to a wide variety of PLA-based sustainable materials.</p> +<p>Two highly crystalline 2D acceptors, ATIC-C11 and ATIC-BO, with acenaphthene-expanded quinoxaline central cores, have been demonstrated with very different characteristics in ternary organic solar cells (OSCs). The difference in side chains induces their distinctive molecular packing mode and unique crystal structure, in which ATIC-C11 displays a 3D structure with an elliptical framework, and ATIC-BO gives a rectangular framework. Their high crystallinity contributes to organized molecular packing in ternary devices, thus low energetic disorder and suppressed energy loss. Through the analysis of morphology and carrier kinetics, it is found that ATIC-BO's strong self-aggregation and immiscibility induce large aggregates and severely impede charge transfer (CT) and dissociation. Conversely, ATIC-C11's suitable crystallinity and compatibility positively regulate the crystalline kinetics during film formation, thus forming much-ordered molecular packing and favorable phase separation size in blend films. As a result, ATIC-C11-based ternary devices achieve a high efficiency of 19.28% with potential in scalability and stability, which is the top-ranking efficiency among nonhalogenated solvent-processed OSCs. This work not only displays highly efficient and stable halogen-free solvent-processed organic photovoltaics (OPVs), but also offers a new thought for material design and selection rule on the third component in highly efficient ternary OSCs.</p> -Chenyang Hu, -Yu Zhang, -Xuan Pang, -Xuesi Chen +Yongwen Lang, +Hanjian Lai, +Yuang Fu, +Ruijie Ma, +Patrick W. K. Fong, +Heng Li, +Kuan Liu, +Xuechun Yang, +Xinhui Lu, +Tiangang Yang, +Gang Li, +Feng He - Review - Poly(Lactic Acid): Recent Stereochemical Advances and New Materials Engineering - 10.1002/adma.202412185 + Research Article + Balanced Miscibility and Crystallinity by 2D Acceptors Enabled Halogen‐Free Solvent‐Processed Organic Solar Cells to Achieve 19.28% Efficiency + 10.1002/adma.202413270 Advanced Materials - 10.1002/adma.202412185 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412185 - Review + 10.1002/adma.202413270 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413270 + Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412276 - Sun, 17 Nov 2024 21:26:07 -0800 - 2024-11-17T09:26:07-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413618 + Tue, 19 Nov 2024 00:17:56 -0800 + 2024-11-19T12:17:56-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412276 - In Situ Fabricated Perovskite Quantum Dots: From Materials to Applications + 10.1002/adma.202413618 + Multifunctional Biocomposite Materials from Chlorella vulgaris Microalgae Advanced Materials, EarlyView. -In situ fabricated perovskite quantum dots (PQDs) simplify the integration into functional systems with enhanced performance. This paper reviews the methodologies and the developments of in situ fabricated PQDs. Furthermore, the fundamental problems in development of PQDs toward industrialization are discussed, such as the photoinduced decomposition under high‐intensity light irradiation, ion migration under electrical bias, and the thermal quenching. +A fabrication and post‐processing technique is introduced to achieve uniform, lightweight, biocomposites based on C. vulgaris through extrusion 3Dprinting. The bioink formulation and dehydration process yield materials with mechanical properties and thermal conductivity comparable to traditional polymer and wood‐based composites. This approach can be adapted to using other microalgae for large‐scale production, in response to increasing global material demand. @@ -135,41 +142,43 @@ In situ fabricated perovskite quantum dots (PQDs) simplify the integration into Abstract -Due to the low formation enthalpy and high defect tolerance, in situ fabricated perovskite quantum dots offer advantages such as easy fabrication and superior optical properties. This paper reviews the methodologies, functional materials of in situ fabricated perovskite quantum dots, including polymer nanocomposites, quantum dots doped glasses, mesoporous nanocomposites, quantum dots‐embedded single crystals, and electroluminescent films. This study further highlights the industrial breakthroughs of in situ fabricated perovskite quantum dots, especially the scale‐up fabrication and stability enhancement. Finally, the fundamental challenges in developing perovskite quantum dots for industrial applications are discussed, with a focus on photoinduced degradation under high‐intensity light irradiation, ion migration under electrical bias and thermal quenching at high temperature. +Extrusion 3D‐printing of biopolymers and natural fiber‐based biocomposites enables the fabrication of complex structures, ranging from implants' scaffolds to eco‐friendly structural materials. However, conventional polymer extrusion requires high energy consumption to reduce viscosity, and natural fiber reinforcement often requires harsh chemical treatments to improve adhesion. We address these challenges by introducing a sustainable framework to fabricate natural biocomposites using Chlorella vulgaris microalgae as the matrix. Through bioink optimization and process refinement, we produced lightweight, multifunctional materials with hierarchical architectures. Infrared spectroscopy analysis reveals that hydrogen bonding plays a critical role in the binding and reinforcement of Chlorella cells by hydroxyethyl cellulose (HEC). As water content decreases, the hydrogen bonding network evolves from water‐mediated interactions to direct hydrogen bonds between HEC and Chlorella, enhancing the mechanical properties. A controlled dehydration process maintains continuous microalgae morphology, preventing cracking. The resulting biocomposites exhibit a bending stiffness of 1.6 GPa and isotropic heat transfer and thermal conductivity of 0.10 W/mK at room temperature, demonstrating effective thermal insulation. These characteristics make Chlorella biocomposites promising candidates for applications requiring both structural performance and thermal insulation, offering a sustainable alternative to conventional materials in response to growing environmental demands. - <img src="https://onlinelibrary.wiley.com/cms/asset/b624cb3f-9084-44dd-95bc-696f7bf755ad/adma202412276-gra-0001-m.png" - alt="In Situ Fabricated Perovskite Quantum Dots: From Materials to Applications"/> -<p>In situ fabricated perovskite quantum dots (PQDs) simplify the integration into functional systems with enhanced performance. This paper reviews the methodologies and the developments of in situ fabricated PQDs. Furthermore, the fundamental problems in development of PQDs toward industrialization are discussed, such as the photoinduced decomposition under high-intensity light irradiation, ion migration under electrical bias, and the thermal quenching. + <img src="https://onlinelibrary.wiley.com/cms/asset/b67b7f26-0ec7-4135-8dd0-1e2aff8af3e7/adma202413618-gra-0001-m.png" + alt="Multifunctional Biocomposite Materials from Chlorella vulgaris Microalgae"/> +<p>A fabrication and post-processing technique is introduced to achieve uniform, lightweight, biocomposites based on <i>C. vulgaris</i> through extrusion 3Dprinting. The bioink formulation and dehydration process yield materials with mechanical properties and thermal conductivity comparable to traditional polymer and wood-based composites. This approach can be adapted to using other microalgae for large-scale production, in response to increasing global material demand. </p> <br/> <h2>Abstract</h2> -<p>Due to the low formation enthalpy and high defect tolerance, in situ fabricated perovskite quantum dots offer advantages such as easy fabrication and superior optical properties. This paper reviews the methodologies, functional materials of in situ fabricated perovskite quantum dots, including polymer nanocomposites, quantum dots doped glasses, mesoporous nanocomposites, quantum dots-embedded single crystals, and electroluminescent films. This study further highlights the industrial breakthroughs of in situ fabricated perovskite quantum dots, especially the scale-up fabrication and stability enhancement. Finally, the fundamental challenges in developing perovskite quantum dots for industrial applications are discussed, with a focus on photoinduced degradation under high-intensity light irradiation, ion migration under electrical bias and thermal quenching at high temperature.</p> +<p>Extrusion 3D-printing of biopolymers and natural fiber-based biocomposites enables the fabrication of complex structures, ranging from implants' scaffolds to eco-friendly structural materials. However, conventional polymer extrusion requires high energy consumption to reduce viscosity, and natural fiber reinforcement often requires harsh chemical treatments to improve adhesion. We address these challenges by introducing a sustainable framework to fabricate natural biocomposites using <i>Chlorella vulgaris</i> microalgae as the matrix. Through bioink optimization and process refinement, we produced lightweight, multifunctional materials with hierarchical architectures. Infrared spectroscopy analysis reveals that hydrogen bonding plays a critical role in the binding and reinforcement of <i>Chlorella</i> cells by hydroxyethyl cellulose (HEC). As water content decreases, the hydrogen bonding network evolves from water-mediated interactions to direct hydrogen bonds between HEC and <i>Chlorella</i>, enhancing the mechanical properties. A controlled dehydration process maintains continuous microalgae morphology, preventing cracking. The resulting biocomposites exhibit a bending stiffness of 1.6 GPa and isotropic heat transfer and thermal conductivity of 0.10 W/mK at room temperature, demonstrating effective thermal insulation. These characteristics make <i>Chlorella</i> biocomposites promising candidates for applications requiring both structural performance and thermal insulation, offering a sustainable alternative to conventional materials in response to growing environmental demands.</p> -Xian‐gang Wu, -Yuyu Jing, -Haizheng Zhong +Israel Kellersztein, +Daniel Tish, +John Pederson, +Martin Bechthold, +Chiara Daraio - Review - In Situ Fabricated Perovskite Quantum Dots: From Materials to Applications - 10.1002/adma.202412276 + Research Article + Multifunctional Biocomposite Materials from Chlorella vulgaris Microalgae + 10.1002/adma.202413618 Advanced Materials - 10.1002/adma.202412276 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412276 - Review + 10.1002/adma.202413618 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413618 + Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411572 - Sun, 17 Nov 2024 21:24:57 -0800 - 2024-11-17T09:24:57-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411558 + Tue, 19 Nov 2024 00:17:25 -0800 + 2024-11-19T12:17:25-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202411572 - Design Principles for Enhancing Both Carrier Mobility and Stretchability in Polymer Semiconductors via Lewis Acid Doping + 10.1002/adma.202411558 + An Ultra‐Miniaturized Fiber Humidity Sensor Based on Near‐Parallel Ion Pathways Induced Efficient Water−Electricity Conversion Advanced Materials, EarlyView. -This study systematically investigates the molecular interactions between the host polymer and Lewis acid dopants, offering an effective strategy to simultaneously enhance the carrier mobility and stretchability of polymer semiconductors. Optimizing lamellar stacking distance and reducing crystallinity promote the dispersion of tris(pentafluorophenyl)borane within the side‐chain regions. Reducing the strength of Lewis base groups in the polymer prevents the formation of excessively strong Lewis acid‐base complexes, thus maintaining chain flexibility. +Well‐designed nanochannels significantly facilitate ion transport due to the stable charge distribution and the confined ions migration within near‐parallel nanostructure, which improves the water‐electricity conversion efficiency of moisture‐sensitive fibers. Optimized nanochannels enable the humidity sensor to improve the response/recovery speed by ≈5 times compared to the disordered nanochannels, demonstrating the indispensable role of nanochannels in the water‐electricity conversion process. @@ -179,45 +188,46 @@ This study systematically investigates the molecular interactions between the ho Abstract -With the rise of skin‐like electronics, devices are increasingly coming into close contact with the human body, creating a demand for polymer semiconductors (PSCs) that combine stretchability with reliable electrical performance. However, balancing mechanical robustness with high carrier mobility remains a challenge. To address this, tris(pentafluorophenyl)borane (BCF) for Lewis acid doping is proposed to improve charge mobility while enhancing stretchability by increasing structural disorder. Through systematic investigation, several key structural principles have been identified to maximize the effectiveness of BCF doping in stretchable PSCs. Notably, increasing the lamellar stacking distance and reducing crystallinity facilitate the incorporation of BCF into the alkyl side‐chain regions, thereby enhancing both mobility and stretchability. Conversely, stronger Lewis base groups in the main chain negatively impact these improvements. These results demonstrate that with a small addition of BCF, a two‐fold increase in carrier mobility is achieved while simultaneously enhancing the crack onset strain to 100%. Furthermore, doped PSCs exhibit stable mobility retention under repeated 30% strains over 1000 cycles. This method of decoupling carrier mobility from mechanical properties opens up new avenues in the search for high‐mobility stretchable PSCs. +Humidity sensors are vital for ambient monitoring, but existing sensors focus on moisture absorption, overlooking the indispensable role of ion channels in the water‐electricity conversion process. Here, an ultra‐miniaturized fiber humidity (MFH) sensor based on near‐parallel ion pathways is presented. The well‐designed nanochannels significantly facilitate ion transport due to the stable charge distribution and the confined ions migration within near‐parallel nanostructure, which improves the water‐electricity conversion efficiency of moisture‐sensitive fibers. Optimized nanochannels enable the MFH sensor to improve the response/recovery speed by ≈5 times compared to the disordered nanochannels. Additionally, the MFH sensor can be woven for ultra‐miniaturization (0.50 mm2), which is much smaller than current sensors. Therefore, the integrated MFH sensor array demonstrated exceptionally high spatial resolution (sensor density of 1 mm−1), highlighting its potential in flexible wearables. This work provides new optimization strategies and assembly means for designing the high‐performance humidity sensors of the next generation. - <img src="https://onlinelibrary.wiley.com/cms/asset/bfca5fcf-841a-423a-b153-a42b14bbae5f/adma202411572-gra-0001-m.png" - alt="Design Principles for Enhancing Both Carrier Mobility and Stretchability in Polymer Semiconductors via Lewis Acid Doping"/> -<p>This study systematically investigates the molecular interactions between the host polymer and Lewis acid dopants, offering an effective strategy to simultaneously enhance the carrier mobility and stretchability of polymer semiconductors. Optimizing lamellar stacking distance and reducing crystallinity promote the dispersion of tris(pentafluorophenyl)borane within the side-chain regions. Reducing the strength of Lewis base groups in the polymer prevents the formation of excessively strong Lewis acid-base complexes, thus maintaining chain flexibility. + <img src="https://onlinelibrary.wiley.com/cms/asset/6c9ff8f0-db16-4f4d-b8f9-69ef5a05d3f4/adma202411558-gra-0001-m.png" + alt="An Ultra-Miniaturized Fiber Humidity Sensor Based on Near-Parallel Ion Pathways Induced Efficient Water−Electricity Conversion"/> +<p>Well-designed nanochannels significantly facilitate ion transport due to the stable charge distribution and the confined ions migration within near-parallel nanostructure, which improves the water-electricity conversion efficiency of moisture-sensitive fibers. Optimized nanochannels enable the humidity sensor to improve the response/recovery speed by ≈5 times compared to the disordered nanochannels, demonstrating the indispensable role of nanochannels in the water-electricity conversion process. </p> <br/> <h2>Abstract</h2> -<p>With the rise of skin-like electronics, devices are increasingly coming into close contact with the human body, creating a demand for polymer semiconductors (PSCs) that combine stretchability with reliable electrical performance. However, balancing mechanical robustness with high carrier mobility remains a challenge. To address this, tris(pentafluorophenyl)borane (BCF) for Lewis acid doping is proposed to improve charge mobility while enhancing stretchability by increasing structural disorder. Through systematic investigation, several key structural principles have been identified to maximize the effectiveness of BCF doping in stretchable PSCs. Notably, increasing the lamellar stacking distance and reducing crystallinity facilitate the incorporation of BCF into the alkyl side-chain regions, thereby enhancing both mobility and stretchability. Conversely, stronger Lewis base groups in the main chain negatively impact these improvements. These results demonstrate that with a small addition of BCF, a two-fold increase in carrier mobility is achieved while simultaneously enhancing the crack onset strain to 100%. Furthermore, doped PSCs exhibit stable mobility retention under repeated 30% strains over 1000 cycles. This method of decoupling carrier mobility from mechanical properties opens up new avenues in the search for high-mobility stretchable PSCs.</p> +<p>Humidity sensors are vital for ambient monitoring, but existing sensors focus on moisture absorption, overlooking the indispensable role of ion channels in the water-electricity conversion process. Here, an ultra-miniaturized fiber humidity (MFH) sensor based on near-parallel ion pathways is presented. The well-designed nanochannels significantly facilitate ion transport due to the stable charge distribution and the confined ions migration within near-parallel nanostructure, which improves the water-electricity conversion efficiency of moisture-sensitive fibers. Optimized nanochannels enable the MFH sensor to improve the response/recovery speed by ≈5 times compared to the disordered nanochannels. Additionally, the MFH sensor can be woven for ultra-miniaturization (0.50 mm<sup>2</sup>), which is much smaller than current sensors. Therefore, the integrated MFH sensor array demonstrated exceptionally high spatial resolution (sensor density of 1 mm<sup>−1</sup>), highlighting its potential in flexible wearables. This work provides new optimization strategies and assembly means for designing the high-performance humidity sensors of the next generation.</p> -Yu‐Ching Weng, -Chung‐Chieh Kang, -Ting‐Wei Chang, -Yi‐Ting Tsai, -Shahid Khan, -Tzu‐Ming Hung, -Chien‐Chung Shih +Qixiang Zhang, +Ziqi Ren, +Peixue Jia, +Junjie Shi, +Jianyu Yin, +Dandan Lei, +Yihua Gao, +Nishuang Liu Research Article - Design Principles for Enhancing Both Carrier Mobility and Stretchability in Polymer Semiconductors via Lewis Acid Doping - 10.1002/adma.202411572 + An Ultra‐Miniaturized Fiber Humidity Sensor Based on Near‐Parallel Ion Pathways Induced Efficient Water−Electricity Conversion + 10.1002/adma.202411558 Advanced Materials - 10.1002/adma.202411572 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411572 + 10.1002/adma.202411558 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411558 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413525 - Sun, 17 Nov 2024 21:24:31 -0800 - 2024-11-17T09:24:31-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412414 + Tue, 19 Nov 2024 00:17:24 -0800 + 2024-11-19T12:17:24-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413525 - Polarization: A Universal Driving Force for Energy, Environment, and Electronics + 10.1002/adma.202412414 + 4H‐SiC Metalens: Mitigating Thermal Drift Effect in High‐Power Laser Irradiation Advanced Materials, EarlyView. -Polarization techniques are revolutionizing material functionalities across energy, environmental, and electronic sectors. This review comprehensively examines polarization mechanisms such as piezoelectric, ferroelectric, and pyroelectric effects, alongside strategies like doping and heterostructures. It highlights its pivotal role in enhancing charge dynamics, modifying surface chemistries, and facilitating energy‐efficient designs in various applications. +A monolithic 4H‐SiC metalens with exceptional thermal stability is applied in high‐power laser applications, achieving diffraction‐limited focusing (NA 0.5, focal length 1 cm). After 1 h of 15W, 1030 nm pulsed laser irradiation, it exhibits only a 3.2 °C temperature rise and a 14 µm focal shift. Cutting 4H‐SiC wafers results in just an 11.4% depth change, marking a significant advance for high‐power laser systems and expanding their application potential. @@ -227,50 +237,46 @@ Polarization techniques are revolutionizing material functionalities across ener Abstract -The sustainable future relies on the synergistic development of energy, environmental, and electronic systems, founded on the development of functional materials by exploring their quantum mechanisms. Effective control over the distribution and behavior of charges within these materials, a basic quantum attribute, is crucial in dictating their physical, chemical, and electronic properties. At the core of charge manipulation lies “polarization”—a ubiquitous phenomenon marked by separating positive and negative charges. This review thoroughly examines polarization techniques, spotlighting their transformative role in catalysis, energy storage, solar cells, and electronics. Starting with the foundational mechanisms underlying various forms of polarization, including piezoelectric, ferroelectric, and pyroelectric effects, the perspective is expanded to cover any asymmetric phenomena that generate internal fields, such as heterostructures and doping. Afterward, the critical role of polarization across various applications, including charge separation, surface chemistry modification, and energy band alignment, is highlighted. Special emphasis is placed on the synergy between polarization and material properties, demonstrating how this interplay is pivotal in overcoming existing technological limitations and unlocking new functionalities. Through a comprehensive analysis, a holistic roadmap is offered for harnessing polarization across the broad spectrum of applications, thus finding sustainable solutions for future energy, environment, and electronics. +Enhancing energy density and efficiency in laser processing hinges on precise beam focusing, yet this often causes severe heat absorption and focus shifts in optical lenses. Traditional cooling methods increase cost and complexity, severely limiting versatility. Here, monolithic silicon carbide (SiC) metalens is introduced, which shows unparalleled thermal stability, integrated with a high‐power laser. This metalens achieves diffraction‐limited focusing with a numerical aperture (NA) of 0.5 and a focal length of 1 cm. Under a 1030 nm pulsed laser at 15 W for 1 h, it shows a minimal temperature rise of 3.2 °C and a tiny focal shift of 14 µm (0.1% relative), only 6% of the shift in conventional lenses. When used to cut a 4H‐SiC substrate with the same laser, the metalens exhibit only an 11.4% change in cutting depth after 1 h of operation, correlating with the focal shift results. The results unveil a groundbreaking class of compact SiC photonics devices nearly impervious to heat absorption, representing a monumental leap for high‐power laser systems and opening new horizons for their applications and efficiency. - <img src="https://onlinelibrary.wiley.com/cms/asset/24b46d69-0a05-4123-90d4-af3250cee7ec/adma202413525-gra-0001-m.png" - alt="Polarization: A Universal Driving Force for Energy, Environment, and Electronics"/> -<p>Polarization techniques are revolutionizing material functionalities across energy, environmental, and electronic sectors. This review comprehensively examines polarization mechanisms such as piezoelectric, ferroelectric, and pyroelectric effects, alongside strategies like doping and heterostructures. It highlights its pivotal role in enhancing charge dynamics, modifying surface chemistries, and facilitating energy-efficient designs in various applications. + <img src="https://onlinelibrary.wiley.com/cms/asset/e206238f-3f56-4a3f-ae49-1d8c2b654ab2/adma202412414-gra-0001-m.png" + alt="4H-SiC Metalens: Mitigating Thermal Drift Effect in High-Power Laser Irradiation"/> +<p>A monolithic 4H-SiC metalens with exceptional thermal stability is applied in high-power laser applications, achieving diffraction-limited focusing (NA 0.5, focal length 1 cm). After 1 h of 15W, 1030 nm pulsed laser irradiation, it exhibits only a 3.2 °C temperature rise and a 14 µm focal shift. Cutting 4H-SiC wafers results in just an 11.4% depth change, marking a significant advance for high-power laser systems and expanding their application potential. </p> <br/> <h2>Abstract</h2> -<p>The sustainable future relies on the synergistic development of energy, environmental, and electronic systems, founded on the development of functional materials by exploring their quantum mechanisms. Effective control over the distribution and behavior of charges within these materials, a basic quantum attribute, is crucial in dictating their physical, chemical, and electronic properties. At the core of charge manipulation lies “polarization”—a ubiquitous phenomenon marked by separating positive and negative charges. This review thoroughly examines polarization techniques, spotlighting their transformative role in catalysis, energy storage, solar cells, and electronics. Starting with the foundational mechanisms underlying various forms of polarization, including piezoelectric, ferroelectric, and pyroelectric effects, the perspective is expanded to cover any asymmetric phenomena that generate internal fields, such as heterostructures and doping. Afterward, the critical role of polarization across various applications, including charge separation, surface chemistry modification, and energy band alignment, is highlighted. Special emphasis is placed on the synergy between polarization and material properties, demonstrating how this interplay is pivotal in overcoming existing technological limitations and unlocking new functionalities. Through a comprehensive analysis, a holistic roadmap is offered for harnessing polarization across the broad spectrum of applications, thus finding sustainable solutions for future energy, environment, and electronics.</p> +<p>Enhancing energy density and efficiency in laser processing hinges on precise beam focusing, yet this often causes severe heat absorption and focus shifts in optical lenses. Traditional cooling methods increase cost and complexity, severely limiting versatility. Here, monolithic silicon carbide (SiC) metalens is introduced, which shows unparalleled thermal stability, integrated with a high-power laser. This metalens achieves diffraction-limited focusing with a numerical aperture (NA) of 0.5 and a focal length of 1 cm. Under a 1030 nm pulsed laser at 15 W for 1 h, it shows a minimal temperature rise of 3.2 °C and a tiny focal shift of 14 µm (0.1% relative), only 6% of the shift in conventional lenses. When used to cut a 4H-SiC substrate with the same laser, the metalens exhibit only an 11.4% change in cutting depth after 1 h of operation, correlating with the focal shift results. The results unveil a groundbreaking class of compact SiC photonics devices nearly impervious to heat absorption, representing a monumental leap for high-power laser systems and opening new horizons for their applications and efficiency.</p> -Xinwei Guan, -Zhihao Lei, -Ruichang Xue, -Zhixuan Li, -Peng Li, -Matthew David, -Jiabao Yi, -Baohua Jia, -Hongwei Huang, -Xiaoning Li, -Tianyi Ma +Boqu Chen, +Xiaoyu Sun, +Xiaoxuan Li, +Lu Cai, +Ding Zhao, +Kaikai Du, +Meiyan Pan, +Min Qiu - Review - Polarization: A Universal Driving Force for Energy, Environment, and Electronics - 10.1002/adma.202413525 + Research Article + 4H‐SiC Metalens: Mitigating Thermal Drift Effect in High‐Power Laser Irradiation + 10.1002/adma.202412414 Advanced Materials - 10.1002/adma.202413525 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413525 - Review + 10.1002/adma.202412414 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412414 + Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413304 - Sun, 17 Nov 2024 21:24:09 -0800 - 2024-11-17T09:24:09-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411856 + Tue, 19 Nov 2024 00:16:49 -0800 + 2024-11-19T12:16:49-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413304 - Synergistic Modulation of Orientation and Steric Hindrance Induced by Alkyl Chain Length in Ammonium Salt Passivator Toward High‐performance Inverted Perovskite Solar Cells and Modules + 10.1002/adma.202411856 + Fire‐Safe Aerogels and Foams for Thermal Insulation: From Materials to Properties Advanced Materials, EarlyView. -Organic ammonium salts with varying alkyl chain lengths are used to passivate perovskite surface defects and optimize energy band alignment. Nonylammonium acetate (NAAc) achieves superior passivation through optimal molecular orientation and minimized steric hindrance, leading to 25.79% PCE in inverted PSCs utilizing vacuum flash technology in ambient conditions. - +Aerogels/foams are ideal thermally insulating materials owing to their low density and low thermal conductivity. To meet their practical applications, these aerogels/foams need to be thermally insulating, mechanically robust and fire‐resistant. Recent advances on fire‐safe thermal‐insulating aerogels/foams are reviewed. Future research opportunities are proposed in response to key challenges for expediting the creation of next‐generation aerogels/foams for better thermal management. @@ -280,51 +286,53 @@ Organic ammonium salts with varying alkyl chain lengths are used to passivate pe Abstract -Organic ammonium salts are extensively utilized for passivating surface defects in perovskite films to mitigate trap‐assisted nonradiative recombination. However, the influence of alkyl chain length on the molecular orientation and spatial steric hindrance of ammonium salt remains underexplored, hindering advancements in more effective passivators. Here, a series of organic ammonium salts is reported with varying alkyl chain lengths to passivate surface defects and optimize band alignment. It is revealed that long alkyl chains promote parallel molecular orientation on the perovskite surface, thereby reinforcing interaction with surface defects, whereas excessive chain length introduces steric hindrance, weakening anion‐perovskite interactions. Nonylammonium acetate (NAAc) with optimal chain length achieves the ideal balance between chemical interactions, resulting in superior passivation. Through NAAc passivation, high‐performance inverted perovskite solar cells (PSCs) and modules are achieved, with power conversion efficiencies (PCE) of 25.79% (certified 25.12%) and 19.62%, respectively. This marks a record PCE for inverted PSCs utilizing vacuum flash technology in ambient conditions. Additionally, the NAAc‐passivated devices retain 91% of their initial PCE after 1200 h of continuous maximum power point operation. This work offers new insights into the interplay between molecular orientation and steric hindrance, advancing the design of high‐performance PSCs. +The ambition of human beings to create a comfortable environment for work and life in a sustainable way has triggered a great need for advanced thermal insulation materials in past decades. Aerogels and foams present great prospects as thermal insulators owing to their low density, good thermal insulation, mechanical robustness, and even high fire resistance. These merits make them suitable for many real‐world applications, such as energy‐saving building materials, thermally protective materials in aircrafts and battery, and warming fabrics. Despite great advances, to date there remains a lack of a comprehensive yet critical review on the thermal insulation materials. Herein, recent progresses in fire‐safe thermal‐insulating aerogels and foams are summarized, and pros/cons of three major categories of aerogels/foams (inorganic, organic and their hybrids) are discussed. Finally, key challenges associated with existing aerogels are discussed and some future opportunities are proposed. This review is expected to expedite the development of advanced aerogels and foams as fire‐safe thermally insulating materials, and to help create a sustainable, safe, and energy‐efficient society. - <img src="https://onlinelibrary.wiley.com/cms/asset/564f615c-ded7-4244-9f3c-94149546c5d7/adma202413304-gra-0001-m.png" - alt="Synergistic Modulation of Orientation and Steric Hindrance Induced by Alkyl Chain Length in Ammonium Salt Passivator Toward High-performance Inverted Perovskite Solar Cells and Modules"/> -<p>Organic ammonium salts with varying alkyl chain lengths are used to passivate perovskite surface defects and optimize energy band alignment. Nonylammonium acetate (NAAc) achieves superior passivation through optimal molecular orientation and minimized steric hindrance, leading to 25.79% PCE in inverted PSCs utilizing vacuum flash technology in ambient conditions. + <img src="https://onlinelibrary.wiley.com/cms/asset/a9c4e82f-f705-41e1-9c73-84899341bb0f/adma202411856-gra-0001-m.png" + alt="Fire-Safe Aerogels and Foams for Thermal Insulation: From Materials to Properties"/> +<p>Aerogels/foams are ideal thermally insulating materials owing to their low density and low thermal conductivity. To meet their practical applications, these aerogels/foams need to be thermally insulating, mechanically robust and fire-resistant. Recent advances on fire-safe thermal-insulating aerogels/foams are reviewed. Future research opportunities are proposed in response to key challenges for expediting the creation of next-generation aerogels/foams for better thermal management. </p> <br/> <h2>Abstract</h2> -<p>Organic ammonium salts are extensively utilized for passivating surface defects in perovskite films to mitigate trap-assisted nonradiative recombination. However, the influence of alkyl chain length on the molecular orientation and spatial steric hindrance of ammonium salt remains underexplored, hindering advancements in more effective passivators. Here, a series of organic ammonium salts is reported with varying alkyl chain lengths to passivate surface defects and optimize band alignment. It is revealed that long alkyl chains promote parallel molecular orientation on the perovskite surface, thereby reinforcing interaction with surface defects, whereas excessive chain length introduces steric hindrance, weakening anion-perovskite interactions. Nonylammonium acetate (NAAc) with optimal chain length achieves the ideal balance between chemical interactions, resulting in superior passivation. Through NAAc passivation, high-performance inverted perovskite solar cells (PSCs) and modules are achieved, with power conversion efficiencies (PCE) of 25.79% (certified 25.12%) and 19.62%, respectively. This marks a record PCE for inverted PSCs utilizing vacuum flash technology in ambient conditions. Additionally, the NAAc-passivated devices retain 91% of their initial PCE after 1200 h of continuous maximum power point operation. This work offers new insights into the interplay between molecular orientation and steric hindrance, advancing the design of high-performance PSCs.</p> +<p>The ambition of human beings to create a comfortable environment for work and life in a sustainable way has triggered a great need for advanced thermal insulation materials in past decades. Aerogels and foams present great prospects as thermal insulators owing to their low density, good thermal insulation, mechanical robustness, and even high fire resistance. These merits make them suitable for many real-world applications, such as energy-saving building materials, thermally protective materials in aircrafts and battery, and warming fabrics. Despite great advances, to date there remains a lack of a comprehensive yet critical review on the thermal insulation materials. Herein, recent progresses in fire-safe thermal-insulating aerogels and foams are summarized, and pros/cons of three major categories of aerogels/foams (inorganic, organic and their hybrids) are discussed. Finally, key challenges associated with existing aerogels are discussed and some future opportunities are proposed. This review is expected to expedite the development of advanced aerogels and foams as fire-safe thermally insulating materials, and to help create a sustainable, safe, and energy-efficient society.</p> -Wenhuan Gao, -Jike Ding, -Quanxing Ma, -Hong Zhang, -Jiajia Zhang, -Zuolin Zhang, -Mengjia Li, -Yang Wang, -Boxue Zhang, -Thierry Pauporté, -Jian‐Xin Tang, -Jiangzhao Chen, -Cong Chen +Jiabing Feng, +Zhewen Ma, +Jianpeng Wu, +Zhezhe Zhou, +Zheng Liu, +Boyou Hou, +Wei Zheng, +Siqi Huo, +Ye‐Tang Pan, +Min Hong, +Qiang Gao, +Ziqi Sun, +Hao Wang, +Pingan Song - Research Article - Synergistic Modulation of Orientation and Steric Hindrance Induced by Alkyl Chain Length in Ammonium Salt Passivator Toward High‐performance Inverted Perovskite Solar Cells and Modules - 10.1002/adma.202413304 + Review + Fire‐Safe Aerogels and Foams for Thermal Insulation: From Materials to Properties + 10.1002/adma.202411856 Advanced Materials - 10.1002/adma.202413304 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413304 - Research Article + 10.1002/adma.202411856 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411856 + Review - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412432 - Sun, 17 Nov 2024 21:23:35 -0800 - 2024-11-17T09:23:35-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412950 + Tue, 19 Nov 2024 00:15:33 -0800 + 2024-11-19T12:15:33-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412432 - Large‐Area Metal–Organic Framework Glasses for Efficient X‐Ray Detection + 10.1002/adma.202412950 + Breaking the Mutual‐Constraint of Bifunctional Oxygen Electrocatalysis via Direct O─O Coupling on High‐Valence Ir Single‐Atom on MnOx Advanced Materials, EarlyView. -Metal–organic framework (MOF) glasses composed of zinc and imidazole derivatives are employed to prepare large‐area and continuous MOF films. The MOF glass detector achieves an outstanding X‐ray sensitivity of 112.8 µC Gyair−1 cm−2 and a detection limit of 0.41 µGyair s−1. These findings pave the way for large‐area MOF‐based X‐ray detectors with practical applications in medical and security screening domains. +Mutual constraint of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional electrocatalysis is ingenuously broken on a high‐valence Ir single atom anchored on manganese oxide bifunctional catalyst through direct O─O coupling, which shows independent pathways for ORR and OER, i.e., associated 4e− pathway for ORR and a novel chemical‐activated concerted mechanism for OER. + @@ -334,56 +342,49 @@ Metal–organic framework (MOF) glasses composed of zinc and imidazole deriv Abstract -Cutting‐edge techniques utilizing continuous films made from pure, novel semiconductive materials offer promising pathways to achieve high performance and cost‐effectiveness for X‐ray detection. Semiconductive metal–organic framework (MOF) glass films are known for their remarkably smooth surface morphology, straightforward synthesis, and capability for large‐area fabrication, presenting a new direction for high‐performance X‐ray detectors. Here, a novel material centered on MOF glasses for highly uniform glass film fabrication customized for X‐ray detection is introduced. MOF glasses, composed of zinc and imidazole derivatives, enable the transition from solid to liquid at low temperatures, facilitating the straightforward preparation of large‐area and continuous MOF films with high mobility for X‐ray device fabrication. Remarkably, MOF glass detectors demonstrate an exceptional sensitivity of 112.8 µC Gyair−1 cm−2 and a detection limit of 0.41 µGyair s−1, making them one of the most sensitive and with the best detection limits reported to date for MOF X‐ray detectors. Clear X‐ray images are successfully conducted using these developed MOF glass detectors for the first time. This breakthrough in X‐ray sensitivity, and detection limit along with the spatial imaging resolution establishes a new standard for developing large‐area and efficient MOF‐based X‐ray detectors with practical applications in medical and security screening. +Insufficient bifunctional activity of electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is the major obstruction to the application of rechargeable metal–air batteries. The primary reason is the mutual constraint of ORR and OER mechanism, involving the same oxygen‐containing intermediates and demonstrating the scaling limitations of the adsorption energies. Herein, it is reported a high‐valence Ir single atom anchored on manganese oxide (IrSA‐MnOx) bifunctional catalyst showing independent pathways for ORR and OER, i.e., associated 4e− pathway on high‐valence Ir site for ORR and a novel chemical‐activated concerted mechanism for OER, where a distinct spontaneous chemical activation process triggers direct O─O coupling. The IrSA‐MnOx therefore delivers outstanding bifunctional activities with remarkably low potential difference (0.635 V) between OER potential at 10 mA cm−2 and ORR half‐wave potential in alkaline solution. This work breaks the scaling limitations and provides a new avenue to design efficient and multifunctional electrocatalysts. - <img src="https://onlinelibrary.wiley.com/cms/asset/799eff21-c054-4c05-8a91-79ad942f5c15/adma202412432-gra-0001-m.png" - alt="Large-Area Metal–Organic Framework Glasses for Efficient X-Ray Detection"/> -<p>Metal–organic framework (MOF) glasses composed of zinc and imidazole derivatives are employed to prepare large-area and continuous MOF films. The MOF glass detector achieves an outstanding X-ray sensitivity of 112.8 µC Gy<sub>air</sub> -<sup>−1</sup> cm<sup>−2</sup> and a detection limit of 0.41 µGy<sub>air</sub> s<sup>−1</sup>. These findings pave the way for large-area MOF-based X-ray detectors with practical applications in medical and security screening domains. + <img src="https://onlinelibrary.wiley.com/cms/asset/d19c2e30-60f8-408a-b98a-4a90b621cad6/adma202412950-gra-0001-m.png" + alt="Breaking the Mutual-Constraint of Bifunctional Oxygen Electrocatalysis via Direct O─O Coupling on High-Valence Ir Single-Atom on MnOx"/> +<p>Mutual constraint of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional electrocatalysis is ingenuously broken on a high-valence Ir single atom anchored on manganese oxide bifunctional catalyst through direct O<i>─</i>O coupling, which shows independent pathways for ORR and OER, i.e., associated 4e<sup>−</sup> pathway for ORR and a novel chemical-activated concerted mechanism for OER. </p> <br/> <h2>Abstract</h2> -<p>Cutting-edge techniques utilizing continuous films made from pure, novel semiconductive materials offer promising pathways to achieve high performance and cost-effectiveness for X-ray detection. Semiconductive metal–organic framework (MOF) glass films are known for their remarkably smooth surface morphology, straightforward synthesis, and capability for large-area fabrication, presenting a new direction for high-performance X-ray detectors. Here, a novel material centered on MOF glasses for highly uniform glass film fabrication customized for X-ray detection is introduced. MOF glasses, composed of zinc and imidazole derivatives, enable the transition from solid to liquid at low temperatures, facilitating the straightforward preparation of large-area and continuous MOF films with high mobility for X-ray device fabrication. Remarkably, MOF glass detectors demonstrate an exceptional sensitivity of 112.8 µC Gy<sub>air</sub> -<sup>−1</sup> cm<sup>−2</sup> and a detection limit of 0.41 µGy<sub>air</sub> s<sup>−1</sup>, making them one of the most sensitive and with the best detection limits reported to date for MOF X-ray detectors. Clear X-ray images are successfully conducted using these developed MOF glass detectors for the first time. This breakthrough in X-ray sensitivity, and detection limit along with the spatial imaging resolution establishes a new standard for developing large-area and efficient MOF-based X-ray detectors with practical applications in medical and security screening.</p> +<p>Insufficient bifunctional activity of electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is the major obstruction to the application of rechargeable metal–air batteries. The primary reason is the mutual constraint of ORR and OER mechanism, involving the same oxygen-containing intermediates and demonstrating the scaling limitations of the adsorption energies. Herein, it is reported a high-valence Ir single atom anchored on manganese oxide (Ir<sub>SA</sub>-MnO<i> + <sub>x</sub> +</i>) bifunctional catalyst showing independent pathways for ORR and OER, i.e., associated 4e<sup>−</sup> pathway on high-valence Ir site for ORR and a novel chemical-activated concerted mechanism for OER, where a distinct spontaneous chemical activation process triggers direct O<i>─</i>O coupling. The Ir<sub>SA</sub>-MnO<i> + <sub>x</sub> +</i> therefore delivers outstanding bifunctional activities with remarkably low potential difference (0.635 V) between OER potential at 10 mA cm<sup>−2</sup> and ORR half-wave potential in alkaline solution. This work breaks the scaling limitations and provides a new avenue to design efficient and multifunctional electrocatalysts.</p> -Xin Zhu, -Tengjiao He, -Xin Song, -Osama Shekhah, -Simil Thomas, -Hao Jiang, -Wentao Wu, -Tengyue He, -Vincent Guillerm, -Aleksander Shkurenko, -Jian‐Xin Wang, -Husam N. Alshareef, -Osman M. Bakr, -Mohamed Eddaoudi, -Omar F. Mohammed +Ziyi Yang, +Fayuan Lai, +Qianjiang Mao, +Chong Liu, +Shengjie Peng, +Xiangfeng Liu, +Tianran Zhang Research Article - Large‐Area Metal–Organic Framework Glasses for Efficient X‐Ray Detection - 10.1002/adma.202412432 + Breaking the Mutual‐Constraint of Bifunctional Oxygen Electrocatalysis via Direct O─O Coupling on High‐Valence Ir Single‐Atom on MnOx + 10.1002/adma.202412950 Advanced Materials - 10.1002/adma.202412432 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412432 + 10.1002/adma.202412950 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412950 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413049 - Sun, 17 Nov 2024 21:23:00 -0800 - 2024-11-17T09:23:00-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414628 + Tue, 19 Nov 2024 00:15:12 -0800 + 2024-11-19T12:15:12-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413049 - Promoting Piezoelectricity in Amino Acids by Fluorination + 10.1002/adma.202414628 + Insight Into Intermediate Behaviors and Design Strategies of Platinum Group Metal‐Based Alkaline Hydrogen Oxidation Catalysts Advanced Materials, EarlyView. -A high piezoelectric amino acid (Cbz‐Phe(4F)) is designed by simple fluorination. Cbz‐Phe(4F) self‐assembles into single crystals with C2 space group. Importantly, Cbz‐Phe(4F) crystals as a flexible piezoelectric sensor for the classification of various nuts and their quality sorting, which includes those as small as individual pumpkin seeds with high sensitivity and accuracy of sorting and quality checks. - +The primary focus of the review is on exploring the intermediate behaviors and catalyst strategies for alkaline hydrogen oxidation reaction on platinum group metal‐based (Pt, Pd, Ir, Ru, Rh‐based) materials. This review aims to provide strong support for comprehensively understanding the intricate alkaline HOR and vigorously developing the hydrogen fuel cell. @@ -393,48 +394,44 @@ A high piezoelectric amino acid (Cbz‐Phe(4F)) is designed by simple fluori Abstract -Bioinspired piezoelectric amino acids and peptides are attracting attention due to their designable sequences, versatile structures, low cost, and biodegradability. However, it remains a challenge to design amino acids and peptides with high piezoelectricity. Herein, a high piezoelectric amino acid by simple fluorination in its side chain is presented. The three phenylalanine derivatives are designed: Cbz‐Phe, Cbz‐Phe(4F), and Cbz‐pentafluoro‐Phe. The effect of fluorination on self‐assembly and piezoelectricity is investigated. Cbz‐Phe(4F) can self‐assemble into crystals with a C2 space group, while Cbz‐Phe and Cbz‐pentafluoro‐Phe form aggregated self‐assemblies. Moreover, Cbz‐Phe(4F) crystals exhibit a remarkably higher piezoelectric coefficient (d33eff$d_{\ 33}^{\ eff}$) of ≈17.9 pm V−1 than Cbz‐Phe and Cbz‐pentafluoro‐Phe. When fabricated as a piezoelectric nanogenerator, it generates an open‐circuit voltage of ≈2.4 V. Importantly, Cbz‐Phe(4F) crystals as a flexible piezoelectric sensor for the classification of various nuts and their quality sorting, which includes those as small as individual pumpkin seeds with high sensitivity and accuracy of sorting and quality checks. When mounted onto soft grippers, the sensor performs the tactile self‐sensing functions. This work provides a promising approach to designing high piezoelectric amino acids by simple fluorination, offering exciting prospects for advancements in bioinspired piezoelectric materials in the application of smart agriculture and soft robotics. +Hydrogen oxidation reaction (HOR) can effectively convert the hydrogen energy through the hydrogen fuel cells, which plays an increasingly important role in the renewable hydrogen cycle. Nevertheless, when the electrolyte pH changes from acid to base, even with platinum group metal (PGM) catalysts, the HOR kinetics declines with several orders of magnitude. More critically, the pivotal role of reaction intermediates and interfacial environment during intermediate behaviors on alkaline HOR remains controversial. Therefore, exploring the exceptional PGM‐based alkaline HOR electrocatalysts and identifying the reaction mechanism are indispensable for promoting the commercial development of hydrogen fuel cells. Consequently, the fundamental understanding of the HOR mechanism is first introduced, with emphases on the adsorption/desorption process of distinct reactive intermediates and the interfacial structure during catalytic process. Subsequently, with the guidance of reaction mechanism, the latest advances in the rational design of advanced PGM‐based (Pt, Pd, Ir, Ru, Rh‐based) alkaline HOR catalysts are discussed, focusing on the correlation between the intermediate behaviors and the electrocatalytic performance. Finally, given that the challenges standing in the development of the alkaline HOR, the prospect for the rational catalysts design and thorough mechanism investigation towards alkaline HOR are emphatically proposed. - <img src="https://onlinelibrary.wiley.com/cms/asset/e0a74388-6412-42a4-b69a-9bc8c1308c68/adma202413049-gra-0001-m.png" - alt="Promoting Piezoelectricity in Amino Acids by Fluorination"/> -<p>A high piezoelectric amino acid (Cbz-Phe(4F)) is designed by simple fluorination. Cbz-Phe(4F) self-assembles into single crystals with C2 space group. Importantly, Cbz-Phe(4F) crystals as a flexible piezoelectric sensor for the classification of various nuts and their quality sorting, which includes those as small as individual pumpkin seeds with high sensitivity and accuracy of sorting and quality checks. + <img src="https://onlinelibrary.wiley.com/cms/asset/9f29408f-eb72-49a7-847a-4a6ce774f3b1/adma202414628-gra-0001-m.png" + alt="Insight Into Intermediate Behaviors and Design Strategies of Platinum Group Metal-Based Alkaline Hydrogen Oxidation Catalysts"/> +<p>The primary focus of the review is on exploring the intermediate behaviors and catalyst strategies for alkaline hydrogen oxidation reaction on platinum group metal-based (Pt, Pd, Ir, Ru, Rh-based) materials. This review aims to provide strong support for comprehensively understanding the intricate alkaline HOR and vigorously developing the hydrogen fuel cell. </p> <br/> <h2>Abstract</h2> -<p>Bioinspired piezoelectric amino acids and peptides are attracting attention due to their designable sequences, versatile structures, low cost, and biodegradability. However, it remains a challenge to design amino acids and peptides with high piezoelectricity. Herein, a high piezoelectric amino acid by simple fluorination in its side chain is presented. The three phenylalanine derivatives are designed: Cbz-Phe, Cbz-Phe(4F), and Cbz-pentafluoro-Phe. The effect of fluorination on self-assembly and piezoelectricity is investigated. Cbz-Phe(4F) can self-assemble into crystals with a C2 space group, while Cbz-Phe and Cbz-pentafluoro-Phe form aggregated self-assemblies. Moreover, Cbz-Phe(4F) crystals exhibit a remarkably higher piezoelectric coefficient (d33eff$d_{\ 33}^{\ eff}$) of ≈17.9 pm V<sup>−1</sup> than Cbz-Phe and Cbz-pentafluoro-Phe. When fabricated as a piezoelectric nanogenerator, it generates an open-circuit voltage of ≈2.4 V. Importantly, Cbz-Phe(4F) crystals as a flexible piezoelectric sensor for the classification of various nuts and their quality sorting, which includes those as small as individual pumpkin seeds with high sensitivity and accuracy of sorting and quality checks. When mounted onto soft grippers, the sensor performs the tactile self-sensing functions. This work provides a promising approach to designing high piezoelectric amino acids by simple fluorination, offering exciting prospects for advancements in bioinspired piezoelectric materials in the application of smart agriculture and soft robotics.</p> +<p>Hydrogen oxidation reaction (HOR) can effectively convert the hydrogen energy through the hydrogen fuel cells, which plays an increasingly important role in the renewable hydrogen cycle. Nevertheless, when the electrolyte pH changes from acid to base, even with platinum group metal (PGM) catalysts, the HOR kinetics declines with several orders of magnitude. More critically, the pivotal role of reaction intermediates and interfacial environment during intermediate behaviors on alkaline HOR remains controversial. Therefore, exploring the exceptional PGM-based alkaline HOR electrocatalysts and identifying the reaction mechanism are indispensable for promoting the commercial development of hydrogen fuel cells. Consequently, the fundamental understanding of the HOR mechanism is first introduced, with emphases on the adsorption/desorption process of distinct reactive intermediates and the interfacial structure during catalytic process. Subsequently, with the guidance of reaction mechanism, the latest advances in the rational design of advanced PGM-based (Pt, Pd, Ir, Ru, Rh-based) alkaline HOR catalysts are discussed, focusing on the correlation between the intermediate behaviors and the electrocatalytic performance. Finally, given that the challenges standing in the development of the alkaline HOR, the prospect for the rational catalysts design and thorough mechanism investigation towards alkaline HOR are emphatically proposed.</p> -Tan Hu, -Jin Pyo Lee, -Peiwen Huang, -Amanda Jiamin Ong, -Jian Yu, -Shuihong Zhu, -Yixuan Jiang, -Zhuo Zhang, -Meital Reches, -Pooi See Lee +Lixin Su, +Hao Wu, +Shaokun Zhang, +Chenxi Cui, +Shengnan Zhou, +Huan Pang - Research Article - Promoting Piezoelectricity in Amino Acids by Fluorination - 10.1002/adma.202413049 + Review + Insight Into Intermediate Behaviors and Design Strategies of Platinum Group Metal‐Based Alkaline Hydrogen Oxidation Catalysts + 10.1002/adma.202414628 Advanced Materials - 10.1002/adma.202413049 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413049 - Research Article + 10.1002/adma.202414628 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414628 + Review - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406727 - Sun, 17 Nov 2024 21:22:09 -0800 - 2024-11-17T09:22:09-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414790 + Tue, 19 Nov 2024 00:14:55 -0800 + 2024-11-19T12:14:55-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202406727 - Spintronic Pathways in a Nonconjugated Radical Polymer Glass + 10.1002/adma.202414790 + Efficient Blade‐Coated Wide‐Bandgap and Tandem Perovskite Solar Cells via a Three‐Step Restraining Strategy Advanced Materials, EarlyView. -A nonconjugated radical polymer with high spin density displays large effective spin mixing conductance, enabling efficient spin transport over long distances at room temperature. +Strict control of crystal growth has historically limited the efficiency of blade‐coated perovskite solar cells compared to spin‐coated devices. Here, a three‐step restraining strategy that employs a functional additive to regulate crystal growth enables efficient blade‐coated perovskite solar cells. This approach achieves a 19.97% efficiency for single‐junction 1.77 eV wide‐bandgap cells and a 27.11% efficiency for 2‐terminal all‐perovskite tandem solar cells. @@ -444,46 +441,57 @@ A nonconjugated radical polymer with high spin density displays large effective Abstract -Radical chemistries have attracted burgeoning attention due to their intriguing technological applications in organic electronics, optoelectronics, and magneto‐responsive systems. However, the potential of these magnetically active glassy polymers to transport spin‐selective currents has not been demonstrated. Here, the spin‐transport characteristics of the radical polymer poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl) (PTEO) allow for sustained spin‐selective currents when incorporated into typical device geometries with magnetically polarized electrodes. Annealing thin films of PTEO above its glass transition temperature results in a giant magnetoresistance effect (i.e., an MR of ≈80%) at 4 K. Additionally, ferromagnetic resonance spin‐pumping results in a relatively large effective spin‐mixing conductance of 1.18 × 1019 m−2 at the NiFe/PTEO interface. Due to the large spin‐density and radical‐radical exchange interactions, there is effective propagation of pure spin currents through PTEO in the NiFe/PTEO/Pd multilayer devices. This results in the transport of spin current over long distances with a spin diffusion length of 90.4 nm. The spin diffusion length and spin mixing conductance values surpass those reported in inorganic and metallic systems and are comparable to conventional doped conjugated polymers. This is the first example of spin transport in a nonconjugated radical polymer, and these findings underscore the promising spin‐transporting potential of radical polymers. +Blade‐coating techniques have attracted significant attention for perovskite solar cells (PSCs) due to their high precursor utilization and simplicity. However, the power conversion efficiency (PCE) of blade‐coated PSCs often lags behind that of spin‐coated devices, mainly due to difficulties in precisely controlling perovskite film formation during pre‐nucleation, heterogeneous nucleation, and crystallization in the blade‐coating and N2‐knife drying processes. In this work, a three‐step restraining strategy is introduced utilizing functional glycine amide hydrochloride to regulate pre‐nucleation clustering, suppress excessive heterogeneous nucleation, and decelerate crystallization, enabling comprehensive control of the perovskite film formation processes. This approach results in enlarged grains, reduced defect densities, and highly oriented crystalline wide‐bandgap perovskite films with significantly prolonged carrier lifetimes, achieving a maximum PCE of 19.97% for 1.77 eV‐bandgap blade‐coated PSCs. Furthermore, two‐terminal tandem cells, composed of wide‐bandgap perovskite top cells and 1.25 eV‐bandgap perovskite bottom cells fabricated via blade coating, yield an impressive PCE of 27.11% (stabilized at 26.87%). This study offers comprehensive insights into controlling pre‐nucleation, heterogeneous nucleation, and crystallization during blade coating, providing valuable guidance for developing high‐performance, large‐area devices in the future. - <img src="https://onlinelibrary.wiley.com/cms/asset/9f44482c-d216-431a-a70b-bb93d811a0e8/adma202406727-gra-0001-m.png" - alt="Spintronic Pathways in a Nonconjugated Radical Polymer Glass"/> -<p>A nonconjugated radical polymer with high spin density displays large effective spin mixing conductance, enabling efficient spin transport over long distances at room temperature. + <img src="https://onlinelibrary.wiley.com/cms/asset/e35a0394-fb3c-40eb-aaa2-c8764b9f9ba4/adma202414790-gra-0001-m.png" + alt="Efficient Blade-Coated Wide-Bandgap and Tandem Perovskite Solar Cells via a Three-Step Restraining Strategy"/> +<p>Strict control of crystal growth has historically limited the efficiency of blade-coated perovskite solar cells compared to spin-coated devices. Here, a three-step restraining strategy that employs a functional additive to regulate crystal growth enables efficient blade-coated perovskite solar cells. This approach achieves a 19.97% efficiency for single-junction 1.77 eV wide-bandgap cells and a 27.11% efficiency for 2-terminal all-perovskite tandem solar cells. </p> <br/> <h2>Abstract</h2> -<p>Radical chemistries have attracted burgeoning attention due to their intriguing technological applications in organic electronics, optoelectronics, and magneto-responsive systems. However, the potential of these magnetically active glassy polymers to transport spin-selective currents has not been demonstrated. Here, the spin-transport characteristics of the radical polymer poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl) (PTEO) allow for sustained spin-selective currents when incorporated into typical device geometries with magnetically polarized electrodes. Annealing thin films of PTEO above its glass transition temperature results in a giant magnetoresistance effect (i.e., an MR of ≈80%) at 4 K. Additionally, ferromagnetic resonance spin-pumping results in a relatively large effective spin-mixing conductance of 1.18 × 10<sup>19</sup> m<sup>−2</sup> at the NiFe/PTEO interface. Due to the large spin-density and radical-radical exchange interactions, there is effective propagation of pure spin currents through PTEO in the NiFe/PTEO/Pd multilayer devices. This results in the transport of spin current over long distances with a spin diffusion length of 90.4 nm. The spin diffusion length and spin mixing conductance values surpass those reported in inorganic and metallic systems and are comparable to conventional doped conjugated polymers. This is the first example of spin transport in a nonconjugated radical polymer, and these findings underscore the promising spin-transporting potential of radical polymers.</p> +<p>Blade-coating techniques have attracted significant attention for perovskite solar cells (PSCs) due to their high precursor utilization and simplicity. However, the power conversion efficiency (PCE) of blade-coated PSCs often lags behind that of spin-coated devices, mainly due to difficulties in precisely controlling perovskite film formation during pre-nucleation, heterogeneous nucleation, and crystallization in the blade-coating and N<sub>2</sub>-knife drying processes. In this work, a three-step restraining strategy is introduced utilizing functional glycine amide hydrochloride to regulate pre-nucleation clustering, suppress excessive heterogeneous nucleation, and decelerate crystallization, enabling comprehensive control of the perovskite film formation processes. This approach results in enlarged grains, reduced defect densities, and highly oriented crystalline wide-bandgap perovskite films with significantly prolonged carrier lifetimes, achieving a maximum PCE of 19.97% for 1.77 eV-bandgap blade-coated PSCs. Furthermore, two-terminal tandem cells, composed of wide-bandgap perovskite top cells and 1.25 eV-bandgap perovskite bottom cells fabricated via blade coating, yield an impressive PCE of 27.11% (stabilized at 26.87%). This study offers comprehensive insights into controlling pre-nucleation, heterogeneous nucleation, and crystallization during blade coating, providing valuable guidance for developing high-performance, large-area devices in the future.</p> -Hamas Tahir, -Carsten Flores‐Hansen, -Sheng‐Ning Hsu, -Zihao Liang, -Jayant Naga, -Neil R. Dilley, -Brett M. Savoie, -Bryan W. Boudouris +Hongyi Fang, +Weicheng Shen, +Hongling Guan, +Guoyi Chen, +Guang Li, +Wei Ai, +Shiqiang Fu, +Zuxiong Xu, +Weiqing Chen, +Peng Jia, +Zixi Yu, +Shuxin Wang, +Zhiqiu Yu, +Qingxian Lin, +Jiahao Wang, +Wenwen Zheng, +Dexin Pu, +Guojia Fang, +Weijun Ke Research Article - Spintronic Pathways in a Nonconjugated Radical Polymer Glass - 10.1002/adma.202406727 + Efficient Blade‐Coated Wide‐Bandgap and Tandem Perovskite Solar Cells via a Three‐Step Restraining Strategy + 10.1002/adma.202414790 Advanced Materials - 10.1002/adma.202406727 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406727 + 10.1002/adma.202414790 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414790 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413060 - Sun, 17 Nov 2024 21:22:04 -0800 - 2024-11-17T09:22:04-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414450 + Tue, 19 Nov 2024 00:14:25 -0800 + 2024-11-19T12:14:25-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413060 - Mesoporous Acridinium‐Based Covalent Organic Framework for Long‐lived Charge‐Separated Exciton Mediated Photocatalytic [4+2] Annulation + 10.1002/adma.202414450 + Hydrogen Bond‐Mediated Self‐Assembly of Carbon Dots Enabling Precise Tuning of Particle and Cluster Luminescence for Advanced Optoelectronic Applications Advanced Materials, EarlyView. -An Acridinium‐based covalent organic framework (COFs) featuring systematic trap states is designed to generate charge‐separated excitons with enhanced lifetime. Large 4 nm‐sized mesoporous channels and ultra‐stable excitons resulted in the COF functioning as an efficient heterogeneous photocatalyst toward Diels‐Alder type oxidative [4+2] annulation with a million times enhanced interfacial charge dissipation response. +A model in which the self‐assembly of carbon dots (CDs) and the corresponding cluster luminescence are modulated by the competitive hydrogen bonding interaction between CDs‐CDs and CDs‐solvent molecules is established. This controlled self‐assembly unlocks exciting potential for advanced optoelectronic applications, including customizable LEDs, secure encryption, and fingerprint authentication, offering new opportunities for technological innovation. @@ -493,50 +501,45 @@ An Acridinium‐based covalent organic framework (COFs) featuring systematic Abstract -Readily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long‐lived charge‐separated excitons. Installing cationic acridinium functionality in a pristine electron‐rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor–acceptor dyad network that performed rapid and efficient oxidative Diels‐Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of ≈4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra‐stable charge‐separated excitons of 1.9 nm diameter with no apparent radiative charge‐recombination pathway, endorsing almost a million times better photo‐response and catalysis than the state‐of‐the‐art. +The effective control over the self‐assembly process of carbon dots (CDs) and their cluster luminescence in the aggregated state is of paramount significance and challenge. This study, for the first time, systematically explores the photoluminescent behavior of CDs in their aggregated state, which is less understood compared to their discrete state. By investigating the effects of concentration and solvent environment, it's demonstrated that CDs could exhibit dual emission properties, shifting from blue particle emissions to red cluster emissions as they aggregate. The key to this tunable luminescence lies in hydrogen bonding, which drives the self‐assembly of CDs and modulates their photo physical properties. These findings reveal that through precise control of aggregation, CDs can be engineered for advanced optoelectronic applications, including tunable light‐emitting diodes (LEDs), secure information encryption, and fingerprint authentication. This report not only deepens the understanding of the underlying mechanisms governing CDs' cluster luminescence but also introduces a novel approach to exploiting their unique properties for technological innovation. - <img src="https://onlinelibrary.wiley.com/cms/asset/4413b778-2419-4472-b608-8b8339d40a6a/adma202413060-gra-0001-m.png" - alt="Mesoporous Acridinium-Based Covalent Organic Framework for Long-lived Charge-Separated Exciton Mediated Photocatalytic [4+2] Annulation"/> -<p>An Acridinium-based covalent organic framework (COFs) featuring systematic trap states is designed to generate charge-separated excitons with enhanced lifetime. Large 4 nm-sized mesoporous channels and ultra-stable excitons resulted in the COF functioning as an efficient heterogeneous photocatalyst toward Diels-Alder type oxidative [4+2] annulation with a million times enhanced interfacial charge dissipation response. + <img src="https://onlinelibrary.wiley.com/cms/asset/be419f9d-8f04-423c-a22b-551930790388/adma202414450-gra-0001-m.png" + alt="Hydrogen Bond-Mediated Self-Assembly of Carbon Dots Enabling Precise Tuning of Particle and Cluster Luminescence for Advanced Optoelectronic Applications"/> +<p>A model in which the self-assembly of carbon dots (CDs) and the corresponding cluster luminescence are modulated by the competitive hydrogen bonding interaction between CDs-CDs and CDs-solvent molecules is established. This controlled self-assembly unlocks exciting potential for advanced optoelectronic applications, including customizable LEDs, secure encryption, and fingerprint authentication, offering new opportunities for technological innovation. </p> <br/> <h2>Abstract</h2> -<p>Readily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long-lived charge-separated excitons. Installing cationic acridinium functionality in a pristine electron-rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor–acceptor dyad network that performed rapid and efficient oxidative Diels-Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of ≈4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra-stable charge-separated excitons of 1.9 nm diameter with no apparent radiative charge-recombination pathway, endorsing almost a million times better photo-response and catalysis than the state-of-the-art.</p> +<p>The effective control over the self-assembly process of carbon dots (CDs) and their cluster luminescence in the aggregated state is of paramount significance and challenge. This study, for the first time, systematically explores the photoluminescent behavior of CDs in their aggregated state, which is less understood compared to their discrete state. By investigating the effects of concentration and solvent environment, it's demonstrated that CDs could exhibit dual emission properties, shifting from blue particle emissions to red cluster emissions as they aggregate. The key to this tunable luminescence lies in hydrogen bonding, which drives the self-assembly of CDs and modulates their photo physical properties. These findings reveal that through precise control of aggregation, CDs can be engineered for advanced optoelectronic applications, including tunable light-emitting diodes (LEDs), secure information encryption, and fingerprint authentication. This report not only deepens the understanding of the underlying mechanisms governing CDs' cluster luminescence but also introduces a novel approach to exploiting their unique properties for technological innovation.</p> -Ipsita Nath, -Jeet Chakraborty, -Kuber Singh Rawat, -Yanwei Ji, -Rundong Wang, -Korneel Molkens, -Nathalie De Geyter, -Rino Morent, -Veronique Van Speybroeck, -Pieter Geiregat, -Pascal Van Der Voort +Chunyu Ji, +Fanhao Zeng, +Wenjun Xu, +Minjie Zhu, +Hongchun Yu, +Han Yang, +Zhili Peng Research Article - Mesoporous Acridinium‐Based Covalent Organic Framework for Long‐lived Charge‐Separated Exciton Mediated Photocatalytic [4+2] Annulation - 10.1002/adma.202413060 + Hydrogen Bond‐Mediated Self‐Assembly of Carbon Dots Enabling Precise Tuning of Particle and Cluster Luminescence for Advanced Optoelectronic Applications + 10.1002/adma.202414450 Advanced Materials - 10.1002/adma.202413060 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413060 + 10.1002/adma.202414450 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414450 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202402191 - Sun, 17 Nov 2024 21:21:20 -0800 - 2024-11-17T09:21:20-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202415138 + Tue, 19 Nov 2024 00:14:24 -0800 + 2024-11-19T12:14:24-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202402191 - Materials Design by Constructing Phase Diagrams for Defects + 10.1002/adma.202415138 + Balancing the Charge Separation and Surface Reaction Dynamics in Twin‐Interface Photocatalysts for Solar‐to‐Hydrogen Production Advanced Materials, EarlyView. -A systematic way to develop defect phase diagrams is proposed for advanced materials design. Phase transformation of a Mg grain boundary is triggered by Ga implantation on a microscopy sample. Transformations of structural units and chemical ordering at the same grain boundary are experimentally traced at atomic resolution and modeled by ab initio simulations to construct the defect phase diagram. - +This study thoroughly investigates the synergistic effects of charge separation and surface reaction dynamics in nano‐twinned photocatalysts by combining multiple time‐resolved spectroscopy (TRPL, fs‐TA, and TRIR) techniques, underscoring the transformative potential of twin structures in photocatalysis, offering a new avenue to synchronize charge transport and surface reactions, and holding broad implications for the development of efficient solar energy conversion systems. @@ -546,54 +549,47 @@ A systematic way to develop defect phase diagrams is proposed for advanced mater Abstract -Phase transformations and crystallographic defects are two essential tools to drive innovations in materials. Bulk materials design via tuning chemical compositions is systematized using phase diagrams. It is shown here that the same thermodynamic concept can be applied to manipulate the chemistry at defects. Grain boundaries in Mg–Ga system are chosen as a model system, because Ga segregates to the boundaries, while simultaneously improving the strength and ductility of Mg alloys. To reveal the role of grain boundaries, correlated atomic‐scale characterization and simulation to scope and build phase diagrams for defects are presented. The discovery is enabled by triggering phase transformations of individual grain boundaries through local alloying, and sequentially imaging the structural and chemical changes using atomic‐resolution scanning transmission electron microscopy. Ab initio simulations determined the thermodynamic stability of grain boundary phases, and found out that increasing Ga content enhances grain boundary cohesion, relating to improved ductility. The methodology to trigger, trace, and simulate defect transformation at atomic resolution enables a systematic development of defect phase diagrams, providing a valuable tool to utilize chemical complexity and phase transformations at defects. +Solar‐driven photocatalytic green hydrogen (H2) evolution reaction presents a promising route toward solar‐to‐chemical fuel conversion. However, its efficiency has been hindered by the desynchronization of fast photogenerated charge carriers and slow surface reaction kinetics. This work introduces a paradigm shift in photocatalyst design by focusing on the synchronization of charge transport and surface reactions through the use of twin structures as a unique platform. With CdS twin structure (CdS‐T) as a model, the role of twin boundaries in modulating surface reactions and facilitating charge migration is systematically investigated. Utilizing transient absorption (TA) and time‐resolved infrared (TRIR) spectroscopies, it is revealed that CdS‐T achieves charge separation on a picosecond timescale and, importantly, the surface reaction at the twin boundary with the involvement of holes also occurs within 100 ps to 3 ns. This synchronization of charge donation and surface regeneration significantly enhances the hydrogen evolution process. Accordingly, CdS‐T exhibits superior activity for visible light photocatalytic H2 production, withthe H2 production rate of 55.61 mmol h−1 g−1 and remarkable stability (>30 h), outperforming pristine CdS significantly. This study underscores the transformative potential of twin structures in photocatalysis, offering a new avenue to synchronize charge transport and surface reactions. - <img src="https://onlinelibrary.wiley.com/cms/asset/49d09af8-1866-4e18-8848-ab46c1f0db03/adma202402191-gra-0001-m.png" - alt="Materials Design by Constructing Phase Diagrams for Defects"/> -<p>A systematic way to develop defect phase diagrams is proposed for advanced materials design. Phase transformation of a Mg grain boundary is triggered by Ga implantation on a microscopy sample. Transformations of structural units and chemical ordering at the same grain boundary are experimentally traced at atomic resolution and modeled by ab initio simulations to construct the defect phase diagram. + <img src="https://onlinelibrary.wiley.com/cms/asset/56e1062b-73a0-47fc-8c47-f330f29d2cbb/adma202415138-gra-0001-m.png" + alt="Balancing the Charge Separation and Surface Reaction Dynamics in Twin-Interface Photocatalysts for Solar-to-Hydrogen Production"/> +<p>This study thoroughly investigates the synergistic effects of charge separation and surface reaction dynamics in nano-twinned photocatalysts by combining multiple time-resolved spectroscopy (TRPL, fs-TA, and TRIR) techniques, underscoring the transformative potential of twin structures in photocatalysis, offering a new avenue to synchronize charge transport and surface reactions, and holding broad implications for the development of efficient solar energy conversion systems. </p> <br/> <h2>Abstract</h2> -<p>Phase transformations and crystallographic defects are two essential tools to drive innovations in materials. Bulk materials design via tuning chemical compositions is systematized using phase diagrams. It is shown here that the same thermodynamic concept can be applied to manipulate the chemistry at defects. Grain boundaries in Mg–Ga system are chosen as a model system, because Ga segregates to the boundaries, while simultaneously improving the strength and ductility of Mg alloys. To reveal the role of grain boundaries, correlated atomic-scale characterization and simulation to scope and build phase diagrams for defects are presented. The discovery is enabled by triggering phase transformations of individual grain boundaries through local alloying, and sequentially imaging the structural and chemical changes using atomic-resolution scanning transmission electron microscopy. Ab initio simulations determined the thermodynamic stability of grain boundary phases, and found out that increasing Ga content enhances grain boundary cohesion, relating to improved ductility. The methodology to trigger, trace, and simulate defect transformation at atomic resolution enables a systematic development of defect phase diagrams, providing a valuable tool to utilize chemical complexity and phase transformations at defects.</p> +<p>Solar-driven photocatalytic green hydrogen (H<sub>2</sub>) evolution reaction presents a promising route toward solar-to-chemical fuel conversion. However, its efficiency has been hindered by the desynchronization of fast photogenerated charge carriers and slow surface reaction kinetics. This work introduces a paradigm shift in photocatalyst design by focusing on the synchronization of charge transport and surface reactions through the use of twin structures as a unique platform. With CdS twin structure (CdS-T) as a model, the role of twin boundaries in modulating surface reactions and facilitating charge migration is systematically investigated. Utilizing transient absorption (TA) and time-resolved infrared (TRIR) spectroscopies, it is revealed that CdS-T achieves charge separation on a picosecond timescale and, importantly, the surface reaction at the twin boundary with the involvement of holes also occurs within 100 ps to 3 ns. This synchronization of charge donation and surface regeneration significantly enhances the hydrogen evolution process. Accordingly, CdS-T exhibits superior activity for visible light photocatalytic H<sub>2</sub> production, withthe H<sub>2</sub> production rate of 55.61 mmol h<sup>−1</sup> g<sup>−1</sup> and remarkable stability (&gt;30 h), outperforming pristine CdS significantly. This study underscores the transformative potential of twin structures in photocatalysis, offering a new avenue to synchronize charge transport and surface reactions.</p> -Xuyang Zhou, -Prince Mathews, -Benjamin Berkels, -Wassilios Delis, -Saba Saood, -Amel Shamseldeen Ali Alhassan, -Philipp Keuter, -Jochen M. Schneider, -Sandra Korte‐Kerzel, -Stefanie Sandlöbes‐Haut, -Dierk Raabe, -Jörg Neugebauer, -Gerhard Dehm, -Tilmann Hickel, -Christina Scheu, -Siyuan Zhang +Meng Dan, +Shan Yu, +Weihua Lin, +Mohamed Abdellah, +Zhen Guo, +Zhao‐Qing Liu, +Tõnu Pullerits, +Kaibo Zheng, +Ying Zhou Research Article - Materials Design by Constructing Phase Diagrams for Defects - 10.1002/adma.202402191 + Balancing the Charge Separation and Surface Reaction Dynamics in Twin‐Interface Photocatalysts for Solar‐to‐Hydrogen Production + 10.1002/adma.202415138 Advanced Materials - 10.1002/adma.202402191 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202402191 + 10.1002/adma.202415138 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202415138 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412014 - Sun, 17 Nov 2024 21:20:38 -0800 - 2024-11-17T09:20:38-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202416210 + Mon, 18 Nov 2024 23:51:06 -0800 + 2024-11-18T11:51:06-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412014 - Effective Dual Cation Release in Quasi‐2D Perovskites for Ultrafast UV Light‐Powered Imaging + 10.1002/adma.202416210 + Dual Near‐Infrared‐Response S‐Scheme Heterojunction with Asymmetric Adsorption Sites for Enhanced Nitrogen Photoreduction Advanced Materials, EarlyView. -Dual cations released from the pre‐deposited inorganic buffer layer effectively repair deep‐level defects in quasi‐2D perovskite films by inducing low‐dimensional phase reconstruction and undercoordinated ion interaction. With enhanced film quality and residual strain modulation, the fabricated photodetector exhibits a drastically improved self‐powered photoresponse, demonstrating high compatibility with pixelated array design for ultrafast image sensing. +Dual NIR‐responsive S‐scheme ZnCoSx/Fe3S4 heterojunction photocatalyst with hollow‐on‐hollow superstructure and asymmetric adsorption sites is designed for efficient nitrogen reduction. An excellent PNRR performance is achieved, with a high NH3 evolution rate of 2523.4  µmol g−1 h−1, AQY value of 9.4% at 400 nm and 8% at 1000 nm, and SCC efficiency of 0.32%. @@ -603,43 +599,47 @@ Dual cations released from the pre‐deposited inorganic buffer layer effect Abstract -Ruddlesden‐Popper quasi‐2D perovskites represent robust candidates for optoelectronic applications, achieving a delicate balance between outstanding photoresponse and stability. However, mitigating the internal defects in polycrystalline films remains challenging, and their optoelectronic performances still lag behind that of their 3D counterparts. This work highlights the profound impact of defect passivation at the buried interface and grain boundaries through a dual‐cation‐release strategy. Cations released from the pre‐deposited inorganic iodide buffer layer effectively repair deep‐level defects by inducing low‐dimensional phase reconstruction and interacting with undercoordinated ions. The resulting quasi‐2D perovskite polycrystalline films feature large grain size (>2 µm) and minimum surface roughness, along with alleviated out‐of‐plane residual tensile strain, which is beneficial for inhibiting the initiation and propagation of cracks. The fabricated photodetector demonstrates drastically improved self‐powered photoresponse capability, with maximum responsivity up to 0.41 A W−1 at 430 nm and an ultrafast response speed of 161 ns / 1.91 µs. Moreover, this strategy is compatible with the photolithography‐assisted hydrophobic‐hydrophilic patterning process for fabricating pixelated photodetector arrays, which enables high‐sensitivity imaging. This study presents a feasible defect passivation approach in quasi‐2D perovskites, thereby providing insights into the fabrication of high‐performance optoelectronic devices. +Photocatalytic nitrogen reduction reaction (PNRR) holds immense promise for sustainable ammonia (NH3) synthesis. However, few photocatalysts can utilize NIR light that carries over 50% of the solar energy for NH3 production with high performance. Herein, a dual NIR‐responsive S‐scheme ZnCoSx/Fe3S4 heterojunction photocatalyst is designed with asymmetric adsorption sites and excellent PNRR performance. The heterojunction possesses a hollow‐on‐hollow superstructure: Fe3S4 nanocrystal‐modified ZnCoSx nanocages as building blocks assemble into spindle‐shaped particles with a spindle‐like cavity. Both Fe3S4 and ZnCoSx are NIR active, allowing efficient utilization of full‐spectrum light. Moreover, an S‐scheme heterojunction is constructed that promotes charge separation. In addition, the Fe/Co dual‐metal sites at the interface enable an asymmetric side‐on adsorption mode of N2, favoring the polarization and activation of N2 molecules. In combination with the promoted mass transfer and active site exposure of hollow superstructure, a superior PNRR performance is achieved, with a high NH3 evolution rate of 2523.4  µmol g−1 h−1, an apparent quantum yield of 9.4% at 400 nm and 8% at 1000 nm, and a solar‐to‐chemical conversion efficiency of 0.32%. The work paves the way for the rational design of advanced heterojunction catalysts for PNRR. - <img src="https://onlinelibrary.wiley.com/cms/asset/e95d8092-a0b7-4d84-91c2-bf3bf60063e9/adma202412014-gra-0001-m.png" - alt="Effective Dual Cation Release in Quasi-2D Perovskites for Ultrafast UV Light-Powered Imaging"/> -<p>Dual cations released from the pre-deposited inorganic buffer layer effectively repair deep-level defects in quasi-2D perovskite films by inducing low-dimensional phase reconstruction and undercoordinated ion interaction. With enhanced film quality and residual strain modulation, the fabricated photodetector exhibits a drastically improved self-powered photoresponse, demonstrating high compatibility with pixelated array design for ultrafast image sensing. + <img src="https://onlinelibrary.wiley.com/cms/asset/5342ef92-4a25-4d69-aded-c59c381fe207/adma202416210-gra-0001-m.png" + alt="Dual Near-Infrared-Response S-Scheme Heterojunction with Asymmetric Adsorption Sites for Enhanced Nitrogen Photoreduction"/> +<p>Dual NIR-responsive S-scheme ZnCoS<sub>x</sub>/Fe<sub>3</sub>S<sub>4</sub> heterojunction photocatalyst with hollow-on-hollow superstructure and asymmetric adsorption sites is designed for efficient nitrogen reduction. An excellent PNRR performance is achieved, with a high NH<sub>3</sub> evolution rate of 2523.4  µmol g<sup>−1</sup> h<sup>−1</sup>, AQY value of 9.4% at 400 nm and 8% at 1000 nm, and SCC efficiency of 0.32%. </p> <br/> <h2>Abstract</h2> -<p>Ruddlesden-Popper quasi-2D perovskites represent robust candidates for optoelectronic applications, achieving a delicate balance between outstanding photoresponse and stability. However, mitigating the internal defects in polycrystalline films remains challenging, and their optoelectronic performances still lag behind that of their 3D counterparts. This work highlights the profound impact of defect passivation at the buried interface and grain boundaries through a dual-cation-release strategy. Cations released from the pre-deposited inorganic iodide buffer layer effectively repair deep-level defects by inducing low-dimensional phase reconstruction and interacting with undercoordinated ions. The resulting quasi-2D perovskite polycrystalline films feature large grain size (&gt;2 µm) and minimum surface roughness, along with alleviated out-of-plane residual tensile strain, which is beneficial for inhibiting the initiation and propagation of cracks. The fabricated photodetector demonstrates drastically improved self-powered photoresponse capability, with maximum responsivity up to 0.41 A W<sup>−1</sup> at 430 nm and an ultrafast response speed of 161 ns / 1.91 µs. Moreover, this strategy is compatible with the photolithography-assisted hydrophobic-hydrophilic patterning process for fabricating pixelated photodetector arrays, which enables high-sensitivity imaging. This study presents a feasible defect passivation approach in quasi-2D perovskites, thereby providing insights into the fabrication of high-performance optoelectronic devices.</p> +<p>Photocatalytic nitrogen reduction reaction (PNRR) holds immense promise for sustainable ammonia (NH<sub>3</sub>) synthesis. However, few photocatalysts can utilize NIR light that carries over 50% of the solar energy for NH<sub>3</sub> production with high performance. Herein, a dual NIR-responsive S-scheme ZnCoS<sub>x</sub>/Fe<sub>3</sub>S<sub>4</sub> heterojunction photocatalyst is designed with asymmetric adsorption sites and excellent PNRR performance. The heterojunction possesses a hollow-on-hollow superstructure: Fe<sub>3</sub>S<sub>4</sub> nanocrystal-modified ZnCoS<sub>x</sub> nanocages as building blocks assemble into spindle-shaped particles with a spindle-like cavity. Both Fe<sub>3</sub>S<sub>4</sub> and ZnCoS<sub>x</sub> are NIR active, allowing efficient utilization of full-spectrum light. Moreover, an S-scheme heterojunction is constructed that promotes charge separation. In addition, the Fe/Co dual-metal sites at the interface enable an asymmetric side-on adsorption mode of N<sub>2</sub>, favoring the polarization and activation of N<sub>2</sub> molecules. In combination with the promoted mass transfer and active site exposure of hollow superstructure, a superior PNRR performance is achieved, with a high NH<sub>3</sub> evolution rate of 2523.4  µmol g<sup>−1</sup> h<sup>−1</sup>, an apparent quantum yield of 9.4% at 400 nm and 8% at 1000 nm, and a solar-to-chemical conversion efficiency of 0.32%. The work paves the way for the rational design of advanced heterojunction catalysts for PNRR.</p> -Xinyu Zhang, -Ziqing Li, -Enliu Hong, -Tingting Yan, -Xiaosheng Fang +Jiaxin Li, +Chaoqi Zhang, +Tong Bao, +Yamin Xi, +Ling Yuan, +Yingying Zou, +Yin Bi, +Chao Liu, +Chengzhong Yu Research Article - Effective Dual Cation Release in Quasi‐2D Perovskites for Ultrafast UV Light‐Powered Imaging - 10.1002/adma.202412014 + Dual Near‐Infrared‐Response S‐Scheme Heterojunction with Asymmetric Adsorption Sites for Enhanced Nitrogen Photoreduction + 10.1002/adma.202416210 Advanced Materials - 10.1002/adma.202412014 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412014 + 10.1002/adma.202416210 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202416210 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411677 - Sat, 16 Nov 2024 04:43:08 -0800 - 2024-11-16T04:43:08-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410604 + Mon, 18 Nov 2024 03:55:49 -0800 + 2024-11-18T03:55:49-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202411677 - All‐In‐One Additive Enabled Efficient and Stable Narrow‐Bandgap Perovskites for Monolithic All‐Perovskite Tandem Solar Cells + 10.1002/adma.202410604 + Field‐Programmable Topographic‐Morphing Array for General‐Purpose Lab‐on‐a‐Chip Systems Advanced Materials, EarlyView. -Herein, an all‐in‐one additive AMPH is proposed, which can not only function as a reducing agent to suppress Sn4+ formation, but also can slow down the crystallization and enhance oxidation resistance of Sn‐Pb films. This advancement enables 23.07% efficient Sn‐Pb perovskite solar cells and 28.73% efficient all‐perovskite tandem solar cells with improved operational stability. +Lab‐on‐a‐chip systems leverage microfluidic chips to enable small‐scale fluid manipulation, holding significant potential to revolutionize science and industry. Inspired by the customizable integrated circuit‐field programmable gate array whose hardware can be reconfigured via software, a conceptual‐new reconfigurable microfluidic chip, field programmable topographic morphing array, is devised with exceptional structural reconfiguration, field programmability, and function scalability for general‐purpose lab‐on‐a‐chip systems. @@ -649,51 +649,42 @@ Herein, an all‐in‐one additive AMPH is proposed, which can not only Abstract -Hybrid tin‐lead (Sn‐Pb) perovskites have garnered increasing attention due to their crucial role in all‐perovskite tandem cells for surpassing the efficiency limit of single‐junction solar cells. However, the easy oxidation of Sn2+ and fast crystallization of Sn‐based perovskite present significant challenges for achieving high‐quality hybrid Sn‐Pb perovskite films, thereby limiting the device's performance and stability. Herein, an all‐in‐one additive, 2‐amino‐3‐mercaptopropanoic acid hydrochloride (AMPH) is proposed, which can function as a reducing agent to suppress the formation of Sn4+ throughout the film preparation. Furthermore, the strong binding between AMPH and Sn‐based precursor significantly slows down the crystallization process, resulting in a high‐quality film with enhanced crystallinity. The remaining AMPH and its oxidation products within the film contribute to improves oxidation resistance and a substantial reduction in defect density, specifically Sn vacancies. Benefiting from the multifunctionalities of AMPH, a power conversion efficiency (PCE) of 23.07% is achieved for single‐junction narrow‐bandgap perovskite solar cells. The best‐performing monolithic all‐perovskite tandem cell also exhibits a PCE of 28.73% (certified 27.83%), which is among the highest efficiency reported yet. The tandem devices can also retain over 85% of their initial efficiencies after 500 hours of continuous operation at the maximum power point under one‐sun illumination. +Lab‐on‐a‐chip systems seek to leverage microfluidic chips to enable small‐scale fluid manipulation, holding significant potential to revolutionize science and industry. However, existing microfluidic chips have been largely designed with static fluid structures for specific single‐purpose applications, which lack adaptability and flexibility for diverse applications. Inspired by the general‐purpose design strategy of the customizable chip of integrated circuit – field programmable gate array whose hardware can be reconfigured via software programming for multifunctionality after manufacturing, a conceptual‐new reconfigurable microfluidic chip — field programmable topographic morphing array (FPTMA) is devised with exceptional structural reconfiguration, field programmability, and function scalability for general‐purpose lab‐on‐a‐chip systems that beyond the reach of current state‐of‐art lab‐on‐chip systems. FPTMA can be software programmed to dynamically shape an elastic meta‐interface from the initial smooth structure into desired time‐varying topographic structures and thus generate spatiotemporal topographic‐morphing‐induced capillary forces to actively manipulate multidroplets in parallel and enable real‐time reconfiguring diverse microfluidic operations/functions/flow networks as well as workflows. It is envisioned that the development of the FPTMA‐driven lab‐on‐a‐chip systems that leverage dynamic interfacial topographies to digitally handle microfluidics would significantly stimulate numerous technological innovations in biology/medicine/chemistry. - <img src="https://onlinelibrary.wiley.com/cms/asset/7d41e142-5364-4682-b706-1cc90c77c50a/adma202411677-gra-0001-m.png" - alt="All-In-One Additive Enabled Efficient and Stable Narrow-Bandgap Perovskites for Monolithic All-Perovskite Tandem Solar Cells"/> -<p>Herein, an all-in-one additive AMPH is proposed, which can not only function as a reducing agent to suppress Sn<sup>4+</sup> formation, but also can slow down the crystallization and enhance oxidation resistance of Sn-Pb films. This advancement enables 23.07% efficient Sn-Pb perovskite solar cells and 28.73% efficient all-perovskite tandem solar cells with improved operational stability. + <img src="https://onlinelibrary.wiley.com/cms/asset/8e12d54a-7cb8-4355-8e87-ce099b367bf6/adma202410604-gra-0001-m.png" + alt="Field-Programmable Topographic-Morphing Array for General-Purpose Lab-on-a-Chip Systems"/> +<p>Lab-on-a-chip systems leverage microfluidic chips to enable small-scale fluid manipulation, holding significant potential to revolutionize science and industry. Inspired by the customizable integrated circuit-field programmable gate array whose hardware can be reconfigured via software, a conceptual-new reconfigurable microfluidic chip, field programmable topographic morphing array, is devised with exceptional structural reconfiguration, field programmability, and function scalability for general-purpose lab-on-a-chip systems. </p> <br/> <h2>Abstract</h2> -<p>Hybrid tin-lead (Sn-Pb) perovskites have garnered increasing attention due to their crucial role in all-perovskite tandem cells for surpassing the efficiency limit of single-junction solar cells. However, the easy oxidation of Sn<sup>2+</sup> and fast crystallization of Sn-based perovskite present significant challenges for achieving high-quality hybrid Sn-Pb perovskite films, thereby limiting the device's performance and stability. Herein, an all-in-one additive, 2-amino-3-mercaptopropanoic acid hydrochloride (AMPH) is proposed, which can function as a reducing agent to suppress the formation of Sn<sup>4+</sup> throughout the film preparation. Furthermore, the strong binding between AMPH and Sn-based precursor significantly slows down the crystallization process, resulting in a high-quality film with enhanced crystallinity. The remaining AMPH and its oxidation products within the film contribute to improves oxidation resistance and a substantial reduction in defect density, specifically Sn vacancies. Benefiting from the multifunctionalities of AMPH, a power conversion efficiency (PCE) of 23.07% is achieved for single-junction narrow-bandgap perovskite solar cells. The best-performing monolithic all-perovskite tandem cell also exhibits a PCE of 28.73% (certified 27.83%), which is among the highest efficiency reported yet. The tandem devices can also retain over 85% of their initial efficiencies after 500 hours of continuous operation at the maximum power point under one-sun illumination.</p> +<p>Lab-on-a-chip systems seek to leverage microfluidic chips to enable small-scale fluid manipulation, holding significant potential to revolutionize science and industry. However, existing microfluidic chips have been largely designed with static fluid structures for specific single-purpose applications, which lack adaptability and flexibility for diverse applications. Inspired by the general-purpose design strategy of the customizable chip of integrated circuit <b>–</b> field programmable gate array whose hardware can be reconfigured via software programming for multifunctionality after manufacturing, a conceptual-new reconfigurable microfluidic chip — field programmable topographic morphing array (<i>FPTMA</i>) is devised with exceptional structural reconfiguration, field programmability, and function scalability for general-purpose lab-on-a-chip systems that beyond the reach of current state-of-art lab-on-chip systems. <i>FPTMA</i> can be software programmed to dynamically shape an elastic meta-interface from the initial smooth structure into desired time-varying topographic structures and thus generate spatiotemporal topographic-morphing-induced capillary forces to actively manipulate multidroplets in parallel and enable real-time reconfiguring diverse microfluidic operations/functions/flow networks as well as workflows. It is envisioned that the development of the <i>FPTMA-driven</i> lab-on-a-chip systems that leverage dynamic interfacial topographies to digitally handle microfluidics would significantly stimulate numerous technological innovations in biology/medicine/chemistry.</p> -Deng Wang, -Mingqian Chen, -Xia Lei, -Yunfan Wang, -Yuqi Bao, -Xiaofeng Huang, -Peide Zhu, -Jie Zeng, -Xingzhu Wang, -SaiWing Tsang, -Fengzhu Li, -Baomin Xu, -Alex K.‐Y. Jen +Yangyang Fan, +Huimin Wu, +Jiao Wang, +Jiu‐an Lv Research Article - All‐In‐One Additive Enabled Efficient and Stable Narrow‐Bandgap Perovskites for Monolithic All‐Perovskite Tandem Solar Cells - 10.1002/adma.202411677 + Field‐Programmable Topographic‐Morphing Array for General‐Purpose Lab‐on‐a‐Chip Systems + 10.1002/adma.202410604 Advanced Materials - 10.1002/adma.202411677 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411677 + 10.1002/adma.202410604 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410604 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413325 - Sat, 16 Nov 2024 04:41:40 -0800 - 2024-11-16T04:41:40-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410779 + Mon, 18 Nov 2024 03:55:39 -0800 + 2024-11-18T03:55:39-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413325 - Engineering Triple‐Phase Interfaces with Hierarchical Carbon Nanocages for High‐Areal‐Capacity All‐Solid‐State Li‐S Batteries + 10.1002/adma.202410779 + Universal Approach for Managing Iodine Migration in Inverted Single‐Junction and Tandem Perovskite Solar Cells Advanced Materials, EarlyView. -In all‐solid‐state lithium‐sulfur batteries, the composite cathode requires multi‐dimensional structural engineering. By integrating sulfur with a hierarchical carbon nanocage (hCNC), the uniform dispersion of sulfur and carbon in the composite cathode and the efficient construction of triple‐phase interfaces are achieved. These enhancements improve the utilization of sulfur, enabling ultra‐high‐capacity battery performance. +This study improves the stability of perovskite solar cells (PSCs) by introducing a Lewis‐acid boronic ester‐containing agent 2,1,3‐benzothiadiazole,5,6‐difluoro‐4,7‐bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl) (BT2F‐2B) into the perovskite precursor solution. It also provides a universal method for enhancing the stability of PSCs and a feasible approach for developing high‐performance and durable PSCs for perovskite systems with different bandgaps. @@ -703,55 +694,49 @@ In all‐solid‐state lithium‐sulfur batteries, the composite cat Abstract -All‐solid‐state lithium‐sulfur batteries (ASSLSBs) have garnered widespread attention due to their advantages of high energy density and enhanced safety. However, the typical composite structure composed of solid‐state electrolyte (SE), discrete conducting carbon black, and microsized sulfur (μ‐S) with long‐range Li+/e− conducting path and huge volume changes, suffers from sluggish charge transport and severe electrochemical‐mechanical failure. In this work, a unique hierarchical carbon nanocage (hCNC) is applied as a continuous conducting network where nanosized sulfur are confined. Due to the synergistic effects of multi‐dimensional (particle, interface, and electrode) structural engineering, this new sulfur‐carbon composite cathode (S@hCNC39) can achieve uniform distribution of sulfur and carbon, and efficiently constructs triple‐phase interfaces, showing enhanced charge‐carrier transport and improved electrochemical‐mechanical stability. Remarkable cycling performance of 89% after 300 cycles at 0.2 C at 30 °C is realized in ASSLSBs assembled with S@hCNC39. Notably, ASSLSBs achieve an ultrahigh areal capacity of 9.95 mAh cm−2 with stable cycling at 60 °C with high sulfur contents of 40% and high sulfur loadings of 6 mg cm−2. These results provide critical insights into the design of rational sulfur‐carbon composites and offer a viable approach to enhance the overall performance of ASSLSBs. +Despite significant progress in the power‐conversion efficiency (PCE) of perovskite solar cells (PSCs), the instability of devices remains a considerable obstacle for commercial applications. This instability primarily originates from the migration of halide ions—particularly iodide ions (I−). Under light exposure and thermal stress, I− migrates and transforms into I2, leading to irreversible degradation and performance loss. To address this issue, we introduced the additive 2,1,3‐benzothiadiazole,5,6‐difluoro‐4,7‐bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl) (BT2F‐2B) into the perovskite. The strong coordination between the unhybridized p orbital and lone‐pair electrons from I− inhibits the deprotonation of MAI/FAI and the subsequent conversion of I− to I₂. The highly electronegative fluorine enhances its electrostatic interaction with I−. Consequently, the synergistic effect of BT2F‐2B effectively suppresses the decomposition of perovskite and the defect density of the iodide vacancies. This approach delivers a PCE over 26% for inverted single‐junction PSCs, with exceptional operational stability. According to the ISOS‐L‐3 testing protocol (maximum power point tracking at 85 °C and 50% relative humidity), treated PSCs retain 85% of their original PCE after 1000 h of aging. When the BT2F‐2B is applied to a wide‐bandgap (1.77 eV) perovskite system, the PCE of all‐perovskite tandem solar cells reaches 27.8%, confirming the universality of the proposed strategy. - <img src="https://onlinelibrary.wiley.com/cms/asset/8a0ad828-5c07-4b1a-83df-a26bd2aa8902/adma202413325-gra-0001-m.png" - alt="Engineering Triple-Phase Interfaces with Hierarchical Carbon Nanocages for High-Areal-Capacity All-Solid-State Li-S Batteries"/> -<p>In all-solid-state lithium-sulfur batteries, the composite cathode requires multi-dimensional structural engineering. By integrating sulfur with a hierarchical carbon nanocage (hCNC), the uniform dispersion of sulfur and carbon in the composite cathode and the efficient construction of triple-phase interfaces are achieved. These enhancements improve the utilization of sulfur, enabling ultra-high-capacity battery performance. + <img src="https://onlinelibrary.wiley.com/cms/asset/77841903-f193-4440-808e-26c9cb735784/adma202410779-gra-0001-m.png" + alt="Universal Approach for Managing Iodine Migration in Inverted Single-Junction and Tandem Perovskite Solar Cells"/> +<p>This study improves the stability of perovskite solar cells (PSCs) by introducing a Lewis-acid boronic ester-containing agent 2,1,3-benzothiadiazole,5,6-difluoro-4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) (BT2F-2B) into the perovskite precursor solution. It also provides a universal method for enhancing the stability of PSCs and a feasible approach for developing high-performance and durable PSCs for perovskite systems with different bandgaps. </p> <br/> <h2>Abstract</h2> -<p>All-solid-state lithium-sulfur batteries (ASSLSBs) have garnered widespread attention due to their advantages of high energy density and enhanced safety. However, the typical composite structure composed of solid-state electrolyte (SE), discrete conducting carbon black, and microsized sulfur (μ-S) with long-range Li<sup>+</sup>/e<sup>−</sup> conducting path and huge volume changes, suffers from sluggish charge transport and severe electrochemical-mechanical failure. In this work, a unique hierarchical carbon nanocage (hCNC) is applied as a continuous conducting network where nanosized sulfur are confined. Due to the synergistic effects of multi-dimensional (particle, interface, and electrode) structural engineering, this new sulfur-carbon composite cathode (S@hCNC39) can achieve uniform distribution of sulfur and carbon, and efficiently constructs triple-phase interfaces, showing enhanced charge-carrier transport and improved electrochemical-mechanical stability. Remarkable cycling performance of 89% after 300 cycles at 0.2 C at 30 °C is realized in ASSLSBs assembled with S@hCNC39. Notably, ASSLSBs achieve an ultrahigh areal capacity of 9.95 mAh cm<sup>−2</sup> with stable cycling at 60 °C with high sulfur contents of 40% and high sulfur loadings of 6 mg cm<sup>−2</sup>. These results provide critical insights into the design of rational sulfur-carbon composites and offer a viable approach to enhance the overall performance of ASSLSBs.</p> +<p>Despite significant progress in the power-conversion efficiency (PCE) of perovskite solar cells (PSCs), the instability of devices remains a considerable obstacle for commercial applications. This instability primarily originates from the migration of halide ions—particularly iodide ions (I<sup>−</sup>). Under light exposure and thermal stress, I<sup>−</sup> migrates and transforms into I<sub>2</sub>, leading to irreversible degradation and performance loss. To address this issue, we introduced the additive 2,1,3-benzothiadiazole,5,6-difluoro-4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) (BT2F-2B) into the perovskite. The strong coordination between the unhybridized p orbital and lone-pair electrons from I<sup>−</sup> inhibits the deprotonation of MAI/FAI and the subsequent conversion of I<sup>−</sup> to I₂. The highly electronegative fluorine enhances its electrostatic interaction with I<sup>−</sup>. Consequently, the synergistic effect of BT2F-2B effectively suppresses the decomposition of perovskite and the defect density of the iodide vacancies. This approach delivers a PCE over 26% for inverted single-junction PSCs, with exceptional operational stability. According to the ISOS-L-3 testing protocol (maximum power point tracking at 85 °C and 50% relative humidity), treated PSCs retain 85% of their original PCE after 1000 h of aging. When the BT2F-2B is applied to a wide-bandgap (1.77 eV) perovskite system, the PCE of all-perovskite tandem solar cells reaches 27.8%, confirming the universality of the proposed strategy.</p> -Yu Luo, -Siyuan Pan, -JingYi Tian, -Yali Liang, -Haoyue Zhong, -Ruqin Ma, -Jiabao Gu, -Yuqi Wu, -Huiyan Zhang, -Hongxin Lin, -Weilin Huang, -Yuxi Deng, -Yu Su, -Zhengliang Gong, -Jianyu Huang, -Zheng Hu, -Yong Yang +Zhenhua Song, +Kexuan Sun, +Yuanyuan Meng, +Zewei Zhu, +Yaohua Wang, +Weifu Zhang, +Yang Bai, +Xiaoyi Lu, +Ruijia Tian, +Chang Liu, +Ziyi Ge Research Article - Engineering Triple‐Phase Interfaces with Hierarchical Carbon Nanocages for High‐Areal‐Capacity All‐Solid‐State Li‐S Batteries - 10.1002/adma.202413325 + Universal Approach for Managing Iodine Migration in Inverted Single‐Junction and Tandem Perovskite Solar Cells + 10.1002/adma.202410779 Advanced Materials - 10.1002/adma.202413325 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413325 + 10.1002/adma.202410779 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410779 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412255 - Sat, 16 Nov 2024 04:39:58 -0800 - 2024-11-16T04:39:58-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409971 + Sun, 17 Nov 2024 23:58:21 -0800 + 2024-11-17T11:58:21-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412255 - Organic Nonvolatile 2T Memory Cell Employing a NOT‐Gate‐Like Architecture Toward Binary Output Level With Enhanced Noise Tolerance + 10.1002/adma.202409971 + Managing Solvent Complexes to Amplify Ripening Process by Covalent Interaction Driving Force Under External Field for Perovskite Photovoltaic Advanced Materials, EarlyView. -This work reports a brand‐new voltage‐readable 2T memory cell employing a NOT‐gate‐like architecture. It combines ferroelectric and nano‐floating‐gate transistors in a voltage divider, achieving high noise tolerance for voltage output memory. Moreover, the conceptual design of the 1T2T FeRAM cell is also developed as a prospect for low‐cost voltage‐readable memory technology in wearable electronic applications. +Liquid crystal molecule is utilized to promote the movement of solvent complexes under external field, thus amplifying ripening process and optimizing the buried interface. Based on this, the efficiency of device reaches 25.24%, and it still maintains 75% of the original efficiency after 1400 h in a damp heat test. @@ -761,49 +746,46 @@ This work reports a brand‐new voltage‐readable 2T memory cell employ Abstract -Organic nonvolatile memory has been considered a low‐cost memory technology for flexible electronics and Internet‐of‐things (IoT). However, a major concern is the nonuniformity of memory units, which is primarily caused by random grain boundaries, interface defects, and charge traps, making it difficult to develop high‐density reliable memory arrays. This nonuniformity problem would induce read error, which is directly caused by the narrow distribution margin of memory states and low noise tolerance in conventional organic memory cells. To break this limitation, a novel 2T memory cell employing a NOT‐gate‐like architecture achieving self‐enhancing noise tolerance is presented. This unique cell consists of a pair of commonly‐gated memory transistors with contradictory “write‐and‐erase” features. It functions as a voltage divider, producing a well‐distinguished binary voltage output capability. The concept and design model of this brand‐new 2T memory cell is thoroughly discussed. It is originally characterized by noise‐tolerant memory cells irrespective of device nonuniformity. The noise tolerance range of this 2T memory cell is also investigated. The binary voltage‐readable memory state with a large noise tolerance range is obtained. Moreover, the conceptual design of the 1T2T FeRAM cell is further developed for low‐cost voltage‐readable memory technology in wearable electronic applications. +Up to now, post‐annealing is most commonly used to post treat the perovskite film to accelerate the ripening process. Nonetheless, the top‐down crystallization mechanism impedes the efficient desolvation of solvent complexes. Thus, residual solvent complexes tend to accumulate at the bottom of the film during the ripening process and deteriorate the device. Here, a new strategy with unique concept is promoted to amplify ripening process of perovskite film, in which a nematic thermotropic liquid crystal (LC) molecular is introduced to facilitate the conversion of solvent complexes by utilizing the liquid crystalline behavior under external field. Upon the concurrent application of thermal and force fields, the covalent interaction between LC and solvent complexes generates a driving force, which promotes upward migration of solvent complexes, thereby facilitating their engagement in the ripening process. In addition, the driving force under external fields assists the flattening of grain boundary grooves. Therefore, film quality is improved efficiently with amplified ripening process and adequately handled buried interface. Based on the positive effects, the devices achieve a champion efficiency of 25.24%, and sustained ≈75% of its initial efficiency level even after undergoing a damp heat test (85 °C/85% RH) for 1400 h. - <img src="https://onlinelibrary.wiley.com/cms/asset/7d86b0e4-9ebf-432d-bff4-ad64646b3e35/adma202412255-gra-0001-m.png" - alt="Organic Nonvolatile 2T Memory Cell Employing a NOT-Gate-Like Architecture Toward Binary Output Level With Enhanced Noise Tolerance"/> -<p>This work reports a brand-new voltage-readable 2T memory cell employing a NOT-gate-like architecture. It combines ferroelectric and nano-floating-gate transistors in a voltage divider, achieving high noise tolerance for voltage output memory. Moreover, the conceptual design of the 1T2T FeRAM cell is also developed as a prospect for low-cost voltage-readable memory technology in wearable electronic applications. + <img src="https://onlinelibrary.wiley.com/cms/asset/e09be2ff-dc40-43b0-a831-6f08ead0e654/adma202409971-gra-0001-m.png" + alt="Managing Solvent Complexes to Amplify Ripening Process by Covalent Interaction Driving Force Under External Field for Perovskite Photovoltaic"/> +<p>Liquid crystal molecule is utilized to promote the movement of solvent complexes under external field, thus amplifying ripening process and optimizing the buried interface. Based on this, the efficiency of device reaches 25.24%, and it still maintains 75% of the original efficiency after 1400 h in a damp heat test. </p> <br/> <h2>Abstract</h2> -<p>Organic nonvolatile memory has been considered a low-cost memory technology for flexible electronics and Internet-of-things (IoT). However, a major concern is the nonuniformity of memory units, which is primarily caused by random grain boundaries, interface defects, and charge traps, making it difficult to develop high-density reliable memory arrays. This nonuniformity problem would induce read error, which is directly caused by the narrow distribution margin of memory states and low noise tolerance in conventional organic memory cells. To break this limitation, a novel 2T memory cell employing a NOT-gate-like architecture achieving self-enhancing noise tolerance is presented. This unique cell consists of a pair of commonly-gated memory transistors with contradictory “write-and-erase” features. It functions as a voltage divider, producing a well-distinguished binary voltage output capability. The concept and design model of this brand-new 2T memory cell is thoroughly discussed. It is originally characterized by noise-tolerant memory cells irrespective of device nonuniformity. The noise tolerance range of this 2T memory cell is also investigated. The binary voltage-readable memory state with a large noise tolerance range is obtained. Moreover, the conceptual design of the 1T2T FeRAM cell is further developed for low-cost voltage-readable memory technology in wearable electronic applications.</p> +<p>Up to now, post-annealing is most commonly used to post treat the perovskite film to accelerate the ripening process. Nonetheless, the top-down crystallization mechanism impedes the efficient desolvation of solvent complexes. Thus, residual solvent complexes tend to accumulate at the bottom of the film during the ripening process and deteriorate the device. Here, a new strategy with unique concept is promoted to amplify ripening process of perovskite film, in which a nematic thermotropic liquid crystal (LC) molecular is introduced to facilitate the conversion of solvent complexes by utilizing the liquid crystalline behavior under external field. Upon the concurrent application of thermal and force fields, the covalent interaction between LC and solvent complexes generates a driving force, which promotes upward migration of solvent complexes, thereby facilitating their engagement in the ripening process. In addition, the driving force under external fields assists the flattening of grain boundary grooves. Therefore, film quality is improved efficiently with amplified ripening process and adequately handled buried interface. Based on the positive effects, the devices achieve a champion efficiency of 25.24%, and sustained ≈75% of its initial efficiency level even after undergoing a damp heat test (85 °C/85% RH) for 1400 h.</p> -Qiang Zhao, -Hanlin Wang, -Zhenjie Ni, -Jie Liu, -Jie Li, -Fangxu Yang, -Liqiang Li, -Lang Jiang, -Yonggang Zhen, -Huanli Dong, -Wenping Hu +Jiajie Hong, +Zhi Xing, +Dengxue Li, +Biao Hu, +Kaiqin Xu, +Xiaotian Hu, +Ting Hu, +Yiwang Chen Research Article - Organic Nonvolatile 2T Memory Cell Employing a NOT‐Gate‐Like Architecture Toward Binary Output Level With Enhanced Noise Tolerance - 10.1002/adma.202412255 + Managing Solvent Complexes to Amplify Ripening Process by Covalent Interaction Driving Force Under External Field for Perovskite Photovoltaic + 10.1002/adma.202409971 Advanced Materials - 10.1002/adma.202412255 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412255 + 10.1002/adma.202409971 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409971 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412257 - Sat, 16 Nov 2024 04:39:25 -0800 - 2024-11-16T04:39:25-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412185 + Sun, 17 Nov 2024 21:26:07 -0800 + 2024-11-17T09:26:07-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412257 - Macroscale Superlubrication Achieved with Shear‐Thinning Semisolid Lubricants + 10.1002/adma.202412185 + Poly(Lactic Acid): Recent Stereochemical Advances and New Materials Engineering Advanced Materials, EarlyView. -This study introduces a semisolid subnanometer nanowire (SNW) superlubricant, which, when combined with various base oils, forms an advanced class of lubricating materials. Based on shear‐thinning properties, these materials achieve ultralow friction (0.008–0.009) and long‐term stability (>120 000 cycles, 12 h), addressing current limitations and offering significant potential for diverse engineering applications. +Poly(lactic acid) (PLA) is a representative biobased and biodegradable polyester among sustainable materials. This review covers the basic structural variety of PLA, current states of stereocontrolled synthesis as well as the relationships between the structures and properties. Moreover, state‐of‐the‐art examples of high‐performance PLA‐based materials within an array of applications (packaging, fibers textiles, biomedicine, healthcare, and electronic devices) are highlighted. @@ -813,46 +795,42 @@ This study introduces a semisolid subnanometer nanowire (SNW) superlubricant, wh Abstract -Macrosuperlubric materials are pivotal for reducing friction and wear in engineering applications. However, current solid superlubricants require intricate fabrication and specific conditions (e.g., vacuum or inert atmospheres), while liquid superlubricants are prone to creep, leakage, and corrosion. Here, a novel semisolid subnanometer nanowire (SNW) superlubrication material based on the shear‐thinning effect is introduced to overcome these challenges. The SNWs achieve an exceptionally low friction coefficient (0.008–0.009) with silicon nitride (Si3N4) and polytetrafluoroethylene (PTFE) tribo‐pairs, demonstrating a brief running‐in period (≈39 s) and stable superlubrication over extended friction (12 h, >120 000 cycles). The combination of the shear‐thinning network structure mechanism, the adsorption membrane mechanism, and hydrodynamic effects provides a synergistic effect, playing a crucial role in achieving superlubricity. Additionally, SNWs can be combined with various base oils to create semisolid gel lubricants with superlubricating properties. This innovative approach addresses the limitations of current superlubrication systems and introduces a new category of semisolid gel lubricants, significantly expanding the applications of superlubrication materials. +Poly(lactic acid) (PLA) is a representative biobased and biodegradable aliphatic polyester and a front‐runner among sustainable materials. As a semicrystalline thermoplastic, PLA exhibits excellent mechanical and physical properties, attracting considerable attention in commodity and medical fields. Stereochemistry is a key factor affecting PLA's properties, and to this end, the engineering of PLA's microstructure for tailored material properties has been an active area of research over the decade. This Review first covers the basic structural variety of PLA. A perspective on the current states of stereocontrolled synthesis as well as the relationships between the structures and properties of PLA stereosequences are included, with an emphasis on record regularity and properties. At last, state‐of‐the‐art examples of high‐performance PLA‐based materials within an array of applications are given, including packaging, fibers, and textiles, healthcare and electronic devices. Among various stereo‐regular sequences of PLA, poly(L‐lactic acid) (PLLA) is the most prominent category and has myriad unique properties and applications. In this regard, cutting‐edge applications of PLLA are mainly overviewed in this review. At the same time, new materials developed based on other PLA stereosequences are highlighted, which holds the potential to a wide variety of PLA‐based sustainable materials. - <img src="https://onlinelibrary.wiley.com/cms/asset/9db464c1-7d1e-441a-90c1-a70bfe37db6c/adma202412257-gra-0001-m.png" - alt="Macroscale Superlubrication Achieved with Shear-Thinning Semisolid Lubricants"/> -<p>This study introduces a semisolid subnanometer nanowire (SNW) superlubricant, which, when combined with various base oils, forms an advanced class of lubricating materials. Based on shear-thinning properties, these materials achieve ultralow friction (0.008–0.009) and long-term stability (&gt;120 000 cycles, 12 h), addressing current limitations and offering significant potential for diverse engineering applications. + <img src="https://onlinelibrary.wiley.com/cms/asset/1253b2be-0c2f-4573-a14a-700148a1331d/adma202412185-gra-0001-m.png" + alt="Poly(Lactic Acid): Recent Stereochemical Advances and New Materials Engineering"/> +<p>Poly(lactic acid) (PLA) is a representative biobased and biodegradable polyester among sustainable materials. This review covers the basic structural variety of PLA, current states of stereocontrolled synthesis as well as the relationships between the structures and properties. Moreover, state-of-the-art examples of high-performance PLA-based materials within an array of applications (packaging, fibers textiles, biomedicine, healthcare, and electronic devices) are highlighted. </p> <br/> <h2>Abstract</h2> -<p>Macrosuperlubric materials are pivotal for reducing friction and wear in engineering applications. However, current solid superlubricants require intricate fabrication and specific conditions (e.g., vacuum or inert atmospheres), while liquid superlubricants are prone to creep, leakage, and corrosion. Here, a novel semisolid subnanometer nanowire (SNW) superlubrication material based on the shear-thinning effect is introduced to overcome these challenges. The SNWs achieve an exceptionally low friction coefficient (0.008–0.009) with silicon nitride (Si<sub>3</sub>N<sub>4</sub>) and polytetrafluoroethylene (PTFE) tribo-pairs, demonstrating a brief running-in period (≈39 s) and stable superlubrication over extended friction (12 h, &gt;120 000 cycles). The combination of the shear-thinning network structure mechanism, the adsorption membrane mechanism, and hydrodynamic effects provides a synergistic effect, playing a crucial role in achieving superlubricity. Additionally, SNWs can be combined with various base oils to create semisolid gel lubricants with superlubricating properties. This innovative approach addresses the limitations of current superlubrication systems and introduces a new category of semisolid gel lubricants, significantly expanding the applications of superlubrication materials.</p> +<p>Poly(lactic acid) (PLA) is a representative biobased and biodegradable aliphatic polyester and a front-runner among sustainable materials. As a semicrystalline thermoplastic, PLA exhibits excellent mechanical and physical properties, attracting considerable attention in commodity and medical fields. Stereochemistry is a key factor affecting PLA's properties, and to this end, the engineering of PLA's microstructure for tailored material properties has been an active area of research over the decade. This Review first covers the basic structural variety of PLA. A perspective on the current states of stereocontrolled synthesis as well as the relationships between the structures and properties of PLA stereosequences are included, with an emphasis on record regularity and properties. At last, state-of-the-art examples of high-performance PLA-based materials within an array of applications are given, including packaging, fibers, and textiles, healthcare and electronic devices. Among various stereo-regular sequences of PLA, poly(L-lactic acid) (PLLA) is the most prominent category and has myriad unique properties and applications. In this regard, cutting-edge applications of PLLA are mainly overviewed in this review. At the same time, new materials developed based on other PLA stereosequences are highlighted, which holds the potential to a wide variety of PLA-based sustainable materials.</p> -Liucheng Wang, -Liqiang Zhang, -Runhao Zheng, -Changhe Du, -Tongtong Yu, -Kunpeng Li, -Weifeng Bu, -Daoai Wang +Chenyang Hu, +Yu Zhang, +Xuan Pang, +Xuesi Chen - Research Article - Macroscale Superlubrication Achieved with Shear‐Thinning Semisolid Lubricants - 10.1002/adma.202412257 + Review + Poly(Lactic Acid): Recent Stereochemical Advances and New Materials Engineering + 10.1002/adma.202412185 Advanced Materials - 10.1002/adma.202412257 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412257 - Research Article + 10.1002/adma.202412185 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412185 + Review - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410950 - Sat, 16 Nov 2024 04:38:36 -0800 - 2024-11-16T04:38:36-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412276 + Sun, 17 Nov 2024 21:26:07 -0800 + 2024-11-17T09:26:07-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202410950 - In‐Plane Chirality Control of a Charge Density Wave by Means of Shear Stress + 10.1002/adma.202412276 + In Situ Fabricated Perovskite Quantum Dots: From Materials to Applications Advanced Materials, EarlyView. -The in‐plane chirality of a Charge Density Wave compound can be controlled by applying shear stress during thermal cycling through an achiral phase. This finding opens the view to optomechanical devices with tunable Raman activity. +In situ fabricated perovskite quantum dots (PQDs) simplify the integration into functional systems with enhanced performance. This paper reviews the methodologies and the developments of in situ fabricated PQDs. Furthermore, the fundamental problems in development of PQDs toward industrialization are discussed, such as the photoinduced decomposition under high‐intensity light irradiation, ion migration under electrical bias, and the thermal quenching. @@ -862,55 +840,41 @@ The in‐plane chirality of a Charge Density Wave compound can be controlled Abstract -The transition metal dichalcogenide 1T‐TaS2 exhibits a Charge Density Wave (CDW) with in‐plane chirality. Due to the rich phase diagram, the Ferro‐Rotational Order (FRO) can be tuned by external stimuli. The FRO is studied by Angle‐Resolved Photoelectron Spectroscopy (ARPES), Raman spectroscopy, and Selected Area Electron Diffraction (SAED). The in‐plane chirality of the CDW is lost at the transition from Nearly‐Commensurate (NC) to In‐Commensurate (IC) phase and can be controlled by applying shear stress to the sample while cooling it through the transition from IC‐CDW to NC‐CDW. Based on these observations, a protocol is proposed to achieve reliable, non‐volatile state switching of the FRO configuration in 1T‐TaS2 bulk crystals. These results pave the way for new functional devices in which in‐plane chirality can be set on demand. +Due to the low formation enthalpy and high defect tolerance, in situ fabricated perovskite quantum dots offer advantages such as easy fabrication and superior optical properties. This paper reviews the methodologies, functional materials of in situ fabricated perovskite quantum dots, including polymer nanocomposites, quantum dots doped glasses, mesoporous nanocomposites, quantum dots‐embedded single crystals, and electroluminescent films. This study further highlights the industrial breakthroughs of in situ fabricated perovskite quantum dots, especially the scale‐up fabrication and stability enhancement. Finally, the fundamental challenges in developing perovskite quantum dots for industrial applications are discussed, with a focus on photoinduced degradation under high‐intensity light irradiation, ion migration under electrical bias and thermal quenching at high temperature. - <img src="https://onlinelibrary.wiley.com/cms/asset/e4f91805-d1e3-476f-a00f-c39180759b83/adma202410950-gra-0001-m.png" - alt="In-Plane Chirality Control of a Charge Density Wave by Means of Shear Stress"/> -<p>The in-plane chirality of a Charge Density Wave compound can be controlled by applying shear stress during thermal cycling through an achiral phase. This finding opens the view to optomechanical devices with tunable Raman activity. + <img src="https://onlinelibrary.wiley.com/cms/asset/b624cb3f-9084-44dd-95bc-696f7bf755ad/adma202412276-gra-0001-m.png" + alt="In Situ Fabricated Perovskite Quantum Dots: From Materials to Applications"/> +<p>In situ fabricated perovskite quantum dots (PQDs) simplify the integration into functional systems with enhanced performance. This paper reviews the methodologies and the developments of in situ fabricated PQDs. Furthermore, the fundamental problems in development of PQDs toward industrialization are discussed, such as the photoinduced decomposition under high-intensity light irradiation, ion migration under electrical bias, and the thermal quenching. </p> <br/> <h2>Abstract</h2> -<p>The transition metal dichalcogenide 1T-TaS<sub>2</sub> exhibits a Charge Density Wave (CDW) with in-plane chirality. Due to the rich phase diagram, the Ferro-Rotational Order (FRO) can be tuned by external stimuli. The FRO is studied by Angle-Resolved Photoelectron Spectroscopy (ARPES), Raman spectroscopy, and Selected Area Electron Diffraction (SAED). The in-plane chirality of the CDW is lost at the transition from Nearly-Commensurate (NC) to In-Commensurate (IC) phase and can be controlled by applying shear stress to the sample while cooling it through the transition from IC-CDW to NC-CDW. Based on these observations, a protocol is proposed to achieve reliable, non-volatile state switching of the FRO configuration in 1T-TaS<sub>2</sub> bulk crystals. These results pave the way for new functional devices in which in-plane chirality can be set on demand.</p> +<p>Due to the low formation enthalpy and high defect tolerance, in situ fabricated perovskite quantum dots offer advantages such as easy fabrication and superior optical properties. This paper reviews the methodologies, functional materials of in situ fabricated perovskite quantum dots, including polymer nanocomposites, quantum dots doped glasses, mesoporous nanocomposites, quantum dots-embedded single crystals, and electroluminescent films. This study further highlights the industrial breakthroughs of in situ fabricated perovskite quantum dots, especially the scale-up fabrication and stability enhancement. Finally, the fundamental challenges in developing perovskite quantum dots for industrial applications are discussed, with a focus on photoinduced degradation under high-intensity light irradiation, ion migration under electrical bias and thermal quenching at high temperature.</p> -Weiyan Qi, -Stefano Ponzoni, -Guénolé Huitric, -Romain Grasset, -Yannis Laplace, -Laurent Cario, -Alberto Zobelli, -Marino Marsi, -Evangelos Papalazarou, -Alexandr Alekhin, -Yann Gallais, -Azzedine Bendounan, -Suk Hyun Sung, -Noah Schnitzer, -Berit Hansen Goodge, -Robert Hovden, -Luca Perfetti +Xian‐gang Wu, +Yuyu Jing, +Haizheng Zhong - Research Article - In‐Plane Chirality Control of a Charge Density Wave by Means of Shear Stress - 10.1002/adma.202410950 + Review + In Situ Fabricated Perovskite Quantum Dots: From Materials to Applications + 10.1002/adma.202412276 Advanced Materials - 10.1002/adma.202410950 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410950 - Research Article + 10.1002/adma.202412276 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412276 + Review - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412667 - Sat, 16 Nov 2024 04:37:57 -0800 - 2024-11-16T04:37:57-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411572 + Sun, 17 Nov 2024 21:24:57 -0800 + 2024-11-17T09:24:57-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412667 - Crystallographic Reorientation Induced by Gradient Solid‐Electrolyte Interphase for Highly Stable Zinc Anode + 10.1002/adma.202411572 + Design Principles for Enhancing Both Carrier Mobility and Stretchability in Polymer Semiconductors via Lewis Acid Doping Advanced Materials, EarlyView. -This study tracks the reaction pathways of Zn2+ from de‐solvation to Zn nucleation and subsequent growth. Advanced operando spectroscopy and crystallography tests reveal that gradient solid‐electrolyte interphase induces crystallographic reorientation from Zn (101) to (002) planes of Zn anode during Zn2+ stripping/plating. The in‐depth depicted crystal regulation method opens new opportunities for the development of long‐lifespan metal batteries. +This study systematically investigates the molecular interactions between the host polymer and Lewis acid dopants, offering an effective strategy to simultaneously enhance the carrier mobility and stretchability of polymer semiconductors. Optimizing lamellar stacking distance and reducing crystallinity promote the dispersion of tris(pentafluorophenyl)borane within the side‐chain regions. Reducing the strength of Lewis base groups in the polymer prevents the formation of excessively strong Lewis acid‐base complexes, thus maintaining chain flexibility. @@ -920,48 +884,45 @@ This study tracks the reaction pathways of Zn2+ from de‐solvation to Zn nu Abstract -Oriented zinc (Zn) electrodeposition is critical for the long‐term performance of aqueous Zn metal batteries. However, the intricate interfacial reactions between the Zn anode and electrolytes hinder a comprehensive understanding of Zn metal deposition. Here, the reaction pathways of Zn deposition and report the preferential formation of Zn single‐crystalline nuclei followed by dense Zn(002) deposition is elucidated, which is induced by a gradient solid‐electrolyte interphase (SEI). The gradient SEI composed of abundant B‐O and C species facilitates faster Zn2+ nucleation rate and smaller nucleus size, promoting the formation of Zn single‐crystalline nuclei. Additionally, the homogeneity and mechanical stability of SEI ensure the crystallographic reorientation of Zn anodes from Zn(101) to (002) planes, efficiently inhibiting dendrite growth and metal corrosion during the Zn2+ stripping/plating process. These advantages significantly enhance the stability of the Zn anode, as demonstrated by the prolonged cycling lifespan of symmetric Zn batteries and exceptional reversibility (>99.5%) over 5000 cycles in Zn//Cu asymmetric batteries. Notably, this strategy also enables the stable operation of anode‐free Zn//I2 batteries with a long lifespan of 3000 cycles. This work advances the understanding of Zn electrochemical behaviors, encompassing Zn nucleation, growth, and Zn2+ stripping/plating. +With the rise of skin‐like electronics, devices are increasingly coming into close contact with the human body, creating a demand for polymer semiconductors (PSCs) that combine stretchability with reliable electrical performance. However, balancing mechanical robustness with high carrier mobility remains a challenge. To address this, tris(pentafluorophenyl)borane (BCF) for Lewis acid doping is proposed to improve charge mobility while enhancing stretchability by increasing structural disorder. Through systematic investigation, several key structural principles have been identified to maximize the effectiveness of BCF doping in stretchable PSCs. Notably, increasing the lamellar stacking distance and reducing crystallinity facilitate the incorporation of BCF into the alkyl side‐chain regions, thereby enhancing both mobility and stretchability. Conversely, stronger Lewis base groups in the main chain negatively impact these improvements. These results demonstrate that with a small addition of BCF, a two‐fold increase in carrier mobility is achieved while simultaneously enhancing the crack onset strain to 100%. Furthermore, doped PSCs exhibit stable mobility retention under repeated 30% strains over 1000 cycles. This method of decoupling carrier mobility from mechanical properties opens up new avenues in the search for high‐mobility stretchable PSCs. - <img src="https://onlinelibrary.wiley.com/cms/asset/97727cf0-33cb-45ae-b066-f6c54661c0a3/adma202412667-gra-0001-m.png" - alt="Crystallographic Reorientation Induced by Gradient Solid-Electrolyte Interphase for Highly Stable Zinc Anode"/> -<p>This study tracks the reaction pathways of Zn2+ from de-solvation to Zn nucleation and subsequent growth. Advanced operando spectroscopy and crystallography tests reveal that gradient solid-electrolyte interphase induces crystallographic reorientation from Zn (101) to (002) planes of Zn anode during Zn2+ stripping/plating. The in-depth depicted crystal regulation method opens new opportunities for the development of long-lifespan metal batteries. + <img src="https://onlinelibrary.wiley.com/cms/asset/bfca5fcf-841a-423a-b153-a42b14bbae5f/adma202411572-gra-0001-m.png" + alt="Design Principles for Enhancing Both Carrier Mobility and Stretchability in Polymer Semiconductors via Lewis Acid Doping"/> +<p>This study systematically investigates the molecular interactions between the host polymer and Lewis acid dopants, offering an effective strategy to simultaneously enhance the carrier mobility and stretchability of polymer semiconductors. Optimizing lamellar stacking distance and reducing crystallinity promote the dispersion of tris(pentafluorophenyl)borane within the side-chain regions. Reducing the strength of Lewis base groups in the polymer prevents the formation of excessively strong Lewis acid-base complexes, thus maintaining chain flexibility. </p> <br/> <h2>Abstract</h2> -<p>Oriented zinc (Zn) electrodeposition is critical for the long-term performance of aqueous Zn metal batteries. However, the intricate interfacial reactions between the Zn anode and electrolytes hinder a comprehensive understanding of Zn metal deposition. Here, the reaction pathways of Zn deposition and report the preferential formation of Zn single-crystalline nuclei followed by dense Zn(002) deposition is elucidated, which is induced by a gradient solid-electrolyte interphase (SEI). The gradient SEI composed of abundant B-O and C species facilitates faster Zn<sup>2+</sup> nucleation rate and smaller nucleus size, promoting the formation of Zn single-crystalline nuclei. Additionally, the homogeneity and mechanical stability of SEI ensure the crystallographic reorientation of Zn anodes from Zn(101) to (002) planes, efficiently inhibiting dendrite growth and metal corrosion during the Zn<sup>2+</sup> stripping/plating process. These advantages significantly enhance the stability of the Zn anode, as demonstrated by the prolonged cycling lifespan of symmetric Zn batteries and exceptional reversibility (&gt;99.5%) over 5000 cycles in Zn//Cu asymmetric batteries. Notably, this strategy also enables the stable operation of anode-free Zn//I<sub>2</sub> batteries with a long lifespan of 3000 cycles. This work advances the understanding of Zn electrochemical behaviors, encompassing Zn nucleation, growth, and Zn<sup>2+</sup> stripping/plating.</p> +<p>With the rise of skin-like electronics, devices are increasingly coming into close contact with the human body, creating a demand for polymer semiconductors (PSCs) that combine stretchability with reliable electrical performance. However, balancing mechanical robustness with high carrier mobility remains a challenge. To address this, tris(pentafluorophenyl)borane (BCF) for Lewis acid doping is proposed to improve charge mobility while enhancing stretchability by increasing structural disorder. Through systematic investigation, several key structural principles have been identified to maximize the effectiveness of BCF doping in stretchable PSCs. Notably, increasing the lamellar stacking distance and reducing crystallinity facilitate the incorporation of BCF into the alkyl side-chain regions, thereby enhancing both mobility and stretchability. Conversely, stronger Lewis base groups in the main chain negatively impact these improvements. These results demonstrate that with a small addition of BCF, a two-fold increase in carrier mobility is achieved while simultaneously enhancing the crack onset strain to 100%. Furthermore, doped PSCs exhibit stable mobility retention under repeated 30% strains over 1000 cycles. This method of decoupling carrier mobility from mechanical properties opens up new avenues in the search for high-mobility stretchable PSCs.</p> -Ming Zhao, -Yanqun Lv, -Jun Qi, -Yong Zhang, -Yadong Du, -Qi Yang, -Yunkai Xu, -Jieshan Qiu, -Jun Lu, -Shimou Chen +Yu‐Ching Weng, +Chung‐Chieh Kang, +Ting‐Wei Chang, +Yi‐Ting Tsai, +Shahid Khan, +Tzu‐Ming Hung, +Chien‐Chung Shih Research Article - Crystallographic Reorientation Induced by Gradient Solid‐Electrolyte Interphase for Highly Stable Zinc Anode - 10.1002/adma.202412667 + Design Principles for Enhancing Both Carrier Mobility and Stretchability in Polymer Semiconductors via Lewis Acid Doping + 10.1002/adma.202411572 Advanced Materials - 10.1002/adma.202412667 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412667 + 10.1002/adma.202411572 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411572 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410575 - Sat, 16 Nov 2024 04:37:14 -0800 - 2024-11-16T04:37:14-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413525 + Sun, 17 Nov 2024 21:24:31 -0800 + 2024-11-17T09:24:31-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202410575 - Improving Oxygen‐Redox‐Active Layered Oxide Cathodes for Sodium‐Ion Batteries Through Crystal Facet Modulation and Fluorinated Interfacial Engineering + 10.1002/adma.202413525 + Polarization: A Universal Driving Force for Energy, Environment, and Electronics Advanced Materials, EarlyView. -Crystal‐facet modulation and fluorinated interfacial engineering via bifunctional electrolyte additive enhances the anionic redox kinetics and structural stability, which endows Na0.67Li0.24Mn0.76O2 with high capacity, superior rate capability, and long cycle stability for sodium‐ion batteries. +Polarization techniques are revolutionizing material functionalities across energy, environmental, and electronic sectors. This review comprehensively examines polarization mechanisms such as piezoelectric, ferroelectric, and pyroelectric effects, alongside strategies like doping and heterostructures. It highlights its pivotal role in enhancing charge dynamics, modifying surface chemistries, and facilitating energy‐efficient designs in various applications. @@ -971,46 +932,50 @@ Crystal‐facet modulation and fluorinated interfacial engineering via bifun Abstract -Layered oxides with active oxygen redox are attractive cathode materials for sodium‐ion batteries (SIBs) due to high capacity but suffer from rapid capacity/voltage deterioration and sluggish reaction kinetics stemming from lattice oxygen release, interfacial side reactions, and structural reconstruction. Herein, a synergistic strategy of crystal‐facet modulation and fluorinated interfacial engineering is proposed to achieve high capacity, superior rate capability, and long cycle stability in Na0.67Li0.24Mn0.76O2. The synthesized single‐crystal Na0.67Li0.24Mn0.76O2 (NLMO{010}) featuring increased {010} active facet exposure exhibits faster anionic redox kinetics and delivers a high capacity (272.4 mAh g−1 at 10 mA g−1) with superior energy density (713.9 Wh kg−1) and rate performance (116.4 mAh g−1 at 1 A g−1). Moreover, by incorporating N‐Fluorobenzenesulfonimide (NFBS) as electrolyte additive, the NLMO{010} cathode retains 84.6% capacity after 400 cycles at 500 mA g−1 with alleviated voltage fade (0.27 mV per cycle). Combined in situ analysis and theoretical calculations unveil dual functionality of NFBS, which results in thin yet durable fluorinated interfaces on the NLMO{010} cathode and hard carbon anode and scavenges highly reactive oxygen species. The results indicate the importance of fast‐ion‐transfer facet engineering and fluorinated electrolyte formulation to enhance oxygen redox‐active cathode materials for high‐energy‐density SIBs. +The sustainable future relies on the synergistic development of energy, environmental, and electronic systems, founded on the development of functional materials by exploring their quantum mechanisms. Effective control over the distribution and behavior of charges within these materials, a basic quantum attribute, is crucial in dictating their physical, chemical, and electronic properties. At the core of charge manipulation lies “polarization”—a ubiquitous phenomenon marked by separating positive and negative charges. This review thoroughly examines polarization techniques, spotlighting their transformative role in catalysis, energy storage, solar cells, and electronics. Starting with the foundational mechanisms underlying various forms of polarization, including piezoelectric, ferroelectric, and pyroelectric effects, the perspective is expanded to cover any asymmetric phenomena that generate internal fields, such as heterostructures and doping. Afterward, the critical role of polarization across various applications, including charge separation, surface chemistry modification, and energy band alignment, is highlighted. Special emphasis is placed on the synergy between polarization and material properties, demonstrating how this interplay is pivotal in overcoming existing technological limitations and unlocking new functionalities. Through a comprehensive analysis, a holistic roadmap is offered for harnessing polarization across the broad spectrum of applications, thus finding sustainable solutions for future energy, environment, and electronics. - <img src="https://onlinelibrary.wiley.com/cms/asset/d0638df7-f42c-47ad-9744-da83cf557935/adma202410575-gra-0001-m.png" - alt="Improving Oxygen-Redox-Active Layered Oxide Cathodes for Sodium-Ion Batteries Through Crystal Facet Modulation and Fluorinated Interfacial Engineering"/> -<p>Crystal-facet modulation and fluorinated interfacial engineering via bifunctional electrolyte additive enhances the anionic redox kinetics and structural stability, which endows Na<sub>0.67</sub>Li<sub>0.24</sub>Mn<sub>0.76</sub>O<sub>2</sub> with high capacity, superior rate capability, and long cycle stability for sodium-ion batteries. + <img src="https://onlinelibrary.wiley.com/cms/asset/24b46d69-0a05-4123-90d4-af3250cee7ec/adma202413525-gra-0001-m.png" + alt="Polarization: A Universal Driving Force for Energy, Environment, and Electronics"/> +<p>Polarization techniques are revolutionizing material functionalities across energy, environmental, and electronic sectors. This review comprehensively examines polarization mechanisms such as piezoelectric, ferroelectric, and pyroelectric effects, alongside strategies like doping and heterostructures. It highlights its pivotal role in enhancing charge dynamics, modifying surface chemistries, and facilitating energy-efficient designs in various applications. </p> <br/> <h2>Abstract</h2> -<p>Layered oxides with active oxygen redox are attractive cathode materials for sodium-ion batteries (SIBs) due to high capacity but suffer from rapid capacity/voltage deterioration and sluggish reaction kinetics stemming from lattice oxygen release, interfacial side reactions, and structural reconstruction. Herein, a synergistic strategy of crystal-facet modulation and fluorinated interfacial engineering is proposed to achieve high capacity, superior rate capability, and long cycle stability in Na<sub>0.67</sub>Li<sub>0.24</sub>Mn<sub>0.76</sub>O<sub>2</sub>. The synthesized single-crystal Na<sub>0.67</sub>Li<sub>0.24</sub>Mn<sub>0.76</sub>O<sub>2</sub> (NLMO{010}) featuring increased {010} active facet exposure exhibits faster anionic redox kinetics and delivers a high capacity (272.4 mAh g<sup>−1</sup> at 10 mA g<sup>−1</sup>) with superior energy density (713.9 Wh kg<sup>−1</sup>) and rate performance (116.4 mAh g<sup>−1</sup> at 1 A g<sup>−1</sup>). Moreover, by incorporating N-Fluorobenzenesulfonimide (NFBS) as electrolyte additive, the NLMO{010} cathode retains 84.6% capacity after 400 cycles at 500 mA g<sup>−1</sup> with alleviated voltage fade (0.27 mV per cycle). Combined in situ analysis and theoretical calculations unveil dual functionality of NFBS, which results in thin yet durable fluorinated interfaces on the NLMO{010} cathode and hard carbon anode and scavenges highly reactive oxygen species. The results indicate the importance of fast-ion-transfer facet engineering and fluorinated electrolyte formulation to enhance oxygen redox-active cathode materials for high-energy-density SIBs.</p> +<p>The sustainable future relies on the synergistic development of energy, environmental, and electronic systems, founded on the development of functional materials by exploring their quantum mechanisms. Effective control over the distribution and behavior of charges within these materials, a basic quantum attribute, is crucial in dictating their physical, chemical, and electronic properties. At the core of charge manipulation lies “polarization”—a ubiquitous phenomenon marked by separating positive and negative charges. This review thoroughly examines polarization techniques, spotlighting their transformative role in catalysis, energy storage, solar cells, and electronics. Starting with the foundational mechanisms underlying various forms of polarization, including piezoelectric, ferroelectric, and pyroelectric effects, the perspective is expanded to cover any asymmetric phenomena that generate internal fields, such as heterostructures and doping. Afterward, the critical role of polarization across various applications, including charge separation, surface chemistry modification, and energy band alignment, is highlighted. Special emphasis is placed on the synergy between polarization and material properties, demonstrating how this interplay is pivotal in overcoming existing technological limitations and unlocking new functionalities. Through a comprehensive analysis, a holistic roadmap is offered for harnessing polarization across the broad spectrum of applications, thus finding sustainable solutions for future energy, environment, and electronics.</p> -Yiran Sun, -Junying Weng, -Pengfei Zhou, -Wenyong Yuan, -Yihao Pan, -Xiaozhong Wu, -Jin Zhou, -Fangyi Cheng +Xinwei Guan, +Zhihao Lei, +Ruichang Xue, +Zhixuan Li, +Peng Li, +Matthew David, +Jiabao Yi, +Baohua Jia, +Hongwei Huang, +Xiaoning Li, +Tianyi Ma - Research Article - Improving Oxygen‐Redox‐Active Layered Oxide Cathodes for Sodium‐Ion Batteries Through Crystal Facet Modulation and Fluorinated Interfacial Engineering - 10.1002/adma.202410575 + Review + Polarization: A Universal Driving Force for Energy, Environment, and Electronics + 10.1002/adma.202413525 Advanced Materials - 10.1002/adma.202410575 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410575 - Research Article + 10.1002/adma.202413525 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413525 + Review - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414578 - Sat, 16 Nov 2024 04:36:41 -0800 - 2024-11-16T04:36:41-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413304 + Sun, 17 Nov 2024 21:24:09 -0800 + 2024-11-17T09:24:09-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202414578 - Enhanced Stability and Brightness through Co‐Substitution: Promoting Plant Growth with Green‐Excited Deep Red Phosphor Ca1‐zSrzLi1‐xMg2xAl3‐xN4:yEu2+ + 10.1002/adma.202413304 + Synergistic Modulation of Orientation and Steric Hindrance Induced by Alkyl Chain Length in Ammonium Salt Passivator Toward High‐performance Inverted Perovskite Solar Cells and Modules Advanced Materials, EarlyView. -This research presents a new phosphor that effectively converts green light into deep red light, which is advantageous for plant growth, thereby facilitating spectral regulation and enhancing luminescence. The phosphor can be efficiently excited by sunlight, thereby optimizing sunlight utilization. Furthermore, the material exhibits exceptional stability and efficiency for use in outdoor agricultural lighting applications. +Organic ammonium salts with varying alkyl chain lengths are used to passivate perovskite surface defects and optimize energy band alignment. Nonylammonium acetate (NAAc) achieves superior passivation through optimal molecular orientation and minimized steric hindrance, leading to 25.79% PCE in inverted PSCs utilizing vacuum flash technology in ambient conditions. + @@ -1020,43 +985,51 @@ This research presents a new phosphor that effectively converts green light into Abstract -The research utilized a strategy of chemical unit co‐substitution, successfully developing a novel blue‐green to green excited, deep red‐emitting phosphor, Ca1‐zSrzLi1‐xMg2xAl3‐xN4:yEu2+ (CLA‐2xM‐zS:yEu, 0≤x≤0.8, 0.003≤y≤0.01, 0≤z≤1), through the replacement of [Li−Al]4+ by [Mg−Mg]4+. This phosphor uniquely converts unusable green light to growth‐enhancing deep red, optimizing it for outdoor agriculture. Doping with Sr creates traps, causing a redshift in emission peaks, as confirmed by 7Li nuclear magnetic resonance (NMR) spectra, indicating Li presence and lattice changes. Ca0.2Sr0.8Li0.5MgAl2.5N4:0.005Eu2+ (CLAM‐0.8S) phosphor maintained high luminescence intensity under extreme conditions of 85 °C/85% RH, demonstrating excellent photoluminescence performance and chemical stability, compared with conventional SrLi0.5MgAl2.5N4:0.005Eu2+ (SLMA) and SrLiAl3N4:0.005Eu2+(SLA). Experimental results surprised that the unique Ca0.2Sr0.8Li0.8Mg0.4Al2.8N4:0.005Eu2+ (CLA‐0.4M‐0.8S) prepared light‐converting film, which is mainly excited by green light, demonstrated a 20% increase in optical density of Chlorella compared to the PP film and a remarkable 97.5% increase compared to the control group without any film. These findings suggest that this film has significant potential for applications in outdoor agriculture and other fields. +Organic ammonium salts are extensively utilized for passivating surface defects in perovskite films to mitigate trap‐assisted nonradiative recombination. However, the influence of alkyl chain length on the molecular orientation and spatial steric hindrance of ammonium salt remains underexplored, hindering advancements in more effective passivators. Here, a series of organic ammonium salts is reported with varying alkyl chain lengths to passivate surface defects and optimize band alignment. It is revealed that long alkyl chains promote parallel molecular orientation on the perovskite surface, thereby reinforcing interaction with surface defects, whereas excessive chain length introduces steric hindrance, weakening anion‐perovskite interactions. Nonylammonium acetate (NAAc) with optimal chain length achieves the ideal balance between chemical interactions, resulting in superior passivation. Through NAAc passivation, high‐performance inverted perovskite solar cells (PSCs) and modules are achieved, with power conversion efficiencies (PCE) of 25.79% (certified 25.12%) and 19.62%, respectively. This marks a record PCE for inverted PSCs utilizing vacuum flash technology in ambient conditions. Additionally, the NAAc‐passivated devices retain 91% of their initial PCE after 1200 h of continuous maximum power point operation. This work offers new insights into the interplay between molecular orientation and steric hindrance, advancing the design of high‐performance PSCs. - <img src="https://onlinelibrary.wiley.com/cms/asset/875b49e5-a4c4-41d0-817d-e93bba08edb9/adma202414578-gra-0001-m.png" - alt="Enhanced Stability and Brightness through Co-Substitution: Promoting Plant Growth with Green-Excited Deep Red Phosphor Ca1-zSrzLi1-xMg2xAl3-xN4:yEu2+"/> -<p>This research presents a new phosphor that effectively converts green light into deep red light, which is advantageous for plant growth, thereby facilitating spectral regulation and enhancing luminescence. The phosphor can be efficiently excited by sunlight, thereby optimizing sunlight utilization. Furthermore, the material exhibits exceptional stability and efficiency for use in outdoor agricultural lighting applications. + <img src="https://onlinelibrary.wiley.com/cms/asset/564f615c-ded7-4244-9f3c-94149546c5d7/adma202413304-gra-0001-m.png" + alt="Synergistic Modulation of Orientation and Steric Hindrance Induced by Alkyl Chain Length in Ammonium Salt Passivator Toward High-performance Inverted Perovskite Solar Cells and Modules"/> +<p>Organic ammonium salts with varying alkyl chain lengths are used to passivate perovskite surface defects and optimize energy band alignment. Nonylammonium acetate (NAAc) achieves superior passivation through optimal molecular orientation and minimized steric hindrance, leading to 25.79% PCE in inverted PSCs utilizing vacuum flash technology in ambient conditions. </p> <br/> <h2>Abstract</h2> -<p>The research utilized a strategy of chemical unit co-substitution, successfully developing a novel blue-green to green excited, deep red-emitting phosphor, Ca<sub>1-z</sub>Sr<sub>z</sub>Li<sub>1-x</sub>Mg<sub>2x</sub>Al<sub>3-x</sub>N<sub>4</sub>:yEu<sup>2+</sup> (CLA-2xM-zS:yEu, 0≤x≤0.8, 0.003≤y≤0.01, 0≤z≤1), through the replacement of [Li−Al]<sup>4+</sup> by [Mg−Mg]<sup>4+</sup>. This phosphor uniquely converts unusable green light to growth-enhancing deep red, optimizing it for outdoor agriculture. Doping with Sr creates traps, causing a redshift in emission peaks, as confirmed by <sup>7</sup>Li nuclear magnetic resonance (NMR) spectra, indicating Li presence and lattice changes. Ca<sub>0.2</sub>Sr<sub>0.8</sub>Li<sub>0.5</sub>MgAl<sub>2.5</sub>N<sub>4</sub>:0.005Eu<sup>2+</sup> (CLAM-0.8S) phosphor maintained high luminescence intensity under extreme conditions of 85 °C/85% RH, demonstrating excellent photoluminescence performance and chemical stability, compared with conventional SrLi<sub>0.5</sub>MgAl<sub>2.5</sub>N<sub>4</sub>:0.005Eu<sup>2+</sup> (SLMA) and SrLiAl<sub>3</sub>N<sub>4</sub>:0.005Eu<sup>2+</sup>(SLA). Experimental results surprised that the unique Ca<sub>0.2</sub>Sr<sub>0.8</sub>Li<sub>0.8</sub>Mg<sub>0.4</sub>Al<sub>2.8</sub>N<sub>4</sub>:0.005Eu<sup>2+</sup> (CLA-0.4M-0.8S) prepared light-converting film, which is mainly excited by green light, demonstrated a 20% increase in optical density of Chlorella compared to the PP film and a remarkable 97.5% increase compared to the control group without any film. These findings suggest that this film has significant potential for applications in outdoor agriculture and other fields.</p> +<p>Organic ammonium salts are extensively utilized for passivating surface defects in perovskite films to mitigate trap-assisted nonradiative recombination. However, the influence of alkyl chain length on the molecular orientation and spatial steric hindrance of ammonium salt remains underexplored, hindering advancements in more effective passivators. Here, a series of organic ammonium salts is reported with varying alkyl chain lengths to passivate surface defects and optimize band alignment. It is revealed that long alkyl chains promote parallel molecular orientation on the perovskite surface, thereby reinforcing interaction with surface defects, whereas excessive chain length introduces steric hindrance, weakening anion-perovskite interactions. Nonylammonium acetate (NAAc) with optimal chain length achieves the ideal balance between chemical interactions, resulting in superior passivation. Through NAAc passivation, high-performance inverted perovskite solar cells (PSCs) and modules are achieved, with power conversion efficiencies (PCE) of 25.79% (certified 25.12%) and 19.62%, respectively. This marks a record PCE for inverted PSCs utilizing vacuum flash technology in ambient conditions. Additionally, the NAAc-passivated devices retain 91% of their initial PCE after 1200 h of continuous maximum power point operation. This work offers new insights into the interplay between molecular orientation and steric hindrance, advancing the design of high-performance PSCs.</p> -Pengpeng Wang, -Yuhua Wang, -Zebin Li, -Haoyang Wang, -Takatoshi Seto +Wenhuan Gao, +Jike Ding, +Quanxing Ma, +Hong Zhang, +Jiajia Zhang, +Zuolin Zhang, +Mengjia Li, +Yang Wang, +Boxue Zhang, +Thierry Pauporté, +Jian‐Xin Tang, +Jiangzhao Chen, +Cong Chen Research Article - Enhanced Stability and Brightness through Co‐Substitution: Promoting Plant Growth with Green‐Excited Deep Red Phosphor Ca1‐zSrzLi1‐xMg2xAl3‐xN4:yEu2+ - 10.1002/adma.202414578 + Synergistic Modulation of Orientation and Steric Hindrance Induced by Alkyl Chain Length in Ammonium Salt Passivator Toward High‐performance Inverted Perovskite Solar Cells and Modules + 10.1002/adma.202413304 Advanced Materials - 10.1002/adma.202414578 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414578 + 10.1002/adma.202413304 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413304 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412154 - Sat, 16 Nov 2024 04:36:20 -0800 - 2024-11-16T04:36:20-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412432 + Sun, 17 Nov 2024 21:23:35 -0800 + 2024-11-17T09:23:35-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412154 - LysSYL‐Loaded pH‐Switchable Self‐Assembling Peptide Hydrogels Promote Methicillin‐Resistant Staphylococcus Aureus Elimination and Wound Healing + 10.1002/adma.202412432 + Large‐Area Metal–Organic Framework Glasses for Efficient X‐Ray Detection Advanced Materials, EarlyView. -The LysSYL‐loaded L5 can assemble pH‐sensitive L5@LysSYL hydrogels at neutral pH and exhibit the slow‐release effect of LysSYL at acidic pH. L5@LysSYL hydrogels effectively eliminate MRSA through multiple synergistic modes, including bacterial membrane disruption, cross‐wall disturbing, and cell separation inhibition. Moreover, L5@LysSYL hydrogels promote wound healing and show promise as a wound dressing for the management of wound infections. +Metal–organic framework (MOF) glasses composed of zinc and imidazole derivatives are employed to prepare large‐area and continuous MOF films. The MOF glass detector achieves an outstanding X‐ray sensitivity of 112.8 µC Gyair−1 cm−2 and a detection limit of 0.41 µGyair s−1. These findings pave the way for large‐area MOF‐based X‐ray detectors with practical applications in medical and security screening domains. @@ -1066,58 +1039,55 @@ The LysSYL‐loaded L5 can assemble pH‐sensitive L5@LysSYL hydrogels a Abstract -Staphylococcus aureus (S. aureus), especially methicillin‐resistant S. aureus (MRSA), causes wound infections, whose treatment remains a clinical challenge. Bacterium‐infected wounds often create acidic niches with a pH 4.5–6.5. Endolysin LysSYL, which is derived from phage SYL, shows promise as an antistaphylococcal agent. However, endolysins generally exhibit instability and possess low bioavailability in acidic microenvironments. Here, an array of self‐assembling peptides is designed, and peptide L5 is screened out based on its gel formation property and bioavailability. L5 exerted a pH‐switchable antimicrobial effect (pH 5.5) and formed biocompatible hydrogels at neutral pH (pH 7.4). The LysSYL‐loaded L5 can assemble L5@LysSYL hydrogels, increase thermal stability, and exhibit the slow‐release effect of LysSYL. Effective elimination of S. aureus is achieved by L5@LysSYL through bacterial membrane disruption and cell separation inhibition. Moreover, L5@LysSYL hydrogels exhibit great potential in promoting wound healing in a mouse wound model infected by MRSA. Furthermore, L5@LysSYL hydrogels are safe and can decrease the cytokine levels and increase the number of key factors for vessel formation, which contribute to wound healing. Overall, the self‐assembling L5@LysSYL can effectively clean MRSA and promote wound healing, which suggests its potential as a pH‐sensitive wound dressing for the management of wound infections. +Cutting‐edge techniques utilizing continuous films made from pure, novel semiconductive materials offer promising pathways to achieve high performance and cost‐effectiveness for X‐ray detection. Semiconductive metal–organic framework (MOF) glass films are known for their remarkably smooth surface morphology, straightforward synthesis, and capability for large‐area fabrication, presenting a new direction for high‐performance X‐ray detectors. Here, a novel material centered on MOF glasses for highly uniform glass film fabrication customized for X‐ray detection is introduced. MOF glasses, composed of zinc and imidazole derivatives, enable the transition from solid to liquid at low temperatures, facilitating the straightforward preparation of large‐area and continuous MOF films with high mobility for X‐ray device fabrication. Remarkably, MOF glass detectors demonstrate an exceptional sensitivity of 112.8 µC Gyair−1 cm−2 and a detection limit of 0.41 µGyair s−1, making them one of the most sensitive and with the best detection limits reported to date for MOF X‐ray detectors. Clear X‐ray images are successfully conducted using these developed MOF glass detectors for the first time. This breakthrough in X‐ray sensitivity, and detection limit along with the spatial imaging resolution establishes a new standard for developing large‐area and efficient MOF‐based X‐ray detectors with practical applications in medical and security screening. - <img src="https://onlinelibrary.wiley.com/cms/asset/9b35ff68-a0c0-488e-9761-946a30d0861a/adma202412154-gra-0001-m.png" - alt="LysSYL-Loaded pH-Switchable Self-Assembling Peptide Hydrogels Promote Methicillin-Resistant Staphylococcus Aureus Elimination and Wound Healing"/> -<p>The LysSYL-loaded L5 can assemble pH-sensitive L5@LysSYL hydrogels at neutral pH and exhibit the slow-release effect of LysSYL at acidic pH. L5@LysSYL hydrogels effectively eliminate MRSA through multiple synergistic modes, including bacterial membrane disruption, cross-wall disturbing, and cell separation inhibition. Moreover, L5@LysSYL hydrogels promote wound healing and show promise as a wound dressing for the management of wound infections. + <img src="https://onlinelibrary.wiley.com/cms/asset/799eff21-c054-4c05-8a91-79ad942f5c15/adma202412432-gra-0001-m.png" + alt="Large-Area Metal–Organic Framework Glasses for Efficient X-Ray Detection"/> +<p>Metal–organic framework (MOF) glasses composed of zinc and imidazole derivatives are employed to prepare large-area and continuous MOF films. The MOF glass detector achieves an outstanding X-ray sensitivity of 112.8 µC Gy<sub>air</sub> +<sup>−1</sup> cm<sup>−2</sup> and a detection limit of 0.41 µGy<sub>air</sub> s<sup>−1</sup>. These findings pave the way for large-area MOF-based X-ray detectors with practical applications in medical and security screening domains. </p> <br/> <h2>Abstract</h2> -<p><i>Staphylococcus aureus</i> (<i>S. aureus</i>), especially methicillin-resistant <i>S. aureus</i> (MRSA), causes wound infections, whose treatment remains a clinical challenge. Bacterium-infected wounds often create acidic niches with a pH 4.5–6.5. Endolysin LysSYL, which is derived from phage SYL, shows promise as an antistaphylococcal agent. However, endolysins generally exhibit instability and possess low bioavailability in acidic microenvironments. Here, an array of self-assembling peptides is designed, and peptide L5 is screened out based on its gel formation property and bioavailability. L5 exerted a pH-switchable antimicrobial effect (pH 5.5) and formed biocompatible hydrogels at neutral pH (pH 7.4). The LysSYL-loaded L5 can assemble L5@LysSYL hydrogels, increase thermal stability, and exhibit the slow-release effect of LysSYL. Effective elimination of <i>S. aureus</i> is achieved by L5@LysSYL through bacterial membrane disruption and cell separation inhibition. Moreover, L5@LysSYL hydrogels exhibit great potential in promoting wound healing in a mouse wound model infected by MRSA. Furthermore, L5@LysSYL hydrogels are safe and can decrease the cytokine levels and increase the number of key factors for vessel formation, which contribute to wound healing. Overall, the self-assembling L5@LysSYL can effectively clean MRSA and promote wound healing, which suggests its potential as a pH-sensitive wound dressing for the management of wound infections.</p> +<p>Cutting-edge techniques utilizing continuous films made from pure, novel semiconductive materials offer promising pathways to achieve high performance and cost-effectiveness for X-ray detection. Semiconductive metal–organic framework (MOF) glass films are known for their remarkably smooth surface morphology, straightforward synthesis, and capability for large-area fabrication, presenting a new direction for high-performance X-ray detectors. Here, a novel material centered on MOF glasses for highly uniform glass film fabrication customized for X-ray detection is introduced. MOF glasses, composed of zinc and imidazole derivatives, enable the transition from solid to liquid at low temperatures, facilitating the straightforward preparation of large-area and continuous MOF films with high mobility for X-ray device fabrication. Remarkably, MOF glass detectors demonstrate an exceptional sensitivity of 112.8 µC Gy<sub>air</sub> +<sup>−1</sup> cm<sup>−2</sup> and a detection limit of 0.41 µGy<sub>air</sub> s<sup>−1</sup>, making them one of the most sensitive and with the best detection limits reported to date for MOF X-ray detectors. Clear X-ray images are successfully conducted using these developed MOF glass detectors for the first time. This breakthrough in X-ray sensitivity, and detection limit along with the spatial imaging resolution establishes a new standard for developing large-area and efficient MOF-based X-ray detectors with practical applications in medical and security screening.</p> -He Liu, -Xuemei Wei, -Huagang Peng, -Yi Yang, -Zhen Hu, -Yifan Rao, -Zhefen Wang, -Jianxiong Dou, -Xiaonan Huang, -Qiwen Hu, -Li Tan, -Yuting Wang, -Juan Chen, -Lu Liu, -Yuhua Yang, -Jianghong Wu, -Xiaomei Hu, -Shuguang Lu, -Weilong Shang, -Xiancai Rao +Xin Zhu, +Tengjiao He, +Xin Song, +Osama Shekhah, +Simil Thomas, +Hao Jiang, +Wentao Wu, +Tengyue He, +Vincent Guillerm, +Aleksander Shkurenko, +Jian‐Xin Wang, +Husam N. Alshareef, +Osman M. Bakr, +Mohamed Eddaoudi, +Omar F. Mohammed Research Article - LysSYL‐Loaded pH‐Switchable Self‐Assembling Peptide Hydrogels Promote Methicillin‐Resistant Staphylococcus Aureus Elimination and Wound Healing - 10.1002/adma.202412154 + Large‐Area Metal–Organic Framework Glasses for Efficient X‐Ray Detection + 10.1002/adma.202412432 Advanced Materials - 10.1002/adma.202412154 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412154 + 10.1002/adma.202412432 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412432 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414045 - Sat, 16 Nov 2024 04:35:29 -0800 - 2024-11-16T04:35:29-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413049 + Sun, 17 Nov 2024 21:23:00 -0800 + 2024-11-17T09:23:00-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202414045 - Making Interfacial Solar Evaporation of Seawater Faster than Fresh Water + 10.1002/adma.202413049 + Promoting Piezoelectricity in Amino Acids by Fluorination Advanced Materials, EarlyView. -A facile and general strategy is developed to make real seawater evaporation faster than pure water. By simply introducing specific mineral materials into the floating photothermal evaporator, Mg2+ and Ca2+ ions in seawater are accumulated at the photothermal interfaces by spontaneous ion exchange, which disturb the hydrogen bonds of water molecules, and reduce the evaporation enthalpy of seawater. +A high piezoelectric amino acid (Cbz‐Phe(4F)) is designed by simple fluorination. Cbz‐Phe(4F) self‐assembles into single crystals with C2 space group. Importantly, Cbz‐Phe(4F) crystals as a flexible piezoelectric sensor for the classification of various nuts and their quality sorting, which includes those as small as individual pumpkin seeds with high sensitivity and accuracy of sorting and quality checks. @@ -1128,56 +1098,48 @@ A facile and general strategy is developed to make real seawater evaporation fas Abstract -Interfacial solar evaporation‐based seawater desalination is regarded as one of the most promising strategies to alleviate freshwater scarcity. However, the solar evaporation rate of real seawater is significantly constricted by the ubiquitous salts present in seawater. In addition to the common issue of salt accumulation on the evaporation surface during solar evaporation, strong hydration between salt ions and water molecules leads to a lower evaporation rate for real seawater compared to pure water. Here a facile and general strategy is developed to reverse this occurrence, that is, making real seawater evaporation faster than pure water. By simply introducing specific mineral materials into the floating photothermal evaporator, ion exchange at air–water interfaces directly results in a decrease in seawater evaporation enthalpy, and consequently achieves much higher seawater evaporation rates compared to pure water. This process is spontaneously realized during seawater solar evaporation. Considering the current enormous clean water production from evaporation‐based desalination plants, such an evaporation performance improvement can remarkably increase annual clean water production, benefiting millions of people worldwide. +Bioinspired piezoelectric amino acids and peptides are attracting attention due to their designable sequences, versatile structures, low cost, and biodegradability. However, it remains a challenge to design amino acids and peptides with high piezoelectricity. Herein, a high piezoelectric amino acid by simple fluorination in its side chain is presented. The three phenylalanine derivatives are designed: Cbz‐Phe, Cbz‐Phe(4F), and Cbz‐pentafluoro‐Phe. The effect of fluorination on self‐assembly and piezoelectricity is investigated. Cbz‐Phe(4F) can self‐assemble into crystals with a C2 space group, while Cbz‐Phe and Cbz‐pentafluoro‐Phe form aggregated self‐assemblies. Moreover, Cbz‐Phe(4F) crystals exhibit a remarkably higher piezoelectric coefficient (d33eff$d_{\ 33}^{\ eff}$) of ≈17.9 pm V−1 than Cbz‐Phe and Cbz‐pentafluoro‐Phe. When fabricated as a piezoelectric nanogenerator, it generates an open‐circuit voltage of ≈2.4 V. Importantly, Cbz‐Phe(4F) crystals as a flexible piezoelectric sensor for the classification of various nuts and their quality sorting, which includes those as small as individual pumpkin seeds with high sensitivity and accuracy of sorting and quality checks. When mounted onto soft grippers, the sensor performs the tactile self‐sensing functions. This work provides a promising approach to designing high piezoelectric amino acids by simple fluorination, offering exciting prospects for advancements in bioinspired piezoelectric materials in the application of smart agriculture and soft robotics. - <img src="https://onlinelibrary.wiley.com/cms/asset/2efce3da-a516-4a5c-abe9-e36592d9f0b2/adma202414045-gra-0001-m.png" - alt="Making Interfacial Solar Evaporation of Seawater Faster than Fresh Water"/> -<p>A facile and general strategy is developed to make real seawater evaporation faster than pure water. By simply introducing specific mineral materials into the floating photothermal evaporator, Mg<sup>2+</sup> and Ca<sup>2+</sup> ions in seawater are accumulated at the photothermal interfaces by spontaneous ion exchange, which disturb the hydrogen bonds of water molecules, and reduce the evaporation enthalpy of seawater. + <img src="https://onlinelibrary.wiley.com/cms/asset/e0a74388-6412-42a4-b69a-9bc8c1308c68/adma202413049-gra-0001-m.png" + alt="Promoting Piezoelectricity in Amino Acids by Fluorination"/> +<p>A high piezoelectric amino acid (Cbz-Phe(4F)) is designed by simple fluorination. Cbz-Phe(4F) self-assembles into single crystals with C2 space group. Importantly, Cbz-Phe(4F) crystals as a flexible piezoelectric sensor for the classification of various nuts and their quality sorting, which includes those as small as individual pumpkin seeds with high sensitivity and accuracy of sorting and quality checks. </p> <br/> <h2>Abstract</h2> -<p>Interfacial solar evaporation-based seawater desalination is regarded as one of the most promising strategies to alleviate freshwater scarcity. However, the solar evaporation rate of real seawater is significantly constricted by the ubiquitous salts present in seawater. In addition to the common issue of salt accumulation on the evaporation surface during solar evaporation, strong hydration between salt ions and water molecules leads to a lower evaporation rate for real seawater compared to pure water. Here a facile and general strategy is developed to reverse this occurrence, that is, making real seawater evaporation faster than pure water. By simply introducing specific mineral materials into the floating photothermal evaporator, ion exchange at air–water interfaces directly results in a decrease in seawater evaporation enthalpy, and consequently achieves much higher seawater evaporation rates compared to pure water. This process is spontaneously realized during seawater solar evaporation. Considering the current enormous clean water production from evaporation-based desalination plants, such an evaporation performance improvement can remarkably increase annual clean water production, benefiting millions of people worldwide.</p> +<p>Bioinspired piezoelectric amino acids and peptides are attracting attention due to their designable sequences, versatile structures, low cost, and biodegradability. However, it remains a challenge to design amino acids and peptides with high piezoelectricity. Herein, a high piezoelectric amino acid by simple fluorination in its side chain is presented. The three phenylalanine derivatives are designed: Cbz-Phe, Cbz-Phe(4F), and Cbz-pentafluoro-Phe. The effect of fluorination on self-assembly and piezoelectricity is investigated. Cbz-Phe(4F) can self-assemble into crystals with a C2 space group, while Cbz-Phe and Cbz-pentafluoro-Phe form aggregated self-assemblies. Moreover, Cbz-Phe(4F) crystals exhibit a remarkably higher piezoelectric coefficient (d33eff$d_{\ 33}^{\ eff}$) of ≈17.9 pm V<sup>−1</sup> than Cbz-Phe and Cbz-pentafluoro-Phe. When fabricated as a piezoelectric nanogenerator, it generates an open-circuit voltage of ≈2.4 V. Importantly, Cbz-Phe(4F) crystals as a flexible piezoelectric sensor for the classification of various nuts and their quality sorting, which includes those as small as individual pumpkin seeds with high sensitivity and accuracy of sorting and quality checks. When mounted onto soft grippers, the sensor performs the tactile self-sensing functions. This work provides a promising approach to designing high piezoelectric amino acids by simple fluorination, offering exciting prospects for advancements in bioinspired piezoelectric materials in the application of smart agriculture and soft robotics.</p> -Huimin Yu, -Huanyu Jin, -Meijia Qiu, -Yunzheng Liang, -Peng Sun, -Chuanqi Cheng, -Pan Wu, -Yida Wang, -Xuan Wu, -Dewei Chu, -Min Zheng, -Tong Qiu, -Yi Lu, -Bin Zhang, -Wenjie Mai, -Xiaofei Yang, -Gary Owens, -Haolan Xu +Tan Hu, +Jin Pyo Lee, +Peiwen Huang, +Amanda Jiamin Ong, +Jian Yu, +Shuihong Zhu, +Yixuan Jiang, +Zhuo Zhang, +Meital Reches, +Pooi See Lee Research Article - Making Interfacial Solar Evaporation of Seawater Faster than Fresh Water - 10.1002/adma.202414045 + Promoting Piezoelectricity in Amino Acids by Fluorination + 10.1002/adma.202413049 Advanced Materials - 10.1002/adma.202414045 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414045 + 10.1002/adma.202413049 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413049 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202415101 - Sat, 16 Nov 2024 04:35:00 -0800 - 2024-11-16T04:35:00-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406727 + Sun, 17 Nov 2024 21:22:09 -0800 + 2024-11-17T09:22:09-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202415101 - Fabrication of Ultrahigh‐Loading Dual Copper Sites in Nitrogen‐Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral Conditions + 10.1002/adma.202406727 + Spintronic Pathways in a Nonconjugated Radical Polymer Glass Advanced Materials, EarlyView. -Cuobpy complex is assembled into the cages of MAF‐4 as a host‐guest precursor, and pyrolyzed it into a highly loaded dual copper (21 wt%) nitrogen‐doped carbon catalyst, which exhibits an exceptional performance for eCO2RR, achieving a Faradaic efficiency of 52% and a current density of 180 mA cm−2 at −1.4 V vs. RHE. +A nonconjugated radical polymer with high spin density displays large effective spin mixing conductance, enabling efficient spin transport over long distances at room temperature. @@ -1187,44 +1149,46 @@ Cuobpy complex is assembled into the cages of MAF‐4 as a host‐guest Abstract -Synthesis of high‐loading atomic‐level dispersed catalysts for highly efficient electrochemical CO2 reduction reaction (eCO2RR) to ethylene (C2H4) in neutral electrolyte remain challenging tasks. To address common aggregation issues, a host‐guest strategy is employed, by using a metal‐azolate framework (MAF‐4) with nanocages as the host and a dinuclear Cu(I) complex as the guest, to form precursors for pyrolysis into a series of nitrogen‐doped porous carbons (NPCs) with varying loadings of dual copper sites, namely NPCMAF‐4‐Cu2‐21 (21.2 wt%), NPCMAF‐4‐Cu2‐11 (10.6 wt%), and NPCMAF‐4‐Cu2‐7 (6.9 wt%). Interestingly, as the loading of dual copper sites increased from 6.9 to 21.2 wt%, the partial current density for eCO2RR to yield C2H4 also gradually increased from 38.7 to 93.6 mA cm−2. In a 0.1 m KHCO3 electrolyte, at −1.4 V versus reversible hydrogen electrode (vs. RHE), NPCMAF‐4‐Cu2‐21 exhibits the excellent performance with a Faradaic efficiency of 52% and a current density of 180 mA cm−2. Such performance can be attributed to the presence of ultrahigh‐loading dual copper sites, which promotes C─C coupling and the formation of C2 products. The findings demonstrate the confinement effect of MAF‐4 with nanocages is conducive to the preparation of high‐loading atomic‐level catalysts. +Radical chemistries have attracted burgeoning attention due to their intriguing technological applications in organic electronics, optoelectronics, and magneto‐responsive systems. However, the potential of these magnetically active glassy polymers to transport spin‐selective currents has not been demonstrated. Here, the spin‐transport characteristics of the radical polymer poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl) (PTEO) allow for sustained spin‐selective currents when incorporated into typical device geometries with magnetically polarized electrodes. Annealing thin films of PTEO above its glass transition temperature results in a giant magnetoresistance effect (i.e., an MR of ≈80%) at 4 K. Additionally, ferromagnetic resonance spin‐pumping results in a relatively large effective spin‐mixing conductance of 1.18 × 1019 m−2 at the NiFe/PTEO interface. Due to the large spin‐density and radical‐radical exchange interactions, there is effective propagation of pure spin currents through PTEO in the NiFe/PTEO/Pd multilayer devices. This results in the transport of spin current over long distances with a spin diffusion length of 90.4 nm. The spin diffusion length and spin mixing conductance values surpass those reported in inorganic and metallic systems and are comparable to conventional doped conjugated polymers. This is the first example of spin transport in a nonconjugated radical polymer, and these findings underscore the promising spin‐transporting potential of radical polymers. - <img src="https://onlinelibrary.wiley.com/cms/asset/d935aa97-2130-4a6a-8aa8-c492fb8941f7/adma202415101-gra-0001-m.png" - alt="Fabrication of Ultrahigh-Loading Dual Copper Sites in Nitrogen-Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral Conditions"/> -<p><b>Cuobpy</b> complex is assembled into the cages of <b>MAF-4</b> as a host-guest precursor, and pyrolyzed it into a highly loaded dual copper (21 wt%) nitrogen-doped carbon catalyst, which exhibits an exceptional performance for eCO<sub>2</sub>RR, achieving a Faradaic efficiency of 52% and a current density of 180 mA cm<sup>−2</sup> at −1.4 V <i>v</i> -<i>s</i>. RHE. + <img src="https://onlinelibrary.wiley.com/cms/asset/9f44482c-d216-431a-a70b-bb93d811a0e8/adma202406727-gra-0001-m.png" + alt="Spintronic Pathways in a Nonconjugated Radical Polymer Glass"/> +<p>A nonconjugated radical polymer with high spin density displays large effective spin mixing conductance, enabling efficient spin transport over long distances at room temperature. </p> <br/> <h2>Abstract</h2> -<p>Synthesis of high-loading atomic-level dispersed catalysts for highly efficient electrochemical CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR) to ethylene (C<sub>2</sub>H<sub>4</sub>) in neutral electrolyte remain challenging tasks. To address common aggregation issues, a host-guest strategy is employed, by using a metal-azolate framework (<b>MAF-4</b>) with nanocages as the host and a dinuclear Cu(I) complex as the guest, to form precursors for pyrolysis into a series of nitrogen-doped porous carbons (NPCs) with varying loadings of dual copper sites, namely <b>NPC<sub>MAF-4</sub>-Cu<sub>2</sub>-21</b> (21.2 wt%), <b>NPC<sub>MAF-4</sub>-Cu<sub>2</sub>-11</b> (10.6 wt%), and <b>NPC<sub>MAF-4</sub>-Cu<sub>2</sub>-7</b> (6.9 wt%). Interestingly, as the loading of dual copper sites increased from 6.9 to 21.2 wt%, the partial current density for eCO<sub>2</sub>RR to yield C<sub>2</sub>H<sub>4</sub> also gradually increased from 38.7 to 93.6 mA cm<sup>−2</sup>. In a 0.1 <span class="smallCaps">m</span> KHCO<sub>3</sub> electrolyte, at −1.4 V versus reversible hydrogen electrode (<i>vs</i>. RHE), <b>NPC<sub>MAF-4</sub>-Cu<sub>2</sub>-21</b> exhibits the excellent performance with a Faradaic efficiency of 52% and a current density of 180 mA cm<sup>−2</sup>. Such performance can be attributed to the presence of ultrahigh-loading dual copper sites, which promotes C─C coupling and the formation of C<sub>2</sub> products. The findings demonstrate the confinement effect of <b>MAF-4</b> with nanocages is conducive to the preparation of high-loading atomic-level catalysts.</p> +<p>Radical chemistries have attracted burgeoning attention due to their intriguing technological applications in organic electronics, optoelectronics, and magneto-responsive systems. However, the potential of these magnetically active glassy polymers to transport spin-selective currents has not been demonstrated. Here, the spin-transport characteristics of the radical polymer poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl) (PTEO) allow for sustained spin-selective currents when incorporated into typical device geometries with magnetically polarized electrodes. Annealing thin films of PTEO above its glass transition temperature results in a giant magnetoresistance effect (i.e., an MR of ≈80%) at 4 K. Additionally, ferromagnetic resonance spin-pumping results in a relatively large effective spin-mixing conductance of 1.18 × 10<sup>19</sup> m<sup>−2</sup> at the NiFe/PTEO interface. Due to the large spin-density and radical-radical exchange interactions, there is effective propagation of pure spin currents through PTEO in the NiFe/PTEO/Pd multilayer devices. This results in the transport of spin current over long distances with a spin diffusion length of 90.4 nm. The spin diffusion length and spin mixing conductance values surpass those reported in inorganic and metallic systems and are comparable to conventional doped conjugated polymers. This is the first example of spin transport in a nonconjugated radical polymer, and these findings underscore the promising spin-transporting potential of radical polymers.</p> -Jin‐Meng Heng, -Hao‐Lin Zhu, -Zhen‐Hua Zhao, -Pei‐Qin Liao, -Xiao‐Ming Chen +Hamas Tahir, +Carsten Flores‐Hansen, +Sheng‐Ning Hsu, +Zihao Liang, +Jayant Naga, +Neil R. Dilley, +Brett M. Savoie, +Bryan W. Boudouris Research Article - Fabrication of Ultrahigh‐Loading Dual Copper Sites in Nitrogen‐Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral Conditions - 10.1002/adma.202415101 + Spintronic Pathways in a Nonconjugated Radical Polymer Glass + 10.1002/adma.202406727 Advanced Materials - 10.1002/adma.202415101 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202415101 + 10.1002/adma.202406727 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406727 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414365 - Sat, 16 Nov 2024 04:29:23 -0800 - 2024-11-16T04:29:23-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413060 + Sun, 17 Nov 2024 21:22:04 -0800 + 2024-11-17T09:22:04-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202414365 - Enhancing Radiofrequency Ablation for Hepatocellular Carcinoma: Nano‐Epidrug Effects on Immune Modulation and Antigenicity Restoration + 10.1002/adma.202413060 + Mesoporous Acridinium‐Based Covalent Organic Framework for Long‐lived Charge‐Separated Exciton Mediated Photocatalytic [4+2] Annulation Advanced Materials, EarlyView. -A nano‐epidrug (MFMP) is developed to enhance radiofrequency ablation for hepatocellular carcinoma. This is achieved through the demethylation of cGAS DNA, demethylation of EGFR mRNA, and phosphorylation of TBK1 protein, which collectively influence immune modulation and antigenicity restoration, ultimately suppressing the recurrence and metastasis of hepatocellular carcinoma. +An Acridinium‐based covalent organic framework (COFs) featuring systematic trap states is designed to generate charge‐separated excitons with enhanced lifetime. Large 4 nm‐sized mesoporous channels and ultra‐stable excitons resulted in the COF functioning as an efficient heterogeneous photocatalyst toward Diels‐Alder type oxidative [4+2] annulation with a million times enhanced interfacial charge dissipation response. @@ -1234,49 +1198,50 @@ A nano‐epidrug (MFMP) is developed to enhance radiofrequency ablation for Abstract -Radiofrequency ablation (RFA), a critical therapy for hepatocellular carcinoma (HCC), carries a significant risk of recurrence and metastasis, particularly owing to mechanisms involving immune evasion and antigen downregulation via epigenetic modifications. This study introduces a “nano‐epidrug” named MFMP. MFMP, which is composed of hollow mesoporous manganese dioxide (MnO2) nanoparticles, FIDAS‐5 as an MAT2A inhibitor, macrophage membrane, and anti‐PD‐L1 (aPD‐L1), targets HCC cells. By selectively binding to these cells, MFMP initially reverses immune suppression via PD‐L1 inhibition. After endocytosis, MFMP disassembles in the tumor microenvironment, releasing FIDAS‐5 and Mn2+. FIDAS‐5 prevents cGAS methylation, whereas Mn2+ aids STING pathway restoration. In addition, FIDAS‐5 reduces m6A RNA modification, suppressing EGFR expression. These changes enhance HCC antigenicity to promote cytotoxic T cell recognition and cytotoxic killing. Furthermore, MFMP mediates immunogenic cell death in HCC by synergizing with RFA through cGAS DNA demethylation, EGFR mRNA demethylation, and TBK1 protein phosphorylation, thereby inhibiting recurrence and metastasis and enhancing immune memory. Thus, MFMP is a potential adjunctive therapy requiring clinical validation. +Readily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long‐lived charge‐separated excitons. Installing cationic acridinium functionality in a pristine electron‐rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor–acceptor dyad network that performed rapid and efficient oxidative Diels‐Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of ≈4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra‐stable charge‐separated excitons of 1.9 nm diameter with no apparent radiative charge‐recombination pathway, endorsing almost a million times better photo‐response and catalysis than the state‐of‐the‐art. - <img src="https://onlinelibrary.wiley.com/cms/asset/8dbce337-0480-46ff-9a7c-212f01ca97a1/adma202414365-gra-0001-m.png" - alt="Enhancing Radiofrequency Ablation for Hepatocellular Carcinoma: Nano-Epidrug Effects on Immune Modulation and Antigenicity Restoration"/> -<p>A nano-epidrug (MFMP) is developed to enhance radiofrequency ablation for hepatocellular carcinoma. This is achieved through the demethylation of cGAS DNA, demethylation of EGFR mRNA, and phosphorylation of TBK1 protein, which collectively influence immune modulation and antigenicity restoration, ultimately suppressing the recurrence and metastasis of hepatocellular carcinoma. + <img src="https://onlinelibrary.wiley.com/cms/asset/4413b778-2419-4472-b608-8b8339d40a6a/adma202413060-gra-0001-m.png" + alt="Mesoporous Acridinium-Based Covalent Organic Framework for Long-lived Charge-Separated Exciton Mediated Photocatalytic [4+2] Annulation"/> +<p>An Acridinium-based covalent organic framework (COFs) featuring systematic trap states is designed to generate charge-separated excitons with enhanced lifetime. Large 4 nm-sized mesoporous channels and ultra-stable excitons resulted in the COF functioning as an efficient heterogeneous photocatalyst toward Diels-Alder type oxidative [4+2] annulation with a million times enhanced interfacial charge dissipation response. </p> <br/> <h2>Abstract</h2> -<p>Radiofrequency ablation (RFA), a critical therapy for hepatocellular carcinoma (HCC), carries a significant risk of recurrence and metastasis, particularly owing to mechanisms involving immune evasion and antigen downregulation via epigenetic modifications. This study introduces a “nano-epidrug” named MFMP. MFMP, which is composed of hollow mesoporous manganese dioxide (MnO<sub>2</sub>) nanoparticles, FIDAS-5 as an MAT2A inhibitor, macrophage membrane, and anti-PD-L1 (aPD-L1), targets HCC cells. By selectively binding to these cells, MFMP initially reverses immune suppression via PD-L1 inhibition. After endocytosis, MFMP disassembles in the tumor microenvironment, releasing FIDAS-5 and Mn<sup>2+</sup>. FIDAS-5 prevents cGAS methylation, whereas Mn<sup>2+</sup> aids STING pathway restoration. In addition, FIDAS-5 reduces m<sup>6</sup>A RNA modification, suppressing EGFR expression. These changes enhance HCC antigenicity to promote cytotoxic T cell recognition and cytotoxic killing. Furthermore, MFMP mediates immunogenic cell death in HCC by synergizing with RFA through cGAS DNA demethylation, EGFR mRNA demethylation, and TBK1 protein phosphorylation, thereby inhibiting recurrence and metastasis and enhancing immune memory. Thus, MFMP is a potential adjunctive therapy requiring clinical validation.</p> +<p>Readily tuneable porosity and redox properties of covalent organic frameworks (COFs) result in highly customizable photocatalysts featuring extended electronic delocalization. However, fast charge recombination in COFs severely limits their photocatalytic activities. Herein a new mode of COF photocatalyst design strategy to introduce systematic trap states is programmed, which aids the formation and stabilization of long-lived charge-separated excitons. Installing cationic acridinium functionality in a pristine electron-rich triphenylamine COF via postsynthetic modification resulted in a semiconducting photocatalytic donor–acceptor dyad network that performed rapid and efficient oxidative Diels-Alder type [4+2] annulation of styrenes and alkynes to fused aromatic compounds under the atmospheric condition in good to excellent yields. Large mesopores of ≈4 nm diameter ensured efficient mass flow within the COF channel. It is confirmed that the catalytic performance of COF originates from the ultra-stable charge-separated excitons of 1.9 nm diameter with no apparent radiative charge-recombination pathway, endorsing almost a million times better photo-response and catalysis than the state-of-the-art.</p> -Xiaocheng Li, -Yahui Liu, -Jianji Ke, -Zhihua Wang, -Mingda Han, -Ning Wang, -Qiannan Miao, -Bingru Shao, -Dan Zhou, -Fei Yan, -Bai Ji +Ipsita Nath, +Jeet Chakraborty, +Kuber Singh Rawat, +Yanwei Ji, +Rundong Wang, +Korneel Molkens, +Nathalie De Geyter, +Rino Morent, +Veronique Van Speybroeck, +Pieter Geiregat, +Pascal Van Der Voort Research Article - Enhancing Radiofrequency Ablation for Hepatocellular Carcinoma: Nano‐Epidrug Effects on Immune Modulation and Antigenicity Restoration - 10.1002/adma.202414365 + Mesoporous Acridinium‐Based Covalent Organic Framework for Long‐lived Charge‐Separated Exciton Mediated Photocatalytic [4+2] Annulation + 10.1002/adma.202413060 Advanced Materials - 10.1002/adma.202414365 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414365 + 10.1002/adma.202413060 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413060 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410368 - Sat, 16 Nov 2024 04:26:44 -0800 - 2024-11-16T04:26:44-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202402191 + Sun, 17 Nov 2024 21:21:20 -0800 + 2024-11-17T09:21:20-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202410368 - Nanomaterial‐Mediated Reprogramming of Macrophages to Inhibit Refractory Muscle Fibrosis + 10.1002/adma.202402191 + Materials Design by Constructing Phase Diagrams for Defects Advanced Materials, EarlyView. -Local injection of the cationic nanomaterial prevents refractory muscle fibrosis and restores muscle function after acute injury. This anti‐fibrotic effect results from the cell‐free nucleic acids (cfNA)‐TLR7/9‐dependent orchestration of the macrophages and fibro‐adipogenic progenitors (FAPs), leading to an optimized inflammation‐fibrogenesis balance. The reciprocal cross‐talk between macrophages and FAPs serves as a promising therapeutic target for treating refractory muscle fibrosis. +A systematic way to develop defect phase diagrams is proposed for advanced materials design. Phase transformation of a Mg grain boundary is triggered by Ga implantation on a microscopy sample. Transformations of structural units and chemical ordering at the same grain boundary are experimentally traced at atomic resolution and modeled by ab initio simulations to construct the defect phase diagram. + @@ -1286,55 +1251,54 @@ Local injection of the cationic nanomaterial prevents refractory muscle fibrosis Abstract -Orofacial muscles are particularly prone to refractory fibrosis after injury, leading to a negative effect on the patient's quality of life and limited therapeutic options. Gaining insights into innate inflammatory response‐fibrogenesis homeostasis can aid in the development of new therapeutic strategies for muscle fibrosis. In this study, the crucial role of macrophages is identified in the regulation of orofacial muscle fibrogenesis after injury. Hypothesizing that orchestrating macrophage polarization and functions will be beneficial for fibrosis treatment, nanomaterials are engineered with polyethylenimine functionalization to regulate the macrophage phenotype by capturing negatively charged cell‐free nucleic acids (cfNAs). This cationic nanomaterial reduces macrophage‐related inflammation in vitr and demonstrates excellent efficacy in preventing orofacial muscle fibrosis in vivo. Single‐cell RNA sequencing reveals that the cationic nanomaterial reduces the proportion of profibrotic Gal3+ macrophages through the cfNA‐mediated TLR7/9‐NF‐κB signaling pathway, resulting in a shift in profibrotic fibro‐adipogenic progenitors (FAPs) from the matrix‐producing Fabp4+ subcluster to the matrix‐degrading Igf1+ subcluster. The study highlights a strategy to target innate inflammatory response‐fibrogenesis homeostasis and suggests that cationic nanomaterials can be exploited for treating refractory fibrosis. +Phase transformations and crystallographic defects are two essential tools to drive innovations in materials. Bulk materials design via tuning chemical compositions is systematized using phase diagrams. It is shown here that the same thermodynamic concept can be applied to manipulate the chemistry at defects. Grain boundaries in Mg–Ga system are chosen as a model system, because Ga segregates to the boundaries, while simultaneously improving the strength and ductility of Mg alloys. To reveal the role of grain boundaries, correlated atomic‐scale characterization and simulation to scope and build phase diagrams for defects are presented. The discovery is enabled by triggering phase transformations of individual grain boundaries through local alloying, and sequentially imaging the structural and chemical changes using atomic‐resolution scanning transmission electron microscopy. Ab initio simulations determined the thermodynamic stability of grain boundary phases, and found out that increasing Ga content enhances grain boundary cohesion, relating to improved ductility. The methodology to trigger, trace, and simulate defect transformation at atomic resolution enables a systematic development of defect phase diagrams, providing a valuable tool to utilize chemical complexity and phase transformations at defects. - <img src="https://onlinelibrary.wiley.com/cms/asset/49fe605a-6014-45d2-9ae1-90ce29116b85/adma202410368-gra-0001-m.png" - alt="Nanomaterial-Mediated Reprogramming of Macrophages to Inhibit Refractory Muscle Fibrosis"/> -<p>Local injection of the cationic nanomaterial prevents refractory muscle fibrosis and restores muscle function after acute injury. This anti-fibrotic effect results from the cell-free nucleic acids (cfNA)-TLR7/9-dependent orchestration of the macrophages and fibro-adipogenic progenitors (FAPs), leading to an optimized inflammation-fibrogenesis balance. The reciprocal cross-talk between macrophages and FAPs serves as a promising therapeutic target for treating refractory muscle fibrosis. + <img src="https://onlinelibrary.wiley.com/cms/asset/49d09af8-1866-4e18-8848-ab46c1f0db03/adma202402191-gra-0001-m.png" + alt="Materials Design by Constructing Phase Diagrams for Defects"/> +<p>A systematic way to develop defect phase diagrams is proposed for advanced materials design. Phase transformation of a Mg grain boundary is triggered by Ga implantation on a microscopy sample. Transformations of structural units and chemical ordering at the same grain boundary are experimentally traced at atomic resolution and modeled by ab initio simulations to construct the defect phase diagram. </p> <br/> <h2>Abstract</h2> -<p>Orofacial muscles are particularly prone to refractory fibrosis after injury, leading to a negative effect on the patient's quality of life and limited therapeutic options. Gaining insights into innate inflammatory response-fibrogenesis homeostasis can aid in the development of new therapeutic strategies for muscle fibrosis. In this study, the crucial role of macrophages is identified in the regulation of orofacial muscle fibrogenesis after injury. Hypothesizing that orchestrating macrophage polarization and functions will be beneficial for fibrosis treatment, nanomaterials are engineered with polyethylenimine functionalization to regulate the macrophage phenotype by capturing negatively charged cell-free nucleic acids (cfNAs). This cationic nanomaterial reduces macrophage-related inflammation in vitr and demonstrates excellent efficacy in preventing orofacial muscle fibrosis in vivo. Single-cell RNA sequencing reveals that the cationic nanomaterial reduces the proportion of profibrotic Gal3<sup>+</sup> macrophages through the cfNA-mediated TLR7/9-NF-κB signaling pathway, resulting in a shift in profibrotic fibro-adipogenic progenitors (FAPs) from the matrix-producing Fabp4<sup>+</sup> subcluster to the matrix-degrading Igf1<sup>+</sup> subcluster. The study highlights a strategy to target innate inflammatory response-fibrogenesis homeostasis and suggests that cationic nanomaterials can be exploited for treating refractory fibrosis.</p> +<p>Phase transformations and crystallographic defects are two essential tools to drive innovations in materials. Bulk materials design via tuning chemical compositions is systematized using phase diagrams. It is shown here that the same thermodynamic concept can be applied to manipulate the chemistry at defects. Grain boundaries in Mg–Ga system are chosen as a model system, because Ga segregates to the boundaries, while simultaneously improving the strength and ductility of Mg alloys. To reveal the role of grain boundaries, correlated atomic-scale characterization and simulation to scope and build phase diagrams for defects are presented. The discovery is enabled by triggering phase transformations of individual grain boundaries through local alloying, and sequentially imaging the structural and chemical changes using atomic-resolution scanning transmission electron microscopy. Ab initio simulations determined the thermodynamic stability of grain boundary phases, and found out that increasing Ga content enhances grain boundary cohesion, relating to improved ductility. The methodology to trigger, trace, and simulate defect transformation at atomic resolution enables a systematic development of defect phase diagrams, providing a valuable tool to utilize chemical complexity and phase transformations at defects.</p> -Xu Cheng, -Hao Sui, -Fangman Chen, -Chenghao Li, -Meijun Du, -Shiming Zhang, -Jiali Chen, -Jinfeng Dou, -Yixuan Huang, -Xiaochun Xie, -Chuanxu Cheng, -Renjie Yang, -Chao Yang, -Bing Shi, -Dan Shao, -Kam W. Leong, -Hanyao Huang +Xuyang Zhou, +Prince Mathews, +Benjamin Berkels, +Wassilios Delis, +Saba Saood, +Amel Shamseldeen Ali Alhassan, +Philipp Keuter, +Jochen M. Schneider, +Sandra Korte‐Kerzel, +Stefanie Sandlöbes‐Haut, +Dierk Raabe, +Jörg Neugebauer, +Gerhard Dehm, +Tilmann Hickel, +Christina Scheu, +Siyuan Zhang Research Article - Nanomaterial‐Mediated Reprogramming of Macrophages to Inhibit Refractory Muscle Fibrosis - 10.1002/adma.202410368 + Materials Design by Constructing Phase Diagrams for Defects + 10.1002/adma.202402191 Advanced Materials - 10.1002/adma.202410368 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410368 + 10.1002/adma.202402191 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202402191 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202402987 - Sat, 16 Nov 2024 04:26:18 -0800 - 2024-11-16T04:26:18-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412014 + Sun, 17 Nov 2024 21:20:38 -0800 + 2024-11-17T09:20:38-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202402987 - Understanding, Mimicking, and Mitigating Radiolytic Damage to Polymers in Liquid Phase Transmission Electron Microscopy + 10.1002/adma.202412014 + Effective Dual Cation Release in Quasi‐2D Perovskites for Ultrafast UV Light‐Powered Imaging Advanced Materials, EarlyView. -This work addresses radiolytic damage to polymers in liquid phase transmission electron microscopy (LP‐TEM), which restricts its routine use in soft matter science. It quantifies polymer degradation behaviors across all conceivable (LP‐)TEM environments, mimics beam‐induced damage using UV light and hydrogen peroxide, evaluates hydroxyl radical scavengers and proposes effective strategies for damage mitigation. +Dual cations released from the pre‐deposited inorganic buffer layer effectively repair deep‐level defects in quasi‐2D perovskite films by inducing low‐dimensional phase reconstruction and undercoordinated ion interaction. With enhanced film quality and residual strain modulation, the fabricated photodetector exhibits a drastically improved self‐powered photoresponse, demonstrating high compatibility with pixelated array design for ultrafast image sensing. @@ -1344,52 +1308,43 @@ This work addresses radiolytic damage to polymers in liquid phase transmission e Abstract -Advances in liquid phase transmission electron microscopy (LP‐TEM) have enabled the monitoring of polymer dynamics in solution at the nanoscale, but radiolytic damage during LP‐TEM imaging limits its routine use in polymer science. This study focuses on understanding, mimicking, and mitigating radiolytic damage observed in functional polymers in LP‐TEM. It is quantitatively demonstrated how polymer damage occurs across all conceivable (LP‐)TEM environments, and the key characteristics and differences between polymer degradation in water vapor and liquid water are elucidated. Importantly, it is shown that the hydroxyl radical‐rich environment in LP‐TEM can be approximated by UV light irradiation in the presence of hydrogen peroxide, allowing the use of bulk techniques to probe damage at the polymer chain level. Finally, the protective effects of commonly used hydroxyl radical scavengers are compared, revealing that the effectiveness of graphene's protection is distance‐dependent. The work provides detailed methodological guidance and establishes a baseline for polymer degradation in LP‐TEM, paving the way for future research on nanoscale tracking of shape transitions and drug encapsulation of polymer assemblies in solution. +Ruddlesden‐Popper quasi‐2D perovskites represent robust candidates for optoelectronic applications, achieving a delicate balance between outstanding photoresponse and stability. However, mitigating the internal defects in polycrystalline films remains challenging, and their optoelectronic performances still lag behind that of their 3D counterparts. This work highlights the profound impact of defect passivation at the buried interface and grain boundaries through a dual‐cation‐release strategy. Cations released from the pre‐deposited inorganic iodide buffer layer effectively repair deep‐level defects by inducing low‐dimensional phase reconstruction and interacting with undercoordinated ions. The resulting quasi‐2D perovskite polycrystalline films feature large grain size (>2 µm) and minimum surface roughness, along with alleviated out‐of‐plane residual tensile strain, which is beneficial for inhibiting the initiation and propagation of cracks. The fabricated photodetector demonstrates drastically improved self‐powered photoresponse capability, with maximum responsivity up to 0.41 A W−1 at 430 nm and an ultrafast response speed of 161 ns / 1.91 µs. Moreover, this strategy is compatible with the photolithography‐assisted hydrophobic‐hydrophilic patterning process for fabricating pixelated photodetector arrays, which enables high‐sensitivity imaging. This study presents a feasible defect passivation approach in quasi‐2D perovskites, thereby providing insights into the fabrication of high‐performance optoelectronic devices. - <img src="https://onlinelibrary.wiley.com/cms/asset/1c27b99e-7d14-4ea7-aa4c-04fae6ab0968/adma202402987-gra-0001-m.png" - alt="Understanding, Mimicking, and Mitigating Radiolytic Damage to Polymers in Liquid Phase Transmission Electron Microscopy"/> -<p>This work addresses radiolytic damage to polymers in liquid phase transmission electron microscopy (LP-TEM), which restricts its routine use in soft matter science. It quantifies polymer degradation behaviors across all conceivable (LP-)TEM environments, mimics beam-induced damage using UV light and hydrogen peroxide, evaluates hydroxyl radical scavengers and proposes effective strategies for damage mitigation. + <img src="https://onlinelibrary.wiley.com/cms/asset/e95d8092-a0b7-4d84-91c2-bf3bf60063e9/adma202412014-gra-0001-m.png" + alt="Effective Dual Cation Release in Quasi-2D Perovskites for Ultrafast UV Light-Powered Imaging"/> +<p>Dual cations released from the pre-deposited inorganic buffer layer effectively repair deep-level defects in quasi-2D perovskite films by inducing low-dimensional phase reconstruction and undercoordinated ion interaction. With enhanced film quality and residual strain modulation, the fabricated photodetector exhibits a drastically improved self-powered photoresponse, demonstrating high compatibility with pixelated array design for ultrafast image sensing. </p> <br/> <h2>Abstract</h2> -<p>Advances in liquid phase transmission electron microscopy (LP-TEM) have enabled the monitoring of polymer dynamics in solution at the nanoscale, but radiolytic damage during LP-TEM imaging limits its routine use in polymer science. This study focuses on understanding, mimicking, and mitigating radiolytic damage observed in functional polymers in LP-TEM. It is quantitatively demonstrated how polymer damage occurs across all conceivable (LP-)TEM environments, and the key characteristics and differences between polymer degradation in water vapor and liquid water are elucidated. Importantly, it is shown that the hydroxyl radical-rich environment in LP-TEM can be approximated by UV light irradiation in the presence of hydrogen peroxide, allowing the use of bulk techniques to probe damage at the polymer chain level. Finally, the protective effects of commonly used hydroxyl radical scavengers are compared, revealing that the effectiveness of graphene's protection is distance-dependent. The work provides detailed methodological guidance and establishes a baseline for polymer degradation in LP-TEM, paving the way for future research on nanoscale tracking of shape transitions and drug encapsulation of polymer assemblies in solution.</p> +<p>Ruddlesden-Popper quasi-2D perovskites represent robust candidates for optoelectronic applications, achieving a delicate balance between outstanding photoresponse and stability. However, mitigating the internal defects in polycrystalline films remains challenging, and their optoelectronic performances still lag behind that of their 3D counterparts. This work highlights the profound impact of defect passivation at the buried interface and grain boundaries through a dual-cation-release strategy. Cations released from the pre-deposited inorganic iodide buffer layer effectively repair deep-level defects by inducing low-dimensional phase reconstruction and interacting with undercoordinated ions. The resulting quasi-2D perovskite polycrystalline films feature large grain size (&gt;2 µm) and minimum surface roughness, along with alleviated out-of-plane residual tensile strain, which is beneficial for inhibiting the initiation and propagation of cracks. The fabricated photodetector demonstrates drastically improved self-powered photoresponse capability, with maximum responsivity up to 0.41 A W<sup>−1</sup> at 430 nm and an ultrafast response speed of 161 ns / 1.91 µs. Moreover, this strategy is compatible with the photolithography-assisted hydrophobic-hydrophilic patterning process for fabricating pixelated photodetector arrays, which enables high-sensitivity imaging. This study presents a feasible defect passivation approach in quasi-2D perovskites, thereby providing insights into the fabrication of high-performance optoelectronic devices.</p> -Hanglong Wu, -Hongyu Sun, -Roy A. J. F. Oerlemans, -Siyu Li, -Jingxin Shao, -Jianhong Wang, -Rick R. M. Joosten, -Xianwen Lou, -Yingtong Luo, -Hongkui Zheng, -Loai K. E. A. Abdelmohsen, -H. Hugo Pérez Garza, -Jan C. M. van Hest, -Heiner Friedrich +Xinyu Zhang, +Ziqing Li, +Enliu Hong, +Tingting Yan, +Xiaosheng Fang Research Article - Understanding, Mimicking, and Mitigating Radiolytic Damage to Polymers in Liquid Phase Transmission Electron Microscopy - 10.1002/adma.202402987 + Effective Dual Cation Release in Quasi‐2D Perovskites for Ultrafast UV Light‐Powered Imaging + 10.1002/adma.202412014 Advanced Materials - 10.1002/adma.202402987 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202402987 + 10.1002/adma.202412014 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412014 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202415100 - Sat, 16 Nov 2024 04:04:43 -0800 - 2024-11-16T04:04:43-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411677 + Sat, 16 Nov 2024 04:43:08 -0800 + 2024-11-16T04:43:08-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202415100 - Stable Surface Contact with Tailored Alkylamine Pyridine Derivatives for High‐Performance Inverted Perovskite Solar Cells + 10.1002/adma.202411677 + All‐In‐One Additive Enabled Efficient and Stable Narrow‐Bandgap Perovskites for Monolithic All‐Perovskite Tandem Solar Cells Advanced Materials, EarlyView. -In this study, the relationship between the configuration of the studied amino pyridine derivatives and their passivation effects has been meticulously investigated to enhance the electrical properties of perovskite surfaces, which enable the inverted FA1‐xCsxPbI3 PSC to yield an encouraging efficiency of 25.65% (certified 25.45%, certified steady‐state efficiency 25.06%) with the tailored 3‐(2‐aminoethyl)pyridine (3‐PyEA) surface passivator. +Herein, an all‐in‐one additive AMPH is proposed, which can not only function as a reducing agent to suppress Sn4+ formation, but also can slow down the crystallization and enhance oxidation resistance of Sn‐Pb films. This advancement enables 23.07% efficient Sn‐Pb perovskite solar cells and 28.73% efficient all‐perovskite tandem solar cells with improved operational stability. @@ -1399,56 +1354,51 @@ In this study, the relationship between the configuration of the studied amino p Abstract -Formamidinium‐cesium lead triiodide (FA1‐xCsxPbI3) perovskite holds great promise for perovskite solar cells (PSCs) with both high efficiency and stability. However, the defective perovskite surfaces induced by defects and residual tensile strain largely limit the photovoltaic performance of the corresponding devices. Here, the passivation capability of alkylamine‐modified pyridine derivatives for the surface defects of FA1‐xCsxPbI3 perovskite is systematically studied. Among the studied surface passivators, 3‐(2‐aminoethyl)pyridine (3‐PyEA) with the suitable size is demonstrated to be the most effective in reducing surface iodine impurities and defects (VI and I2) through its strong coordination with Npyridine. Additionally, the tail amino group (─NH2) from 3‐PyEA can react with FA+ cations to reduce the surface roughness of perovskite films, and the reaction products can also passivate FA vacancies (VFA), and further strengthen their binding interaction to perovskite surfaces. These merits lead to suppressed nonradiative recombination loss, the release of residual tensile stress for the perovskite films, and a favorable energy‐level alignment at the perovskite/[6,6]‐phenyl‐C61‐butyric acid methyl ester interface. Consequently, the resulting inverted FA1‐xCsxPbI3 PSCs obtain an impressive power conversion efficiency (PCE) of 25.65% (certified 25.45%, certified steady‐state efficiency 25.06%), along with retaining 96.5% of the initial PCE after 1800 h of 1‐sun operation at 55 °C in air. +Hybrid tin‐lead (Sn‐Pb) perovskites have garnered increasing attention due to their crucial role in all‐perovskite tandem cells for surpassing the efficiency limit of single‐junction solar cells. However, the easy oxidation of Sn2+ and fast crystallization of Sn‐based perovskite present significant challenges for achieving high‐quality hybrid Sn‐Pb perovskite films, thereby limiting the device's performance and stability. Herein, an all‐in‐one additive, 2‐amino‐3‐mercaptopropanoic acid hydrochloride (AMPH) is proposed, which can function as a reducing agent to suppress the formation of Sn4+ throughout the film preparation. Furthermore, the strong binding between AMPH and Sn‐based precursor significantly slows down the crystallization process, resulting in a high‐quality film with enhanced crystallinity. The remaining AMPH and its oxidation products within the film contribute to improves oxidation resistance and a substantial reduction in defect density, specifically Sn vacancies. Benefiting from the multifunctionalities of AMPH, a power conversion efficiency (PCE) of 23.07% is achieved for single‐junction narrow‐bandgap perovskite solar cells. The best‐performing monolithic all‐perovskite tandem cell also exhibits a PCE of 28.73% (certified 27.83%), which is among the highest efficiency reported yet. The tandem devices can also retain over 85% of their initial efficiencies after 500 hours of continuous operation at the maximum power point under one‐sun illumination. - <img src="https://onlinelibrary.wiley.com/cms/asset/9b0c05f2-653a-4098-9795-ecec391ddd5e/adma202415100-gra-0001-m.png" - alt="Stable Surface Contact with Tailored Alkylamine Pyridine Derivatives for High-Performance Inverted Perovskite Solar Cells"/> -<p>In this study, the relationship between the configuration of the studied amino pyridine derivatives and their passivation effects has been meticulously investigated to enhance the electrical properties of perovskite surfaces, which enable the inverted FA<sub>1-x</sub>Cs<sub>x</sub>PbI<sub>3</sub> PSC to yield an encouraging efficiency of 25.65% (certified 25.45%, certified steady-state efficiency 25.06%) with the tailored 3-(2-aminoethyl)pyridine (3-PyEA) surface passivator. + <img src="https://onlinelibrary.wiley.com/cms/asset/7d41e142-5364-4682-b706-1cc90c77c50a/adma202411677-gra-0001-m.png" + alt="All-In-One Additive Enabled Efficient and Stable Narrow-Bandgap Perovskites for Monolithic All-Perovskite Tandem Solar Cells"/> +<p>Herein, an all-in-one additive AMPH is proposed, which can not only function as a reducing agent to suppress Sn<sup>4+</sup> formation, but also can slow down the crystallization and enhance oxidation resistance of Sn-Pb films. This advancement enables 23.07% efficient Sn-Pb perovskite solar cells and 28.73% efficient all-perovskite tandem solar cells with improved operational stability. </p> <br/> <h2>Abstract</h2> -<p>Formamidinium-cesium lead triiodide (FA<sub>1-x</sub>Cs<sub>x</sub>PbI<sub>3</sub>) perovskite holds great promise for perovskite solar cells (PSCs) with both high efficiency and stability. However, the defective perovskite surfaces induced by defects and residual tensile strain largely limit the photovoltaic performance of the corresponding devices. Here, the passivation capability of alkylamine-modified pyridine derivatives for the surface defects of FA<sub>1-x</sub>Cs<sub>x</sub>PbI<sub>3</sub> perovskite is systematically studied. Among the studied surface passivators, 3-(2-aminoethyl)pyridine (3-PyEA) with the suitable size is demonstrated to be the most effective in reducing surface iodine impurities and defects (V<sub>I</sub> and I<sub>2</sub>) through its strong coordination with N<sub>pyridine</sub>. Additionally, the tail amino group (─NH<sub>2</sub>) from 3-PyEA can react with FA<sup>+</sup> cations to reduce the surface roughness of perovskite films, and the reaction products can also passivate FA vacancies (V<sub>FA</sub>), and further strengthen their binding interaction to perovskite surfaces. These merits lead to suppressed nonradiative recombination loss, the release of residual tensile stress for the perovskite films, and a favorable energy-level alignment at the perovskite/[6,6]-phenyl-C<sub>61</sub>-butyric acid methyl ester interface. Consequently, the resulting inverted FA<sub>1-x</sub>Cs<sub>x</sub>PbI<sub>3</sub> PSCs obtain an impressive power conversion efficiency (PCE) of 25.65% (certified 25.45%, certified steady-state efficiency 25.06%), along with retaining 96.5% of the initial PCE after 1800 h of 1-sun operation at 55 °C in air.</p> +<p>Hybrid tin-lead (Sn-Pb) perovskites have garnered increasing attention due to their crucial role in all-perovskite tandem cells for surpassing the efficiency limit of single-junction solar cells. However, the easy oxidation of Sn<sup>2+</sup> and fast crystallization of Sn-based perovskite present significant challenges for achieving high-quality hybrid Sn-Pb perovskite films, thereby limiting the device's performance and stability. Herein, an all-in-one additive, 2-amino-3-mercaptopropanoic acid hydrochloride (AMPH) is proposed, which can function as a reducing agent to suppress the formation of Sn<sup>4+</sup> throughout the film preparation. Furthermore, the strong binding between AMPH and Sn-based precursor significantly slows down the crystallization process, resulting in a high-quality film with enhanced crystallinity. The remaining AMPH and its oxidation products within the film contribute to improves oxidation resistance and a substantial reduction in defect density, specifically Sn vacancies. Benefiting from the multifunctionalities of AMPH, a power conversion efficiency (PCE) of 23.07% is achieved for single-junction narrow-bandgap perovskite solar cells. The best-performing monolithic all-perovskite tandem cell also exhibits a PCE of 28.73% (certified 27.83%), which is among the highest efficiency reported yet. The tandem devices can also retain over 85% of their initial efficiencies after 500 hours of continuous operation at the maximum power point under one-sun illumination.</p> -Sanwan Liu, -Zhenxing Sun, +Deng Wang, +Mingqian Chen, Xia Lei, -Tianyin Miao, -Qisen Zhou, -Rui Chen, -Jianan Wang, -Fumeng Ren, -Yongyan Pan, -Yong Cai, -Zhengtian Tan, -Wenguang Liu, -Xiaoxuan Liu, -Jingbai Li, -Yong Zhang, +Yunfan Wang, +Yuqi Bao, +Xiaofeng Huang, +Peide Zhu, +Jie Zeng, +Xingzhu Wang, +SaiWing Tsang, +Fengzhu Li, Baomin Xu, -Zonghao Liu, -Wei Chen +Alex K.‐Y. Jen Research Article - Stable Surface Contact with Tailored Alkylamine Pyridine Derivatives for High‐Performance Inverted Perovskite Solar Cells - 10.1002/adma.202415100 + All‐In‐One Additive Enabled Efficient and Stable Narrow‐Bandgap Perovskites for Monolithic All‐Perovskite Tandem Solar Cells + 10.1002/adma.202411677 Advanced Materials - 10.1002/adma.202415100 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202415100 + 10.1002/adma.202411677 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411677 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410336 - Fri, 15 Nov 2024 01:01:05 -0800 - 2024-11-15T01:01:05-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413325 + Sat, 16 Nov 2024 04:41:40 -0800 + 2024-11-16T04:41:40-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202410336 - Flexible Meta‐Tape with Wide Gamut, Low Lightness and Low Infrared Emissivity for Visible‐Infrared Camouflage + 10.1002/adma.202413325 + Engineering Triple‐Phase Interfaces with Hierarchical Carbon Nanocages for High‐Areal‐Capacity All‐Solid‐State Li‐S Batteries Advanced Materials, EarlyView. -A tape‐like metamaterial (meta‐tape) formed by self‐assembled gold nanoparticles in an ultrathin nanoporous alumina (UNA) template. The ultrathin meta‐tapes can exhibit different colors with wide gamut and low lightness from 20 to 40, enabling low color difference under various backgrounds down to 1.2 L*a*b*. The infrared emissivity is simultaneously suppressed down to 3.8% across 3 – 14 µm. The outstanding optical performances are well preserved under various mechanical and thermal stability tests. +In all‐solid‐state lithium‐sulfur batteries, the composite cathode requires multi‐dimensional structural engineering. By integrating sulfur with a hierarchical carbon nanocage (hCNC), the uniform dispersion of sulfur and carbon in the composite cathode and the efficient construction of triple‐phase interfaces are achieved. These enhancements improve the utilization of sulfur, enabling ultra‐high‐capacity battery performance. @@ -1458,45 +1408,55 @@ A tape‐like metamaterial (meta‐tape) formed by self‐assembled Abstract -Full‐spectral optical camouflage is of broad interest and in urgent demand because of everlasting safety pursuit in modern society. However, the widely existing dim scenarios call for not only broadband low thermal detectivity but also wide‐gamut camouflaging colors with both low lightness and minimal chromatism. Here, a tape‐like metamaterial (meta‐tape) with broad spectral manipulation bandwidth from visible to mid‐infrared is demonstrated. The ultrathin meta‐tapes can exhibit different colors with wide gamut and low lightness from 20 to 40, enabling low color difference under various backgrounds down to 1.2 L*a*b*. The infrared emissivity is simultaneously suppressed down to 3.8% across 3 – 14 µm. The outstanding optical performances are well preserved under various mechanical and thermal stability tests. The pronounced multispectral camouflage, combined with flexible and robust tape‐like nature, makes the meta‐tape a promising solution for VIS‐IR compatible camouflage in diverse scenarios. +All‐solid‐state lithium‐sulfur batteries (ASSLSBs) have garnered widespread attention due to their advantages of high energy density and enhanced safety. However, the typical composite structure composed of solid‐state electrolyte (SE), discrete conducting carbon black, and microsized sulfur (μ‐S) with long‐range Li+/e− conducting path and huge volume changes, suffers from sluggish charge transport and severe electrochemical‐mechanical failure. In this work, a unique hierarchical carbon nanocage (hCNC) is applied as a continuous conducting network where nanosized sulfur are confined. Due to the synergistic effects of multi‐dimensional (particle, interface, and electrode) structural engineering, this new sulfur‐carbon composite cathode (S@hCNC39) can achieve uniform distribution of sulfur and carbon, and efficiently constructs triple‐phase interfaces, showing enhanced charge‐carrier transport and improved electrochemical‐mechanical stability. Remarkable cycling performance of 89% after 300 cycles at 0.2 C at 30 °C is realized in ASSLSBs assembled with S@hCNC39. Notably, ASSLSBs achieve an ultrahigh areal capacity of 9.95 mAh cm−2 with stable cycling at 60 °C with high sulfur contents of 40% and high sulfur loadings of 6 mg cm−2. These results provide critical insights into the design of rational sulfur‐carbon composites and offer a viable approach to enhance the overall performance of ASSLSBs. - <img src="https://onlinelibrary.wiley.com/cms/asset/5c629601-6be0-48bf-a60c-c12c74cac83c/adma202410336-gra-0001-m.png" - alt="Flexible Meta-Tape with Wide Gamut, Low Lightness and Low Infrared Emissivity for Visible-Infrared Camouflage"/> -<p>A tape-like metamaterial (meta-tape) formed by self-assembled gold nanoparticles in an ultrathin nanoporous alumina (UNA) template. The ultrathin meta-tapes can exhibit different colors with wide gamut and low lightness from 20 to 40, enabling low color difference under various backgrounds down to 1.2 <i>L</i>*<i>a</i>*<i>b</i>*. The infrared emissivity is simultaneously suppressed down to 3.8% across 3 – 14 µm. The outstanding optical performances are well preserved under various mechanical and thermal stability tests. + <img src="https://onlinelibrary.wiley.com/cms/asset/8a0ad828-5c07-4b1a-83df-a26bd2aa8902/adma202413325-gra-0001-m.png" + alt="Engineering Triple-Phase Interfaces with Hierarchical Carbon Nanocages for High-Areal-Capacity All-Solid-State Li-S Batteries"/> +<p>In all-solid-state lithium-sulfur batteries, the composite cathode requires multi-dimensional structural engineering. By integrating sulfur with a hierarchical carbon nanocage (hCNC), the uniform dispersion of sulfur and carbon in the composite cathode and the efficient construction of triple-phase interfaces are achieved. These enhancements improve the utilization of sulfur, enabling ultra-high-capacity battery performance. </p> <br/> <h2>Abstract</h2> -<p>Full-spectral optical camouflage is of broad interest and in urgent demand because of everlasting safety pursuit in modern society. However, the widely existing dim scenarios call for not only broadband low thermal detectivity but also wide-gamut camouflaging colors with both low lightness and minimal chromatism. Here, a tape-like metamaterial (meta-tape) with broad spectral manipulation bandwidth from visible to mid-infrared is demonstrated. The ultrathin meta-tapes can exhibit different colors with wide gamut and low lightness from 20 to 40, enabling low color difference under various backgrounds down to 1.2 <i>L</i>*<i>a</i>*<i>b</i>*. The infrared emissivity is simultaneously suppressed down to 3.8% across 3 – 14 µm. The outstanding optical performances are well preserved under various mechanical and thermal stability tests. The pronounced multispectral camouflage, combined with flexible and robust tape-like nature, makes the meta-tape a promising solution for VIS-IR compatible camouflage in diverse scenarios.</p> +<p>All-solid-state lithium-sulfur batteries (ASSLSBs) have garnered widespread attention due to their advantages of high energy density and enhanced safety. However, the typical composite structure composed of solid-state electrolyte (SE), discrete conducting carbon black, and microsized sulfur (μ-S) with long-range Li<sup>+</sup>/e<sup>−</sup> conducting path and huge volume changes, suffers from sluggish charge transport and severe electrochemical-mechanical failure. In this work, a unique hierarchical carbon nanocage (hCNC) is applied as a continuous conducting network where nanosized sulfur are confined. Due to the synergistic effects of multi-dimensional (particle, interface, and electrode) structural engineering, this new sulfur-carbon composite cathode (S@hCNC39) can achieve uniform distribution of sulfur and carbon, and efficiently constructs triple-phase interfaces, showing enhanced charge-carrier transport and improved electrochemical-mechanical stability. Remarkable cycling performance of 89% after 300 cycles at 0.2 C at 30 °C is realized in ASSLSBs assembled with S@hCNC39. Notably, ASSLSBs achieve an ultrahigh areal capacity of 9.95 mAh cm<sup>−2</sup> with stable cycling at 60 °C with high sulfur contents of 40% and high sulfur loadings of 6 mg cm<sup>−2</sup>. These results provide critical insights into the design of rational sulfur-carbon composites and offer a viable approach to enhance the overall performance of ASSLSBs.</p> -Zhenhui Lin, -Qile Wu, -Xuqi Liu, -Haiyang Ma, -Hui Liu, -Lin Zhou, -Jia Zhu +Yu Luo, +Siyuan Pan, +JingYi Tian, +Yali Liang, +Haoyue Zhong, +Ruqin Ma, +Jiabao Gu, +Yuqi Wu, +Huiyan Zhang, +Hongxin Lin, +Weilin Huang, +Yuxi Deng, +Yu Su, +Zhengliang Gong, +Jianyu Huang, +Zheng Hu, +Yong Yang Research Article - Flexible Meta‐Tape with Wide Gamut, Low Lightness and Low Infrared Emissivity for Visible‐Infrared Camouflage - 10.1002/adma.202410336 + Engineering Triple‐Phase Interfaces with Hierarchical Carbon Nanocages for High‐Areal‐Capacity All‐Solid‐State Li‐S Batteries + 10.1002/adma.202413325 Advanced Materials - 10.1002/adma.202410336 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410336 + 10.1002/adma.202413325 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413325 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414379 - Fri, 15 Nov 2024 01:00:37 -0800 - 2024-11-15T01:00:37-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412255 + Sat, 16 Nov 2024 04:39:58 -0800 + 2024-11-16T04:39:58-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202414379 - Eco‐Friendly High‐Performance Symmetric All‐COF/Graphene Aqueous Zinc‐Ion Batteries + 10.1002/adma.202412255 + Organic Nonvolatile 2T Memory Cell Employing a NOT‐Gate‐Like Architecture Toward Binary Output Level With Enhanced Noise Tolerance Advanced Materials, EarlyView. -A covalent organic framework (COF) integrating dual redox active sites is designed as an electrode material. The introduction of strong electron‐withdrawing CO ensures extended electron delocalization and synergistically enhances the proton storage with graphene loading strategy. Additionally, a concept of symmetric all‐COF/graphene aqueous zinc‐ion battery with high application value is realized based on the well‐designed composite electrode. +This work reports a brand‐new voltage‐readable 2T memory cell employing a NOT‐gate‐like architecture. It combines ferroelectric and nano‐floating‐gate transistors in a voltage divider, achieving high noise tolerance for voltage output memory. Moreover, the conceptual design of the 1T2T FeRAM cell is also developed as a prospect for low‐cost voltage‐readable memory technology in wearable electronic applications. @@ -1506,49 +1466,49 @@ A covalent organic framework (COF) integrating dual redox active sites is design Abstract -Developing high‐performance aqueous symmetric all‐organic batteries (SAOBs) by replacing metal‐based batteries or batteries with organic electrolytes is highly attractive to achieve a greener rechargeable world. However, such a new energy storage system still exhibits unsatisfactory rate capability and cycling stability due to the limitations in electrode materials screening. Here, a novel covalent organic framework (COF) containing abundant CN and CO for the electrode material is designed, which is combined with graphene and assembled into all‐COF/graphene batteries for the first time. Moreover, the co‐storage of Zn2+ and H+ in COF can be achieved in a mild aqueous electrolyte. Impressively, benefiting from the extended porous structure of COF, plentiful active reaction sites, more extensive electron delocalization from CO modification at molecular level, as well as enhanced fast H+ storage capacity of graphene and CO in COF, this kind of SAOBs show excellent cycle life and high rate performance (over 15000 cycles with a capacity of 80 mAh g−1 at a high current density of 5 A g−1 in pouch cell). This work will open a new window for the design of high‐performance aqueous organic batteries, further moving toward a more eco‐friendly electrochemical world. +Organic nonvolatile memory has been considered a low‐cost memory technology for flexible electronics and Internet‐of‐things (IoT). However, a major concern is the nonuniformity of memory units, which is primarily caused by random grain boundaries, interface defects, and charge traps, making it difficult to develop high‐density reliable memory arrays. This nonuniformity problem would induce read error, which is directly caused by the narrow distribution margin of memory states and low noise tolerance in conventional organic memory cells. To break this limitation, a novel 2T memory cell employing a NOT‐gate‐like architecture achieving self‐enhancing noise tolerance is presented. This unique cell consists of a pair of commonly‐gated memory transistors with contradictory “write‐and‐erase” features. It functions as a voltage divider, producing a well‐distinguished binary voltage output capability. The concept and design model of this brand‐new 2T memory cell is thoroughly discussed. It is originally characterized by noise‐tolerant memory cells irrespective of device nonuniformity. The noise tolerance range of this 2T memory cell is also investigated. The binary voltage‐readable memory state with a large noise tolerance range is obtained. Moreover, the conceptual design of the 1T2T FeRAM cell is further developed for low‐cost voltage‐readable memory technology in wearable electronic applications. - <img src="https://onlinelibrary.wiley.com/cms/asset/8bbacaac-d7a5-4b32-b5bd-95adb5cee891/adma202414379-gra-0001-m.png" - alt="Eco-Friendly High-Performance Symmetric All-COF/Graphene Aqueous Zinc-Ion Batteries"/> -<p>A covalent organic framework (COF) integrating dual redox active sites is designed as an electrode material. The introduction of strong electron-withdrawing CO ensures extended electron delocalization and synergistically enhances the proton storage with graphene loading strategy. Additionally, a concept of symmetric all-COF/graphene aqueous zinc-ion battery with high application value is realized based on the well-designed composite electrode. + <img src="https://onlinelibrary.wiley.com/cms/asset/7d86b0e4-9ebf-432d-bff4-ad64646b3e35/adma202412255-gra-0001-m.png" + alt="Organic Nonvolatile 2T Memory Cell Employing a NOT-Gate-Like Architecture Toward Binary Output Level With Enhanced Noise Tolerance"/> +<p>This work reports a brand-new voltage-readable 2T memory cell employing a NOT-gate-like architecture. It combines ferroelectric and nano-floating-gate transistors in a voltage divider, achieving high noise tolerance for voltage output memory. Moreover, the conceptual design of the 1T2T FeRAM cell is also developed as a prospect for low-cost voltage-readable memory technology in wearable electronic applications. </p> <br/> <h2>Abstract</h2> -<p>Developing high-performance aqueous symmetric all-organic batteries (SAOBs) by replacing metal-based batteries or batteries with organic electrolytes is highly attractive to achieve a greener rechargeable world. However, such a new energy storage system still exhibits unsatisfactory rate capability and cycling stability due to the limitations in electrode materials screening. Here, a novel covalent organic framework (COF) containing abundant CN and CO for the electrode material is designed, which is combined with graphene and assembled into all-COF/graphene batteries for the first time. Moreover, the co-storage of Zn<sup>2+</sup> and H<sup>+</sup> in COF can be achieved in a mild aqueous electrolyte. Impressively, benefiting from the extended porous structure of COF, plentiful active reaction sites, more extensive electron delocalization from CO modification at molecular level, as well as enhanced fast H<sup>+</sup> storage capacity of graphene and CO in COF, this kind of SAOBs show excellent cycle life and high rate performance (over 15000 cycles with a capacity of 80 mAh g<sup>−1</sup> at a high current density of 5 A g<sup>−1</sup> in pouch cell). This work will open a new window for the design of high-performance aqueous organic batteries, further moving toward a more eco-friendly electrochemical world.</p> +<p>Organic nonvolatile memory has been considered a low-cost memory technology for flexible electronics and Internet-of-things (IoT). However, a major concern is the nonuniformity of memory units, which is primarily caused by random grain boundaries, interface defects, and charge traps, making it difficult to develop high-density reliable memory arrays. This nonuniformity problem would induce read error, which is directly caused by the narrow distribution margin of memory states and low noise tolerance in conventional organic memory cells. To break this limitation, a novel 2T memory cell employing a NOT-gate-like architecture achieving self-enhancing noise tolerance is presented. This unique cell consists of a pair of commonly-gated memory transistors with contradictory “write-and-erase” features. It functions as a voltage divider, producing a well-distinguished binary voltage output capability. The concept and design model of this brand-new 2T memory cell is thoroughly discussed. It is originally characterized by noise-tolerant memory cells irrespective of device nonuniformity. The noise tolerance range of this 2T memory cell is also investigated. The binary voltage-readable memory state with a large noise tolerance range is obtained. Moreover, the conceptual design of the 1T2T FeRAM cell is further developed for low-cost voltage-readable memory technology in wearable electronic applications.</p> -Pengshu Yi, -Zhiheng Li, -Longli Ma, -Bingjian Feng, -Zhu Liu, -Yongshuai Liu, -Wenyi Lu, -Shaochong Cao, -Huayi Fang, -Mingxin Ye, -Jianfeng Shen +Qiang Zhao, +Hanlin Wang, +Zhenjie Ni, +Jie Liu, +Jie Li, +Fangxu Yang, +Liqiang Li, +Lang Jiang, +Yonggang Zhen, +Huanli Dong, +Wenping Hu Research Article - Eco‐Friendly High‐Performance Symmetric All‐COF/Graphene Aqueous Zinc‐Ion Batteries - 10.1002/adma.202414379 + Organic Nonvolatile 2T Memory Cell Employing a NOT‐Gate‐Like Architecture Toward Binary Output Level With Enhanced Noise Tolerance + 10.1002/adma.202412255 Advanced Materials - 10.1002/adma.202414379 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414379 + 10.1002/adma.202412255 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412255 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413967 - Fri, 15 Nov 2024 00:59:36 -0800 - 2024-11-15T12:59:36-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412257 + Sat, 16 Nov 2024 04:39:25 -0800 + 2024-11-16T04:39:25-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413967 - Inducing Efficient and Multiwavelength Circularly Polarized Emission From Perovskite Nanocrystals Using Chiral Metasurfaces + 10.1002/adma.202412257 + Macroscale Superlubrication Achieved with Shear‐Thinning Semisolid Lubricants Advanced Materials, EarlyView. -Circularly polarized emission of high dissymmetry (glum ≈ 0.56) is achieved from perovskite halide nanocrystals by depositing them on arrays of prefabricated resonant 2D gammadions. By using different materials, a hybrid photonic structure is managed to design with TiO2 and Au materials, in order to obtain resonances in the whole visible spectrum demonstrating the generation of multi‐wavelength circularly polarised light. +This study introduces a semisolid subnanometer nanowire (SNW) superlubricant, which, when combined with various base oils, forms an advanced class of lubricating materials. Based on shear‐thinning properties, these materials achieve ultralow friction (0.008–0.009) and long‐term stability (>120 000 cycles, 12 h), addressing current limitations and offering significant potential for diverse engineering applications. @@ -1558,44 +1518,46 @@ Circularly polarized emission of high dissymmetry (glum ≈ 0.56) is achieve Abstract -Chiral nano‐emitters have recently received great research attention due to their technological applications and the need for a fundamental scientific understanding of the structure‐property nexus of these nanoscale materials. Lead halide perovskite nanocrystals (LHP NCs) with many interesting optical properties have anticipated great promise for generating chiral emission. However, inducing high anisotropy chiral emission from achiral perovskite NCs remains challenging. Although chiral ligands have been used to induce chirality, their anisotropy factors (glum) are low [10−3 to 10−2]. Herein, the generation of high anisotropy circularly polarized photoluminescence (CPL) from LHP NCs is demonstrated using chiral metasurfaces by depositing nanocrystals on top of prefabricated resonant photonic structures (2D gammadion arrays). This scalable approach results in CPL with glum to a record high of 0.56 for perovskite NCs. Furthermore, the differences between high‐index dielectric chiral metasurfaces and metallic ones are explored for inducing chiral emission. More importantly, the generation of simultaneous multi‐wavelength circularly polarized light is demonstrated by combining dielectric and metallic chiral metasurfaces. +Macrosuperlubric materials are pivotal for reducing friction and wear in engineering applications. However, current solid superlubricants require intricate fabrication and specific conditions (e.g., vacuum or inert atmospheres), while liquid superlubricants are prone to creep, leakage, and corrosion. Here, a novel semisolid subnanometer nanowire (SNW) superlubrication material based on the shear‐thinning effect is introduced to overcome these challenges. The SNWs achieve an exceptionally low friction coefficient (0.008–0.009) with silicon nitride (Si3N4) and polytetrafluoroethylene (PTFE) tribo‐pairs, demonstrating a brief running‐in period (≈39 s) and stable superlubrication over extended friction (12 h, >120 000 cycles). The combination of the shear‐thinning network structure mechanism, the adsorption membrane mechanism, and hydrodynamic effects provides a synergistic effect, playing a crucial role in achieving superlubricity. Additionally, SNWs can be combined with various base oils to create semisolid gel lubricants with superlubricating properties. This innovative approach addresses the limitations of current superlubrication systems and introduces a new category of semisolid gel lubricants, significantly expanding the applications of superlubrication materials. - <img src="https://onlinelibrary.wiley.com/cms/asset/6e95ed78-9632-4be8-b1ce-c0ab0d6de383/adma202413967-gra-0001-m.png" - alt="Inducing Efficient and Multiwavelength Circularly Polarized Emission From Perovskite Nanocrystals Using Chiral Metasurfaces"/> -<p>Circularly polarized emission of high dissymmetry (g<sub>lum</sub> ≈ 0.56) is achieved from perovskite halide nanocrystals by depositing them on arrays of prefabricated resonant 2D gammadions. By using different materials, a hybrid photonic structure is managed to design with TiO<sub>2</sub> and Au materials, in order to obtain resonances in the whole visible spectrum demonstrating the generation of multi-wavelength circularly polarised light. + <img src="https://onlinelibrary.wiley.com/cms/asset/9db464c1-7d1e-441a-90c1-a70bfe37db6c/adma202412257-gra-0001-m.png" + alt="Macroscale Superlubrication Achieved with Shear-Thinning Semisolid Lubricants"/> +<p>This study introduces a semisolid subnanometer nanowire (SNW) superlubricant, which, when combined with various base oils, forms an advanced class of lubricating materials. Based on shear-thinning properties, these materials achieve ultralow friction (0.008–0.009) and long-term stability (&gt;120 000 cycles, 12 h), addressing current limitations and offering significant potential for diverse engineering applications. </p> <br/> <h2>Abstract</h2> -<p>Chiral nano-emitters have recently received great research attention due to their technological applications and the need for a fundamental scientific understanding of the structure-property nexus of these nanoscale materials. Lead halide perovskite nanocrystals (LHP NCs) with many interesting optical properties have anticipated great promise for generating chiral emission. However, inducing high anisotropy chiral emission from achiral perovskite NCs remains challenging. Although chiral ligands have been used to induce chirality, their anisotropy factors (g<sub>lum</sub>) are low [10<sup>−3</sup> to 10<sup>−2</sup>]. Herein, the generation of high anisotropy circularly polarized photoluminescence (CPL) from LHP NCs is demonstrated using chiral metasurfaces by depositing nanocrystals on top of prefabricated resonant photonic structures (2D gammadion arrays). This scalable approach results in CPL with g<sub>lum</sub> to a record high of 0.56 for perovskite NCs. Furthermore, the differences between high-index dielectric chiral metasurfaces and metallic ones are explored for inducing chiral emission. More importantly, the generation of simultaneous multi-wavelength circularly polarized light is demonstrated by combining dielectric and metallic chiral metasurfaces.</p> +<p>Macrosuperlubric materials are pivotal for reducing friction and wear in engineering applications. However, current solid superlubricants require intricate fabrication and specific conditions (e.g., vacuum or inert atmospheres), while liquid superlubricants are prone to creep, leakage, and corrosion. Here, a novel semisolid subnanometer nanowire (SNW) superlubrication material based on the shear-thinning effect is introduced to overcome these challenges. The SNWs achieve an exceptionally low friction coefficient (0.008–0.009) with silicon nitride (Si<sub>3</sub>N<sub>4</sub>) and polytetrafluoroethylene (PTFE) tribo-pairs, demonstrating a brief running-in period (≈39 s) and stable superlubrication over extended friction (12 h, &gt;120 000 cycles). The combination of the shear-thinning network structure mechanism, the adsorption membrane mechanism, and hydrodynamic effects provides a synergistic effect, playing a crucial role in achieving superlubricity. Additionally, SNWs can be combined with various base oils to create semisolid gel lubricants with superlubricating properties. This innovative approach addresses the limitations of current superlubrication systems and introduces a new category of semisolid gel lubricants, significantly expanding the applications of superlubrication materials.</p> -Nadesh Fiuza‐Maneiro, -Jose Mendoza‐Carreño, -Sergio Gómez‐Graña, -Maria Isabel Alonso, -Lakshminarayana Polavarapu, -Agustín Mihi +Liucheng Wang, +Liqiang Zhang, +Runhao Zheng, +Changhe Du, +Tongtong Yu, +Kunpeng Li, +Weifeng Bu, +Daoai Wang Research Article - Inducing Efficient and Multiwavelength Circularly Polarized Emission From Perovskite Nanocrystals Using Chiral Metasurfaces - 10.1002/adma.202413967 + Macroscale Superlubrication Achieved with Shear‐Thinning Semisolid Lubricants + 10.1002/adma.202412257 Advanced Materials - 10.1002/adma.202413967 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413967 + 10.1002/adma.202412257 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412257 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412895 - Fri, 15 Nov 2024 00:59:20 -0800 - 2024-11-15T12:59:20-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410950 + Sat, 16 Nov 2024 04:38:36 -0800 + 2024-11-16T04:38:36-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412895 - Adaptive Opto‐Thermal‐Hydrodynamic Manipulation and Polymerization (AOTHMAP) for 4D Colloidal Patterning + 10.1002/adma.202410950 + In‐Plane Chirality Control of a Charge Density Wave by Means of Shear Stress Advanced Materials, EarlyView. -The research introduces a novel 4D patterning method called AOTHMAP, which utilizes adaptive opto‐thermal‐hydrodynamic manipulation for precise colloidal patterning. This technique facilitates the automatic transport, positioning, and immobilization of colloidal particles with a single laser beam. AOTHMAP improves customization and efficiency in creating dynamic microstructures and biological patterns, showcasing significant potential in intelligent manufacturing, optoelectronics, and biofabrication. +The in‐plane chirality of a Charge Density Wave compound can be controlled by applying shear stress during thermal cycling through an achiral phase. This finding opens the view to optomechanical devices with tunable Raman activity. @@ -1605,101 +1567,55 @@ The research introduces a novel 4D patterning method called AOTHMAP, which utili Abstract -Precision colloidal patterning holds great promise in constructing customizable micro/nanostructures and functional frameworks, which showcases significant application values across various fields, from intelligent manufacturing to optoelectronic integration and biofabrication. Here, a direct 4D patterning method via adaptive opto‐thermal‐hydrodynamic manipulation and polymerization (AOTHMAP) with single‐particle resolution is reported. This approach utilizes a single laser beam to automatically transport, position, and immobilize colloidal particles through the adaptive utilization of light‐induced hydrodynamic force, optical force, and photothermal polymerization. The AOTHMAP enables precise 1D, 2D, and 3D patterning of colloidal particles of varying sizes and materials, facilitating the construction of customizable microstructures with complex shapes. Furthermore, by harnessing the pH‐responsive properties of hydrogel adhesives, the AOTHMAP further enables 4D patterning by dynamic alteration of patterned structures through shrinkage, restructuring, and cloaking. Notably, the AOTHMAP also enables biological patterning of functional bio‐structures such as bio‐micromotors. The AOTHMAP offers a simple and efficient strategy for colloidal patterning with high versatility and flexibility, which holds great promises for the construction of functional colloidal microstructures in intelligent manufacturing, as well as optoelectronic integration and biofabrication. +The transition metal dichalcogenide 1T‐TaS2 exhibits a Charge Density Wave (CDW) with in‐plane chirality. Due to the rich phase diagram, the Ferro‐Rotational Order (FRO) can be tuned by external stimuli. The FRO is studied by Angle‐Resolved Photoelectron Spectroscopy (ARPES), Raman spectroscopy, and Selected Area Electron Diffraction (SAED). The in‐plane chirality of the CDW is lost at the transition from Nearly‐Commensurate (NC) to In‐Commensurate (IC) phase and can be controlled by applying shear stress to the sample while cooling it through the transition from IC‐CDW to NC‐CDW. Based on these observations, a protocol is proposed to achieve reliable, non‐volatile state switching of the FRO configuration in 1T‐TaS2 bulk crystals. These results pave the way for new functional devices in which in‐plane chirality can be set on demand. - <img src="https://onlinelibrary.wiley.com/cms/asset/83f790d6-4e88-4186-8550-ba1c581f6450/adma202412895-gra-0001-m.png" - alt="Adaptive Opto-Thermal-Hydrodynamic Manipulation and Polymerization (AOTHMAP) for 4D Colloidal Patterning"/> -<p>The research introduces a novel 4D patterning method called AOTHMAP, which utilizes adaptive opto-thermal-hydrodynamic manipulation for precise colloidal patterning. This technique facilitates the automatic transport, positioning, and immobilization of colloidal particles with a single laser beam. AOTHMAP improves customization and efficiency in creating dynamic microstructures and biological patterns, showcasing significant potential in intelligent manufacturing, optoelectronics, and biofabrication. + <img src="https://onlinelibrary.wiley.com/cms/asset/e4f91805-d1e3-476f-a00f-c39180759b83/adma202410950-gra-0001-m.png" + alt="In-Plane Chirality Control of a Charge Density Wave by Means of Shear Stress"/> +<p>The in-plane chirality of a Charge Density Wave compound can be controlled by applying shear stress during thermal cycling through an achiral phase. This finding opens the view to optomechanical devices with tunable Raman activity. </p> <br/> <h2>Abstract</h2> -<p>Precision colloidal patterning holds great promise in constructing customizable micro/nanostructures and functional frameworks, which showcases significant application values across various fields, from intelligent manufacturing to optoelectronic integration and biofabrication. Here, a direct 4D patterning method via adaptive opto-thermal-hydrodynamic manipulation and polymerization (AOTHMAP) with single-particle resolution is reported. This approach utilizes a single laser beam to automatically transport, position, and immobilize colloidal particles through the adaptive utilization of light-induced hydrodynamic force, optical force, and photothermal polymerization. The AOTHMAP enables precise 1D, 2D, and 3D patterning of colloidal particles of varying sizes and materials, facilitating the construction of customizable microstructures with complex shapes. Furthermore, by harnessing the pH-responsive properties of hydrogel adhesives, the AOTHMAP further enables 4D patterning by dynamic alteration of patterned structures through shrinkage, restructuring, and cloaking. Notably, the AOTHMAP also enables biological patterning of functional bio-structures such as bio-micromotors. The AOTHMAP offers a simple and efficient strategy for colloidal patterning with high versatility and flexibility, which holds great promises for the construction of functional colloidal microstructures in intelligent manufacturing, as well as optoelectronic integration and biofabrication.</p> +<p>The transition metal dichalcogenide 1T-TaS<sub>2</sub> exhibits a Charge Density Wave (CDW) with in-plane chirality. Due to the rich phase diagram, the Ferro-Rotational Order (FRO) can be tuned by external stimuli. The FRO is studied by Angle-Resolved Photoelectron Spectroscopy (ARPES), Raman spectroscopy, and Selected Area Electron Diffraction (SAED). The in-plane chirality of the CDW is lost at the transition from Nearly-Commensurate (NC) to In-Commensurate (IC) phase and can be controlled by applying shear stress to the sample while cooling it through the transition from IC-CDW to NC-CDW. Based on these observations, a protocol is proposed to achieve reliable, non-volatile state switching of the FRO configuration in 1T-TaS<sub>2</sub> bulk crystals. These results pave the way for new functional devices in which in-plane chirality can be set on demand.</p> -Yang Shi, -Lianrou Liu, -Jingping Huang, -Jianyun Xiong, -Shuhan Zhong, -Guoshuai Zhu, -Xing Li, -Ziyi He, -Ting Pan, -Hongbao Xin, -Baojun Li - - Research Article - Adaptive Opto‐Thermal‐Hydrodynamic Manipulation and Polymerization (AOTHMAP) for 4D Colloidal Patterning - 10.1002/adma.202412895 - Advanced Materials - 10.1002/adma.202412895 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412895 - Research Article - - - https://onlinelibrary.wiley.com/doi/10.1002/adma.202401648 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 - Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202401648 - Iridium Single‐Atom‐Ensembles Stabilized on Mn‐Substituted Spinel Oxide for Durable Acidic Water Electrolysis - Advanced Materials, Volume 36, Issue 46, November 14, 2024. - -The limited stability of single‐atom‐catalyst and Ir/Ru‐based oxides in acidic oxygen evolution reaction (OER) is a long‐standing issue. Herein, an innovative strategy is presented to fabricate short‐range Ir single‐atom‐ensembles on Mn‐substituted spinel Co3O4, which effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, demonstrating excellent activity and stability for acidic OER. - - - - - - - - -Abstract -Exploring single‐atom‐catalysts for the acidic oxygen evolution reaction (OER) is of paramount importance for cost‐effective hydrogen production via acidic water electrolyzers. However, the limited durability of most single‐atom‐catalysts and Ir/Ru‐based oxides under harsh acidic OER conditions, primarily attributed to excessive lattice oxygen participation resulting in metal‐leaching and structural collapse, hinders their practical application. Herein, an innovative strategy is developed to fabricate short‐range Ir single‐atom‐ensembles (IrSAE) stabilized on the surface of Mn‐substituted spinel Co3O4 (IrSAE‐CMO), which exhibits excellent mass activity and significantly improved durability (degradation‐rate: ≈2 mV h−1), outperforming benchmark IrO2 (≈44 mV h−1) and conventional Irsingle‐atoms on pristine‐Co3O4 for acidic OER. First‐principle calculations reveal that Mn‐substitution in the octahedral sites of Co3O4 substantially reduces the migration energy barrier for Irsingle‐atoms on the CMO surface compared to pristine‐Co3O4, facilitating the migration of Irsingle‐atoms to form strongly correlated IrSAE during pyrolysis. Extensive ex situ characterization, operando X‐ray absorption and Raman spectroscopies, pH‐dependence activity tests, and theoretical calculations indicate that the rigid IrSAE with appropriate Ir–Ir distance stabilized on the CMO surface effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, thereby mitigating Ir‐dissolution and structural collapse, boosting the stability in an acidic environment. - - <img src="https://onlinelibrary.wiley.com/cms/asset/c3929564-30a6-4a79-815f-9696f9d976f0/adma202401648-gra-0001-m.png" - alt="Iridium Single-Atom-Ensembles Stabilized on Mn-Substituted Spinel Oxide for Durable Acidic Water Electrolysis"/> -<p>The limited stability of single-atom-catalyst and Ir/Ru-based oxides in acidic oxygen evolution reaction (OER) is a long-standing issue. Herein, an innovative strategy is presented to fabricate short-range Ir single-atom-ensembles on Mn-substituted spinel Co<sub>3</sub>O<sub>4</sub>, which effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, demonstrating excellent activity and stability for acidic OER. - -</p> -<br/> -<h2>Abstract</h2> -<p>Exploring single-atom-catalysts for the acidic oxygen evolution reaction (OER) is of paramount importance for cost-effective hydrogen production via acidic water electrolyzers. However, the limited durability of most single-atom-catalysts and Ir/Ru-based oxides under harsh acidic OER conditions, primarily attributed to excessive lattice oxygen participation resulting in metal-leaching and structural collapse, hinders their practical application. Herein, an innovative strategy is developed to fabricate short-range Ir single-atom-ensembles (Ir<sub>SAE</sub>) stabilized on the surface of Mn-substituted spinel Co<sub>3</sub>O<sub>4</sub> (Ir<sub>SAE</sub>-CMO), which exhibits excellent mass activity and significantly improved durability (degradation-rate: ≈2 mV h<sup>−1</sup>), outperforming benchmark IrO<sub>2</sub> (≈44 mV h<sup>−1</sup>) and conventional Ir<sub>single-atoms</sub> on pristine-Co<sub>3</sub>O<sub>4</sub> for acidic OER. First-principle calculations reveal that Mn-substitution in the octahedral sites of Co<sub>3</sub>O<sub>4</sub> substantially reduces the migration energy barrier for Ir<sub>single-atoms</sub> on the CMO surface compared to pristine-Co<sub>3</sub>O<sub>4</sub>, facilitating the migration of Ir<sub>single-atoms</sub> to form strongly correlated Ir<sub>SAE</sub> during pyrolysis. Extensive ex situ characterization, operando X-ray absorption and Raman spectroscopies, pH-dependence activity tests, and theoretical calculations indicate that the rigid Ir<sub>SAE</sub> with appropriate Ir–Ir distance stabilized on the CMO surface effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, thereby mitigating Ir-dissolution and structural collapse, boosting the stability in an acidic environment.</p> - -Ashwani Kumar, -Marcos Gil‐Sepulcre, -Jinsun Lee, -Viet Q. Bui, -Yue Wang, -Olaf Rüdiger, -Min Gyu Kim, -Serena DeBeer, -Harun Tüysüz +Weiyan Qi, +Stefano Ponzoni, +Guénolé Huitric, +Romain Grasset, +Yannis Laplace, +Laurent Cario, +Alberto Zobelli, +Marino Marsi, +Evangelos Papalazarou, +Alexandr Alekhin, +Yann Gallais, +Azzedine Bendounan, +Suk Hyun Sung, +Noah Schnitzer, +Berit Hansen Goodge, +Robert Hovden, +Luca Perfetti Research Article - Iridium Single‐Atom‐Ensembles Stabilized on Mn‐Substituted Spinel Oxide for Durable Acidic Water Electrolysis - 10.1002/adma.202401648 + In‐Plane Chirality Control of a Charge Density Wave by Means of Shear Stress + 10.1002/adma.202410950 Advanced Materials - 10.1002/adma.202401648 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202401648 + 10.1002/adma.202410950 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410950 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403066 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412667 + Sat, 16 Nov 2024 04:37:57 -0800 + 2024-11-16T04:37:57-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202403066 - Robust Electric‐Field Control of Colossal Exchange Bias in CrI3 Homotrilayer - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202412667 + Crystallographic Reorientation Induced by Gradient Solid‐Electrolyte Interphase for Highly Stable Zinc Anode + Advanced Materials, EarlyView. -A robust electric‐field control of exchange bias (EB) effect and magnetism transition is realized in a pure CrI3 homotrilayer. The doping from the Y‐doped HfO2 substrate alters the interlayer coupling of intrinsic CrI3 trilayer and further causes the EB effect. The gate voltage reverses the magnetization direction layer‐by‐layer in homotrilayer CrI3, leading to a colossal EB modulation of 0.48 T. +This study tracks the reaction pathways of Zn2+ from de‐solvation to Zn nucleation and subsequent growth. Advanced operando spectroscopy and crystallography tests reveal that gradient solid‐electrolyte interphase induces crystallographic reorientation from Zn (101) to (002) planes of Zn anode during Zn2+ stripping/plating. The in‐depth depicted crystal regulation method opens new opportunities for the development of long‐lifespan metal batteries. @@ -1709,51 +1625,48 @@ A robust electric‐field control of exchange bias (EB) effect and magn Abstract -Controlling exchange bias (EB) by electric fields is crucial for next‐generation magnetic random access memories and spintronics with ultralow energy consumption and ultrahigh speed. Multiferroic heterostructures have been traditionally used to electrically control EB and interfacial ferromagnetism through weak/indirect coupling between ferromagnetic and ferroelectric films. However, three major bottlenecks (lattice mismatch, interface defects, and weak/indirect coupling in multiferroic heterostructures) remain, resulting in only a few tens of milli‐tesla EB field. Here, this study reports a robust electric‐field control recipe to dynamically tailor the EB effect in a pure CrI3 homotrilayer on a ferroelectric Y‐doped HfO2 (HYO) substrate, and demonstrate a colossal and tunable EB field (HE) from −0.15 to +0.33 T, giving rise to an EB modulation of 0.48 T. The charge doping due to ferroelectric HYO film divides a homo‐configuration of CrI3 homotrilayer into one antiferromagnetic (AFM) bilayer CrI3 and one ferromagnetic (FM) monolayer CrI3, favoring direct exchange coupling. The synergies of charge doping and electric field induce a transition of magnetic orders from AFM to FM phase in bilayer CrI3, which is also supported by first‐principles calculations, leading to the robust electric control of colossal EB effect. The results therefore open numerous opportunities for exploring 2D spintronics, memories, and braininspired in‐memory computing. +Oriented zinc (Zn) electrodeposition is critical for the long‐term performance of aqueous Zn metal batteries. However, the intricate interfacial reactions between the Zn anode and electrolytes hinder a comprehensive understanding of Zn metal deposition. Here, the reaction pathways of Zn deposition and report the preferential formation of Zn single‐crystalline nuclei followed by dense Zn(002) deposition is elucidated, which is induced by a gradient solid‐electrolyte interphase (SEI). The gradient SEI composed of abundant B‐O and C species facilitates faster Zn2+ nucleation rate and smaller nucleus size, promoting the formation of Zn single‐crystalline nuclei. Additionally, the homogeneity and mechanical stability of SEI ensure the crystallographic reorientation of Zn anodes from Zn(101) to (002) planes, efficiently inhibiting dendrite growth and metal corrosion during the Zn2+ stripping/plating process. These advantages significantly enhance the stability of the Zn anode, as demonstrated by the prolonged cycling lifespan of symmetric Zn batteries and exceptional reversibility (>99.5%) over 5000 cycles in Zn//Cu asymmetric batteries. Notably, this strategy also enables the stable operation of anode‐free Zn//I2 batteries with a long lifespan of 3000 cycles. This work advances the understanding of Zn electrochemical behaviors, encompassing Zn nucleation, growth, and Zn2+ stripping/plating. - <img src="https://onlinelibrary.wiley.com/cms/asset/1d5cb345-314e-4c31-8f54-61f954041226/adma202403066-gra-0001-m.png" - alt="Robust Electric-Field Control of Colossal Exchange Bias in CrI3 Homotrilayer"/> -<p>A robust electric-field control of exchange bias (EB) effect and magnetism transition is realized in a pure CrI<sub>3</sub> homotrilayer. The doping from the Y-doped HfO<sub>2</sub> substrate alters the interlayer coupling of intrinsic CrI<sub>3</sub> trilayer and further causes the EB effect. The gate voltage reverses the magnetization direction layer-by-layer in homotrilayer CrI<sub>3</sub>, leading to a colossal EB modulation of 0.48 T. + <img src="https://onlinelibrary.wiley.com/cms/asset/97727cf0-33cb-45ae-b066-f6c54661c0a3/adma202412667-gra-0001-m.png" + alt="Crystallographic Reorientation Induced by Gradient Solid-Electrolyte Interphase for Highly Stable Zinc Anode"/> +<p>This study tracks the reaction pathways of Zn2+ from de-solvation to Zn nucleation and subsequent growth. Advanced operando spectroscopy and crystallography tests reveal that gradient solid-electrolyte interphase induces crystallographic reorientation from Zn (101) to (002) planes of Zn anode during Zn2+ stripping/plating. The in-depth depicted crystal regulation method opens new opportunities for the development of long-lifespan metal batteries. </p> <br/> <h2>Abstract</h2> -<p>Controlling exchange bias (EB) by electric fields is crucial for next-generation magnetic random access memories and spintronics with ultralow energy consumption and ultrahigh speed. Multiferroic heterostructures have been traditionally used to electrically control EB and interfacial ferromagnetism through weak/indirect coupling between ferromagnetic and ferroelectric films. However, three major bottlenecks (lattice mismatch, interface defects, and weak/indirect coupling in multiferroic heterostructures) remain, resulting in only a few tens of milli-tesla EB field. Here, this study reports a robust electric-field control recipe to dynamically tailor the EB effect in a pure CrI<sub>3</sub> homotrilayer on a ferroelectric Y-doped HfO<sub>2</sub> (HYO) substrate, and demonstrate a colossal and tunable EB field (<i>H<sub>E</sub> -</i>) from −0.15 to +0.33 T, giving rise to an EB modulation of 0.48 T. The charge doping due to ferroelectric HYO film divides a homo-configuration of CrI<sub>3</sub> homotrilayer into one antiferromagnetic (AFM) bilayer CrI<sub>3</sub> and one ferromagnetic (FM) monolayer CrI<sub>3</sub>, favoring direct exchange coupling. The synergies of charge doping and electric field induce a transition of magnetic orders from AFM to FM phase in bilayer CrI<sub>3</sub>, which is also supported by first-principles calculations, leading to the robust electric control of colossal EB effect. The results therefore open numerous opportunities for exploring 2D spintronics, memories, and braininspired in-memory computing.</p> +<p>Oriented zinc (Zn) electrodeposition is critical for the long-term performance of aqueous Zn metal batteries. However, the intricate interfacial reactions between the Zn anode and electrolytes hinder a comprehensive understanding of Zn metal deposition. Here, the reaction pathways of Zn deposition and report the preferential formation of Zn single-crystalline nuclei followed by dense Zn(002) deposition is elucidated, which is induced by a gradient solid-electrolyte interphase (SEI). The gradient SEI composed of abundant B-O and C species facilitates faster Zn<sup>2+</sup> nucleation rate and smaller nucleus size, promoting the formation of Zn single-crystalline nuclei. Additionally, the homogeneity and mechanical stability of SEI ensure the crystallographic reorientation of Zn anodes from Zn(101) to (002) planes, efficiently inhibiting dendrite growth and metal corrosion during the Zn<sup>2+</sup> stripping/plating process. These advantages significantly enhance the stability of the Zn anode, as demonstrated by the prolonged cycling lifespan of symmetric Zn batteries and exceptional reversibility (&gt;99.5%) over 5000 cycles in Zn//Cu asymmetric batteries. Notably, this strategy also enables the stable operation of anode-free Zn//I<sub>2</sub> batteries with a long lifespan of 3000 cycles. This work advances the understanding of Zn electrochemical behaviors, encompassing Zn nucleation, growth, and Zn<sup>2+</sup> stripping/plating.</p> -Yuting Niu, -Zhen Liu, -Ke Wang, -Wanlei Ai, -Tao Gong, -Tao Liu, -Lei Bi, -Gang Zhang, -Longjiang Deng, -Bo Peng +Ming Zhao, +Yanqun Lv, +Jun Qi, +Yong Zhang, +Yadong Du, +Qi Yang, +Yunkai Xu, +Jieshan Qiu, +Jun Lu, +Shimou Chen Research Article - Robust Electric‐Field Control of Colossal Exchange Bias in CrI3 Homotrilayer - 10.1002/adma.202403066 + Crystallographic Reorientation Induced by Gradient Solid‐Electrolyte Interphase for Highly Stable Zinc Anode + 10.1002/adma.202412667 Advanced Materials - 10.1002/adma.202403066 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403066 + 10.1002/adma.202412667 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412667 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403612 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410575 + Sat, 16 Nov 2024 04:37:14 -0800 + 2024-11-16T04:37:14-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202403612 - Sono‐Triggered Biomimetically Nanoantibiotics Mediate Precise Sequential Therapy of MRSA‐Induced Lung Infection - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202410575 + Improving Oxygen‐Redox‐Active Layered Oxide Cathodes for Sodium‐Ion Batteries Through Crystal Facet Modulation and Fluorinated Interfacial Engineering + Advanced Materials, EarlyView. -AMV@NanoCip, a novel biomimetic nanomedicine, integrates PBP2a antibody‐presenting nanovesicles with self‐assembled ciprofloxacin nanoparticles exhibiting sonodynamic properties. This formulation demonstrates exceptional MRSA‐targeting and antibacterial efficacy, achieving 99.99% sterilization in vitro and significant bacterial reduction in a pneumonia model. The sequential treatment strategy, combining adhesion, membrane disruption, and synergistic therapy, presents a promising approach for combating bacterial infections. +Crystal‐facet modulation and fluorinated interfacial engineering via bifunctional electrolyte additive enhances the anionic redox kinetics and structural stability, which endows Na0.67Li0.24Mn0.76O2 with high capacity, superior rate capability, and long cycle stability for sodium‐ion batteries. @@ -1763,50 +1676,46 @@ AMV@NanoCip, a novel biomimetic nanomedicine, integrates PBP2a antibody‐pr Abstract -Bacterial‐induced lower respiratory tract infections are a growing global health concern, exacerbated by the inefficacy of conventional antibiotics and delivery methods to effectively target the lower respiratory tract, leading to suboptimal therapeutic outcomes. To address this challenge, this work engineers PBP2a antibody‐presenting membrane nanovesicles (AMVs) specifically designed to target the penicillin‐binding protein variant on the surface of methicillin‐resistant Staphylococcus aureus (MRSA). Concurrently, this work develops pure ciprofloxacin nanoparticles (NanoCip) that, for the first time, exhibits exceptional self‐generated sonodynamic properties, attributed to hydrogen‐bond‐driven self‐assembly, while maintaining their inherent pharmacological efficacy. These NanoCip particles are integrated with AMVs to create a novel biomimetic nanomedicine, AMV@NanoCip. This formulation demonstrated remarkable MRSA‐targeting affinity in both in vitro and in vivo models, significantly enhancing antibacterial activity. Upon ultrasound stimulation, AMV@NanoCip achieves over 99.99% sterilization of MRSA in vitro, with a reduction exceeding 5.14 Log CFU. Prokaryotic transcriptomic analysis further elucidates the synergistic mechanisms by which AMV@NanoCip, coupled with ultrasound, disrupts the MRSA exoskeleton. In a MRSA‐induced pneumonia animal model, AMV@NanoCip+US results in a substantial bacterial load reduction in the lungs (99.99%, 4.02 Log CFU). This sequential treatment strategy (adhesion‐membrane disruption‐synergistic therapy) offers significant promise as an innovative therapeutic approach for combating bacterial infections. +Layered oxides with active oxygen redox are attractive cathode materials for sodium‐ion batteries (SIBs) due to high capacity but suffer from rapid capacity/voltage deterioration and sluggish reaction kinetics stemming from lattice oxygen release, interfacial side reactions, and structural reconstruction. Herein, a synergistic strategy of crystal‐facet modulation and fluorinated interfacial engineering is proposed to achieve high capacity, superior rate capability, and long cycle stability in Na0.67Li0.24Mn0.76O2. The synthesized single‐crystal Na0.67Li0.24Mn0.76O2 (NLMO{010}) featuring increased {010} active facet exposure exhibits faster anionic redox kinetics and delivers a high capacity (272.4 mAh g−1 at 10 mA g−1) with superior energy density (713.9 Wh kg−1) and rate performance (116.4 mAh g−1 at 1 A g−1). Moreover, by incorporating N‐Fluorobenzenesulfonimide (NFBS) as electrolyte additive, the NLMO{010} cathode retains 84.6% capacity after 400 cycles at 500 mA g−1 with alleviated voltage fade (0.27 mV per cycle). Combined in situ analysis and theoretical calculations unveil dual functionality of NFBS, which results in thin yet durable fluorinated interfaces on the NLMO{010} cathode and hard carbon anode and scavenges highly reactive oxygen species. The results indicate the importance of fast‐ion‐transfer facet engineering and fluorinated electrolyte formulation to enhance oxygen redox‐active cathode materials for high‐energy‐density SIBs. - <img src="https://onlinelibrary.wiley.com/cms/asset/d16f2b10-0cdc-452d-911c-add9bab8984b/adma202403612-gra-0001-m.png" - alt="Sono-Triggered Biomimetically Nanoantibiotics Mediate Precise Sequential Therapy of MRSA-Induced Lung Infection"/> -<p>AMV@NanoCip, a novel biomimetic nanomedicine, integrates PBP2a antibody-presenting nanovesicles with self-assembled ciprofloxacin nanoparticles exhibiting sonodynamic properties. This formulation demonstrates exceptional MRSA-targeting and antibacterial efficacy, achieving 99.99% sterilization in vitro and significant bacterial reduction in a pneumonia model. The sequential treatment strategy, combining adhesion, membrane disruption, and synergistic therapy, presents a promising approach for combating bacterial infections. + <img src="https://onlinelibrary.wiley.com/cms/asset/d0638df7-f42c-47ad-9744-da83cf557935/adma202410575-gra-0001-m.png" + alt="Improving Oxygen-Redox-Active Layered Oxide Cathodes for Sodium-Ion Batteries Through Crystal Facet Modulation and Fluorinated Interfacial Engineering"/> +<p>Crystal-facet modulation and fluorinated interfacial engineering via bifunctional electrolyte additive enhances the anionic redox kinetics and structural stability, which endows Na<sub>0.67</sub>Li<sub>0.24</sub>Mn<sub>0.76</sub>O<sub>2</sub> with high capacity, superior rate capability, and long cycle stability for sodium-ion batteries. </p> <br/> <h2>Abstract</h2> -<p>Bacterial-induced lower respiratory tract infections are a growing global health concern, exacerbated by the inefficacy of conventional antibiotics and delivery methods to effectively target the lower respiratory tract, leading to suboptimal therapeutic outcomes. To address this challenge, this work engineers PBP2a antibody-presenting membrane nanovesicles (AMVs) specifically designed to target the penicillin-binding protein variant on the surface of methicillin-resistant <i>Staphylococcus aureus</i> (MRSA). Concurrently, this work develops pure ciprofloxacin nanoparticles (NanoCip) that, for the first time, exhibits exceptional self-generated sonodynamic properties, attributed to hydrogen-bond-driven self-assembly, while maintaining their inherent pharmacological efficacy. These NanoCip particles are integrated with AMVs to create a novel biomimetic nanomedicine, AMV@NanoCip. This formulation demonstrated remarkable MRSA-targeting affinity in both in vitro and in vivo models, significantly enhancing antibacterial activity. Upon ultrasound stimulation, AMV@NanoCip achieves over 99.99% sterilization of MRSA in vitro, with a reduction exceeding 5.14 Log CFU. Prokaryotic transcriptomic analysis further elucidates the synergistic mechanisms by which AMV@NanoCip, coupled with ultrasound, disrupts the MRSA exoskeleton. In a MRSA-induced pneumonia animal model, AMV@NanoCip+US results in a substantial bacterial load reduction in the lungs (99.99%, 4.02 Log CFU). This sequential treatment strategy (adhesion-membrane disruption-synergistic therapy) offers significant promise as an innovative therapeutic approach for combating bacterial infections.</p> +<p>Layered oxides with active oxygen redox are attractive cathode materials for sodium-ion batteries (SIBs) due to high capacity but suffer from rapid capacity/voltage deterioration and sluggish reaction kinetics stemming from lattice oxygen release, interfacial side reactions, and structural reconstruction. Herein, a synergistic strategy of crystal-facet modulation and fluorinated interfacial engineering is proposed to achieve high capacity, superior rate capability, and long cycle stability in Na<sub>0.67</sub>Li<sub>0.24</sub>Mn<sub>0.76</sub>O<sub>2</sub>. The synthesized single-crystal Na<sub>0.67</sub>Li<sub>0.24</sub>Mn<sub>0.76</sub>O<sub>2</sub> (NLMO{010}) featuring increased {010} active facet exposure exhibits faster anionic redox kinetics and delivers a high capacity (272.4 mAh g<sup>−1</sup> at 10 mA g<sup>−1</sup>) with superior energy density (713.9 Wh kg<sup>−1</sup>) and rate performance (116.4 mAh g<sup>−1</sup> at 1 A g<sup>−1</sup>). Moreover, by incorporating N-Fluorobenzenesulfonimide (NFBS) as electrolyte additive, the NLMO{010} cathode retains 84.6% capacity after 400 cycles at 500 mA g<sup>−1</sup> with alleviated voltage fade (0.27 mV per cycle). Combined in situ analysis and theoretical calculations unveil dual functionality of NFBS, which results in thin yet durable fluorinated interfaces on the NLMO{010} cathode and hard carbon anode and scavenges highly reactive oxygen species. The results indicate the importance of fast-ion-transfer facet engineering and fluorinated electrolyte formulation to enhance oxygen redox-active cathode materials for high-energy-density SIBs.</p> -Linyu Ding, -Xiaoliu Liang, -Jiaxin Ma, -Xue Liu, -Yang Zhang, -Qiuyue Long, -Zihao Wen, -Zihao Teng, -Lai Jiang, -Gang Liu +Yiran Sun, +Junying Weng, +Pengfei Zhou, +Wenyong Yuan, +Yihao Pan, +Xiaozhong Wu, +Jin Zhou, +Fangyi Cheng Research Article - Sono‐Triggered Biomimetically Nanoantibiotics Mediate Precise Sequential Therapy of MRSA‐Induced Lung Infection - 10.1002/adma.202403612 + Improving Oxygen‐Redox‐Active Layered Oxide Cathodes for Sodium‐Ion Batteries Through Crystal Facet Modulation and Fluorinated Interfacial Engineering + 10.1002/adma.202410575 Advanced Materials - 10.1002/adma.202403612 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403612 + 10.1002/adma.202410575 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410575 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403985 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414578 + Sat, 16 Nov 2024 04:36:41 -0800 + 2024-11-16T04:36:41-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202403985 - Mimicking Antiferroelectrics with Ferroelectric Superlattices - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202414578 + Enhanced Stability and Brightness through Co‐Substitution: Promoting Plant Growth with Green‐Excited Deep Red Phosphor Ca1‐zSrzLi1‐xMg2xAl3‐xN4:yEu2+ + Advanced Materials, EarlyView. -Antiferroelectrics are promising materials for applications in energy storage, solid‐state cooling, and negative‐capacitance devices. This study demonstrates that antiferroelectric‐like behavior can be electrostatically engineered in ferroelectric superlattices. An electric field induces a reversible transition from a stable in‐plane polarized state to a state with in‐plane and out‐of‐plane polarized nanodomains that mimics, at the domain level, the nonpolar‐to‐polar transition of traditional antiferroelectrics. +This research presents a new phosphor that effectively converts green light into deep red light, which is advantageous for plant growth, thereby facilitating spectral regulation and enhancing luminescence. The phosphor can be efficiently excited by sunlight, thereby optimizing sunlight utilization. Furthermore, the material exhibits exceptional stability and efficiency for use in outdoor agricultural lighting applications. @@ -1816,50 +1725,43 @@ Antiferroelectrics are promising materials for applications in energy storage, s Abstract -Antiferroelectric oxides are promising materials for applications in high‐density energy storage, solid‐state cooling, and negative capacitance devices. However, the range of oxide antiferroelectrics available today is rather limited. In this work, it is demonstrated that antiferroelectric properties can be electrostatically engineered in artificially layered ferroelectric superlattices. Using a combination of synchrotron X‐ray nanodiffraction, scanning transmission electron microscopy, macroscopic electrical measurements, and lateral and vertical piezoresponse force microscopy in parallel‐plate capacitor geometry, a highly reversible field‐induced transition is observed from a stable in‐plane polarized state to a state with in‐plane and out‐of‐plane polarized nanodomains that mimics, at the domain level, the nonpolar to polar transition of traditional antiferroelectrics, with corresponding polarization‐voltage double hysteresis and comparable energy storage capacity. Furthermore, it is found that such superlattices exhibit large out‐of‐plane dielectric responses without involving flux‐closure domain dynamics. These results demonstrate that electrostatic and strain engineering in artificially layered materials offers a promising route for the creation of synthetic antiferroelectrics. +The research utilized a strategy of chemical unit co‐substitution, successfully developing a novel blue‐green to green excited, deep red‐emitting phosphor, Ca1‐zSrzLi1‐xMg2xAl3‐xN4:yEu2+ (CLA‐2xM‐zS:yEu, 0≤x≤0.8, 0.003≤y≤0.01, 0≤z≤1), through the replacement of [Li−Al]4+ by [Mg−Mg]4+. This phosphor uniquely converts unusable green light to growth‐enhancing deep red, optimizing it for outdoor agriculture. Doping with Sr creates traps, causing a redshift in emission peaks, as confirmed by 7Li nuclear magnetic resonance (NMR) spectra, indicating Li presence and lattice changes. Ca0.2Sr0.8Li0.5MgAl2.5N4:0.005Eu2+ (CLAM‐0.8S) phosphor maintained high luminescence intensity under extreme conditions of 85 °C/85% RH, demonstrating excellent photoluminescence performance and chemical stability, compared with conventional SrLi0.5MgAl2.5N4:0.005Eu2+ (SLMA) and SrLiAl3N4:0.005Eu2+(SLA). Experimental results surprised that the unique Ca0.2Sr0.8Li0.8Mg0.4Al2.8N4:0.005Eu2+ (CLA‐0.4M‐0.8S) prepared light‐converting film, which is mainly excited by green light, demonstrated a 20% increase in optical density of Chlorella compared to the PP film and a remarkable 97.5% increase compared to the control group without any film. These findings suggest that this film has significant potential for applications in outdoor agriculture and other fields. - <img src="https://onlinelibrary.wiley.com/cms/asset/c95564f6-b0e2-4825-a4d5-27a435ff8f89/adma202403985-gra-0001-m.png" - alt="Mimicking Antiferroelectrics with Ferroelectric Superlattices"/> -<p>Antiferroelectrics are promising materials for applications in energy storage, solid-state cooling, and negative-capacitance devices. This study demonstrates that antiferroelectric-like behavior can be electrostatically engineered in ferroelectric superlattices. An electric field induces a reversible transition from a stable in-plane polarized state to a state with in-plane and out-of-plane polarized nanodomains that mimics, at the domain level, the nonpolar-to-polar transition of traditional antiferroelectrics. + <img src="https://onlinelibrary.wiley.com/cms/asset/875b49e5-a4c4-41d0-817d-e93bba08edb9/adma202414578-gra-0001-m.png" + alt="Enhanced Stability and Brightness through Co-Substitution: Promoting Plant Growth with Green-Excited Deep Red Phosphor Ca1-zSrzLi1-xMg2xAl3-xN4:yEu2+"/> +<p>This research presents a new phosphor that effectively converts green light into deep red light, which is advantageous for plant growth, thereby facilitating spectral regulation and enhancing luminescence. The phosphor can be efficiently excited by sunlight, thereby optimizing sunlight utilization. Furthermore, the material exhibits exceptional stability and efficiency for use in outdoor agricultural lighting applications. </p> <br/> <h2>Abstract</h2> -<p>Antiferroelectric oxides are promising materials for applications in high-density energy storage, solid-state cooling, and negative capacitance devices. However, the range of oxide antiferroelectrics available today is rather limited. In this work, it is demonstrated that antiferroelectric properties can be electrostatically engineered in artificially layered ferroelectric superlattices. Using a combination of synchrotron X-ray nanodiffraction, scanning transmission electron microscopy, macroscopic electrical measurements, and lateral and vertical piezoresponse force microscopy in parallel-plate capacitor geometry, a highly reversible field-induced transition is observed from a stable in-plane polarized state to a state with in-plane and out-of-plane polarized nanodomains that mimics, at the domain level, the nonpolar to polar transition of traditional antiferroelectrics, with corresponding polarization-voltage double hysteresis and comparable energy storage capacity. Furthermore, it is found that such superlattices exhibit large out-of-plane dielectric responses without involving flux-closure domain dynamics. These results demonstrate that electrostatic and strain engineering in artificially layered materials offers a promising route for the creation of synthetic antiferroelectrics.</p> +<p>The research utilized a strategy of chemical unit co-substitution, successfully developing a novel blue-green to green excited, deep red-emitting phosphor, Ca<sub>1-z</sub>Sr<sub>z</sub>Li<sub>1-x</sub>Mg<sub>2x</sub>Al<sub>3-x</sub>N<sub>4</sub>:yEu<sup>2+</sup> (CLA-2xM-zS:yEu, 0≤x≤0.8, 0.003≤y≤0.01, 0≤z≤1), through the replacement of [Li−Al]<sup>4+</sup> by [Mg−Mg]<sup>4+</sup>. This phosphor uniquely converts unusable green light to growth-enhancing deep red, optimizing it for outdoor agriculture. Doping with Sr creates traps, causing a redshift in emission peaks, as confirmed by <sup>7</sup>Li nuclear magnetic resonance (NMR) spectra, indicating Li presence and lattice changes. Ca<sub>0.2</sub>Sr<sub>0.8</sub>Li<sub>0.5</sub>MgAl<sub>2.5</sub>N<sub>4</sub>:0.005Eu<sup>2+</sup> (CLAM-0.8S) phosphor maintained high luminescence intensity under extreme conditions of 85 °C/85% RH, demonstrating excellent photoluminescence performance and chemical stability, compared with conventional SrLi<sub>0.5</sub>MgAl<sub>2.5</sub>N<sub>4</sub>:0.005Eu<sup>2+</sup> (SLMA) and SrLiAl<sub>3</sub>N<sub>4</sub>:0.005Eu<sup>2+</sup>(SLA). Experimental results surprised that the unique Ca<sub>0.2</sub>Sr<sub>0.8</sub>Li<sub>0.8</sub>Mg<sub>0.4</sub>Al<sub>2.8</sub>N<sub>4</sub>:0.005Eu<sup>2+</sup> (CLA-0.4M-0.8S) prepared light-converting film, which is mainly excited by green light, demonstrated a 20% increase in optical density of Chlorella compared to the PP film and a remarkable 97.5% increase compared to the control group without any film. These findings suggest that this film has significant potential for applications in outdoor agriculture and other fields.</p> -Chunhai Yin, -Yaqi Li, -Edoardo Zatterin, -Dorin Rusu, -Evgenios Stylianidis, -Marios Hadjimichael, -Hugo Aramberri, -Jorge Iñiguez‐González, -Michele Conroy, -Pavlo Zubko +Pengpeng Wang, +Yuhua Wang, +Zebin Li, +Haoyang Wang, +Takatoshi Seto Research Article - Mimicking Antiferroelectrics with Ferroelectric Superlattices - 10.1002/adma.202403985 + Enhanced Stability and Brightness through Co‐Substitution: Promoting Plant Growth with Green‐Excited Deep Red Phosphor Ca1‐zSrzLi1‐xMg2xAl3‐xN4:yEu2+ + 10.1002/adma.202414578 Advanced Materials - 10.1002/adma.202403985 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403985 + 10.1002/adma.202414578 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414578 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202404384 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412154 + Sat, 16 Nov 2024 04:36:20 -0800 + 2024-11-16T04:36:20-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202404384 - Ordered Transfer from 3D‐Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202412154 + LysSYL‐Loaded pH‐Switchable Self‐Assembling Peptide Hydrogels Promote Methicillin‐Resistant Staphylococcus Aureus Elimination and Wound Healing + Advanced Materials, EarlyView. -3D‐oriented metal‐organic framework (MOF) films are used as templates for the fabrication of oriented porous polymer films and patterns. MOF films are prepared via heteroepitaxial growth; X‐ray sensitivity is achieved using an azide‐functionalized linker. X‐ray irradiation degrades the MOF film in exposed regions; masked areas are cross‐linked via azide‐alkyne coupling. Acidic treatment affords polymeric films and patterns with anisotropic fluorescent properties. +The LysSYL‐loaded L5 can assemble pH‐sensitive L5@LysSYL hydrogels at neutral pH and exhibit the slow‐release effect of LysSYL at acidic pH. L5@LysSYL hydrogels effectively eliminate MRSA through multiple synergistic modes, including bacterial membrane disruption, cross‐wall disturbing, and cell separation inhibition. Moreover, L5@LysSYL hydrogels promote wound healing and show promise as a wound dressing for the management of wound infections. @@ -1869,53 +1771,58 @@ Pavlo Zubko Abstract -Films and patterns of 3D‐oriented metal‐organic frameworks (MOFs) afford well‐ordered pore structures extending across centimeter‐scale areas. These macroscopic domains of aligned pores are pivotal to enhance diffusion along specific pathways and orient functional guests. The anisotropic properties emerging from this alignment are beneficial for applications in ion conductivity and photonics. However, the structure of 3D‐oriented MOF films and patterns can rapidly degrade under humid and acidic conditions. Thus, more durable 3D‐ordered porous systems are desired for practical applications. Here, oriented porous polymer films and patterns are prepared by using heteroepitaxially oriented N3‐functionalized MOF films as precursor materials. The film fabrication protocol utilizes an azide–alkyne cycloaddition on the Cu2(AzBPDC)2DABCO MOF. The micropatterning protocol exploits the X‐ray sensitivity of azide groups in Cu2(AzBPDC)2DABCO, enabling selective degradation in the irradiated areas. The masked regions of the MOF film retain their N3‐functionality, allowing for subsequent cross‐linking through azide‐alkyne coupling. Subsequent acidic treatment removes the Cu ions from the MOF, yielding porous polymer micro‐patterns. The polymer has high chemical stability and shows an anisotropic fluorescent response. The use of 3D‐oriented MOF systems as precursors for the fabrication of oriented porous polymers will facilitate the progress of optical components for photonic applications. +Staphylococcus aureus (S. aureus), especially methicillin‐resistant S. aureus (MRSA), causes wound infections, whose treatment remains a clinical challenge. Bacterium‐infected wounds often create acidic niches with a pH 4.5–6.5. Endolysin LysSYL, which is derived from phage SYL, shows promise as an antistaphylococcal agent. However, endolysins generally exhibit instability and possess low bioavailability in acidic microenvironments. Here, an array of self‐assembling peptides is designed, and peptide L5 is screened out based on its gel formation property and bioavailability. L5 exerted a pH‐switchable antimicrobial effect (pH 5.5) and formed biocompatible hydrogels at neutral pH (pH 7.4). The LysSYL‐loaded L5 can assemble L5@LysSYL hydrogels, increase thermal stability, and exhibit the slow‐release effect of LysSYL. Effective elimination of S. aureus is achieved by L5@LysSYL through bacterial membrane disruption and cell separation inhibition. Moreover, L5@LysSYL hydrogels exhibit great potential in promoting wound healing in a mouse wound model infected by MRSA. Furthermore, L5@LysSYL hydrogels are safe and can decrease the cytokine levels and increase the number of key factors for vessel formation, which contribute to wound healing. Overall, the self‐assembling L5@LysSYL can effectively clean MRSA and promote wound healing, which suggests its potential as a pH‐sensitive wound dressing for the management of wound infections. - <img src="https://onlinelibrary.wiley.com/cms/asset/9a505e7d-02bb-40f8-9586-e1555df4ed8c/adma202404384-gra-0001-m.png" - alt="Ordered Transfer from 3D-Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns"/> -<p>3D-oriented metal-organic framework (MOF) films are used as templates for the fabrication of oriented porous polymer films and patterns. MOF films are prepared via heteroepitaxial growth; X-ray sensitivity is achieved using an azide-functionalized linker. X-ray irradiation degrades the MOF film in exposed regions; masked areas are cross-linked via azide-alkyne coupling. Acidic treatment affords polymeric films and patterns with anisotropic fluorescent properties. + <img src="https://onlinelibrary.wiley.com/cms/asset/9b35ff68-a0c0-488e-9761-946a30d0861a/adma202412154-gra-0001-m.png" + alt="LysSYL-Loaded pH-Switchable Self-Assembling Peptide Hydrogels Promote Methicillin-Resistant Staphylococcus Aureus Elimination and Wound Healing"/> +<p>The LysSYL-loaded L5 can assemble pH-sensitive L5@LysSYL hydrogels at neutral pH and exhibit the slow-release effect of LysSYL at acidic pH. L5@LysSYL hydrogels effectively eliminate MRSA through multiple synergistic modes, including bacterial membrane disruption, cross-wall disturbing, and cell separation inhibition. Moreover, L5@LysSYL hydrogels promote wound healing and show promise as a wound dressing for the management of wound infections. </p> <br/> <h2>Abstract</h2> -<p>Films and patterns of 3D-oriented metal-organic frameworks (MOFs) afford well-ordered pore structures extending across centimeter-scale areas. These macroscopic domains of aligned pores are pivotal to enhance diffusion along specific pathways and orient functional guests. The anisotropic properties emerging from this alignment are beneficial for applications in ion conductivity and photonics. However, the structure of 3D-oriented MOF films and patterns can rapidly degrade under humid and acidic conditions. Thus, more durable 3D-ordered porous systems are desired for practical applications. Here, oriented porous polymer films and patterns are prepared by using heteroepitaxially oriented N<sub>3</sub>-functionalized MOF films as precursor materials. The film fabrication protocol utilizes an azide–alkyne cycloaddition on the Cu<sub>2</sub>(AzBPDC)<sub>2</sub>DABCO MOF. The micropatterning protocol exploits the X-ray sensitivity of azide groups in Cu<sub>2</sub>(AzBPDC)<sub>2</sub>DABCO, enabling selective degradation in the irradiated areas. The masked regions of the MOF film retain their N<sub>3</sub>-functionality, allowing for subsequent cross-linking through azide-alkyne coupling. Subsequent acidic treatment removes the Cu ions from the MOF, yielding porous polymer micro-patterns. The polymer has high chemical stability and shows an anisotropic fluorescent response. The use of 3D-oriented MOF systems as precursors for the fabrication of oriented porous polymers will facilitate the progress of optical components for photonic applications.</p> +<p><i>Staphylococcus aureus</i> (<i>S. aureus</i>), especially methicillin-resistant <i>S. aureus</i> (MRSA), causes wound infections, whose treatment remains a clinical challenge. Bacterium-infected wounds often create acidic niches with a pH 4.5–6.5. Endolysin LysSYL, which is derived from phage SYL, shows promise as an antistaphylococcal agent. However, endolysins generally exhibit instability and possess low bioavailability in acidic microenvironments. Here, an array of self-assembling peptides is designed, and peptide L5 is screened out based on its gel formation property and bioavailability. L5 exerted a pH-switchable antimicrobial effect (pH 5.5) and formed biocompatible hydrogels at neutral pH (pH 7.4). The LysSYL-loaded L5 can assemble L5@LysSYL hydrogels, increase thermal stability, and exhibit the slow-release effect of LysSYL. Effective elimination of <i>S. aureus</i> is achieved by L5@LysSYL through bacterial membrane disruption and cell separation inhibition. Moreover, L5@LysSYL hydrogels exhibit great potential in promoting wound healing in a mouse wound model infected by MRSA. Furthermore, L5@LysSYL hydrogels are safe and can decrease the cytokine levels and increase the number of key factors for vessel formation, which contribute to wound healing. Overall, the self-assembling L5@LysSYL can effectively clean MRSA and promote wound healing, which suggests its potential as a pH-sensitive wound dressing for the management of wound infections.</p> -Lea A. Brandner, -Benedetta Marmiroli, -Mercedes Linares‐Moreau, -Mariano Barella, -Behnaz Abbasgholi‐NA, -Miriam de J. Velásquez‐Hernández, -Kate L. Flint, -Simone Dal Zilio, -Guillermo P. Acuna, -Heimo Wolinski, -Heinz Amenitsch, -Christian J. Doonan, -Paolo Falcaro +He Liu, +Xuemei Wei, +Huagang Peng, +Yi Yang, +Zhen Hu, +Yifan Rao, +Zhefen Wang, +Jianxiong Dou, +Xiaonan Huang, +Qiwen Hu, +Li Tan, +Yuting Wang, +Juan Chen, +Lu Liu, +Yuhua Yang, +Jianghong Wu, +Xiaomei Hu, +Shuguang Lu, +Weilong Shang, +Xiancai Rao Research Article - Ordered Transfer from 3D‐Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns - 10.1002/adma.202404384 + LysSYL‐Loaded pH‐Switchable Self‐Assembling Peptide Hydrogels Promote Methicillin‐Resistant Staphylococcus Aureus Elimination and Wound Healing + 10.1002/adma.202412154 Advanced Materials - 10.1002/adma.202404384 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202404384 + 10.1002/adma.202412154 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412154 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202404766 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414045 + Sat, 16 Nov 2024 04:35:29 -0800 + 2024-11-16T04:35:29-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202404766 - Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202414045 + Making Interfacial Solar Evaporation of Seawater Faster than Fresh Water + Advanced Materials, EarlyView. -The intricate world of tumor microstructures bears great significance in cancer diagnostics and therapy. This study delves into the magnetic relaxation response of magnetic nanoparticles within tumors, unraveling insights into cancer cell distribution, stromal components, and vascularization. Measuring magnetic relaxation time and analyzing tumor structures paves the way for noninvasive cancer diagnostics and therapeutics using magnetic nanoparticles. +A facile and general strategy is developed to make real seawater evaporation faster than pure water. By simply introducing specific mineral materials into the floating photothermal evaporator, Mg2+ and Ca2+ ions in seawater are accumulated at the photothermal interfaces by spontaneous ion exchange, which disturb the hydrogen bonds of water molecules, and reduce the evaporation enthalpy of seawater. @@ -1926,48 +1833,56 @@ The intricate world of tumor microstructures bears great significance in cancer Abstract -Tumor microscopic structure is crucial for determining properties such as cancer type, disease state (key for early diagnosis), and novel therapeutic strategies. Magnetic particle imaging is an early cancer diagnostic tool using magnetic nanoparticles as a tracer, which actualizes cancer theranostics in combination with hyperthermia treatment using the abilities of magnetic nanoparticles as a heat source. This study focuses on the microscopic structures associated with cancer cell distribution, the stromal compartment, and vascularization in different kinds of living tumors by analyzing the intratumor magnetic relaxation response of magnetic nanoparticles injected into the tumors. Furthermore, this study describes a sequential system for the measurement of magnetic relaxation time and analysis of the intratumor structure using nonbiological samples such as viscous fluids and solidified magnetic nanoparticles. Particularly, the fine discriminability achieved by reconstructing a distribution map representing the relationship between magnetic relaxation time and viscosity of medium is demonstrated, based on experimental data with a limited condition number. Observing tumor microscopic structure through the dynamic magnetization response of intratumor magnetic nanoparticles is a low‐invasive tool for analyzing tumor tissue without dissection. It holds promise for the advancement of biomedical applications, such as early cancer theranostics, using magnetic nanoparticles. +Interfacial solar evaporation‐based seawater desalination is regarded as one of the most promising strategies to alleviate freshwater scarcity. However, the solar evaporation rate of real seawater is significantly constricted by the ubiquitous salts present in seawater. In addition to the common issue of salt accumulation on the evaporation surface during solar evaporation, strong hydration between salt ions and water molecules leads to a lower evaporation rate for real seawater compared to pure water. Here a facile and general strategy is developed to reverse this occurrence, that is, making real seawater evaporation faster than pure water. By simply introducing specific mineral materials into the floating photothermal evaporator, ion exchange at air–water interfaces directly results in a decrease in seawater evaporation enthalpy, and consequently achieves much higher seawater evaporation rates compared to pure water. This process is spontaneously realized during seawater solar evaporation. Considering the current enormous clean water production from evaporation‐based desalination plants, such an evaporation performance improvement can remarkably increase annual clean water production, benefiting millions of people worldwide. - <img src="https://onlinelibrary.wiley.com/cms/asset/2c4e15e2-b0b7-4f62-a856-9e60a56e7056/adma202404766-gra-0001-m.png" - alt="Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles"/> -<p>The intricate world of tumor microstructures bears great significance in cancer diagnostics and therapy. This study delves into the magnetic relaxation response of magnetic nanoparticles within tumors, unraveling insights into cancer cell distribution, stromal components, and vascularization. Measuring magnetic relaxation time and analyzing tumor structures paves the way for noninvasive cancer diagnostics and therapeutics using magnetic nanoparticles. + <img src="https://onlinelibrary.wiley.com/cms/asset/2efce3da-a516-4a5c-abe9-e36592d9f0b2/adma202414045-gra-0001-m.png" + alt="Making Interfacial Solar Evaporation of Seawater Faster than Fresh Water"/> +<p>A facile and general strategy is developed to make real seawater evaporation faster than pure water. By simply introducing specific mineral materials into the floating photothermal evaporator, Mg<sup>2+</sup> and Ca<sup>2+</sup> ions in seawater are accumulated at the photothermal interfaces by spontaneous ion exchange, which disturb the hydrogen bonds of water molecules, and reduce the evaporation enthalpy of seawater. </p> <br/> <h2>Abstract</h2> -<p>Tumor microscopic structure is crucial for determining properties such as cancer type, disease state (key for early diagnosis), and novel therapeutic strategies. Magnetic particle imaging is an early cancer diagnostic tool using magnetic nanoparticles as a tracer, which actualizes cancer theranostics in combination with hyperthermia treatment using the abilities of magnetic nanoparticles as a heat source. This study focuses on the microscopic structures associated with cancer cell distribution, the stromal compartment, and vascularization in different kinds of living tumors by analyzing the intratumor magnetic relaxation response of magnetic nanoparticles injected into the tumors. Furthermore, this study describes a sequential system for the measurement of magnetic relaxation time and analysis of the intratumor structure using nonbiological samples such as viscous fluids and solidified magnetic nanoparticles. Particularly, the fine discriminability achieved by reconstructing a distribution map representing the relationship between magnetic relaxation time and viscosity of medium is demonstrated, based on experimental data with a limited condition number. Observing tumor microscopic structure through the dynamic magnetization response of intratumor magnetic nanoparticles is a low-invasive tool for analyzing tumor tissue without dissection. It holds promise for the advancement of biomedical applications, such as early cancer theranostics, using magnetic nanoparticles.</p> +<p>Interfacial solar evaporation-based seawater desalination is regarded as one of the most promising strategies to alleviate freshwater scarcity. However, the solar evaporation rate of real seawater is significantly constricted by the ubiquitous salts present in seawater. In addition to the common issue of salt accumulation on the evaporation surface during solar evaporation, strong hydration between salt ions and water molecules leads to a lower evaporation rate for real seawater compared to pure water. Here a facile and general strategy is developed to reverse this occurrence, that is, making real seawater evaporation faster than pure water. By simply introducing specific mineral materials into the floating photothermal evaporator, ion exchange at air–water interfaces directly results in a decrease in seawater evaporation enthalpy, and consequently achieves much higher seawater evaporation rates compared to pure water. This process is spontaneously realized during seawater solar evaporation. Considering the current enormous clean water production from evaporation-based desalination plants, such an evaporation performance improvement can remarkably increase annual clean water production, benefiting millions of people worldwide.</p> -Satoshi Ota, -Hiroki Kosaka, -Keita Honda, -Kota Hoshino, -Haruki Goto, -Masato Futagawa, -Yasushi Takemura, -Kosuke Shimizu +Huimin Yu, +Huanyu Jin, +Meijia Qiu, +Yunzheng Liang, +Peng Sun, +Chuanqi Cheng, +Pan Wu, +Yida Wang, +Xuan Wu, +Dewei Chu, +Min Zheng, +Tong Qiu, +Yi Lu, +Bin Zhang, +Wenjie Mai, +Xiaofei Yang, +Gary Owens, +Haolan Xu Research Article - Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles - 10.1002/adma.202404766 + Making Interfacial Solar Evaporation of Seawater Faster than Fresh Water + 10.1002/adma.202414045 Advanced Materials - 10.1002/adma.202404766 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202404766 + 10.1002/adma.202414045 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414045 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202405509 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202415101 + Sat, 16 Nov 2024 04:35:00 -0800 + 2024-11-16T04:35:00-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202405509 - In Vivo Optogenetics Based on Heavy Metal‐Free Photon Upconversion Nanoparticles - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202415101 + Fabrication of Ultrahigh‐Loading Dual Copper Sites in Nitrogen‐Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral Conditions + Advanced Materials, EarlyView. -In vivo, optogenetics using photon upconversion (TTA‐UC) based on triplet‐triplet annihilation is demonstrated. The modification of a thermally‐activated delayed fluorescence (TADF) sensitizer with a bromo group promotes intersystem crossing and enables high TTA‐UC efficiency at weak excitation light intensities even without using heavy metals. Air‐stable UC nanoparticles exhibiting red‐to‐blue TTA‐UC induce EGFP expression in the mouse brain. +Cuobpy complex is assembled into the cages of MAF‐4 as a host‐guest precursor, and pyrolyzed it into a highly loaded dual copper (21 wt%) nitrogen‐doped carbon catalyst, which exhibits an exceptional performance for eCO2RR, achieving a Faradaic efficiency of 52% and a current density of 180 mA cm−2 at −1.4 V vs. RHE. @@ -1977,49 +1892,44 @@ In vivo, optogenetics using photon upconversion (TTA‐UC) based on triplet& Abstract -Photon upconversion (UC) from red or near‐infrared (NIR) light to blue light is promising for in vivo optogenetics. However, the examples of in vivo optogenetics have been limited to lanthanide inorganic UC nanoparticles, and there have been no examples of optogenetics without using heavy metals. Here the first example of in vivo optogenetics using biocompatible heavy metal‐free TTA‐UC nanoemulsions is shown. A new organic TADF sensitizer, a boron difluoride curcuminoid derivative modified with a bromo group, can promote intersystem crossing to the excited triplet state, significantly improving TTA‐UC efficiency. The TTA‐UC nanoparticles formed from biocompatible surfactants and methyl oleate acquire water dispersibility and remarkable oxygen tolerance. By combining with genome engineering technology using the blue light‐responding photoactivatable Cre‐recombinase (PA‐Cre), TTA‐UC nanoparticles promote Cre‐reporter EGFP expression in neurons in vitro and in vivo. The results open new opportunities toward deep‐tissue control of neural activities based on heavy metal‐free fully organic UC systems. +Synthesis of high‐loading atomic‐level dispersed catalysts for highly efficient electrochemical CO2 reduction reaction (eCO2RR) to ethylene (C2H4) in neutral electrolyte remain challenging tasks. To address common aggregation issues, a host‐guest strategy is employed, by using a metal‐azolate framework (MAF‐4) with nanocages as the host and a dinuclear Cu(I) complex as the guest, to form precursors for pyrolysis into a series of nitrogen‐doped porous carbons (NPCs) with varying loadings of dual copper sites, namely NPCMAF‐4‐Cu2‐21 (21.2 wt%), NPCMAF‐4‐Cu2‐11 (10.6 wt%), and NPCMAF‐4‐Cu2‐7 (6.9 wt%). Interestingly, as the loading of dual copper sites increased from 6.9 to 21.2 wt%, the partial current density for eCO2RR to yield C2H4 also gradually increased from 38.7 to 93.6 mA cm−2. In a 0.1 m KHCO3 electrolyte, at −1.4 V versus reversible hydrogen electrode (vs. RHE), NPCMAF‐4‐Cu2‐21 exhibits the excellent performance with a Faradaic efficiency of 52% and a current density of 180 mA cm−2. Such performance can be attributed to the presence of ultrahigh‐loading dual copper sites, which promotes C─C coupling and the formation of C2 products. The findings demonstrate the confinement effect of MAF‐4 with nanocages is conducive to the preparation of high‐loading atomic‐level catalysts. - <img src="https://onlinelibrary.wiley.com/cms/asset/8fb0fe63-67a9-432c-bd5f-4aa991d8f2f7/adma202405509-gra-0001-m.png" - alt="In Vivo Optogenetics Based on Heavy Metal-Free Photon Upconversion Nanoparticles"/> -<p>In vivo, optogenetics using photon upconversion (TTA-UC) based on triplet-triplet annihilation is demonstrated. The modification of a thermally-activated delayed fluorescence (TADF) sensitizer with a bromo group promotes intersystem crossing and enables high TTA-UC efficiency at weak excitation light intensities even without using heavy metals. Air-stable UC nanoparticles exhibiting red-to-blue TTA-UC induce EGFP expression in the mouse brain. + <img src="https://onlinelibrary.wiley.com/cms/asset/d935aa97-2130-4a6a-8aa8-c492fb8941f7/adma202415101-gra-0001-m.png" + alt="Fabrication of Ultrahigh-Loading Dual Copper Sites in Nitrogen-Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral Conditions"/> +<p><b>Cuobpy</b> complex is assembled into the cages of <b>MAF-4</b> as a host-guest precursor, and pyrolyzed it into a highly loaded dual copper (21 wt%) nitrogen-doped carbon catalyst, which exhibits an exceptional performance for eCO<sub>2</sub>RR, achieving a Faradaic efficiency of 52% and a current density of 180 mA cm<sup>−2</sup> at −1.4 V <i>v</i> +<i>s</i>. RHE. </p> <br/> <h2>Abstract</h2> -<p>Photon upconversion (UC) from red or near-infrared (NIR) light to blue light is promising for in vivo optogenetics. However, the examples of in vivo optogenetics have been limited to lanthanide inorganic UC nanoparticles, and there have been no examples of optogenetics without using heavy metals. Here the first example of in vivo optogenetics using biocompatible heavy metal-free TTA-UC nanoemulsions is shown. A new organic TADF sensitizer, a boron difluoride curcuminoid derivative modified with a bromo group, can promote intersystem crossing to the excited triplet state, significantly improving TTA-UC efficiency. The TTA-UC nanoparticles formed from biocompatible surfactants and methyl oleate acquire water dispersibility and remarkable oxygen tolerance. By combining with genome engineering technology using the blue light-responding photoactivatable Cre-recombinase (PA-Cre), TTA-UC nanoparticles promote Cre-reporter EGFP expression in neurons in vitro and in vivo. The results open new opportunities toward deep-tissue control of neural activities based on heavy metal-free fully organic UC systems.</p> +<p>Synthesis of high-loading atomic-level dispersed catalysts for highly efficient electrochemical CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR) to ethylene (C<sub>2</sub>H<sub>4</sub>) in neutral electrolyte remain challenging tasks. To address common aggregation issues, a host-guest strategy is employed, by using a metal-azolate framework (<b>MAF-4</b>) with nanocages as the host and a dinuclear Cu(I) complex as the guest, to form precursors for pyrolysis into a series of nitrogen-doped porous carbons (NPCs) with varying loadings of dual copper sites, namely <b>NPC<sub>MAF-4</sub>-Cu<sub>2</sub>-21</b> (21.2 wt%), <b>NPC<sub>MAF-4</sub>-Cu<sub>2</sub>-11</b> (10.6 wt%), and <b>NPC<sub>MAF-4</sub>-Cu<sub>2</sub>-7</b> (6.9 wt%). Interestingly, as the loading of dual copper sites increased from 6.9 to 21.2 wt%, the partial current density for eCO<sub>2</sub>RR to yield C<sub>2</sub>H<sub>4</sub> also gradually increased from 38.7 to 93.6 mA cm<sup>−2</sup>. In a 0.1 <span class="smallCaps">m</span> KHCO<sub>3</sub> electrolyte, at −1.4 V versus reversible hydrogen electrode (<i>vs</i>. RHE), <b>NPC<sub>MAF-4</sub>-Cu<sub>2</sub>-21</b> exhibits the excellent performance with a Faradaic efficiency of 52% and a current density of 180 mA cm<sup>−2</sup>. Such performance can be attributed to the presence of ultrahigh-loading dual copper sites, which promotes C─C coupling and the formation of C<sub>2</sub> products. The findings demonstrate the confinement effect of <b>MAF-4</b> with nanocages is conducive to the preparation of high-loading atomic-level catalysts.</p> -Masanori Uji, -Jumpei Kondo, -Chikako Hara‐Miyauchi, -Saori Akimoto, -Rena Haruki, -Yoichi Sasaki, -Nobuo Kimizuka, -Itsuki Ajioka, -Nobuhiro Yanai +Jin‐Meng Heng, +Hao‐Lin Zhu, +Zhen‐Hua Zhao, +Pei‐Qin Liao, +Xiao‐Ming Chen Research Article - In Vivo Optogenetics Based on Heavy Metal‐Free Photon Upconversion Nanoparticles - 10.1002/adma.202405509 + Fabrication of Ultrahigh‐Loading Dual Copper Sites in Nitrogen‐Doped Porous Carbons Boosting Electroreduction of CO2 to C2H4 Under Neutral Conditions + 10.1002/adma.202415101 Advanced Materials - 10.1002/adma.202405509 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202405509 + 10.1002/adma.202415101 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202415101 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202405805 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414365 + Sat, 16 Nov 2024 04:29:23 -0800 + 2024-11-16T04:29:23-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202405805 - Multi‐Functional Biomaterial for the Treatment and Prevention of Central Line‐Associated Bloodstream Infections - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202414365 + Enhancing Radiofrequency Ablation for Hepatocellular Carcinoma: Nano‐Epidrug Effects on Immune Modulation and Antigenicity Restoration + Advanced Materials, EarlyView. -SteriGel is an injectable tissue adhesive hydrogel engineered to address central line‐associated bloodstream infection (CLABSI). With its combined antimicrobial and wound‐healing capabilities, SteriGel shows great potential for preventing and treating CLABSI. The hydrogel can effectively infiltrate the skin incision site surrounding the catheter, quickly solidify upon injection, adhere to skin tissue, and endure external pressures, thus guaranteeing sustained antimicrobial and healing effects. +A nano‐epidrug (MFMP) is developed to enhance radiofrequency ablation for hepatocellular carcinoma. This is achieved through the demethylation of cGAS DNA, demethylation of EGFR mRNA, and phosphorylation of TBK1 protein, which collectively influence immune modulation and antigenicity restoration, ultimately suppressing the recurrence and metastasis of hepatocellular carcinoma. @@ -2029,47 +1939,49 @@ SteriGel is an injectable tissue adhesive hydrogel engineered to address central Abstract -Central venous catheters are among the most used medical devices in hospitals today. Despite advances in modern medicine, catheter infections remain prevalent, causing significant morbidity and mortality worldwide. Here, SteriGel is reported, which is a multifunctional hydrogel engineered to prevent and treat central line‐associated bloodstream infections (CLABSI). The mechanical properties of SteriGel are optimized to ensure appropriate gelation kinetics, bio‐adhesiveness, stretchability, and recoverability to promote durability upon application and to provide persistent protection against infection. In vitro assays demonstrated that SteriGel exhibits long‐term antimicrobial efficacy and has bactericidal effects against highly resistant patient‐derived pathogens known to be frequently associated with CLABSI. SteriGel outperformed Biopatch, which is a clinically used device for CLABSI, in ex vivo cadaver studies that simulate clinical scenarios. Furthermore, SteriGel has biocompatible, pro‐healing, and anti‐inflammatory properties in vitro and in a rat subcutaneous injection model, suggesting a potential synergistic effect in the prevention and treatment of CLABSI. SteriGel is a multifunctional adherent biomaterial with potent antimicrobial effects for sustained sterility while promoting healing of the catheter incision site to protect against infection. +Radiofrequency ablation (RFA), a critical therapy for hepatocellular carcinoma (HCC), carries a significant risk of recurrence and metastasis, particularly owing to mechanisms involving immune evasion and antigen downregulation via epigenetic modifications. This study introduces a “nano‐epidrug” named MFMP. MFMP, which is composed of hollow mesoporous manganese dioxide (MnO2) nanoparticles, FIDAS‐5 as an MAT2A inhibitor, macrophage membrane, and anti‐PD‐L1 (aPD‐L1), targets HCC cells. By selectively binding to these cells, MFMP initially reverses immune suppression via PD‐L1 inhibition. After endocytosis, MFMP disassembles in the tumor microenvironment, releasing FIDAS‐5 and Mn2+. FIDAS‐5 prevents cGAS methylation, whereas Mn2+ aids STING pathway restoration. In addition, FIDAS‐5 reduces m6A RNA modification, suppressing EGFR expression. These changes enhance HCC antigenicity to promote cytotoxic T cell recognition and cytotoxic killing. Furthermore, MFMP mediates immunogenic cell death in HCC by synergizing with RFA through cGAS DNA demethylation, EGFR mRNA demethylation, and TBK1 protein phosphorylation, thereby inhibiting recurrence and metastasis and enhancing immune memory. Thus, MFMP is a potential adjunctive therapy requiring clinical validation. - <img src="https://onlinelibrary.wiley.com/cms/asset/a7304de3-46cc-4fe9-a0e2-b8df16d5ac21/adma202405805-gra-0001-m.png" - alt="Multi-Functional Biomaterial for the Treatment and Prevention of Central Line-Associated Bloodstream Infections"/> -<p>SteriGel is an injectable tissue adhesive hydrogel engineered to address central line-associated bloodstream infection (CLABSI). With its combined antimicrobial and wound-healing capabilities, SteriGel shows great potential for preventing and treating CLABSI. The hydrogel can effectively infiltrate the skin incision site surrounding the catheter, quickly solidify upon injection, adhere to skin tissue, and endure external pressures, thus guaranteeing sustained antimicrobial and healing effects. + <img src="https://onlinelibrary.wiley.com/cms/asset/8dbce337-0480-46ff-9a7c-212f01ca97a1/adma202414365-gra-0001-m.png" + alt="Enhancing Radiofrequency Ablation for Hepatocellular Carcinoma: Nano-Epidrug Effects on Immune Modulation and Antigenicity Restoration"/> +<p>A nano-epidrug (MFMP) is developed to enhance radiofrequency ablation for hepatocellular carcinoma. This is achieved through the demethylation of cGAS DNA, demethylation of EGFR mRNA, and phosphorylation of TBK1 protein, which collectively influence immune modulation and antigenicity restoration, ultimately suppressing the recurrence and metastasis of hepatocellular carcinoma. </p> <br/> <h2>Abstract</h2> -<p>Central venous catheters are among the most used medical devices in hospitals today. Despite advances in modern medicine, catheter infections remain prevalent, causing significant morbidity and mortality worldwide. Here, SteriGel is reported, which is a multifunctional hydrogel engineered to prevent and treat central line-associated bloodstream infections (CLABSI). The mechanical properties of SteriGel are optimized to ensure appropriate gelation kinetics, bio-adhesiveness, stretchability, and recoverability to promote durability upon application and to provide persistent protection against infection. In vitro assays demonstrated that SteriGel exhibits long-term antimicrobial efficacy and has bactericidal effects against highly resistant patient-derived pathogens known to be frequently associated with CLABSI. SteriGel outperformed Biopatch, which is a clinically used device for CLABSI, in ex vivo cadaver studies that simulate clinical scenarios. Furthermore, SteriGel has biocompatible, pro-healing, and anti-inflammatory properties in vitro and in a rat subcutaneous injection model, suggesting a potential synergistic effect in the prevention and treatment of CLABSI. SteriGel is a multifunctional adherent biomaterial with potent antimicrobial effects for sustained sterility while promoting healing of the catheter incision site to protect against infection.</p> +<p>Radiofrequency ablation (RFA), a critical therapy for hepatocellular carcinoma (HCC), carries a significant risk of recurrence and metastasis, particularly owing to mechanisms involving immune evasion and antigen downregulation via epigenetic modifications. This study introduces a “nano-epidrug” named MFMP. MFMP, which is composed of hollow mesoporous manganese dioxide (MnO<sub>2</sub>) nanoparticles, FIDAS-5 as an MAT2A inhibitor, macrophage membrane, and anti-PD-L1 (aPD-L1), targets HCC cells. By selectively binding to these cells, MFMP initially reverses immune suppression via PD-L1 inhibition. After endocytosis, MFMP disassembles in the tumor microenvironment, releasing FIDAS-5 and Mn<sup>2+</sup>. FIDAS-5 prevents cGAS methylation, whereas Mn<sup>2+</sup> aids STING pathway restoration. In addition, FIDAS-5 reduces m<sup>6</sup>A RNA modification, suppressing EGFR expression. These changes enhance HCC antigenicity to promote cytotoxic T cell recognition and cytotoxic killing. Furthermore, MFMP mediates immunogenic cell death in HCC by synergizing with RFA through cGAS DNA demethylation, EGFR mRNA demethylation, and TBK1 protein phosphorylation, thereby inhibiting recurrence and metastasis and enhancing immune memory. Thus, MFMP is a potential adjunctive therapy requiring clinical validation.</p> -Jinjoo Kim, -Hyeongseop Keum, -Hassan Albadawi, -Zefu Zhang, -Erin H. Graf, -Enes Cevik, -Rahmi Oklu +Xiaocheng Li, +Yahui Liu, +Jianji Ke, +Zhihua Wang, +Mingda Han, +Ning Wang, +Qiannan Miao, +Bingru Shao, +Dan Zhou, +Fei Yan, +Bai Ji Research Article - Multi‐Functional Biomaterial for the Treatment and Prevention of Central Line‐Associated Bloodstream Infections - 10.1002/adma.202405805 + Enhancing Radiofrequency Ablation for Hepatocellular Carcinoma: Nano‐Epidrug Effects on Immune Modulation and Antigenicity Restoration + 10.1002/adma.202414365 Advanced Materials - 10.1002/adma.202405805 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202405805 + 10.1002/adma.202414365 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414365 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406290 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410368 + Sat, 16 Nov 2024 04:26:44 -0800 + 2024-11-16T04:26:44-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202406290 - Twist‐Controlled Ferroelectricity and Emergent Multiferroicity in WSe2 Bilayers - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202410368 + Nanomaterial‐Mediated Reprogramming of Macrophages to Inhibit Refractory Muscle Fibrosis + Advanced Materials, EarlyView. -The twisted tungsten diselenide (WSe2) bilayers stacked along with monolayer graphene exhibit noticeable room temperature ferroelectricity that decreases with twist angle within the range 0° < θ < 3°, and disappears completely for θ ≥ 4°. This variation aligns with moiré length scale‐controlled ferroelectric dynamics (0° < θ < 3°), while loss beyond 4° may relate to twist‐controlled commensurate to non‐commensurate transitions. Also, 3° twisted WSe2 exhibits ferroelectric and correlation‐driven ferromagnetic ordering, indicating twist‐controlled multiferroic behavior. +Local injection of the cationic nanomaterial prevents refractory muscle fibrosis and restores muscle function after acute injury. This anti‐fibrotic effect results from the cell‐free nucleic acids (cfNA)‐TLR7/9‐dependent orchestration of the macrophages and fibro‐adipogenic progenitors (FAPs), leading to an optimized inflammation‐fibrogenesis balance. The reciprocal cross‐talk between macrophages and FAPs serves as a promising therapeutic target for treating refractory muscle fibrosis. @@ -2079,58 +1991,55 @@ The twisted tungsten diselenide (WSe2) bilayers stacked along with monolayer gra Abstract -Recently, researchers have been investigating artificial ferroelectricity, which arises when inversion symmetry is broken in certain R‐stacked, i.e., zero‐degree twisted, van der Waals (vdW) bilayers. Here, the study reports the twist‐controlled ferroelectricity in tungsten diselenide (WSe2) bilayers. The findings show noticeable room temperature ferroelectricity that decreases with twist angle within the range 0° < θ < 3°, and disappears completely for θ ≥ 4°. This variation aligns with moiré length scale‐controlled ferroelectric dynamics (0° < θ < 3°), while loss beyond 4° may relate to twist‐controlled commensurate to non‐commensurate transitions. This twist‐controlled ferroelectricity serves as a spectroscopic tool for detecting transitions between commensurate and incommensurate moiré patterns. At 5.5 K, 3° twisted WSe2 exhibits ferroelectric and correlation‐driven ferromagnetic ordering, indicating twist‐controlled multiferroic behavior. The study offers insights into twist‐controlled coexisting ferro‐ordering and serves as valuable spectroscopic tools. +Orofacial muscles are particularly prone to refractory fibrosis after injury, leading to a negative effect on the patient's quality of life and limited therapeutic options. Gaining insights into innate inflammatory response‐fibrogenesis homeostasis can aid in the development of new therapeutic strategies for muscle fibrosis. In this study, the crucial role of macrophages is identified in the regulation of orofacial muscle fibrogenesis after injury. Hypothesizing that orchestrating macrophage polarization and functions will be beneficial for fibrosis treatment, nanomaterials are engineered with polyethylenimine functionalization to regulate the macrophage phenotype by capturing negatively charged cell‐free nucleic acids (cfNAs). This cationic nanomaterial reduces macrophage‐related inflammation in vitr and demonstrates excellent efficacy in preventing orofacial muscle fibrosis in vivo. Single‐cell RNA sequencing reveals that the cationic nanomaterial reduces the proportion of profibrotic Gal3+ macrophages through the cfNA‐mediated TLR7/9‐NF‐κB signaling pathway, resulting in a shift in profibrotic fibro‐adipogenic progenitors (FAPs) from the matrix‐producing Fabp4+ subcluster to the matrix‐degrading Igf1+ subcluster. The study highlights a strategy to target innate inflammatory response‐fibrogenesis homeostasis and suggests that cationic nanomaterials can be exploited for treating refractory fibrosis. - <img src="https://onlinelibrary.wiley.com/cms/asset/bea8864a-8805-4884-ae91-cd4688de214d/adma202406290-gra-0001-m.png" - alt="Twist-Controlled Ferroelectricity and Emergent Multiferroicity in WSe2 Bilayers"/> -<p>The twisted tungsten diselenide (WSe<sub>2</sub>) bilayers stacked along with monolayer graphene exhibit noticeable room temperature ferroelectricity that decreases with twist angle within the range 0° &lt; <i>θ</i> &lt; 3°, and disappears completely for <i>θ</i> ≥ 4°. This variation aligns with moiré length scale-controlled ferroelectric dynamics (0° &lt; <i>θ</i> &lt; 3°), while loss beyond 4° may relate to twist-controlled commensurate to non-commensurate transitions. Also, 3° twisted WSe<sub>2</sub> exhibits ferroelectric and correlation-driven ferromagnetic ordering, indicating twist-controlled multiferroic behavior. + <img src="https://onlinelibrary.wiley.com/cms/asset/49fe605a-6014-45d2-9ae1-90ce29116b85/adma202410368-gra-0001-m.png" + alt="Nanomaterial-Mediated Reprogramming of Macrophages to Inhibit Refractory Muscle Fibrosis"/> +<p>Local injection of the cationic nanomaterial prevents refractory muscle fibrosis and restores muscle function after acute injury. This anti-fibrotic effect results from the cell-free nucleic acids (cfNA)-TLR7/9-dependent orchestration of the macrophages and fibro-adipogenic progenitors (FAPs), leading to an optimized inflammation-fibrogenesis balance. The reciprocal cross-talk between macrophages and FAPs serves as a promising therapeutic target for treating refractory muscle fibrosis. </p> <br/> <h2>Abstract</h2> -<p>Recently, researchers have been investigating artificial ferroelectricity, which arises when inversion symmetry is broken in certain R-stacked, i.e., zero-degree twisted, van der Waals (vdW) bilayers. Here, the study reports the twist-controlled ferroelectricity in tungsten diselenide (WSe<sub>2</sub>) bilayers. The findings show noticeable room temperature ferroelectricity that decreases with twist angle within the range 0° &lt; <i>θ</i> &lt; 3°, and disappears completely for <i>θ</i> ≥ 4°. This variation aligns with moiré length scale-controlled ferroelectric dynamics (0° &lt; <i>θ</i> &lt; 3°), while loss beyond 4° may relate to twist-controlled commensurate to non-commensurate transitions. This twist-controlled ferroelectricity serves as a spectroscopic tool for detecting transitions between commensurate and incommensurate moiré patterns. At 5.5 K, 3° twisted WSe<sub>2</sub> exhibits ferroelectric and correlation-driven ferromagnetic ordering, indicating twist-controlled multiferroic behavior. The study offers insights into twist-controlled coexisting ferro-ordering and serves as valuable spectroscopic tools.</p> +<p>Orofacial muscles are particularly prone to refractory fibrosis after injury, leading to a negative effect on the patient's quality of life and limited therapeutic options. Gaining insights into innate inflammatory response-fibrogenesis homeostasis can aid in the development of new therapeutic strategies for muscle fibrosis. In this study, the crucial role of macrophages is identified in the regulation of orofacial muscle fibrogenesis after injury. Hypothesizing that orchestrating macrophage polarization and functions will be beneficial for fibrosis treatment, nanomaterials are engineered with polyethylenimine functionalization to regulate the macrophage phenotype by capturing negatively charged cell-free nucleic acids (cfNAs). This cationic nanomaterial reduces macrophage-related inflammation in vitr and demonstrates excellent efficacy in preventing orofacial muscle fibrosis in vivo. Single-cell RNA sequencing reveals that the cationic nanomaterial reduces the proportion of profibrotic Gal3<sup>+</sup> macrophages through the cfNA-mediated TLR7/9-NF-κB signaling pathway, resulting in a shift in profibrotic fibro-adipogenic progenitors (FAPs) from the matrix-producing Fabp4<sup>+</sup> subcluster to the matrix-degrading Igf1<sup>+</sup> subcluster. The study highlights a strategy to target innate inflammatory response-fibrogenesis homeostasis and suggests that cationic nanomaterials can be exploited for treating refractory fibrosis.</p> -Yasir Hassan, -Budhi Singh, -Minwoong Joe, -Byoung‐Min Son, -Tien Dat Ngo, -Younggeun Jang, -Shaili Sett, -Arup Singha, -Rabindra Biswas, -Monika Bhakar, -Kenji Watanabe, -Takashi Taniguchi, -Varun Raghunathan, -Goutam Sheet, -Zonghoon Lee, -Won Jong Yoo, -Pawan Kumar Srivastava, -Changgu Lee +Xu Cheng, +Hao Sui, +Fangman Chen, +Chenghao Li, +Meijun Du, +Shiming Zhang, +Jiali Chen, +Jinfeng Dou, +Yixuan Huang, +Xiaochun Xie, +Chuanxu Cheng, +Renjie Yang, +Chao Yang, +Bing Shi, +Dan Shao, +Kam W. Leong, +Hanyao Huang Research Article - Twist‐Controlled Ferroelectricity and Emergent Multiferroicity in WSe2 Bilayers - 10.1002/adma.202406290 + Nanomaterial‐Mediated Reprogramming of Macrophages to Inhibit Refractory Muscle Fibrosis + 10.1002/adma.202410368 Advanced Materials - 10.1002/adma.202406290 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406290 + 10.1002/adma.202410368 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410368 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406348 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202402987 + Sat, 16 Nov 2024 04:26:18 -0800 + 2024-11-16T04:26:18-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202406348 - Toward a Radically Simple Multi‐Modal Nasal Spray for Preventing Respiratory Infections - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202402987 + Understanding, Mimicking, and Mitigating Radiolytic Damage to Polymers in Liquid Phase Transmission Electron Microscopy + Advanced Materials, EarlyView. -A pathogen capture and neutralizing spray (PCANS) is reported to prevent respiratory infections through a multi‐modal approach. PCANS coats the nasal cavity, capturing large respiratory droplets and serving as a physical barrier against viruses and bacteria, while neutralizing them with over 99.99% effectiveness. In mice, PCANS shows nasal retention for ≈8 hours and offers pre‐exposure protection against lethal viral infections. +This work addresses radiolytic damage to polymers in liquid phase transmission electron microscopy (LP‐TEM), which restricts its routine use in soft matter science. It quantifies polymer degradation behaviors across all conceivable (LP‐)TEM environments, mimics beam‐induced damage using UV light and hydrogen peroxide, evaluates hydroxyl radical scavengers and proposes effective strategies for damage mitigation. @@ -2140,65 +2049,52 @@ A pathogen capture and neutralizing spray (PCANS) is reported to prevent respira Abstract -Nasal sprays for pre‐exposure prophylaxis against respiratory infections show limited protection (20–70%), largely due to their single mechanism of action—either neutralizing pathogens or blocking their entry at the nasal lining, and a failure to maximize the capture of respiratory droplets, allowing them to potentially rebound and reach deeper airways. This report introduces the Pathogen Capture and Neutralizing Spray (PCANS), which utilizes a multi‐modal approach to enhance efficacy. PCANS coats the nasal cavity, capturing large respiratory droplets from the air, and serving as a physical barrier against a broad spectrum of viruses and bacteria, while rapidly neutralizing them with over 99.99% effectiveness. The formulation consists of excipients identified from the FDA's Inactive Ingredient Database and Generally Recognized as Safe list to maximize efficacy for each step in the multi‐modal approach. PCANS demonstrates nasal retention for up to 8 hours in mice. In a severe Influenza A mouse model, a single pre‐exposure dose of PCANS leads to a >99.99% reduction in lung viral titer and ensures 100% survival, compared to 0% in the control group. PCANS suppresses pathological manifestations and offers protection for at least 4 hours. This data suggest PCANS as a promising daily‐use prophylactic against respiratory infections. +Advances in liquid phase transmission electron microscopy (LP‐TEM) have enabled the monitoring of polymer dynamics in solution at the nanoscale, but radiolytic damage during LP‐TEM imaging limits its routine use in polymer science. This study focuses on understanding, mimicking, and mitigating radiolytic damage observed in functional polymers in LP‐TEM. It is quantitatively demonstrated how polymer damage occurs across all conceivable (LP‐)TEM environments, and the key characteristics and differences between polymer degradation in water vapor and liquid water are elucidated. Importantly, it is shown that the hydroxyl radical‐rich environment in LP‐TEM can be approximated by UV light irradiation in the presence of hydrogen peroxide, allowing the use of bulk techniques to probe damage at the polymer chain level. Finally, the protective effects of commonly used hydroxyl radical scavengers are compared, revealing that the effectiveness of graphene's protection is distance‐dependent. The work provides detailed methodological guidance and establishes a baseline for polymer degradation in LP‐TEM, paving the way for future research on nanoscale tracking of shape transitions and drug encapsulation of polymer assemblies in solution. - <img src="https://onlinelibrary.wiley.com/cms/asset/207eb752-7e84-492c-a789-3ab72ec32107/adma202406348-gra-0001-m.png" - alt="Toward a Radically Simple Multi-Modal Nasal Spray for Preventing Respiratory Infections"/> -<p>A pathogen capture and neutralizing spray (PCANS) is reported to prevent respiratory infections through a multi-modal approach. PCANS coats the nasal cavity, capturing large respiratory droplets and serving as a physical barrier against viruses and bacteria, while neutralizing them with over 99.99% effectiveness. In mice, PCANS shows nasal retention for ≈8 hours and offers pre-exposure protection against lethal viral infections. + <img src="https://onlinelibrary.wiley.com/cms/asset/1c27b99e-7d14-4ea7-aa4c-04fae6ab0968/adma202402987-gra-0001-m.png" + alt="Understanding, Mimicking, and Mitigating Radiolytic Damage to Polymers in Liquid Phase Transmission Electron Microscopy"/> +<p>This work addresses radiolytic damage to polymers in liquid phase transmission electron microscopy (LP-TEM), which restricts its routine use in soft matter science. It quantifies polymer degradation behaviors across all conceivable (LP-)TEM environments, mimics beam-induced damage using UV light and hydrogen peroxide, evaluates hydroxyl radical scavengers and proposes effective strategies for damage mitigation. </p> <br/> <h2>Abstract</h2> -<p>Nasal sprays for pre-exposure prophylaxis against respiratory infections show limited protection (20–70%), largely due to their single mechanism of action—either neutralizing pathogens or blocking their entry at the nasal lining, and a failure to maximize the capture of respiratory droplets, allowing them to potentially rebound and reach deeper airways. This report introduces the Pathogen Capture and Neutralizing Spray (PCANS), which utilizes a multi-modal approach to enhance efficacy. PCANS coats the nasal cavity, capturing large respiratory droplets from the air, and serving as a physical barrier against a broad spectrum of viruses and bacteria, while rapidly neutralizing them with over 99.99% effectiveness. The formulation consists of excipients identified from the FDA's Inactive Ingredient Database and Generally Recognized as Safe list to maximize efficacy for each step in the multi-modal approach. PCANS demonstrates nasal retention for up to 8 hours in mice. In a severe Influenza A mouse model, a single pre-exposure dose of PCANS leads to a &gt;99.99% reduction in lung viral titer and ensures 100% survival, compared to 0% in the control group. PCANS suppresses pathological manifestations and offers protection for at least 4 hours. This data suggest PCANS as a promising daily-use prophylactic against respiratory infections.</p> +<p>Advances in liquid phase transmission electron microscopy (LP-TEM) have enabled the monitoring of polymer dynamics in solution at the nanoscale, but radiolytic damage during LP-TEM imaging limits its routine use in polymer science. This study focuses on understanding, mimicking, and mitigating radiolytic damage observed in functional polymers in LP-TEM. It is quantitatively demonstrated how polymer damage occurs across all conceivable (LP-)TEM environments, and the key characteristics and differences between polymer degradation in water vapor and liquid water are elucidated. Importantly, it is shown that the hydroxyl radical-rich environment in LP-TEM can be approximated by UV light irradiation in the presence of hydrogen peroxide, allowing the use of bulk techniques to probe damage at the polymer chain level. Finally, the protective effects of commonly used hydroxyl radical scavengers are compared, revealing that the effectiveness of graphene's protection is distance-dependent. The work provides detailed methodological guidance and establishes a baseline for polymer degradation in LP-TEM, paving the way for future research on nanoscale tracking of shape transitions and drug encapsulation of polymer assemblies in solution.</p> -John Joseph, -Helna Mary Baby, -Joselyn Rojas Quintero, -Devin Kenney, -Yohannes A Mebratu, -Eshant Bhatia, -Purna Shah, -Kabir Swain, -Dongtak Lee, -Shahdeep Kaur, -Xiang‐Ling Li, -John Mwangi, -Olivia Snapper, -Remya Nair, -Eli Agus, -Sruthi Ranganathan, -Julian Kage, -Jingjing Gao, -James N Luo, -Anthony Yu, -Dongsung Park, -Florian Douam, -Yohannes Tesfaigzi, -Jeffrey M Karp, -Nitin Joshi +Hanglong Wu, +Hongyu Sun, +Roy A. J. F. Oerlemans, +Siyu Li, +Jingxin Shao, +Jianhong Wang, +Rick R. M. Joosten, +Xianwen Lou, +Yingtong Luo, +Hongkui Zheng, +Loai K. E. A. Abdelmohsen, +H. Hugo Pérez Garza, +Jan C. M. van Hest, +Heiner Friedrich Research Article - Toward a Radically Simple Multi‐Modal Nasal Spray for Preventing Respiratory Infections - 10.1002/adma.202406348 + Understanding, Mimicking, and Mitigating Radiolytic Damage to Polymers in Liquid Phase Transmission Electron Microscopy + 10.1002/adma.202402987 Advanced Materials - 10.1002/adma.202406348 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406348 + 10.1002/adma.202402987 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202402987 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406559 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202415100 + Sat, 16 Nov 2024 04:04:43 -0800 + 2024-11-16T04:04:43-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202406559 - β‐Ga2O3 Nanoribbon with Ultra‐High Solar‐Blind Ultraviolet Polarization Ratio - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202415100 + Stable Surface Contact with Tailored Alkylamine Pyridine Derivatives for High‐Performance Inverted Perovskite Solar Cells + Advanced Materials, EarlyView. -Due to the anisotropy of the ultra‐wide bandgap semiconductor β‐Ga2O3, it can be prepared as a solar‐blind UV detector and is intrinsically sensitive to polarized light without the need of polarizers. This β‐Ga2O3‐based detector has an ultra‐high polarization ratio and is commercially viable. This suggests a new strategy for solar‐blind ultraviolet polarization detection and also provides promising solar‐blind optical communication. +In this study, the relationship between the configuration of the studied amino pyridine derivatives and their passivation effects has been meticulously investigated to enhance the electrical properties of perovskite surfaces, which enable the inverted FA1‐xCsxPbI3 PSC to yield an encouraging efficiency of 25.65% (certified 25.45%, certified steady‐state efficiency 25.06%) with the tailored 3‐(2‐aminoethyl)pyridine (3‐PyEA) surface passivator. @@ -2208,49 +2104,56 @@ Due to the anisotropy of the ultra‐wide bandgap semiconductor β‐ Abstract -Solar‐blind ultraviolet (UV) detection plays a critical role in imaging and communication due to its low‐noise background, high signal‐to‐noise ratio, and strong anti‐interference capabilities. Detecting the polarization state of UV light can enhance image information and expand the communication dimension. Although polarization detection is explored in visible and infrared light, and applied in fields such as astrophysics and submarine seismic wave detection, solar‐blind UV polarization detection remains largely unreported. This is primarily due to the challenge of creating UV polarizers with high transmittance, high extinction ratio, and strong resistance to UV radiation. In this study, it is discovered that the space symmetry breaking of the β‐Ga2O3’s b–c plane results in a significant optical absorption dichroic ratio. Leveraging β‐Ga2O3’s high solar‐blind UV response, a lensless solar‐blind UV polarization‐sensitive photodetector, circumventing the challenges associated with solar‐blind UV polarizers is designed. This photodetector exhibits an exceptionally high intrinsic polarization ratio under 254 nm linearly polarized light, approximately two orders of magnitude higher than other reported nanomaterial‐based polarization‐sensitive photodetectors. Additionally, it demonstrates significant advantages in solar‐blind UV imaging and light communication. This work introduces a novel strategy for solar‐blind ultraviolet polarization detection and offers a promising approach for solar‐blind light communication. +Formamidinium‐cesium lead triiodide (FA1‐xCsxPbI3) perovskite holds great promise for perovskite solar cells (PSCs) with both high efficiency and stability. However, the defective perovskite surfaces induced by defects and residual tensile strain largely limit the photovoltaic performance of the corresponding devices. Here, the passivation capability of alkylamine‐modified pyridine derivatives for the surface defects of FA1‐xCsxPbI3 perovskite is systematically studied. Among the studied surface passivators, 3‐(2‐aminoethyl)pyridine (3‐PyEA) with the suitable size is demonstrated to be the most effective in reducing surface iodine impurities and defects (VI and I2) through its strong coordination with Npyridine. Additionally, the tail amino group (─NH2) from 3‐PyEA can react with FA+ cations to reduce the surface roughness of perovskite films, and the reaction products can also passivate FA vacancies (VFA), and further strengthen their binding interaction to perovskite surfaces. These merits lead to suppressed nonradiative recombination loss, the release of residual tensile stress for the perovskite films, and a favorable energy‐level alignment at the perovskite/[6,6]‐phenyl‐C61‐butyric acid methyl ester interface. Consequently, the resulting inverted FA1‐xCsxPbI3 PSCs obtain an impressive power conversion efficiency (PCE) of 25.65% (certified 25.45%, certified steady‐state efficiency 25.06%), along with retaining 96.5% of the initial PCE after 1800 h of 1‐sun operation at 55 °C in air. - <img src="https://onlinelibrary.wiley.com/cms/asset/2d7a2906-ab42-4839-9392-9af33dec5bb1/adma202406559-gra-0001-m.png" - alt="β-Ga2O3 Nanoribbon with Ultra-High Solar-Blind Ultraviolet Polarization Ratio"/> -<p>Due to the anisotropy of the ultra-wide bandgap semiconductor <i>β</i>-Ga<sub>2</sub>O<sub>3</sub>, it can be prepared as a solar-blind UV detector and is intrinsically sensitive to polarized light without the need of polarizers. This <i>β</i>-Ga<sub>2</sub>O<sub>3</sub>-based detector has an ultra-high polarization ratio and is commercially viable. This suggests a new strategy for solar-blind ultraviolet polarization detection and also provides promising solar-blind optical communication. + <img src="https://onlinelibrary.wiley.com/cms/asset/9b0c05f2-653a-4098-9795-ecec391ddd5e/adma202415100-gra-0001-m.png" + alt="Stable Surface Contact with Tailored Alkylamine Pyridine Derivatives for High-Performance Inverted Perovskite Solar Cells"/> +<p>In this study, the relationship between the configuration of the studied amino pyridine derivatives and their passivation effects has been meticulously investigated to enhance the electrical properties of perovskite surfaces, which enable the inverted FA<sub>1-x</sub>Cs<sub>x</sub>PbI<sub>3</sub> PSC to yield an encouraging efficiency of 25.65% (certified 25.45%, certified steady-state efficiency 25.06%) with the tailored 3-(2-aminoethyl)pyridine (3-PyEA) surface passivator. </p> <br/> <h2>Abstract</h2> -<p>Solar-blind ultraviolet (UV) detection plays a critical role in imaging and communication due to its low-noise background, high signal-to-noise ratio, and strong anti-interference capabilities. Detecting the polarization state of UV light can enhance image information and expand the communication dimension. Although polarization detection is explored in visible and infrared light, and applied in fields such as astrophysics and submarine seismic wave detection, solar-blind UV polarization detection remains largely unreported. This is primarily due to the challenge of creating UV polarizers with high transmittance, high extinction ratio, and strong resistance to UV radiation. In this study, it is discovered that the space symmetry breaking of the <i>β</i>-Ga<sub>2</sub>O<sub>3</sub>’s b–c plane results in a significant optical absorption dichroic ratio. Leveraging <i>β</i>-Ga<sub>2</sub>O<sub>3</sub>’s high solar-blind UV response, a lensless solar-blind UV polarization-sensitive photodetector, circumventing the challenges associated with solar-blind UV polarizers is designed. This photodetector exhibits an exceptionally high intrinsic polarization ratio under 254 nm linearly polarized light, approximately two orders of magnitude higher than other reported nanomaterial-based polarization-sensitive photodetectors. Additionally, it demonstrates significant advantages in solar-blind UV imaging and light communication. This work introduces a novel strategy for solar-blind ultraviolet polarization detection and offers a promising approach for solar-blind light communication.</p> +<p>Formamidinium-cesium lead triiodide (FA<sub>1-x</sub>Cs<sub>x</sub>PbI<sub>3</sub>) perovskite holds great promise for perovskite solar cells (PSCs) with both high efficiency and stability. However, the defective perovskite surfaces induced by defects and residual tensile strain largely limit the photovoltaic performance of the corresponding devices. Here, the passivation capability of alkylamine-modified pyridine derivatives for the surface defects of FA<sub>1-x</sub>Cs<sub>x</sub>PbI<sub>3</sub> perovskite is systematically studied. Among the studied surface passivators, 3-(2-aminoethyl)pyridine (3-PyEA) with the suitable size is demonstrated to be the most effective in reducing surface iodine impurities and defects (V<sub>I</sub> and I<sub>2</sub>) through its strong coordination with N<sub>pyridine</sub>. Additionally, the tail amino group (─NH<sub>2</sub>) from 3-PyEA can react with FA<sup>+</sup> cations to reduce the surface roughness of perovskite films, and the reaction products can also passivate FA vacancies (V<sub>FA</sub>), and further strengthen their binding interaction to perovskite surfaces. These merits lead to suppressed nonradiative recombination loss, the release of residual tensile stress for the perovskite films, and a favorable energy-level alignment at the perovskite/[6,6]-phenyl-C<sub>61</sub>-butyric acid methyl ester interface. Consequently, the resulting inverted FA<sub>1-x</sub>Cs<sub>x</sub>PbI<sub>3</sub> PSCs obtain an impressive power conversion efficiency (PCE) of 25.65% (certified 25.45%, certified steady-state efficiency 25.06%), along with retaining 96.5% of the initial PCE after 1800 h of 1-sun operation at 55 °C in air.</p> -Kai Zhao, -Juehan Yang, -Pan Wang, -Ziqi Zhou, -Haoran Long, -Kaiyao Xin, -Can Liu, -Zheng Han, -Kaihui Liu, -Zhongming Wei +Sanwan Liu, +Zhenxing Sun, +Xia Lei, +Tianyin Miao, +Qisen Zhou, +Rui Chen, +Jianan Wang, +Fumeng Ren, +Yongyan Pan, +Yong Cai, +Zhengtian Tan, +Wenguang Liu, +Xiaoxuan Liu, +Jingbai Li, +Yong Zhang, +Baomin Xu, +Zonghao Liu, +Wei Chen Research Article - β‐Ga2O3 Nanoribbon with Ultra‐High Solar‐Blind Ultraviolet Polarization Ratio - 10.1002/adma.202406559 + Stable Surface Contact with Tailored Alkylamine Pyridine Derivatives for High‐Performance Inverted Perovskite Solar Cells + 10.1002/adma.202415100 Advanced Materials - 10.1002/adma.202406559 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406559 + 10.1002/adma.202415100 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202415100 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406611 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410336 + Fri, 15 Nov 2024 01:01:05 -0800 + 2024-11-15T01:01:05-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202406611 - Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities - Advanced Materials, Volume 36, Issue 46, November 14, 2024. - The buckling of cylindrical shell structures upon depressurization is a well‐known phenomenon. If the shells are made of soft materials, the post‐buckling deformation can be fully recovered. Through a combination of experiments and simulations, the occurrence of a secondary instability in shells with a high buckling wave number is identified, which suddenly activates a coupled twisting‐folding deformation mode. This rich nonlinear behavior is harnessed to design soft robotic systems capable of executing sequential tasks with a single input signal. + + + 10.1002/adma.202410336 + Flexible Meta‐Tape with Wide Gamut, Low Lightness and Low Infrared Emissivity for Visible‐Infrared Camouflage + Advanced Materials, EarlyView. + +A tape‐like metamaterial (meta‐tape) formed by self‐assembled gold nanoparticles in an ultrathin nanoporous alumina (UNA) template. The ultrathin meta‐tapes can exhibit different colors with wide gamut and low lightness from 20 to 40, enabling low color difference under various backgrounds down to 1.2 L*a*b*. The infrared emissivity is simultaneously suppressed down to 3.8% across 3 – 14 µm. The outstanding optical performances are well preserved under various mechanical and thermal stability tests. @@ -2260,46 +2163,45 @@ Zhongming Wei Abstract -The substantial deformation exhibited by hyperelastic cylindrical shells under pressurization makes them an ideal platform for programmable inflatable structures. If negative pressure is applied, the cylindrical shell will buckle, leading to a sequence of rich deformation modes, all of which are fully recoverable due to the hyperelastic material choice. While the initial buckling event under vacuum is well understood, here, the post‐buckling regime is explored and a region in the design space is identified in which a coupled twisting‐contraction deformation mode occurs; by carefully controlling the geometry of our homogeneous shells, the proportion of contraction versus twist can be controlled. Additionally, bending as a post‐buckling deformation mode can be unlocked by varying the thickness of our shells across the circumference. Since these soft shells can fully recover from substantial deformations caused by buckling, then these instability‐driven deformations are harnessed to build soft machines capable of a programmable sequence of movements with a single actuation input. +Full‐spectral optical camouflage is of broad interest and in urgent demand because of everlasting safety pursuit in modern society. However, the widely existing dim scenarios call for not only broadband low thermal detectivity but also wide‐gamut camouflaging colors with both low lightness and minimal chromatism. Here, a tape‐like metamaterial (meta‐tape) with broad spectral manipulation bandwidth from visible to mid‐infrared is demonstrated. The ultrathin meta‐tapes can exhibit different colors with wide gamut and low lightness from 20 to 40, enabling low color difference under various backgrounds down to 1.2 L*a*b*. The infrared emissivity is simultaneously suppressed down to 3.8% across 3 – 14 µm. The outstanding optical performances are well preserved under various mechanical and thermal stability tests. The pronounced multispectral camouflage, combined with flexible and robust tape‐like nature, makes the meta‐tape a promising solution for VIS‐IR compatible camouflage in diverse scenarios. - <img src="https://onlinelibrary.wiley.com/cms/asset/33d24a1a-c9c5-4c49-ad5e-dbf3f609dd5c/adma202406611-gra-0001-m.png" - alt="Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities"/><p>The buckling of cylindrical shell structures upon depressurization is a well-known phenomenon. If the shells are made of soft materials, the post-buckling deformation can be fully recovered. Through a combination of experiments and simulations, the occurrence of a secondary instability in shells with a high buckling wave number is identified, which suddenly activates a coupled twisting-folding deformation mode. This rich nonlinear behavior is harnessed to design soft robotic systems capable of executing sequential tasks with a single input signal. + <img src="https://onlinelibrary.wiley.com/cms/asset/5c629601-6be0-48bf-a60c-c12c74cac83c/adma202410336-gra-0001-m.png" + alt="Flexible Meta-Tape with Wide Gamut, Low Lightness and Low Infrared Emissivity for Visible-Infrared Camouflage"/> +<p>A tape-like metamaterial (meta-tape) formed by self-assembled gold nanoparticles in an ultrathin nanoporous alumina (UNA) template. The ultrathin meta-tapes can exhibit different colors with wide gamut and low lightness from 20 to 40, enabling low color difference under various backgrounds down to 1.2 <i>L</i>*<i>a</i>*<i>b</i>*. The infrared emissivity is simultaneously suppressed down to 3.8% across 3 – 14 µm. The outstanding optical performances are well preserved under various mechanical and thermal stability tests. </p> <br/> <h2>Abstract</h2> -<p>The substantial deformation exhibited by hyperelastic cylindrical shells under pressurization makes them an ideal platform for programmable inflatable structures. If negative pressure is applied, the cylindrical shell will buckle, leading to a sequence of rich deformation modes, all of which are fully recoverable due to the hyperelastic material choice. While the initial buckling event under vacuum is well understood, here, the post-buckling regime is explored and a region in the design space is identified in which a coupled twisting-contraction deformation mode occurs; by carefully controlling the geometry of our homogeneous shells, the proportion of contraction versus twist can be controlled. Additionally, bending as a post-buckling deformation mode can be unlocked by varying the thickness of our shells across the circumference. Since these soft shells can fully recover from substantial deformations caused by buckling, then these instability-driven deformations are harnessed to build soft machines capable of a programmable sequence of movements with a single actuation input.</p> +<p>Full-spectral optical camouflage is of broad interest and in urgent demand because of everlasting safety pursuit in modern society. However, the widely existing dim scenarios call for not only broadband low thermal detectivity but also wide-gamut camouflaging colors with both low lightness and minimal chromatism. Here, a tape-like metamaterial (meta-tape) with broad spectral manipulation bandwidth from visible to mid-infrared is demonstrated. The ultrathin meta-tapes can exhibit different colors with wide gamut and low lightness from 20 to 40, enabling low color difference under various backgrounds down to 1.2 <i>L</i>*<i>a</i>*<i>b</i>*. The infrared emissivity is simultaneously suppressed down to 3.8% across 3 – 14 µm. The outstanding optical performances are well preserved under various mechanical and thermal stability tests. The pronounced multispectral camouflage, combined with flexible and robust tape-like nature, makes the meta-tape a promising solution for VIS-IR compatible camouflage in diverse scenarios.</p> -Yi Yang, -Helen Read, -Mohammed Sbai, -Ahmad Zareei, -Antonio Elia Forte, -David Melancon, -Katia Bertoldi +Zhenhui Lin, +Qile Wu, +Xuqi Liu, +Haiyang Ma, +Hui Liu, +Lin Zhou, +Jia Zhu Research Article - Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities - 10.1002/adma.202406611 + Flexible Meta‐Tape with Wide Gamut, Low Lightness and Low Infrared Emissivity for Visible‐Infrared Camouflage + 10.1002/adma.202410336 Advanced Materials - 10.1002/adma.202406611 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406611 + 10.1002/adma.202410336 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410336 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406706 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414379 + Fri, 15 Nov 2024 01:00:37 -0800 + 2024-11-15T01:00:37-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202406706 - Ions‐induced Assembly of Perovskite Nanocomposites for Highly Efficient Light‐Emitting Diodes with EQE Exceeding 30% - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202414379 + Eco‐Friendly High‐Performance Symmetric All‐COF/Graphene Aqueous Zinc‐Ion Batteries + Advanced Materials, EarlyView. -This paper presents an ions‐induced crystallization method to synthesize perovskite dual‐phase nanocomposites of CsPbBr3 and Cs4PbBr6. This approach enlarges grain sizes, reduces trap density, and improves both light extraction efficiency and electrical characteristics. Consequently, green perovskite light‐emitting diodes with a maximum external quantum efficiencie exceeding 30% and a narrow full width at half‐maximum of 18 nm are achieved. +A covalent organic framework (COF) integrating dual redox active sites is designed as an electrode material. The introduction of strong electron‐withdrawing CO ensures extended electron delocalization and synergistically enhances the proton storage with graphene loading strategy. Additionally, a concept of symmetric all‐COF/graphene aqueous zinc‐ion battery with high application value is realized based on the well‐designed composite electrode. @@ -2309,55 +2211,49 @@ This paper presents an ions‐induced crystallization method to synthesize p Abstract -Metal halide perovskites, a cost‐effective class of semiconductos, hold great promise for display technologies that demand high‐efficiency, color‐pure light‐emitting diodes (LEDs). Early research on three‐dimensional (3D) perovskites showed low radiative efficiencies due to modest exciton binding energies. To inprove luminescence, reducing dimensionality or grain size has been a common approach. However, dividing the perovskite lattice into smaller units may hinder carrier transport, compromising electrical performance. Moreover, the increased surface area introduce additional surface trap states, leading to greater non‐radiative recombination. Here, an ions‐induced growth method is employed to assembe lattice‐anchored perovskite nanocomposites for efficient LEDs with high color purity. This approach enables the nanocomposite thin films, composed of 3D CsPbBr3 and its variant of zero‐dimensional (0D) Cs4PbBr6, to feature significant low trap‐assisted nonradiative recombination, enhanced light out‐coupling with a corrugated surface, and well‐balanced charge carrier transport. Based on the resultant 3D/0D perovskite nanocomposites, the perovskite LEDs (PeLEDs) achieving an remarkable external quantum efficiency of 31.0% at the emission peak of 521 nm with a narrow full width at half‐maximum of only 18 nm. This sets a new benchmark for color purity in high performance PeLED research, highlighting the significant advantage of this approach. +Developing high‐performance aqueous symmetric all‐organic batteries (SAOBs) by replacing metal‐based batteries or batteries with organic electrolytes is highly attractive to achieve a greener rechargeable world. However, such a new energy storage system still exhibits unsatisfactory rate capability and cycling stability due to the limitations in electrode materials screening. Here, a novel covalent organic framework (COF) containing abundant CN and CO for the electrode material is designed, which is combined with graphene and assembled into all‐COF/graphene batteries for the first time. Moreover, the co‐storage of Zn2+ and H+ in COF can be achieved in a mild aqueous electrolyte. Impressively, benefiting from the extended porous structure of COF, plentiful active reaction sites, more extensive electron delocalization from CO modification at molecular level, as well as enhanced fast H+ storage capacity of graphene and CO in COF, this kind of SAOBs show excellent cycle life and high rate performance (over 15000 cycles with a capacity of 80 mAh g−1 at a high current density of 5 A g−1 in pouch cell). This work will open a new window for the design of high‐performance aqueous organic batteries, further moving toward a more eco‐friendly electrochemical world. - <img src="https://onlinelibrary.wiley.com/cms/asset/7d1faf85-53e4-45c7-9036-a853cd291528/adma202406706-gra-0001-m.png" - alt="Ions-induced Assembly of Perovskite Nanocomposites for Highly Efficient Light-Emitting Diodes with EQE Exceeding 30%"/> -<p>This paper presents an ions-induced crystallization method to synthesize perovskite dual-phase nanocomposites of CsPbBr<sub>3</sub> and Cs<sub>4</sub>PbBr<sub>6</sub>. This approach enlarges grain sizes, reduces trap density, and improves both light extraction efficiency and electrical characteristics. Consequently, green perovskite light-emitting diodes with a maximum external quantum efficiencie exceeding 30% and a narrow full width at half-maximum of 18 nm are achieved. + <img src="https://onlinelibrary.wiley.com/cms/asset/8bbacaac-d7a5-4b32-b5bd-95adb5cee891/adma202414379-gra-0001-m.png" + alt="Eco-Friendly High-Performance Symmetric All-COF/Graphene Aqueous Zinc-Ion Batteries"/> +<p>A covalent organic framework (COF) integrating dual redox active sites is designed as an electrode material. The introduction of strong electron-withdrawing CO ensures extended electron delocalization and synergistically enhances the proton storage with graphene loading strategy. Additionally, a concept of symmetric all-COF/graphene aqueous zinc-ion battery with high application value is realized based on the well-designed composite electrode. </p> <br/> <h2>Abstract</h2> -<p>Metal halide perovskites, a cost-effective class of semiconductos, hold great promise for display technologies that demand high-efficiency, color-pure light-emitting diodes (LEDs). Early research on three-dimensional (3D) perovskites showed low radiative efficiencies due to modest exciton binding energies. To inprove luminescence, reducing dimensionality or grain size has been a common approach. However, dividing the perovskite lattice into smaller units may hinder carrier transport, compromising electrical performance. Moreover, the increased surface area introduce additional surface trap states, leading to greater non-radiative recombination. Here, an ions-induced growth method is employed to assembe lattice-anchored perovskite nanocomposites for efficient LEDs with high color purity. This approach enables the nanocomposite thin films, composed of 3D CsPbBr<sub>3</sub> and its variant of zero-dimensional (0D) Cs<sub>4</sub>PbBr<sub>6</sub>, to feature significant low trap-assisted nonradiative recombination, enhanced light out-coupling with a corrugated surface, and well-balanced charge carrier transport. Based on the resultant 3D/0D perovskite nanocomposites, the perovskite LEDs (PeLEDs) achieving an remarkable external quantum efficiency of 31.0% at the emission peak of 521 nm with a narrow full width at half-maximum of only 18 nm. This sets a new benchmark for color purity in high performance PeLED research, highlighting the significant advantage of this approach.</p> +<p>Developing high-performance aqueous symmetric all-organic batteries (SAOBs) by replacing metal-based batteries or batteries with organic electrolytes is highly attractive to achieve a greener rechargeable world. However, such a new energy storage system still exhibits unsatisfactory rate capability and cycling stability due to the limitations in electrode materials screening. Here, a novel covalent organic framework (COF) containing abundant CN and CO for the electrode material is designed, which is combined with graphene and assembled into all-COF/graphene batteries for the first time. Moreover, the co-storage of Zn<sup>2+</sup> and H<sup>+</sup> in COF can be achieved in a mild aqueous electrolyte. Impressively, benefiting from the extended porous structure of COF, plentiful active reaction sites, more extensive electron delocalization from CO modification at molecular level, as well as enhanced fast H<sup>+</sup> storage capacity of graphene and CO in COF, this kind of SAOBs show excellent cycle life and high rate performance (over 15000 cycles with a capacity of 80 mAh g<sup>−1</sup> at a high current density of 5 A g<sup>−1</sup> in pouch cell). This work will open a new window for the design of high-performance aqueous organic batteries, further moving toward a more eco-friendly electrochemical world.</p> -Zhaohui Xing, -Guangrong Jin, -Qing Du, -Peiyuan Pang, -Tanghao Liu, -Yang Shen, -Dengliang Zhang, -Bufan Yu, -Yue Liang, -Dezhi Yang, -Jianxin Tang, -Lei Wang, -Guichuan Xing, -Jiangshan Chen, -Dongge Ma +Pengshu Yi, +Zhiheng Li, +Longli Ma, +Bingjian Feng, +Zhu Liu, +Yongshuai Liu, +Wenyi Lu, +Shaochong Cao, +Huayi Fang, +Mingxin Ye, +Jianfeng Shen Research Article - Ions‐induced Assembly of Perovskite Nanocomposites for Highly Efficient Light‐Emitting Diodes with EQE Exceeding 30% - 10.1002/adma.202406706 + Eco‐Friendly High‐Performance Symmetric All‐COF/Graphene Aqueous Zinc‐Ion Batteries + 10.1002/adma.202414379 Advanced Materials - 10.1002/adma.202406706 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406706 + 10.1002/adma.202414379 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414379 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406772 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413967 + Fri, 15 Nov 2024 00:59:36 -0800 + 2024-11-15T12:59:36-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202406772 - Giant Hall Switching by Surface‐State‐Mediated Spin‐Orbit Torque in a Hard Ferromagnetic Topological Insulator - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202413967 + Inducing Efficient and Multiwavelength Circularly Polarized Emission From Perovskite Nanocrystals Using Chiral Metasurfaces + Advanced Materials, EarlyView. -Highly efficient current‐driven spin‐orbit torque (SOT) switching is observed in a hard ferromagnetic topological insulator (TI), V‐doped (Bi,Sb)2Te3 (VBST), with a record large switched anomalous Hall resistance of 9.2 kΩ by current. The SOT efficiency is significantly enhanced by Fermi level tuning, as VBST exhibits a transition from edge‐state‐mediated to surface‐state‐mediated transport. +Circularly polarized emission of high dissymmetry (glum ≈ 0.56) is achieved from perovskite halide nanocrystals by depositing them on arrays of prefabricated resonant 2D gammadions. By using different materials, a hybrid photonic structure is managed to design with TiO2 and Au materials, in order to obtain resonances in the whole visible spectrum demonstrating the generation of multi‐wavelength circularly polarised light. @@ -2367,61 +2263,44 @@ Highly efficient current‐driven spin‐orbit torque (SOT) switching is Abstract -Topological insulators (TI) and magnetic topological insulators (MTI) can apply highly efficient spin‐orbit torque (SOT) and manipulate the magnetization with their unique topological surface states (TSS) with ultrahigh efficiency. Here, efficient SOT switching of a hard MTI, V‐doped (Bi,Sb)2Te3 (VBST), with a large coercive field that can prevent the influence of an external magnetic field, is demonstrated. A giant switched anomalous Hall resistance of 9.2 kΩ is realized, among the largest of all SOT systems, which makes the Hall channel a good readout and eliminates the need to fabricate complicated magnetic tunnel junction (MTJ) structures. The SOT switching current density can be reduced to 2.8 × 105 A cm−2, indicating its high efficiency. Moreover, as the Fermi level is moved away from the Dirac point by both gate and composition tuning, VBST exhibits a transition from edge‐state‐mediated to surface‐state‐mediated transport, thus enhancing the SOT effective field to (1.56 ± 0.12) × 10−6 T A−1 cm2 and the interfacial charge‐to‐spin conversion efficiency to 3.9 ± 0.3 nm−1. The findings establish VBST as an extraordinary candidate for energy‐efficient magnetic memory devices. +Chiral nano‐emitters have recently received great research attention due to their technological applications and the need for a fundamental scientific understanding of the structure‐property nexus of these nanoscale materials. Lead halide perovskite nanocrystals (LHP NCs) with many interesting optical properties have anticipated great promise for generating chiral emission. However, inducing high anisotropy chiral emission from achiral perovskite NCs remains challenging. Although chiral ligands have been used to induce chirality, their anisotropy factors (glum) are low [10−3 to 10−2]. Herein, the generation of high anisotropy circularly polarized photoluminescence (CPL) from LHP NCs is demonstrated using chiral metasurfaces by depositing nanocrystals on top of prefabricated resonant photonic structures (2D gammadion arrays). This scalable approach results in CPL with glum to a record high of 0.56 for perovskite NCs. Furthermore, the differences between high‐index dielectric chiral metasurfaces and metallic ones are explored for inducing chiral emission. More importantly, the generation of simultaneous multi‐wavelength circularly polarized light is demonstrated by combining dielectric and metallic chiral metasurfaces. - <img src="https://onlinelibrary.wiley.com/cms/asset/b5536829-d79c-4a54-99c9-08ccfb19309c/adma202406772-gra-0001-m.png" - alt="Giant Hall Switching by Surface-State-Mediated Spin-Orbit Torque in a Hard Ferromagnetic Topological Insulator"/> -<p>Highly efficient current-driven spin-orbit torque (SOT) switching is observed in a hard ferromagnetic topological insulator (TI), V-doped (Bi,Sb)<sub>2</sub>Te<sub>3</sub> (VBST), with a record large switched anomalous Hall resistance of 9.2 kΩ by current. The SOT efficiency is significantly enhanced by Fermi level tuning, as VBST exhibits a transition from edge-state-mediated to surface-state-mediated transport. + <img src="https://onlinelibrary.wiley.com/cms/asset/6e95ed78-9632-4be8-b1ce-c0ab0d6de383/adma202413967-gra-0001-m.png" + alt="Inducing Efficient and Multiwavelength Circularly Polarized Emission From Perovskite Nanocrystals Using Chiral Metasurfaces"/> +<p>Circularly polarized emission of high dissymmetry (g<sub>lum</sub> ≈ 0.56) is achieved from perovskite halide nanocrystals by depositing them on arrays of prefabricated resonant 2D gammadions. By using different materials, a hybrid photonic structure is managed to design with TiO<sub>2</sub> and Au materials, in order to obtain resonances in the whole visible spectrum demonstrating the generation of multi-wavelength circularly polarised light. </p> <br/> <h2>Abstract</h2> -<p>Topological insulators (TI) and magnetic topological insulators (MTI) can apply highly efficient spin-orbit torque (SOT) and manipulate the magnetization with their unique topological surface states (TSS) with ultrahigh efficiency. Here, efficient SOT switching of a hard MTI, V-doped (Bi,Sb)<sub>2</sub>Te<sub>3</sub> (VBST), with a large coercive field that can prevent the influence of an external magnetic field, is demonstrated. A giant switched anomalous Hall resistance of 9.2 kΩ is realized, among the largest of all SOT systems, which makes the Hall channel a good readout and eliminates the need to fabricate complicated magnetic tunnel junction (MTJ) structures. The SOT switching current density can be reduced to 2.8 × 10<sup>5 </sup>A<sup> </sup>cm<sup>−2</sup>, indicating its high efficiency. Moreover, as the Fermi level is moved away from the Dirac point by both gate and composition tuning, VBST exhibits a transition from edge-state-mediated to surface-state-mediated transport, thus enhancing the SOT effective field to (1.56 ± 0.12) × 10<sup>−6 </sup>T<sup> </sup>A<sup>−1 </sup>cm<sup>2</sup> and the interfacial charge-to-spin conversion efficiency to 3.9 ± 0.3 nm<sup>−1</sup>. The findings establish VBST as an extraordinary candidate for energy-efficient magnetic memory devices.</p> +<p>Chiral nano-emitters have recently received great research attention due to their technological applications and the need for a fundamental scientific understanding of the structure-property nexus of these nanoscale materials. Lead halide perovskite nanocrystals (LHP NCs) with many interesting optical properties have anticipated great promise for generating chiral emission. However, inducing high anisotropy chiral emission from achiral perovskite NCs remains challenging. Although chiral ligands have been used to induce chirality, their anisotropy factors (g<sub>lum</sub>) are low [10<sup>−3</sup> to 10<sup>−2</sup>]. Herein, the generation of high anisotropy circularly polarized photoluminescence (CPL) from LHP NCs is demonstrated using chiral metasurfaces by depositing nanocrystals on top of prefabricated resonant photonic structures (2D gammadion arrays). This scalable approach results in CPL with g<sub>lum</sub> to a record high of 0.56 for perovskite NCs. Furthermore, the differences between high-index dielectric chiral metasurfaces and metallic ones are explored for inducing chiral emission. More importantly, the generation of simultaneous multi-wavelength circularly polarized light is demonstrated by combining dielectric and metallic chiral metasurfaces.</p> -Lixuan Tai, -Haoran He, -Su Kong Chong, -Huairuo Zhang, -Hanshen Huang, -Gang Qiu, -Yuxing Ren, -Yaochen Li, -Hung‐Yu Yang, -Ting‐Hsun Yang, -Xiang Dong, -Bingqian Dai, -Tao Qu, -Qingyuan Shu, -Quanjun Pan, -Peng Zhang, -Fei Xue, -Jie Li, -Albert V. Davydov, -Kang L. Wang +Nadesh Fiuza‐Maneiro, +Jose Mendoza‐Carreño, +Sergio Gómez‐Graña, +Maria Isabel Alonso, +Lakshminarayana Polavarapu, +Agustín Mihi Research Article - Giant Hall Switching by Surface‐State‐Mediated Spin‐Orbit Torque in a Hard Ferromagnetic Topological Insulator - 10.1002/adma.202406772 + Inducing Efficient and Multiwavelength Circularly Polarized Emission From Perovskite Nanocrystals Using Chiral Metasurfaces + 10.1002/adma.202413967 Advanced Materials - 10.1002/adma.202406772 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406772 + 10.1002/adma.202413967 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413967 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407009 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412895 + Fri, 15 Nov 2024 00:59:20 -0800 + 2024-11-15T12:59:20-08:00 Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202407009 - Elastocaloric Heat Pump by Twist Induced Periodical Non‐Linear Stress for Low Hysteresis and High Carnot Efficiency - Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + 10.1002/adma.202412895 + Adaptive Opto‐Thermal‐Hydrodynamic Manipulation and Polymerization (AOTHMAP) for 4D Colloidal Patterning + Advanced Materials, EarlyView. -Fiber twisting induces periodic non‐linear stress, leading to high elastocaloric performance and material COP. A novel elastocaloric heat pump is designed using this technique, incorporating a three‐port valve and a pump to separate the cooling and heating media, which results in low hysteresis, high efficiency, enhanced durability, and excellent cooling. - +The research introduces a novel 4D patterning method called AOTHMAP, which utilizes adaptive opto‐thermal‐hydrodynamic manipulation for precise colloidal patterning. This technique facilitates the automatic transport, positioning, and immobilization of colloidal particles with a single laser beam. AOTHMAP improves customization and efficiency in creating dynamic microstructures and biological patterns, showcasing significant potential in intelligent manufacturing, optoelectronics, and biofabrication. @@ -2431,53 +2310,49 @@ Fiber twisting induces periodic non‐linear stress, leading to high elastoc Abstract -Elastocaloric cooling is one of the most promising solid‐state cooling approaches to address the issues of energy shortage and global warming. However, the cooling efficiency and cycle life of this technology need to be improved, and the required driving force shall be reduced. Here, a novel elastocaloric heat pump by periodic non‐linear stress is developed by employing fiber twisting and separated cooling and heating media. The non‐linear stress generated by fiber twisting yields a hierarchical, rigid‐yet‐flexible architecture and a periodic entropy spatial distribution, which result in a low mechanical hysteresis work and a high cooling efficiency (a maximum material coefficient of performance (COP) of 30.8 and a maximum Carnot efficiency of 82%). The torsional non‐linear stress inhibits crack propagation and results in a highly extended cycle life (14752 cycles, more than ten times of fiber stretching). The heat pump exhibits a maximum average temperature span of 25.6 K, a maximum specific cooling power of 1850 W Kg−1, a maximum device COP of 19.5, and a maximum device power of 5.0 W, under each optimal condition. +Precision colloidal patterning holds great promise in constructing customizable micro/nanostructures and functional frameworks, which showcases significant application values across various fields, from intelligent manufacturing to optoelectronic integration and biofabrication. Here, a direct 4D patterning method via adaptive opto‐thermal‐hydrodynamic manipulation and polymerization (AOTHMAP) with single‐particle resolution is reported. This approach utilizes a single laser beam to automatically transport, position, and immobilize colloidal particles through the adaptive utilization of light‐induced hydrodynamic force, optical force, and photothermal polymerization. The AOTHMAP enables precise 1D, 2D, and 3D patterning of colloidal particles of varying sizes and materials, facilitating the construction of customizable microstructures with complex shapes. Furthermore, by harnessing the pH‐responsive properties of hydrogel adhesives, the AOTHMAP further enables 4D patterning by dynamic alteration of patterned structures through shrinkage, restructuring, and cloaking. Notably, the AOTHMAP also enables biological patterning of functional bio‐structures such as bio‐micromotors. The AOTHMAP offers a simple and efficient strategy for colloidal patterning with high versatility and flexibility, which holds great promises for the construction of functional colloidal microstructures in intelligent manufacturing, as well as optoelectronic integration and biofabrication. - <img src="https://onlinelibrary.wiley.com/cms/asset/72418722-ab2e-4dde-adbc-04d413f37578/adma202407009-gra-0001-m.png" - alt="Elastocaloric Heat Pump by Twist Induced Periodical Non-Linear Stress for Low Hysteresis and High Carnot Efficiency"/> -<p>Fiber twisting induces periodic non-linear stress, leading to high elastocaloric performance and material COP. A novel elastocaloric heat pump is designed using this technique, incorporating a three-port valve and a pump to separate the cooling and heating media, which results in low hysteresis, high efficiency, enhanced durability, and excellent cooling. + <img src="https://onlinelibrary.wiley.com/cms/asset/83f790d6-4e88-4186-8550-ba1c581f6450/adma202412895-gra-0001-m.png" + alt="Adaptive Opto-Thermal-Hydrodynamic Manipulation and Polymerization (AOTHMAP) for 4D Colloidal Patterning"/> +<p>The research introduces a novel 4D patterning method called AOTHMAP, which utilizes adaptive opto-thermal-hydrodynamic manipulation for precise colloidal patterning. This technique facilitates the automatic transport, positioning, and immobilization of colloidal particles with a single laser beam. AOTHMAP improves customization and efficiency in creating dynamic microstructures and biological patterns, showcasing significant potential in intelligent manufacturing, optoelectronics, and biofabrication. </p> <br/> <h2>Abstract</h2> -<p>Elastocaloric cooling is one of the most promising solid-state cooling approaches to address the issues of energy shortage and global warming. However, the cooling efficiency and cycle life of this technology need to be improved, and the required driving force shall be reduced. Here, a novel elastocaloric heat pump by periodic non-linear stress is developed by employing fiber twisting and separated cooling and heating media. The non-linear stress generated by fiber twisting yields a hierarchical, rigid-yet-flexible architecture and a periodic entropy spatial distribution, which result in a low mechanical hysteresis work and a high cooling efficiency (a maximum material coefficient of performance (<i>COP</i>) of 30.8 and a maximum Carnot efficiency of 82%). The torsional non-linear stress inhibits crack propagation and results in a highly extended cycle life (14752 cycles, more than ten times of fiber stretching). The heat pump exhibits a maximum average temperature span of 25.6 K, a maximum specific cooling power of 1850 W Kg<sup>−1</sup>, a maximum device <i>COP</i> of 19.5, and a maximum device power of 5.0 W, under each optimal condition.</p> +<p>Precision colloidal patterning holds great promise in constructing customizable micro/nanostructures and functional frameworks, which showcases significant application values across various fields, from intelligent manufacturing to optoelectronic integration and biofabrication. Here, a direct 4D patterning method via adaptive opto-thermal-hydrodynamic manipulation and polymerization (AOTHMAP) with single-particle resolution is reported. This approach utilizes a single laser beam to automatically transport, position, and immobilize colloidal particles through the adaptive utilization of light-induced hydrodynamic force, optical force, and photothermal polymerization. The AOTHMAP enables precise 1D, 2D, and 3D patterning of colloidal particles of varying sizes and materials, facilitating the construction of customizable microstructures with complex shapes. Furthermore, by harnessing the pH-responsive properties of hydrogel adhesives, the AOTHMAP further enables 4D patterning by dynamic alteration of patterned structures through shrinkage, restructuring, and cloaking. Notably, the AOTHMAP also enables biological patterning of functional bio-structures such as bio-micromotors. The AOTHMAP offers a simple and efficient strategy for colloidal patterning with high versatility and flexibility, which holds great promises for the construction of functional colloidal microstructures in intelligent manufacturing, as well as optoelectronic integration and biofabrication.</p> -Yicheng Xiao, -Guangkai Mei, -Danyang Feng, -Wubin Zhao, -Wenjin Guo, -Xueqi Leng, -Dong Qian, -Weiqiang Zhao, -Jie Bai, -Zongqian Wang, -Meifang Zhu, -Xiang Zhou, -Zunfeng Liu +Yang Shi, +Lianrou Liu, +Jingping Huang, +Jianyun Xiong, +Shuhan Zhong, +Guoshuai Zhu, +Xing Li, +Ziyi He, +Ting Pan, +Hongbao Xin, +Baojun Li Research Article - Elastocaloric Heat Pump by Twist Induced Periodical Non‐Linear Stress for Low Hysteresis and High Carnot Efficiency - 10.1002/adma.202407009 + Adaptive Opto‐Thermal‐Hydrodynamic Manipulation and Polymerization (AOTHMAP) for 4D Colloidal Patterning + 10.1002/adma.202412895 Advanced Materials - 10.1002/adma.202407009 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407009 + 10.1002/adma.202412895 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412895 Research Article - 36 - 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407124 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202401648 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202407124 - A Perspective on Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals + 10.1002/adma.202401648 + Iridium Single‐Atom‐Ensembles Stabilized on Mn‐Substituted Spinel Oxide for Durable Acidic Water Electrolysis Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This perspective covers the material design strategies for the Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals. It also highlights how lab‐scale catalysis can be translated to real‐time industrial level consumption of flue gas mixture by electrochemical catalysis. +The limited stability of single‐atom‐catalyst and Ir/Ru‐based oxides in acidic oxygen evolution reaction (OER) is a long‐standing issue. Herein, an innovative strategy is presented to fabricate short‐range Ir single‐atom‐ensembles on Mn‐substituted spinel Co3O4, which effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, demonstrating excellent activity and stability for acidic OER. @@ -2487,42 +2362,49 @@ This perspective covers the material design strategies for the Electrochemical P Abstract -Electrochemical CO2 reduction reaction (eCO2RR) has been explored extensively for mitigation of noxious CO2 gas generating C1 and C2+ hydrocarbons and oxygenates as value‐added fuels and chemicals with remarkable selectivity. The source of CO2 being a pure CO2 feed, it does not fully satisfy the real‐time digestion of industrial exhausts. Besides the detrimental effect of noxious gas mixture leading to global warming, there is a huge capital investment in purifying the flue gas mixtures from industries. The presence of other impurity gases affects the eCO2RR mechanism and its activity and selectivity toward C2+ products dwindle drastically. Impurities like NOx, SOx, O2, N2, and halide ions present in flue gas mixture reduce the conversion and selectivity of eCO2RR significantly. Instead of wiping out these impurities via separation processes, new strategies from material chemistry and electrochemistry can open new avenues for turning foes to friends! In this perspective, the co‐electroreduction will vividly discussed and supporting role of different heteroatom‐containing impurity gases with CO2, generating highly stable C─N, C─S, C─X bonds, and highlight the existing limitations and providing probable solutions for attaining further success in this field and translating this to industrial exhaust streams. +Exploring single‐atom‐catalysts for the acidic oxygen evolution reaction (OER) is of paramount importance for cost‐effective hydrogen production via acidic water electrolyzers. However, the limited durability of most single‐atom‐catalysts and Ir/Ru‐based oxides under harsh acidic OER conditions, primarily attributed to excessive lattice oxygen participation resulting in metal‐leaching and structural collapse, hinders their practical application. Herein, an innovative strategy is developed to fabricate short‐range Ir single‐atom‐ensembles (IrSAE) stabilized on the surface of Mn‐substituted spinel Co3O4 (IrSAE‐CMO), which exhibits excellent mass activity and significantly improved durability (degradation‐rate: ≈2 mV h−1), outperforming benchmark IrO2 (≈44 mV h−1) and conventional Irsingle‐atoms on pristine‐Co3O4 for acidic OER. First‐principle calculations reveal that Mn‐substitution in the octahedral sites of Co3O4 substantially reduces the migration energy barrier for Irsingle‐atoms on the CMO surface compared to pristine‐Co3O4, facilitating the migration of Irsingle‐atoms to form strongly correlated IrSAE during pyrolysis. Extensive ex situ characterization, operando X‐ray absorption and Raman spectroscopies, pH‐dependence activity tests, and theoretical calculations indicate that the rigid IrSAE with appropriate Ir–Ir distance stabilized on the CMO surface effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, thereby mitigating Ir‐dissolution and structural collapse, boosting the stability in an acidic environment. - <img src="https://onlinelibrary.wiley.com/cms/asset/ba8f8b23-69f5-4966-b14c-2806f67bcbd9/adma202407124-gra-0001-m.png" - alt="A Perspective on Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals"/> -<p>This perspective covers the material design strategies for the Electrochemical Point Source Utilization of CO<sub>2</sub> and Other Flue Gas Components to Value Added Chemicals. It also highlights how lab-scale catalysis can be translated to real-time industrial level consumption of flue gas mixture by electrochemical catalysis. + <img src="https://onlinelibrary.wiley.com/cms/asset/c3929564-30a6-4a79-815f-9696f9d976f0/adma202401648-gra-0001-m.png" + alt="Iridium Single-Atom-Ensembles Stabilized on Mn-Substituted Spinel Oxide for Durable Acidic Water Electrolysis"/> +<p>The limited stability of single-atom-catalyst and Ir/Ru-based oxides in acidic oxygen evolution reaction (OER) is a long-standing issue. Herein, an innovative strategy is presented to fabricate short-range Ir single-atom-ensembles on Mn-substituted spinel Co<sub>3</sub>O<sub>4</sub>, which effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, demonstrating excellent activity and stability for acidic OER. </p> <br/> <h2>Abstract</h2> -<p>Electrochemical CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR) has been explored extensively for mitigation of noxious CO<sub>2</sub> gas generating C<sub>1</sub> and C<sub>2+</sub> hydrocarbons and oxygenates as value-added fuels and chemicals with remarkable selectivity. The source of CO<sub>2</sub> being a pure CO<sub>2</sub> feed, it does not fully satisfy the real-time digestion of industrial exhausts. Besides the detrimental effect of noxious gas mixture leading to global warming, there is a huge capital investment in purifying the flue gas mixtures from industries. The presence of other impurity gases affects the eCO<sub>2</sub>RR mechanism and its activity and selectivity toward C<sub>2+</sub> products dwindle drastically. Impurities like NO<sub>x</sub>, SO<sub>x</sub>, O<sub>2</sub>, N<sub>2</sub>, and halide ions present in flue gas mixture reduce the conversion and selectivity of eCO<sub>2</sub>RR significantly. Instead of wiping out these impurities via separation processes, new strategies from material chemistry and electrochemistry can open new avenues for turning foes to friends! In this perspective, the co-electroreduction will vividly discussed and supporting role of different heteroatom-containing impurity gases with CO<sub>2</sub>, generating highly stable C─N, C─S, C─X bonds, and highlight the existing limitations and providing probable solutions for attaining further success in this field and translating this to industrial exhaust streams.</p> +<p>Exploring single-atom-catalysts for the acidic oxygen evolution reaction (OER) is of paramount importance for cost-effective hydrogen production via acidic water electrolyzers. However, the limited durability of most single-atom-catalysts and Ir/Ru-based oxides under harsh acidic OER conditions, primarily attributed to excessive lattice oxygen participation resulting in metal-leaching and structural collapse, hinders their practical application. Herein, an innovative strategy is developed to fabricate short-range Ir single-atom-ensembles (Ir<sub>SAE</sub>) stabilized on the surface of Mn-substituted spinel Co<sub>3</sub>O<sub>4</sub> (Ir<sub>SAE</sub>-CMO), which exhibits excellent mass activity and significantly improved durability (degradation-rate: ≈2 mV h<sup>−1</sup>), outperforming benchmark IrO<sub>2</sub> (≈44 mV h<sup>−1</sup>) and conventional Ir<sub>single-atoms</sub> on pristine-Co<sub>3</sub>O<sub>4</sub> for acidic OER. First-principle calculations reveal that Mn-substitution in the octahedral sites of Co<sub>3</sub>O<sub>4</sub> substantially reduces the migration energy barrier for Ir<sub>single-atoms</sub> on the CMO surface compared to pristine-Co<sub>3</sub>O<sub>4</sub>, facilitating the migration of Ir<sub>single-atoms</sub> to form strongly correlated Ir<sub>SAE</sub> during pyrolysis. Extensive ex situ characterization, operando X-ray absorption and Raman spectroscopies, pH-dependence activity tests, and theoretical calculations indicate that the rigid Ir<sub>SAE</sub> with appropriate Ir–Ir distance stabilized on the CMO surface effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, thereby mitigating Ir-dissolution and structural collapse, boosting the stability in an acidic environment.</p> -Soumi Mondal, -Sebastian C. Peter +Ashwani Kumar, +Marcos Gil‐Sepulcre, +Jinsun Lee, +Viet Q. Bui, +Yue Wang, +Olaf Rüdiger, +Min Gyu Kim, +Serena DeBeer, +Harun Tüysüz - Perspective - A Perspective on Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals - 10.1002/adma.202407124 + Research Article + Iridium Single‐Atom‐Ensembles Stabilized on Mn‐Substituted Spinel Oxide for Durable Acidic Water Electrolysis + 10.1002/adma.202401648 Advanced Materials - 10.1002/adma.202407124 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407124 - Perspective + 10.1002/adma.202401648 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202401648 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407305 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403066 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202407305 - Conjugated Polymer‐Based Photo‐Crosslinker for Efficient Photo‐Patterning of Polymer Semiconductors + 10.1002/adma.202403066 + Robust Electric‐Field Control of Colossal Exchange Bias in CrI3 Homotrilayer Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A new conjugated polymer‐based photo‐crosslinker, PN3, with phenyl‐substituted azide groups in the side chains, is developed for efficient photo‐patterning of polymer semiconductors with superior performance, featuring a significantly low UV light exposure dose, high sensitivity (S), and high contrast (γ). +A robust electric‐field control of exchange bias (EB) effect and magnetism transition is realized in a pure CrI3 homotrilayer. The doping from the Y‐doped HfO2 substrate alters the interlayer coupling of intrinsic CrI3 trilayer and further causes the EB effect. The gate voltage reverses the magnetization direction layer‐by‐layer in homotrilayer CrI3, leading to a colossal EB modulation of 0.48 T. @@ -2532,51 +2414,51 @@ A new conjugated polymer‐based photo‐crosslinker, PN3, with phenyl&# Abstract -Photo‐patterning of polymer semiconductors using photo‐crosslinkers has shown potential for organic circuit fabrication via solution processing techniques. However, the performance of patterning, including resolution (R), UV light exposure dose, sensitivity (S), and contrast (γ), remains unsatisfactory. In this study, a novel conjugated polymer based photo‐crosslinker (PN3, Figure 1a) is reported for the first time, which entails phenyl‐substituted azide groups in its side chains. Due to the potential π–π interactions between the conjugated backbone of PN3 and those of polymer semiconductors, PN3 exhibits superior miscibility with polymer semiconductors compared to the commonly used small molecule photo‐crosslinker 4Bx (Figure 1a). Consequently, photo‐patterning of polymer semiconductors with PN3 demonstrates improved performance with much lower UV light exposure dose, higher S and higher γ compared to 4Bx. By utilizing electron beam lithography, patterned arrays of polymer semiconductors with resolutions down to 500 nm and clearer edges are successfully fabricated using PN3. Furthermore, patterned arrays of PDPP4T, the p‐type semiconductor (Figure 1b), after being doped, can function as source‐drain electrodes for fabricating field‐effect transistors (FETs) with comparable charge mobility and significantly lower sub‐threshold swing value compared to those with gold electrodes. +Controlling exchange bias (EB) by electric fields is crucial for next‐generation magnetic random access memories and spintronics with ultralow energy consumption and ultrahigh speed. Multiferroic heterostructures have been traditionally used to electrically control EB and interfacial ferromagnetism through weak/indirect coupling between ferromagnetic and ferroelectric films. However, three major bottlenecks (lattice mismatch, interface defects, and weak/indirect coupling in multiferroic heterostructures) remain, resulting in only a few tens of milli‐tesla EB field. Here, this study reports a robust electric‐field control recipe to dynamically tailor the EB effect in a pure CrI3 homotrilayer on a ferroelectric Y‐doped HfO2 (HYO) substrate, and demonstrate a colossal and tunable EB field (HE) from −0.15 to +0.33 T, giving rise to an EB modulation of 0.48 T. The charge doping due to ferroelectric HYO film divides a homo‐configuration of CrI3 homotrilayer into one antiferromagnetic (AFM) bilayer CrI3 and one ferromagnetic (FM) monolayer CrI3, favoring direct exchange coupling. The synergies of charge doping and electric field induce a transition of magnetic orders from AFM to FM phase in bilayer CrI3, which is also supported by first‐principles calculations, leading to the robust electric control of colossal EB effect. The results therefore open numerous opportunities for exploring 2D spintronics, memories, and braininspired in‐memory computing. - <img src="https://onlinelibrary.wiley.com/cms/asset/bc33a272-2dbf-4582-88e3-0a2bbd947c2e/adma202407305-gra-0001-m.png" - alt="Conjugated Polymer-Based Photo-Crosslinker for Efficient Photo-Patterning of Polymer Semiconductors"/> -<p>A new conjugated polymer-based photo-crosslinker, <b>PN3</b>, with phenyl-substituted azide groups in the side chains, is developed for efficient photo-patterning of polymer semiconductors with superior performance, featuring a significantly low UV light exposure dose, high sensitivity (<i>S</i>), and high contrast (<i>γ</i>). + <img src="https://onlinelibrary.wiley.com/cms/asset/1d5cb345-314e-4c31-8f54-61f954041226/adma202403066-gra-0001-m.png" + alt="Robust Electric-Field Control of Colossal Exchange Bias in CrI3 Homotrilayer"/> +<p>A robust electric-field control of exchange bias (EB) effect and magnetism transition is realized in a pure CrI<sub>3</sub> homotrilayer. The doping from the Y-doped HfO<sub>2</sub> substrate alters the interlayer coupling of intrinsic CrI<sub>3</sub> trilayer and further causes the EB effect. The gate voltage reverses the magnetization direction layer-by-layer in homotrilayer CrI<sub>3</sub>, leading to a colossal EB modulation of 0.48 T. </p> <br/> <h2>Abstract</h2> -<p>Photo-patterning of polymer semiconductors using photo-crosslinkers has shown potential for organic circuit fabrication via solution processing techniques. However, the performance of patterning, including resolution (<i>R</i>), UV light exposure dose, sensitivity (<i>S</i>), and contrast (<i>γ</i>), remains unsatisfactory. In this study, a novel conjugated polymer based photo-crosslinker (<b>PN3</b>, Figure 1a) is reported for the first time, which entails phenyl-substituted azide groups in its side chains. Due to the potential <i>π</i>–<i>π</i> interactions between the conjugated backbone of <b>PN3</b> and those of polymer semiconductors, <b>PN3</b> exhibits superior miscibility with polymer semiconductors compared to the commonly used small molecule photo-crosslinker <b>4Bx</b> (Figure 1a). Consequently, photo-patterning of polymer semiconductors with <b>PN3</b> demonstrates improved performance with much lower UV light exposure dose, higher <i>S</i> and higher <i>γ</i> compared to <b>4Bx</b>. By utilizing electron beam lithography, patterned arrays of polymer semiconductors with resolutions down to 500 nm and clearer edges are successfully fabricated using <b>PN3</b>. Furthermore, patterned arrays of <b>PDPP4T</b>, the <i>p</i>-type semiconductor (Figure 1b), after being doped, can function as source-drain electrodes for fabricating field-effect transistors (FETs) with comparable charge mobility and significantly lower sub-threshold swing value compared to those with gold electrodes.</p> +<p>Controlling exchange bias (EB) by electric fields is crucial for next-generation magnetic random access memories and spintronics with ultralow energy consumption and ultrahigh speed. Multiferroic heterostructures have been traditionally used to electrically control EB and interfacial ferromagnetism through weak/indirect coupling between ferromagnetic and ferroelectric films. However, three major bottlenecks (lattice mismatch, interface defects, and weak/indirect coupling in multiferroic heterostructures) remain, resulting in only a few tens of milli-tesla EB field. Here, this study reports a robust electric-field control recipe to dynamically tailor the EB effect in a pure CrI<sub>3</sub> homotrilayer on a ferroelectric Y-doped HfO<sub>2</sub> (HYO) substrate, and demonstrate a colossal and tunable EB field (<i>H<sub>E</sub> +</i>) from −0.15 to +0.33 T, giving rise to an EB modulation of 0.48 T. The charge doping due to ferroelectric HYO film divides a homo-configuration of CrI<sub>3</sub> homotrilayer into one antiferromagnetic (AFM) bilayer CrI<sub>3</sub> and one ferromagnetic (FM) monolayer CrI<sub>3</sub>, favoring direct exchange coupling. The synergies of charge doping and electric field induce a transition of magnetic orders from AFM to FM phase in bilayer CrI<sub>3</sub>, which is also supported by first-principles calculations, leading to the robust electric control of colossal EB effect. The results therefore open numerous opportunities for exploring 2D spintronics, memories, and braininspired in-memory computing.</p> -Xiang Xue, -Cheng Li, -Qi Zhou, -Xiaobo Yu, -Chenying Gao, -Kaiyuan Chenchai, -Junchao Liao, -Zhichun Shangguan, -Xisha Zhang, -Guanxin Zhang, -Deqing Zhang +Yuting Niu, +Zhen Liu, +Ke Wang, +Wanlei Ai, +Tao Gong, +Tao Liu, +Lei Bi, +Gang Zhang, +Longjiang Deng, +Bo Peng Research Article - Conjugated Polymer‐Based Photo‐Crosslinker for Efficient Photo‐Patterning of Polymer Semiconductors - 10.1002/adma.202407305 + Robust Electric‐Field Control of Colossal Exchange Bias in CrI3 Homotrilayer + 10.1002/adma.202403066 Advanced Materials - 10.1002/adma.202407305 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407305 + 10.1002/adma.202403066 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403066 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407663 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403612 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202407663 - Controlling the Relaxation Dynamics of Polymer Networks by Combining Associative and Dissociative Dynamic Covalent Bonds + 10.1002/adma.202403612 + Sono‐Triggered Biomimetically Nanoantibiotics Mediate Precise Sequential Therapy of MRSA‐Induced Lung Infection Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The network topology and spatial structure of dynamic covalent polymer networks can be designed independently from their temporal structure and dynamic nature by the judicious combination of two distinctly different dynamic covalent chemistries. This enables improved extrusion‐based additive manufacturing, healing without creep and shape memory at time scales where the dissociative chemistry is activated and the associative chemistry remains inactive. +AMV@NanoCip, a novel biomimetic nanomedicine, integrates PBP2a antibody‐presenting nanovesicles with self‐assembled ciprofloxacin nanoparticles exhibiting sonodynamic properties. This formulation demonstrates exceptional MRSA‐targeting and antibacterial efficacy, achieving 99.99% sterilization in vitro and significant bacterial reduction in a pneumonia model. The sequential treatment strategy, combining adhesion, membrane disruption, and synergistic therapy, presents a promising approach for combating bacterial infections. @@ -2586,44 +2468,50 @@ The network topology and spatial structure of dynamic covalent polymer networks Abstract -Dynamic polymer networks offer a promising solution to key challenges in polymers such as recyclability, processability, and damage repair. However, the trade‐off between combining facile processability, fast self‐healing, and high creep resistance remains a major obstacle to implementation. To overcome this, two very distinct dynamic covalent chemistries, Diels–Alder and transesterification, is combined in a single network. The resulting dual dynamic networks offer an unprecedented set of properties and control over the relaxation times. The system decouples the relaxation dynamics of the network from the spatial motifs, and the tuning of the ratio between chemistries enables to control of the relaxation dynamics over six orders of magnitude. Taking advantage of this control, the composition and rheological behavior is optimized to drastically improve the resolution for extrusion‐based additive manufacturing of dynamic covalent networks. Additionally, two well‐defined and separated stress relaxation peaks are observed at compositions close to 50% of each dynamic chemistry, accentuating the double character of the system's relaxation dynamics. This atypical situation, enables to preparation of self‐healing materials with negligible creep, and with shape‐memory properties solely leveraging the two distinct relaxation dynamics, instead of the glass transition temperature or the melting point. +Bacterial‐induced lower respiratory tract infections are a growing global health concern, exacerbated by the inefficacy of conventional antibiotics and delivery methods to effectively target the lower respiratory tract, leading to suboptimal therapeutic outcomes. To address this challenge, this work engineers PBP2a antibody‐presenting membrane nanovesicles (AMVs) specifically designed to target the penicillin‐binding protein variant on the surface of methicillin‐resistant Staphylococcus aureus (MRSA). Concurrently, this work develops pure ciprofloxacin nanoparticles (NanoCip) that, for the first time, exhibits exceptional self‐generated sonodynamic properties, attributed to hydrogen‐bond‐driven self‐assembly, while maintaining their inherent pharmacological efficacy. These NanoCip particles are integrated with AMVs to create a novel biomimetic nanomedicine, AMV@NanoCip. This formulation demonstrated remarkable MRSA‐targeting affinity in both in vitro and in vivo models, significantly enhancing antibacterial activity. Upon ultrasound stimulation, AMV@NanoCip achieves over 99.99% sterilization of MRSA in vitro, with a reduction exceeding 5.14 Log CFU. Prokaryotic transcriptomic analysis further elucidates the synergistic mechanisms by which AMV@NanoCip, coupled with ultrasound, disrupts the MRSA exoskeleton. In a MRSA‐induced pneumonia animal model, AMV@NanoCip+US results in a substantial bacterial load reduction in the lungs (99.99%, 4.02 Log CFU). This sequential treatment strategy (adhesion‐membrane disruption‐synergistic therapy) offers significant promise as an innovative therapeutic approach for combating bacterial infections. - <img src="https://onlinelibrary.wiley.com/cms/asset/47ef48d8-5239-4320-b3a1-5659f82b6f54/adma202407663-gra-0001-m.png" - alt="Controlling the Relaxation Dynamics of Polymer Networks by Combining Associative and Dissociative Dynamic Covalent Bonds"/> -<p>The network topology and spatial structure of dynamic covalent polymer networks can be designed independently from their temporal structure and dynamic nature by the judicious combination of two distinctly different dynamic covalent chemistries. This enables improved extrusion-based additive manufacturing, healing without creep and shape memory at time scales where the dissociative chemistry is activated and the associative chemistry remains inactive. + <img src="https://onlinelibrary.wiley.com/cms/asset/d16f2b10-0cdc-452d-911c-add9bab8984b/adma202403612-gra-0001-m.png" + alt="Sono-Triggered Biomimetically Nanoantibiotics Mediate Precise Sequential Therapy of MRSA-Induced Lung Infection"/> +<p>AMV@NanoCip, a novel biomimetic nanomedicine, integrates PBP2a antibody-presenting nanovesicles with self-assembled ciprofloxacin nanoparticles exhibiting sonodynamic properties. This formulation demonstrates exceptional MRSA-targeting and antibacterial efficacy, achieving 99.99% sterilization in vitro and significant bacterial reduction in a pneumonia model. The sequential treatment strategy, combining adhesion, membrane disruption, and synergistic therapy, presents a promising approach for combating bacterial infections. </p> <br/> <h2>Abstract</h2> -<p>Dynamic polymer networks offer a promising solution to key challenges in polymers such as recyclability, processability, and damage repair. However, the trade-off between combining facile processability, fast self-healing, and high creep resistance remains a major obstacle to implementation. To overcome this, two very distinct dynamic covalent chemistries, Diels–Alder and transesterification, is combined in a single network. The resulting dual dynamic networks offer an unprecedented set of properties and control over the relaxation times. The system decouples the relaxation dynamics of the network from the spatial motifs, and the tuning of the ratio between chemistries enables to control of the relaxation dynamics over six orders of magnitude. Taking advantage of this control, the composition and rheological behavior is optimized to drastically improve the resolution for extrusion-based additive manufacturing of dynamic covalent networks. Additionally, two well-defined and separated stress relaxation peaks are observed at compositions close to 50% of each dynamic chemistry, accentuating the double character of the system's relaxation dynamics. This atypical situation, enables to preparation of self-healing materials with negligible creep, and with shape-memory properties solely leveraging the two distinct relaxation dynamics, instead of the glass transition temperature or the melting point.</p> +<p>Bacterial-induced lower respiratory tract infections are a growing global health concern, exacerbated by the inefficacy of conventional antibiotics and delivery methods to effectively target the lower respiratory tract, leading to suboptimal therapeutic outcomes. To address this challenge, this work engineers PBP2a antibody-presenting membrane nanovesicles (AMVs) specifically designed to target the penicillin-binding protein variant on the surface of methicillin-resistant <i>Staphylococcus aureus</i> (MRSA). Concurrently, this work develops pure ciprofloxacin nanoparticles (NanoCip) that, for the first time, exhibits exceptional self-generated sonodynamic properties, attributed to hydrogen-bond-driven self-assembly, while maintaining their inherent pharmacological efficacy. These NanoCip particles are integrated with AMVs to create a novel biomimetic nanomedicine, AMV@NanoCip. This formulation demonstrated remarkable MRSA-targeting affinity in both in vitro and in vivo models, significantly enhancing antibacterial activity. Upon ultrasound stimulation, AMV@NanoCip achieves over 99.99% sterilization of MRSA in vitro, with a reduction exceeding 5.14 Log CFU. Prokaryotic transcriptomic analysis further elucidates the synergistic mechanisms by which AMV@NanoCip, coupled with ultrasound, disrupts the MRSA exoskeleton. In a MRSA-induced pneumonia animal model, AMV@NanoCip+US results in a substantial bacterial load reduction in the lungs (99.99%, 4.02 Log CFU). This sequential treatment strategy (adhesion-membrane disruption-synergistic therapy) offers significant promise as an innovative therapeutic approach for combating bacterial infections.</p> -Aleix Costa Cornellà, -Francesca Furia, -Guy Van Assche, -Joost Brancart +Linyu Ding, +Xiaoliu Liang, +Jiaxin Ma, +Xue Liu, +Yang Zhang, +Qiuyue Long, +Zihao Wen, +Zihao Teng, +Lai Jiang, +Gang Liu Research Article - Controlling the Relaxation Dynamics of Polymer Networks by Combining Associative and Dissociative Dynamic Covalent Bonds - 10.1002/adma.202407663 + Sono‐Triggered Biomimetically Nanoantibiotics Mediate Precise Sequential Therapy of MRSA‐Induced Lung Infection + 10.1002/adma.202403612 Advanced Materials - 10.1002/adma.202407663 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407663 + 10.1002/adma.202403612 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403612 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408136 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403985 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408136 - Customized Corneal Cross‐Linking with Microneedle‐Mediated Riboflavin Delivery for Keratoconus Treatment + 10.1002/adma.202403985 + Mimicking Antiferroelectrics with Ferroelectric Superlattices Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Novel customized corneal cross‐linking (CXL) treatment, which utilizes microneedles for targeted riboflavin administration, not only achieves exceptional customized CXL effects comparable to the conventional epi‐off CXL protocol, but also improves visual function by flattening the corneal curvature within the treated zone, paving the way for customized CXL treatment of keratoconus and other corneal pathologies. +Antiferroelectrics are promising materials for applications in energy storage, solid‐state cooling, and negative‐capacitance devices. This study demonstrates that antiferroelectric‐like behavior can be electrostatically engineered in ferroelectric superlattices. An electric field induces a reversible transition from a stable in‐plane polarized state to a state with in‐plane and out‐of‐plane polarized nanodomains that mimics, at the domain level, the nonpolar‐to‐polar transition of traditional antiferroelectrics. @@ -2633,58 +2521,50 @@ Novel customized corneal cross‐linking (CXL) treatment, which utilizes mic Abstract -In this study, a novel customized corneal cross‐linking (CXL) treatment is explored that utilizes microneedles (MNs) for targeted riboflavin (RF) administration prior to the CXL procedure. Unlike the conventional “one‐size‐fits‐all” approach, this protocol offers an option for more precise and efficacious treatment. To simulate a customized corneal crosslinking technique, four distinct microneedle (MN) molds designs, including circular, semi‐circular, annular and butterfly shaped, are crafted for loading an optimized RF‐hyaluronic acid solution and for the subsequent fabrication of MN arrays with varying morphologies. These MNs can gently puncture the corneal epithelium while preserving the integrity of the underlying stromal layer. Following the application of these microneedles, RF solution is replenished to enhance the RF content within the stroma through the punctures created by the MNs, resulting in exceptional customized corneal cross‐linking effects that are comparable to the conventional epi‐off CXL protocol. Additionally, it flattened the corneal curvature within the treated zone and facilitated rapid postoperative recovery of corneal tissue. These findings suggest that the integration of customized microneedle RF delivery with corneal crosslinking technology represents a potential novel treatment modality, holding promise for the tailored treatment of corneal pathologies, and offering a more precise and efficient alternative to traditional methods. +Antiferroelectric oxides are promising materials for applications in high‐density energy storage, solid‐state cooling, and negative capacitance devices. However, the range of oxide antiferroelectrics available today is rather limited. In this work, it is demonstrated that antiferroelectric properties can be electrostatically engineered in artificially layered ferroelectric superlattices. Using a combination of synchrotron X‐ray nanodiffraction, scanning transmission electron microscopy, macroscopic electrical measurements, and lateral and vertical piezoresponse force microscopy in parallel‐plate capacitor geometry, a highly reversible field‐induced transition is observed from a stable in‐plane polarized state to a state with in‐plane and out‐of‐plane polarized nanodomains that mimics, at the domain level, the nonpolar to polar transition of traditional antiferroelectrics, with corresponding polarization‐voltage double hysteresis and comparable energy storage capacity. Furthermore, it is found that such superlattices exhibit large out‐of‐plane dielectric responses without involving flux‐closure domain dynamics. These results demonstrate that electrostatic and strain engineering in artificially layered materials offers a promising route for the creation of synthetic antiferroelectrics. - <img src="https://onlinelibrary.wiley.com/cms/asset/4eca6f08-6644-4cce-83ac-d11b54fddaad/adma202408136-gra-0001-m.png" - alt="Customized Corneal Cross-Linking with Microneedle-Mediated Riboflavin Delivery for Keratoconus Treatment"/> -<p>Novel customized corneal cross-linking (CXL) treatment, which utilizes microneedles for targeted riboflavin administration, not only achieves exceptional customized CXL effects comparable to the conventional epi-off CXL protocol, but also improves visual function by flattening the corneal curvature within the treated zone, paving the way for customized CXL treatment of keratoconus and other corneal pathologies. + <img src="https://onlinelibrary.wiley.com/cms/asset/c95564f6-b0e2-4825-a4d5-27a435ff8f89/adma202403985-gra-0001-m.png" + alt="Mimicking Antiferroelectrics with Ferroelectric Superlattices"/> +<p>Antiferroelectrics are promising materials for applications in energy storage, solid-state cooling, and negative-capacitance devices. This study demonstrates that antiferroelectric-like behavior can be electrostatically engineered in ferroelectric superlattices. An electric field induces a reversible transition from a stable in-plane polarized state to a state with in-plane and out-of-plane polarized nanodomains that mimics, at the domain level, the nonpolar-to-polar transition of traditional antiferroelectrics. </p> <br/> <h2>Abstract</h2> -<p>In this study, a novel customized corneal cross-linking (CXL) treatment is explored that utilizes microneedles (MNs) for targeted riboflavin (RF) administration prior to the CXL procedure. Unlike the conventional “one-size-fits-all” approach, this protocol offers an option for more precise and efficacious treatment. To simulate a customized corneal crosslinking technique, four distinct microneedle (MN) molds designs, including circular, semi-circular, annular and butterfly shaped, are crafted for loading an optimized RF-hyaluronic acid solution and for the subsequent fabrication of MN arrays with varying morphologies. These MNs can gently puncture the corneal epithelium while preserving the integrity of the underlying stromal layer. Following the application of these microneedles, RF solution is replenished to enhance the RF content within the stroma through the punctures created by the MNs, resulting in exceptional customized corneal cross-linking effects that are comparable to the conventional epi-off CXL protocol. Additionally, it flattened the corneal curvature within the treated zone and facilitated rapid postoperative recovery of corneal tissue. These findings suggest that the integration of customized microneedle RF delivery with corneal crosslinking technology represents a potential novel treatment modality, holding promise for the tailored treatment of corneal pathologies, and offering a more precise and efficient alternative to traditional methods.</p> +<p>Antiferroelectric oxides are promising materials for applications in high-density energy storage, solid-state cooling, and negative capacitance devices. However, the range of oxide antiferroelectrics available today is rather limited. In this work, it is demonstrated that antiferroelectric properties can be electrostatically engineered in artificially layered ferroelectric superlattices. Using a combination of synchrotron X-ray nanodiffraction, scanning transmission electron microscopy, macroscopic electrical measurements, and lateral and vertical piezoresponse force microscopy in parallel-plate capacitor geometry, a highly reversible field-induced transition is observed from a stable in-plane polarized state to a state with in-plane and out-of-plane polarized nanodomains that mimics, at the domain level, the nonpolar to polar transition of traditional antiferroelectrics, with corresponding polarization-voltage double hysteresis and comparable energy storage capacity. Furthermore, it is found that such superlattices exhibit large out-of-plane dielectric responses without involving flux-closure domain dynamics. These results demonstrate that electrostatic and strain engineering in artificially layered materials offers a promising route for the creation of synthetic antiferroelectrics.</p> -Mei Yang, -Hongxian Pan, -Tingting Chen, -Xin Chen, -Rui Ning, -Qianfang Ye, -Aodong Chen, -Jiawei Li, -Siheng Li, -Nan Zhao, -Yue Wu, -Xueyu Fu, -Keith M. Meek, -Lingxin Chen, -Xiaoying Wang, -Zhongxing Chen, -Xingtao Zhou, -Jinhai Huang +Chunhai Yin, +Yaqi Li, +Edoardo Zatterin, +Dorin Rusu, +Evgenios Stylianidis, +Marios Hadjimichael, +Hugo Aramberri, +Jorge Iñiguez‐González, +Michele Conroy, +Pavlo Zubko Research Article - Customized Corneal Cross‐Linking with Microneedle‐Mediated Riboflavin Delivery for Keratoconus Treatment - 10.1002/adma.202408136 + Mimicking Antiferroelectrics with Ferroelectric Superlattices + 10.1002/adma.202403985 Advanced Materials - 10.1002/adma.202408136 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408136 + 10.1002/adma.202403985 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403985 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408268 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202404384 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408268 - Upcycling the Spent Graphite Anode Into the Prelithiation Catalyst: A Separator Strategy Toward Anode‐Free Cell Prototyping + 10.1002/adma.202404384 + Ordered Transfer from 3D‐Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Value‐added recycling of spent anode has become an urgent need for the circular battery manufacturing. In this work, Yao et al. developed an “integrated closed‐loop route” to upgrade the spent graphite into the prelithiation catalyst upon the fine tuning of the interlayer spacing and defect concentration, enabling customized prelithiation for the Li‐deficient electrodes. It fulfills both the sustainable supply chain and battery prototyping with higher energy efficiency. +3D‐oriented metal‐organic framework (MOF) films are used as templates for the fabrication of oriented porous polymer films and patterns. MOF films are prepared via heteroepitaxial growth; X‐ray sensitivity is achieved using an azide‐functionalized linker. X‐ray irradiation degrades the MOF film in exposed regions; masked areas are cross‐linked via azide‐alkyne coupling. Acidic treatment affords polymeric films and patterns with anisotropic fluorescent properties. @@ -2694,55 +2574,54 @@ Value‐added recycling of spent anode has become an urgent need for the cir Abstract -The substantial manufacturing of lithium‐ion batteries (LIBs) requires sustainable, circular, and decarbonized recycling strategies. While efforts are concentrated on extracting valuable metals from cathodes using intricate chemical process, the direct, efficient cathode regeneration remains a technological challenge. More urgently, the battery supply chain also requires the value‐added exploitation of retired anodes. Here, a “closed‐loop” approach is proposed to upcycle spent graphite into the prelithiation catalyst, namely the fewer‐layer graphene flakes (FGF), upon the exquisite tuning of interlayer spacing and defect concentration. Since the catalytic FGF mitigates the delithiation energy barrier from calcinated Li5FeO4 nanocrystalline, the composite layer of which cast on the polyolefin substrate thus enables a customized prelithiation capability (98% Li+ utilization) for the retired LiFePO4 recovery. Furthermore, the hydrophobic polymeric modification guarantees the moisture tolerance of Li5FeO4 agents, aligning with commercial battery manufacturing standards. The separator strategy well regulates the interfacial chemistry in the anode‐free pouch cell (LiFePO4||Cu), the prototype of which balances the robust cyclability, energy density up to 386.6 Wh kg−1 as well as the extreme power output of 1159.8 W kg−1. This study not only fulfills the sustainable supply chain with graphite upcycling, but also establishes a generic, viable protocol for the anode‐free cell prototyping. +Films and patterns of 3D‐oriented metal‐organic frameworks (MOFs) afford well‐ordered pore structures extending across centimeter‐scale areas. These macroscopic domains of aligned pores are pivotal to enhance diffusion along specific pathways and orient functional guests. The anisotropic properties emerging from this alignment are beneficial for applications in ion conductivity and photonics. However, the structure of 3D‐oriented MOF films and patterns can rapidly degrade under humid and acidic conditions. Thus, more durable 3D‐ordered porous systems are desired for practical applications. Here, oriented porous polymer films and patterns are prepared by using heteroepitaxially oriented N3‐functionalized MOF films as precursor materials. The film fabrication protocol utilizes an azide–alkyne cycloaddition on the Cu2(AzBPDC)2DABCO MOF. The micropatterning protocol exploits the X‐ray sensitivity of azide groups in Cu2(AzBPDC)2DABCO, enabling selective degradation in the irradiated areas. The masked regions of the MOF film retain their N3‐functionality, allowing for subsequent cross‐linking through azide‐alkyne coupling. Subsequent acidic treatment removes the Cu ions from the MOF, yielding porous polymer micro‐patterns. The polymer has high chemical stability and shows an anisotropic fluorescent response. The use of 3D‐oriented MOF systems as precursors for the fabrication of oriented porous polymers will facilitate the progress of optical components for photonic applications. - <img src="https://onlinelibrary.wiley.com/cms/asset/301292ce-b6a5-4a86-8e24-accf8eddf179/adma202408268-gra-0001-m.png" - alt="Upcycling the Spent Graphite Anode Into the Prelithiation Catalyst: A Separator Strategy Toward Anode-Free Cell Prototyping"/> -<p>Value-added recycling of spent anode has become an urgent need for the circular battery manufacturing. In this work, Yao et al. developed an “integrated closed-loop route” to upgrade the spent graphite into the prelithiation catalyst upon the fine tuning of the interlayer spacing and defect concentration, enabling customized prelithiation for the Li-deficient electrodes. It fulfills both the sustainable supply chain and battery prototyping with higher energy efficiency. + <img src="https://onlinelibrary.wiley.com/cms/asset/9a505e7d-02bb-40f8-9586-e1555df4ed8c/adma202404384-gra-0001-m.png" + alt="Ordered Transfer from 3D-Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns"/> +<p>3D-oriented metal-organic framework (MOF) films are used as templates for the fabrication of oriented porous polymer films and patterns. MOF films are prepared via heteroepitaxial growth; X-ray sensitivity is achieved using an azide-functionalized linker. X-ray irradiation degrades the MOF film in exposed regions; masked areas are cross-linked via azide-alkyne coupling. Acidic treatment affords polymeric films and patterns with anisotropic fluorescent properties. </p> <br/> <h2>Abstract</h2> -<p>The substantial manufacturing of lithium-ion batteries (LIBs) requires sustainable, circular, and decarbonized recycling strategies. While efforts are concentrated on extracting valuable metals from cathodes using intricate chemical process, the direct, efficient cathode regeneration remains a technological challenge. More urgently, the battery supply chain also requires the value-added exploitation of retired anodes. Here, a “closed-loop” approach is proposed to upcycle spent graphite into the prelithiation catalyst, namely the fewer-layer graphene flakes (FGF), upon the exquisite tuning of interlayer spacing and defect concentration. Since the catalytic FGF mitigates the delithiation energy barrier from calcinated Li<sub>5</sub>FeO<sub>4</sub> nanocrystalline, the composite layer of which cast on the polyolefin substrate thus enables a customized prelithiation capability (98% Li<sup>+</sup> utilization) for the retired LiFePO<sub>4</sub> recovery. Furthermore, the hydrophobic polymeric modification guarantees the moisture tolerance of Li<sub>5</sub>FeO<sub>4</sub> agents, aligning with commercial battery manufacturing standards. The separator strategy well regulates the interfacial chemistry in the anode-free pouch cell (LiFePO<sub>4</sub>||Cu), the prototype of which balances the robust cyclability, energy density up to 386.6 Wh kg<sup>−1</sup> as well as the extreme power output of 1159.8 W kg<sup>−1</sup>. This study not only fulfills the sustainable supply chain with graphite upcycling, but also establishes a generic, viable protocol for the anode-free cell prototyping.</p> +<p>Films and patterns of 3D-oriented metal-organic frameworks (MOFs) afford well-ordered pore structures extending across centimeter-scale areas. These macroscopic domains of aligned pores are pivotal to enhance diffusion along specific pathways and orient functional guests. The anisotropic properties emerging from this alignment are beneficial for applications in ion conductivity and photonics. However, the structure of 3D-oriented MOF films and patterns can rapidly degrade under humid and acidic conditions. Thus, more durable 3D-ordered porous systems are desired for practical applications. Here, oriented porous polymer films and patterns are prepared by using heteroepitaxially oriented N<sub>3</sub>-functionalized MOF films as precursor materials. The film fabrication protocol utilizes an azide–alkyne cycloaddition on the Cu<sub>2</sub>(AzBPDC)<sub>2</sub>DABCO MOF. The micropatterning protocol exploits the X-ray sensitivity of azide groups in Cu<sub>2</sub>(AzBPDC)<sub>2</sub>DABCO, enabling selective degradation in the irradiated areas. The masked regions of the MOF film retain their N<sub>3</sub>-functionality, allowing for subsequent cross-linking through azide-alkyne coupling. Subsequent acidic treatment removes the Cu ions from the MOF, yielding porous polymer micro-patterns. The polymer has high chemical stability and shows an anisotropic fluorescent response. The use of 3D-oriented MOF systems as precursors for the fabrication of oriented porous polymers will facilitate the progress of optical components for photonic applications.</p> -Ning Yao, -Fu Liu, -Ahu Shao, -Rongrong Xue, -Qiurong Jia, -Yuyao Liu, -Helin Wang, -Xin Wang, -Yaxin Zhang, -Min Zhang, -Zhiqiao Wang, -Yunsong Li, -Jiawen Tang, -Xiaoyu Tang, -Yue Ma +Lea A. Brandner, +Benedetta Marmiroli, +Mercedes Linares‐Moreau, +Mariano Barella, +Behnaz Abbasgholi‐NA, +Miriam de J. Velásquez‐Hernández, +Kate L. Flint, +Simone Dal Zilio, +Guillermo P. Acuna, +Heimo Wolinski, +Heinz Amenitsch, +Christian J. Doonan, +Paolo Falcaro Research Article - Upcycling the Spent Graphite Anode Into the Prelithiation Catalyst: A Separator Strategy Toward Anode‐Free Cell Prototyping - 10.1002/adma.202408268 + Ordered Transfer from 3D‐Oriented MOF Superstructures to Polymeric Films: Microfabrication, Enhanced Chemical Stability, and Anisotropic Fluorescent Patterns + 10.1002/adma.202404384 Advanced Materials - 10.1002/adma.202408268 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408268 + 10.1002/adma.202404384 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202404384 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408364 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202404766 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408364 - Bioinspired Homonuclear Diatomic Iron Active Site Regulation for Efficient Antifouling Osmotic Energy Conversion + 10.1002/adma.202404766 + Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Inspired by structural and functional models of natural cytochrome c oxidase (CcO), the conformations of the 2 hemes intrinsic to CcO can inspire the biomimetic active site regulation of nanozymes with powerful ROS generation capability for efficient antifouling osmotic energy conversion is demonstrated. The power density of bioinspired membranes reached 6.7 W m−2 and the antimicrobial performance increased 44.5‐fold. +The intricate world of tumor microstructures bears great significance in cancer diagnostics and therapy. This study delves into the magnetic relaxation response of magnetic nanoparticles within tumors, unraveling insights into cancer cell distribution, stromal components, and vascularization. Measuring magnetic relaxation time and analyzing tumor structures paves the way for noninvasive cancer diagnostics and therapeutics using magnetic nanoparticles. + @@ -2752,51 +2631,48 @@ Inspired by structural and functional models of natural cytochrome c oxidase (Cc Abstract -Membrane‐based reverse electrodialysis is globally recognized as a promising technology for harnessing osmotic energy. However, its practical application is greatly restricted by the poor anti‐fouling ability of existing membrane materials. Inspired by the structural and functional models of natural cytochrome c oxidases (CcO), the first use of atomically precise homonuclear diatomic iron composites as high‐performance osmotic energy conversion membranes with excellent anti‐fouling ability is demonstrated. Through rational tuning of the atomic configuration of the diatomic iron sites, the oxidase‐like activity can be precisely tailored, leading to the augmentation of ion throughput and anti‐fouling capacity. Composite membranes featuring direct Fe‐Fe motif configurations embedded within cellulose nanofibers (CNF/Fe‐DACs‐P) surpass state‐of‐the‐art CNF‐based membranes with power densities of ca. 6.7 W m−2 and a 44.5‐fold enhancement in antimicrobial performance. Combined, experimental characterization and density functional theory simulations reveal that homonuclear diatomic iron sites with metal‐metal interactions can achieve ideally balanced adsorption and desorption of intermediates, thus realizing superior oxidase‐like activity, enhanced ionic flux, and excellent antibacterial activity. +Tumor microscopic structure is crucial for determining properties such as cancer type, disease state (key for early diagnosis), and novel therapeutic strategies. Magnetic particle imaging is an early cancer diagnostic tool using magnetic nanoparticles as a tracer, which actualizes cancer theranostics in combination with hyperthermia treatment using the abilities of magnetic nanoparticles as a heat source. This study focuses on the microscopic structures associated with cancer cell distribution, the stromal compartment, and vascularization in different kinds of living tumors by analyzing the intratumor magnetic relaxation response of magnetic nanoparticles injected into the tumors. Furthermore, this study describes a sequential system for the measurement of magnetic relaxation time and analysis of the intratumor structure using nonbiological samples such as viscous fluids and solidified magnetic nanoparticles. Particularly, the fine discriminability achieved by reconstructing a distribution map representing the relationship between magnetic relaxation time and viscosity of medium is demonstrated, based on experimental data with a limited condition number. Observing tumor microscopic structure through the dynamic magnetization response of intratumor magnetic nanoparticles is a low‐invasive tool for analyzing tumor tissue without dissection. It holds promise for the advancement of biomedical applications, such as early cancer theranostics, using magnetic nanoparticles. - <img src="https://onlinelibrary.wiley.com/cms/asset/212e6ab8-0d9c-4b3e-8a88-c13df16b0402/adma202408364-gra-0001-m.png" - alt="Bioinspired Homonuclear Diatomic Iron Active Site Regulation for Efficient Antifouling Osmotic Energy Conversion"/> -<p>Inspired by structural and functional models of natural cytochrome c oxidase (CcO), the conformations of the 2 hemes intrinsic to CcO can inspire the biomimetic active site regulation of nanozymes with powerful ROS generation capability for efficient antifouling osmotic energy conversion is demonstrated. The power density of bioinspired membranes reached 6.7 W m<sup>−2</sup> and the antimicrobial performance increased 44.5-fold. + <img src="https://onlinelibrary.wiley.com/cms/asset/2c4e15e2-b0b7-4f62-a856-9e60a56e7056/adma202404766-gra-0001-m.png" + alt="Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles"/> +<p>The intricate world of tumor microstructures bears great significance in cancer diagnostics and therapy. This study delves into the magnetic relaxation response of magnetic nanoparticles within tumors, unraveling insights into cancer cell distribution, stromal components, and vascularization. Measuring magnetic relaxation time and analyzing tumor structures paves the way for noninvasive cancer diagnostics and therapeutics using magnetic nanoparticles. </p> <br/> <h2>Abstract</h2> -<p>Membrane-based reverse electrodialysis is globally recognized as a promising technology for harnessing osmotic energy. However, its practical application is greatly restricted by the poor anti-fouling ability of existing membrane materials. Inspired by the structural and functional models of natural cytochrome <i>c</i> oxidases (C<i>c</i>O), the first use of atomically precise homonuclear diatomic iron composites as high-performance osmotic energy conversion membranes with excellent anti-fouling ability is demonstrated. Through rational tuning of the atomic configuration of the diatomic iron sites, the oxidase-like activity can be precisely tailored, leading to the augmentation of ion throughput and anti-fouling capacity. Composite membranes featuring direct Fe-Fe motif configurations embedded within cellulose nanofibers (CNF/Fe-DACs-P) surpass state-of-the-art CNF-based membranes with power densities of ca. 6.7 W m<sup>−2</sup> and a 44.5-fold enhancement in antimicrobial performance. Combined, experimental characterization and density functional theory simulations reveal that homonuclear diatomic iron sites with metal-metal interactions can achieve ideally balanced adsorption and desorption of intermediates, thus realizing superior oxidase-like activity, enhanced ionic flux, and excellent antibacterial activity.</p> +<p>Tumor microscopic structure is crucial for determining properties such as cancer type, disease state (key for early diagnosis), and novel therapeutic strategies. Magnetic particle imaging is an early cancer diagnostic tool using magnetic nanoparticles as a tracer, which actualizes cancer theranostics in combination with hyperthermia treatment using the abilities of magnetic nanoparticles as a heat source. This study focuses on the microscopic structures associated with cancer cell distribution, the stromal compartment, and vascularization in different kinds of living tumors by analyzing the intratumor magnetic relaxation response of magnetic nanoparticles injected into the tumors. Furthermore, this study describes a sequential system for the measurement of magnetic relaxation time and analysis of the intratumor structure using nonbiological samples such as viscous fluids and solidified magnetic nanoparticles. Particularly, the fine discriminability achieved by reconstructing a distribution map representing the relationship between magnetic relaxation time and viscosity of medium is demonstrated, based on experimental data with a limited condition number. Observing tumor microscopic structure through the dynamic magnetization response of intratumor magnetic nanoparticles is a low-invasive tool for analyzing tumor tissue without dissection. It holds promise for the advancement of biomedical applications, such as early cancer theranostics, using magnetic nanoparticles.</p> -Zhe Li, -Donghai Wu, -Qingchen Wang, -Qixiang Zhang, -Peng Xu, -Fangning Liu, -Shibo Xi, -Dongwei Ma, -Yizhong Lu, -Lei Jiang, -Zhen Zhang +Satoshi Ota, +Hiroki Kosaka, +Keita Honda, +Kota Hoshino, +Haruki Goto, +Masato Futagawa, +Yasushi Takemura, +Kosuke Shimizu Research Article - Bioinspired Homonuclear Diatomic Iron Active Site Regulation for Efficient Antifouling Osmotic Energy Conversion - 10.1002/adma.202408364 + Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles + 10.1002/adma.202404766 Advanced Materials - 10.1002/adma.202408364 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408364 + 10.1002/adma.202404766 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202404766 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408367 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202405509 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408367 - Robust Growth of 2D Transition Metal Dichalcogenide Vertical Heterostructures via Ammonium‐Assisted CVD Strategy + 10.1002/adma.202405509 + In Vivo Optogenetics Based on Heavy Metal‐Free Photon Upconversion Nanoparticles Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This work demonstrates a universal strategy for robust growth of high‐quality transition metal dichalcogenide (TMD) vertical heterostructures and a novel design concept for the fabrication of high mobility and high responsivity photodetectors based on 2D TMD vertical heterostructures, which holds promise for the next‐generation photodetectors. +In vivo, optogenetics using photon upconversion (TTA‐UC) based on triplet‐triplet annihilation is demonstrated. The modification of a thermally‐activated delayed fluorescence (TADF) sensitizer with a bromo group promotes intersystem crossing and enables high TTA‐UC efficiency at weak excitation light intensities even without using heavy metals. Air‐stable UC nanoparticles exhibiting red‐to‐blue TTA‐UC induce EGFP expression in the mouse brain. @@ -2806,50 +2682,49 @@ This work demonstrates a universal strategy for robust growth of high‐qual Abstract -Two dimension (2D) transition metal dichalcogenides (TMD) heterostructures have opened unparalleled prospects for next‐generation electronic and optoelectronic applications due to their atomic‐scale thickness and distinct physical properties. The chemical vapor deposition (CVD) method is the most feasible approach to prepare 2D TMD heterostructures. However, the synthesis of 2D vertical heterostructures faces competition between in‐plane and out‐of‐plane growth, which makes it difficult to precisely control the growth of vertical heterostructures. Here, a universal and controllable strategy is reported to grow various 2D TMD vertical heterostructures through an ammonium‐assisted CVD process. The ammonium‐assisted strategy shows excellent controllability and operational simplicity to prevent interlayer diffusion/alloying and thermal decomposition of the existed TMD templates. Ab initio simulations demonstrate that the reaction between NH4Cl and MoS2 leads to the formation of MoS3 clusters, promoting the nucleation and growth of 2D MoS2 on existed 2D WS2 layer, thereby leading to the growth of vertical heterostructure. The resulting 2D WSe2/WS2 vertical heterostructure photodetectors demonstrate an outstanding optoelectronic performance, which are comparable to the performances of photodetectors fabricated from mechanically exfoliated and stacked vertical heterostructures. The ammonium‐assisted strategy for robust growth of high‐quality vertical van der Waals heterostructures will facilitate fundamental physics investigations and device applications in electronics and optoelectronics. +Photon upconversion (UC) from red or near‐infrared (NIR) light to blue light is promising for in vivo optogenetics. However, the examples of in vivo optogenetics have been limited to lanthanide inorganic UC nanoparticles, and there have been no examples of optogenetics without using heavy metals. Here the first example of in vivo optogenetics using biocompatible heavy metal‐free TTA‐UC nanoemulsions is shown. A new organic TADF sensitizer, a boron difluoride curcuminoid derivative modified with a bromo group, can promote intersystem crossing to the excited triplet state, significantly improving TTA‐UC efficiency. The TTA‐UC nanoparticles formed from biocompatible surfactants and methyl oleate acquire water dispersibility and remarkable oxygen tolerance. By combining with genome engineering technology using the blue light‐responding photoactivatable Cre‐recombinase (PA‐Cre), TTA‐UC nanoparticles promote Cre‐reporter EGFP expression in neurons in vitro and in vivo. The results open new opportunities toward deep‐tissue control of neural activities based on heavy metal‐free fully organic UC systems. - <img src="https://onlinelibrary.wiley.com/cms/asset/8cb88fe6-efd6-4f6a-9578-c3d066711f62/adma202408367-gra-0001-m.png" - alt="Robust Growth of 2D Transition Metal Dichalcogenide Vertical Heterostructures via Ammonium-Assisted CVD Strategy"/> -<p>This work demonstrates a universal strategy for robust growth of high-quality transition metal dichalcogenide (TMD) vertical heterostructures and a novel design concept for the fabrication of high mobility and high responsivity photodetectors based on 2D TMD vertical heterostructures, which holds promise for the next-generation photodetectors. + <img src="https://onlinelibrary.wiley.com/cms/asset/8fb0fe63-67a9-432c-bd5f-4aa991d8f2f7/adma202405509-gra-0001-m.png" + alt="In Vivo Optogenetics Based on Heavy Metal-Free Photon Upconversion Nanoparticles"/> +<p>In vivo, optogenetics using photon upconversion (TTA-UC) based on triplet-triplet annihilation is demonstrated. The modification of a thermally-activated delayed fluorescence (TADF) sensitizer with a bromo group promotes intersystem crossing and enables high TTA-UC efficiency at weak excitation light intensities even without using heavy metals. Air-stable UC nanoparticles exhibiting red-to-blue TTA-UC induce EGFP expression in the mouse brain. </p> <br/> <h2>Abstract</h2> -<p>Two dimension (2D) transition metal dichalcogenides (TMD) heterostructures have opened unparalleled prospects for next-generation electronic and optoelectronic applications due to their atomic-scale thickness and distinct physical properties. The chemical vapor deposition (CVD) method is the most feasible approach to prepare 2D TMD heterostructures. However, the synthesis of 2D vertical heterostructures faces competition between in-plane and out-of-plane growth, which makes it difficult to precisely control the growth of vertical heterostructures. Here, a universal and controllable strategy is reported to grow various 2D TMD vertical heterostructures through an ammonium-assisted CVD process. The ammonium-assisted strategy shows excellent controllability and operational simplicity to prevent interlayer diffusion/alloying and thermal decomposition of the existed TMD templates. Ab initio simulations demonstrate that the reaction between NH<sub>4</sub>Cl and MoS<sub>2</sub> leads to the formation of MoS<sub>3</sub> clusters, promoting the nucleation and growth of 2D MoS<sub>2</sub> on existed 2D WS<sub>2</sub> layer, thereby leading to the growth of vertical heterostructure. The resulting 2D WSe<sub>2</sub>/WS<sub>2</sub> vertical heterostructure photodetectors demonstrate an outstanding optoelectronic performance, which are comparable to the performances of photodetectors fabricated from mechanically exfoliated and stacked vertical heterostructures. The ammonium-assisted strategy for robust growth of high-quality vertical van der Waals heterostructures will facilitate fundamental physics investigations and device applications in electronics and optoelectronics.</p> +<p>Photon upconversion (UC) from red or near-infrared (NIR) light to blue light is promising for in vivo optogenetics. However, the examples of in vivo optogenetics have been limited to lanthanide inorganic UC nanoparticles, and there have been no examples of optogenetics without using heavy metals. Here the first example of in vivo optogenetics using biocompatible heavy metal-free TTA-UC nanoemulsions is shown. A new organic TADF sensitizer, a boron difluoride curcuminoid derivative modified with a bromo group, can promote intersystem crossing to the excited triplet state, significantly improving TTA-UC efficiency. The TTA-UC nanoparticles formed from biocompatible surfactants and methyl oleate acquire water dispersibility and remarkable oxygen tolerance. By combining with genome engineering technology using the blue light-responding photoactivatable Cre-recombinase (PA-Cre), TTA-UC nanoparticles promote Cre-reporter EGFP expression in neurons in vitro and in vivo. The results open new opportunities toward deep-tissue control of neural activities based on heavy metal-free fully organic UC systems.</p> -Wei Li, -Qiuyin Qin, -Xin Li, -Ying Huangfu, -Dingyi Shen, -Jialing Liu, -Jia Li, -Bo Li, -Ruixia Wu, -Xidong Duan +Masanori Uji, +Jumpei Kondo, +Chikako Hara‐Miyauchi, +Saori Akimoto, +Rena Haruki, +Yoichi Sasaki, +Nobuo Kimizuka, +Itsuki Ajioka, +Nobuhiro Yanai Research Article - Robust Growth of 2D Transition Metal Dichalcogenide Vertical Heterostructures via Ammonium‐Assisted CVD Strategy - 10.1002/adma.202408367 + In Vivo Optogenetics Based on Heavy Metal‐Free Photon Upconversion Nanoparticles + 10.1002/adma.202405509 Advanced Materials - 10.1002/adma.202408367 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408367 + 10.1002/adma.202405509 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202405509 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408400 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202405805 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408400 - Electric Field‐Manipulated Optical Chirality in Ferroelectric Vortex Domains + 10.1002/adma.202405805 + Multi‐Functional Biomaterial for the Treatment and Prevention of Central Line‐Associated Bloodstream Infections Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The self‐assembly ferroelectric nanoislands with polar vortex domains and optical chirality, are designed and fabricated, leading to a reversible and nonvolatile on/off switching of optical chirality by electric fields. Such ferroelectric nanoislands, serving as discrete chiral units, can be integrated into ordered arrays and exhibit capabilities in chiral optical display functionalities. +SteriGel is an injectable tissue adhesive hydrogel engineered to address central line‐associated bloodstream infection (CLABSI). With its combined antimicrobial and wound‐healing capabilities, SteriGel shows great potential for preventing and treating CLABSI. The hydrogel can effectively infiltrate the skin incision site surrounding the catheter, quickly solidify upon injection, adhere to skin tissue, and endure external pressures, thus guaranteeing sustained antimicrobial and healing effects. @@ -2859,56 +2734,47 @@ The self‐assembly ferroelectric nanoislands with polar vortex domains and Abstract -Manipulating optical chirality via electric fields has garnered considerable attention in the realm of both fundamental physics and practical applications. Chiral ferroelectrics, characterized by their inherent optical chirality and switchable spontaneous polarization, are emerging as a promising platform for electronic‐photonic integrated circuits applications. Unlike organics with chiral carbon centers, integrating chirality into technologically mature inorganic ferroelectrics has posed a long‐standing challenge. Here, the successful introduction of chirality is reported into self‐assembly La‐doped BiFeO3 nanoislands, which exhibit ferroelectric vortex domains. By employing synergistic experimental techniques with piezoresponse force microscopy and nonlinear optical second‐harmonic generation probes, a clear correlation between chirality and polarization configuration within these ferroelectric nanoislands is established. Furthermore, the deterministic control of ferroelectric vortex domains and chirality is demonstrated by applying electric fields, enabling reversible and nonvolatile generation and elimination of optically chiral signals. These findings significantly expand the repertoire of field‐controllable chiral systems and lay the groundwork for the development of innovative ferroelectric optoelectronic devices. +Central venous catheters are among the most used medical devices in hospitals today. Despite advances in modern medicine, catheter infections remain prevalent, causing significant morbidity and mortality worldwide. Here, SteriGel is reported, which is a multifunctional hydrogel engineered to prevent and treat central line‐associated bloodstream infections (CLABSI). The mechanical properties of SteriGel are optimized to ensure appropriate gelation kinetics, bio‐adhesiveness, stretchability, and recoverability to promote durability upon application and to provide persistent protection against infection. In vitro assays demonstrated that SteriGel exhibits long‐term antimicrobial efficacy and has bactericidal effects against highly resistant patient‐derived pathogens known to be frequently associated with CLABSI. SteriGel outperformed Biopatch, which is a clinically used device for CLABSI, in ex vivo cadaver studies that simulate clinical scenarios. Furthermore, SteriGel has biocompatible, pro‐healing, and anti‐inflammatory properties in vitro and in a rat subcutaneous injection model, suggesting a potential synergistic effect in the prevention and treatment of CLABSI. SteriGel is a multifunctional adherent biomaterial with potent antimicrobial effects for sustained sterility while promoting healing of the catheter incision site to protect against infection. - <img src="https://onlinelibrary.wiley.com/cms/asset/e3d55abf-c191-4489-b2f1-27a59f75392c/adma202408400-gra-0001-m.png" - alt="Electric Field-Manipulated Optical Chirality in Ferroelectric Vortex Domains"/> -<p>The self-assembly ferroelectric nanoislands with polar vortex domains and optical chirality, are designed and fabricated, leading to a reversible and nonvolatile on/off switching of optical chirality by electric fields. Such ferroelectric nanoislands, serving as discrete chiral units, can be integrated into ordered arrays and exhibit capabilities in chiral optical display functionalities. + <img src="https://onlinelibrary.wiley.com/cms/asset/a7304de3-46cc-4fe9-a0e2-b8df16d5ac21/adma202405805-gra-0001-m.png" + alt="Multi-Functional Biomaterial for the Treatment and Prevention of Central Line-Associated Bloodstream Infections"/> +<p>SteriGel is an injectable tissue adhesive hydrogel engineered to address central line-associated bloodstream infection (CLABSI). With its combined antimicrobial and wound-healing capabilities, SteriGel shows great potential for preventing and treating CLABSI. The hydrogel can effectively infiltrate the skin incision site surrounding the catheter, quickly solidify upon injection, adhere to skin tissue, and endure external pressures, thus guaranteeing sustained antimicrobial and healing effects. </p> <br/> <h2>Abstract</h2> -<p>Manipulating optical chirality via electric fields has garnered considerable attention in the realm of both fundamental physics and practical applications. Chiral ferroelectrics, characterized by their inherent optical chirality and switchable spontaneous polarization, are emerging as a promising platform for electronic-photonic integrated circuits applications. Unlike organics with chiral carbon centers, integrating chirality into technologically mature inorganic ferroelectrics has posed a long-standing challenge. Here, the successful introduction of chirality is reported into self-assembly La-doped BiFeO<sub>3</sub> nanoislands, which exhibit ferroelectric vortex domains. By employing synergistic experimental techniques with piezoresponse force microscopy and nonlinear optical second-harmonic generation probes, a clear correlation between chirality and polarization configuration within these ferroelectric nanoislands is established. Furthermore, the deterministic control of ferroelectric vortex domains and chirality is demonstrated by applying electric fields, enabling reversible and nonvolatile generation and elimination of optically chiral signals. These findings significantly expand the repertoire of field-controllable chiral systems and lay the groundwork for the development of innovative ferroelectric optoelectronic devices.</p> +<p>Central venous catheters are among the most used medical devices in hospitals today. Despite advances in modern medicine, catheter infections remain prevalent, causing significant morbidity and mortality worldwide. Here, SteriGel is reported, which is a multifunctional hydrogel engineered to prevent and treat central line-associated bloodstream infections (CLABSI). The mechanical properties of SteriGel are optimized to ensure appropriate gelation kinetics, bio-adhesiveness, stretchability, and recoverability to promote durability upon application and to provide persistent protection against infection. In vitro assays demonstrated that SteriGel exhibits long-term antimicrobial efficacy and has bactericidal effects against highly resistant patient-derived pathogens known to be frequently associated with CLABSI. SteriGel outperformed Biopatch, which is a clinically used device for CLABSI, in ex vivo cadaver studies that simulate clinical scenarios. Furthermore, SteriGel has biocompatible, pro-healing, and anti-inflammatory properties in vitro and in a rat subcutaneous injection model, suggesting a potential synergistic effect in the prevention and treatment of CLABSI. SteriGel is a multifunctional adherent biomaterial with potent antimicrobial effects for sustained sterility while promoting healing of the catheter incision site to protect against infection.</p> -Haojie Han, -Wei Li, -Qinghua Zhang, -Shiyu Tang, -Yue Wang, -Zongqi Xu, -Yiqun Liu, -Hetian Chen, -Jingkun Gu, -Jing Wang, -Di Yi, -Lin Gu, -Houbing Huang, -Ce‐Wen Nan, -Qian Li, -Jing Ma +Jinjoo Kim, +Hyeongseop Keum, +Hassan Albadawi, +Zefu Zhang, +Erin H. Graf, +Enes Cevik, +Rahmi Oklu Research Article - Electric Field‐Manipulated Optical Chirality in Ferroelectric Vortex Domains - 10.1002/adma.202408400 + Multi‐Functional Biomaterial for the Treatment and Prevention of Central Line‐Associated Bloodstream Infections + 10.1002/adma.202405805 Advanced Materials - 10.1002/adma.202408400 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408400 + 10.1002/adma.202405805 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202405805 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408476 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406290 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408476 - Mechanistic Understanding of the Underlying Energy Storage Mechanism of α‐MnO2‐based Pseudo‐Supercapacitors + 10.1002/adma.202406290 + Twist‐Controlled Ferroelectricity and Emergent Multiferroicity in WSe2 Bilayers Advanced Materials, Volume 36, Issue 46, November 14, 2024. -In this study, the pseudo‐capacitive reaction mechanism of manganese dioxide (α‐MnO2) nano‐supercapacitor is revealed in three ionic liquids by using in situ environmental transmission electron microscopy and further investigating the cycled product of macro‐supercapacitor. The underlying faradic reaction mechanisms of pseudo‐capacitance and superior performance are thoroughly elucidated through extensive experimental characterizations and theoretical analyses, providing insights into the selection of electrolytes in α‐MnO2‐based‐supercapacitors. +The twisted tungsten diselenide (WSe2) bilayers stacked along with monolayer graphene exhibit noticeable room temperature ferroelectricity that decreases with twist angle within the range 0° < θ < 3°, and disappears completely for θ ≥ 4°. This variation aligns with moiré length scale‐controlled ferroelectric dynamics (0° < θ < 3°), while loss beyond 4° may relate to twist‐controlled commensurate to non‐commensurate transitions. Also, 3° twisted WSe2 exhibits ferroelectric and correlation‐driven ferromagnetic ordering, indicating twist‐controlled multiferroic behavior. @@ -2918,50 +2784,58 @@ In this study, the pseudo‐capacitive reaction mechanism of manganese dioxi Abstract -Manganese dioxide (α‐MnO2) has attracted significant research interest in supercapacitors recently. However, the reaction mechanism of α‐MnO2 in supercapacitors remains unclear. Therefore, a nano‐supercapacitor using Environmental transmission electron microscopy (ETEM) is conducted and investigated the reaction mechanism of α‐MnO2 based on three ionic liquids (ILs). It found that in the aprotic ionic liquid (AIL) 1‐ethyl‐3‐methylimidazolium trifluoromethanesulfonate (EMIMOTF), α‐MnO2 nanowires (NWs) undergo an oxidation reaction due to the presence of an active proton at the second position (H2) of the imidazole ring. As a result, α‐MnO2 NWs undergo a phase transition and transform into Mn3O4, exhibiting pseudo‐capacitive properties. Furthermore, characterization of the macroscopic α‐MnO2 electrodes after cycling reveals that after the initial charging cycles, the dominant energy storage mechanism of the supercapacitor transitions from pseudo‐capacitance to a dual‐layer capacitance formed by the combination of Mn3O4 and unreacted α‐MnO2. Simultaneously, due to the coexistence of these two energy storage mechanisms, the specific capacitance of the supercapacitor in EMIMOTF electrolyte reaches up to 80 F g−1, and the cycle number reaches as high as 1000 cycles. The results are expected to provide insights into the selection of electrolytes in supercapacitors and offer a fundamental understanding of the internal reaction mechanisms in capacitors. +Recently, researchers have been investigating artificial ferroelectricity, which arises when inversion symmetry is broken in certain R‐stacked, i.e., zero‐degree twisted, van der Waals (vdW) bilayers. Here, the study reports the twist‐controlled ferroelectricity in tungsten diselenide (WSe2) bilayers. The findings show noticeable room temperature ferroelectricity that decreases with twist angle within the range 0° < θ < 3°, and disappears completely for θ ≥ 4°. This variation aligns with moiré length scale‐controlled ferroelectric dynamics (0° < θ < 3°), while loss beyond 4° may relate to twist‐controlled commensurate to non‐commensurate transitions. This twist‐controlled ferroelectricity serves as a spectroscopic tool for detecting transitions between commensurate and incommensurate moiré patterns. At 5.5 K, 3° twisted WSe2 exhibits ferroelectric and correlation‐driven ferromagnetic ordering, indicating twist‐controlled multiferroic behavior. The study offers insights into twist‐controlled coexisting ferro‐ordering and serves as valuable spectroscopic tools. - <img src="https://onlinelibrary.wiley.com/cms/asset/9dc06df1-751f-44c9-8c95-ab7df7740eec/adma202408476-gra-0001-m.png" - alt="Mechanistic Understanding of the Underlying Energy Storage Mechanism of α-MnO2-based Pseudo-Supercapacitors"/> -<p>In this study, the pseudo-capacitive reaction mechanism of manganese dioxide (α-MnO<sub>2</sub>) nano-supercapacitor is revealed in three ionic liquids by using in situ environmental transmission electron microscopy and further investigating the cycled product of macro-supercapacitor. The underlying faradic reaction mechanisms of pseudo-capacitance and superior performance are thoroughly elucidated through extensive experimental characterizations and theoretical analyses, providing insights into the selection of electrolytes in α-MnO<sub>2</sub>-based-supercapacitors. + <img src="https://onlinelibrary.wiley.com/cms/asset/bea8864a-8805-4884-ae91-cd4688de214d/adma202406290-gra-0001-m.png" + alt="Twist-Controlled Ferroelectricity and Emergent Multiferroicity in WSe2 Bilayers"/> +<p>The twisted tungsten diselenide (WSe<sub>2</sub>) bilayers stacked along with monolayer graphene exhibit noticeable room temperature ferroelectricity that decreases with twist angle within the range 0° &lt; <i>θ</i> &lt; 3°, and disappears completely for <i>θ</i> ≥ 4°. This variation aligns with moiré length scale-controlled ferroelectric dynamics (0° &lt; <i>θ</i> &lt; 3°), while loss beyond 4° may relate to twist-controlled commensurate to non-commensurate transitions. Also, 3° twisted WSe<sub>2</sub> exhibits ferroelectric and correlation-driven ferromagnetic ordering, indicating twist-controlled multiferroic behavior. </p> <br/> <h2>Abstract</h2> -<p>Manganese dioxide (α-MnO<sub>2</sub>) has attracted significant research interest in supercapacitors recently. However, the reaction mechanism of α-MnO<sub>2</sub> in supercapacitors remains unclear. Therefore, a nano-supercapacitor using Environmental transmission electron microscopy (ETEM) is conducted and investigated the reaction mechanism of α-MnO<sub>2</sub> based on three ionic liquids (ILs). It found that in the aprotic ionic liquid (AIL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIMOTF), α-MnO<sub>2</sub> nanowires (NWs) undergo an oxidation reaction due to the presence of an active proton at the second position (H2) of the imidazole ring. As a result, α-MnO<sub>2</sub> NWs undergo a phase transition and transform into Mn<sub>3</sub>O<sub>4</sub>, exhibiting pseudo-capacitive properties. Furthermore, characterization of the macroscopic α-MnO<sub>2</sub> electrodes after cycling reveals that after the initial charging cycles, the dominant energy storage mechanism of the supercapacitor transitions from pseudo-capacitance to a dual-layer capacitance formed by the combination of Mn<sub>3</sub>O<sub>4</sub> and unreacted α-MnO<sub>2</sub>. Simultaneously, due to the coexistence of these two energy storage mechanisms, the specific capacitance of the supercapacitor in EMIMOTF electrolyte reaches up to 80 F g<sup>−1</sup>, and the cycle number reaches as high as 1000 cycles. The results are expected to provide insights into the selection of electrolytes in supercapacitors and offer a fundamental understanding of the internal reaction mechanisms in capacitors.</p> +<p>Recently, researchers have been investigating artificial ferroelectricity, which arises when inversion symmetry is broken in certain R-stacked, i.e., zero-degree twisted, van der Waals (vdW) bilayers. Here, the study reports the twist-controlled ferroelectricity in tungsten diselenide (WSe<sub>2</sub>) bilayers. The findings show noticeable room temperature ferroelectricity that decreases with twist angle within the range 0° &lt; <i>θ</i> &lt; 3°, and disappears completely for <i>θ</i> ≥ 4°. This variation aligns with moiré length scale-controlled ferroelectric dynamics (0° &lt; <i>θ</i> &lt; 3°), while loss beyond 4° may relate to twist-controlled commensurate to non-commensurate transitions. This twist-controlled ferroelectricity serves as a spectroscopic tool for detecting transitions between commensurate and incommensurate moiré patterns. At 5.5 K, 3° twisted WSe<sub>2</sub> exhibits ferroelectric and correlation-driven ferromagnetic ordering, indicating twist-controlled multiferroic behavior. The study offers insights into twist-controlled coexisting ferro-ordering and serves as valuable spectroscopic tools.</p> -Lei Deng, -Zaifa Wang, -Hantao Cui, -Yunna Guo, -Zhangran Ye, -Hui Li, -Xinyu Zhang, -Peng Jia, -Qiaobao Zhang, -Liqiang Zhang +Yasir Hassan, +Budhi Singh, +Minwoong Joe, +Byoung‐Min Son, +Tien Dat Ngo, +Younggeun Jang, +Shaili Sett, +Arup Singha, +Rabindra Biswas, +Monika Bhakar, +Kenji Watanabe, +Takashi Taniguchi, +Varun Raghunathan, +Goutam Sheet, +Zonghoon Lee, +Won Jong Yoo, +Pawan Kumar Srivastava, +Changgu Lee Research Article - Mechanistic Understanding of the Underlying Energy Storage Mechanism of α‐MnO2‐based Pseudo‐Supercapacitors - 10.1002/adma.202408476 + Twist‐Controlled Ferroelectricity and Emergent Multiferroicity in WSe2 Bilayers + 10.1002/adma.202406290 Advanced Materials - 10.1002/adma.202408476 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408476 + 10.1002/adma.202406290 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406290 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408478 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406348 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408478 - A Full‐Process, Fine‐Grained, and Quantitative Rehabilitation Assessment Platform Enabled by On‐Skin Sensors and Multi‐Task Gait Transformer Model + 10.1002/adma.202406348 + Toward a Radically Simple Multi‐Modal Nasal Spray for Preventing Respiratory Infections Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This work develops a full‐process, fine‐grained, and quantitative rehabilitation assessments platform (RAP) supported by on‐skin sensors and a multi‐task gait transformer model for patients with lower limb movement disorders. The RAP can perform multiple assessments including fall risk, walking ability, and rehabilitation progress, covering the whole process of rehabilitation and realizing objective and quantitative rehabilitation assessment. +A pathogen capture and neutralizing spray (PCANS) is reported to prevent respiratory infections through a multi‐modal approach. PCANS coats the nasal cavity, capturing large respiratory droplets and serving as a physical barrier against viruses and bacteria, while neutralizing them with over 99.99% effectiveness. In mice, PCANS shows nasal retention for ≈8 hours and offers pre‐exposure protection against lethal viral infections. @@ -2971,51 +2845,65 @@ This work develops a full‐process, fine‐grained, and quantitative re Abstract -Rehabilitation of patients with lower limb movement disorders is a gradual process, which requires full‐process assessments to guide the implementation of rehabilitation plans. However, the current methods can only complete the assessment in one stage and lack objective and quantitative assessment strategies. Here, a full‐process, fine‐grained, and quantitative rehabilitation assessments platform (RAP) supported by on‐skin sensors and a multi‐task gait transformer (MG‐former) model for patients with lower limb movement disorders is developed. The signal quality and sensitivity of on‐skin sensor is improved by the synthesis of high‐performance triboelectric material and structure design. The MG‐former model can simultaneously perform multiple tasks including binary classification, multiclassification, and regression, corresponding to assessment of fall risk, walking ability, and rehabilitation progress, covering the whole rehabilitation cycle. The RAP can assess the walking ability of 23 hemiplegic patients, which has highly consistent results with the scores by the experienced physician. Furthermore, the MG‐former model outputs fine‐grained assessment results when performing regression task to track slight progress of patients that cannot be captured by conventional scales, facilitating adjustment of rehabilitation plans. This work provides an objective and quantitative platform, which is instructive for physicians and patients to implement effective strategy throughout the whole rehabilitation process. +Nasal sprays for pre‐exposure prophylaxis against respiratory infections show limited protection (20–70%), largely due to their single mechanism of action—either neutralizing pathogens or blocking their entry at the nasal lining, and a failure to maximize the capture of respiratory droplets, allowing them to potentially rebound and reach deeper airways. This report introduces the Pathogen Capture and Neutralizing Spray (PCANS), which utilizes a multi‐modal approach to enhance efficacy. PCANS coats the nasal cavity, capturing large respiratory droplets from the air, and serving as a physical barrier against a broad spectrum of viruses and bacteria, while rapidly neutralizing them with over 99.99% effectiveness. The formulation consists of excipients identified from the FDA's Inactive Ingredient Database and Generally Recognized as Safe list to maximize efficacy for each step in the multi‐modal approach. PCANS demonstrates nasal retention for up to 8 hours in mice. In a severe Influenza A mouse model, a single pre‐exposure dose of PCANS leads to a >99.99% reduction in lung viral titer and ensures 100% survival, compared to 0% in the control group. PCANS suppresses pathological manifestations and offers protection for at least 4 hours. This data suggest PCANS as a promising daily‐use prophylactic against respiratory infections. - <img src="https://onlinelibrary.wiley.com/cms/asset/c8bd47fe-ef61-4d43-8267-ba95e4bfc918/adma202408478-gra-0001-m.png" - alt="A Full-Process, Fine-Grained, and Quantitative Rehabilitation Assessment Platform Enabled by On-Skin Sensors and Multi-Task Gait Transformer Model"/> -<p>This work develops a full-process, fine-grained, and quantitative rehabilitation assessments platform (RAP) supported by on-skin sensors and a multi-task gait transformer model for patients with lower limb movement disorders. The RAP can perform multiple assessments including fall risk, walking ability, and rehabilitation progress, covering the whole process of rehabilitation and realizing objective and quantitative rehabilitation assessment. + <img src="https://onlinelibrary.wiley.com/cms/asset/207eb752-7e84-492c-a789-3ab72ec32107/adma202406348-gra-0001-m.png" + alt="Toward a Radically Simple Multi-Modal Nasal Spray for Preventing Respiratory Infections"/> +<p>A pathogen capture and neutralizing spray (PCANS) is reported to prevent respiratory infections through a multi-modal approach. PCANS coats the nasal cavity, capturing large respiratory droplets and serving as a physical barrier against viruses and bacteria, while neutralizing them with over 99.99% effectiveness. In mice, PCANS shows nasal retention for ≈8 hours and offers pre-exposure protection against lethal viral infections. </p> <br/> <h2>Abstract</h2> -<p>Rehabilitation of patients with lower limb movement disorders is a gradual process, which requires full-process assessments to guide the implementation of rehabilitation plans. However, the current methods can only complete the assessment in one stage and lack objective and quantitative assessment strategies. Here, a full-process, fine-grained, and quantitative rehabilitation assessments platform (RAP) supported by on-skin sensors and a multi-task gait transformer (MG-former) model for patients with lower limb movement disorders is developed. The signal quality and sensitivity of on-skin sensor is improved by the synthesis of high-performance triboelectric material and structure design. The MG-former model can simultaneously perform multiple tasks including binary classification, multiclassification, and regression, corresponding to assessment of fall risk, walking ability, and rehabilitation progress, covering the whole rehabilitation cycle. The RAP can assess the walking ability of 23 hemiplegic patients, which has highly consistent results with the scores by the experienced physician. Furthermore, the MG-former model outputs fine-grained assessment results when performing regression task to track slight progress of patients that cannot be captured by conventional scales, facilitating adjustment of rehabilitation plans. This work provides an objective and quantitative platform, which is instructive for physicians and patients to implement effective strategy throughout the whole rehabilitation process.</p> +<p>Nasal sprays for pre-exposure prophylaxis against respiratory infections show limited protection (20–70%), largely due to their single mechanism of action—either neutralizing pathogens or blocking their entry at the nasal lining, and a failure to maximize the capture of respiratory droplets, allowing them to potentially rebound and reach deeper airways. This report introduces the Pathogen Capture and Neutralizing Spray (PCANS), which utilizes a multi-modal approach to enhance efficacy. PCANS coats the nasal cavity, capturing large respiratory droplets from the air, and serving as a physical barrier against a broad spectrum of viruses and bacteria, while rapidly neutralizing them with over 99.99% effectiveness. The formulation consists of excipients identified from the FDA's Inactive Ingredient Database and Generally Recognized as Safe list to maximize efficacy for each step in the multi-modal approach. PCANS demonstrates nasal retention for up to 8 hours in mice. In a severe Influenza A mouse model, a single pre-exposure dose of PCANS leads to a &gt;99.99% reduction in lung viral titer and ensures 100% survival, compared to 0% in the control group. PCANS suppresses pathological manifestations and offers protection for at least 4 hours. This data suggest PCANS as a promising daily-use prophylactic against respiratory infections.</p> -Zhixin Wang, -Xinrun He, -Tianzhao Bu, -Bo Pang, -Wei Guo, -Zhongyi Tu, -Zhiqiang Zhang, -Xiling Xiao, -Zhouping Yin, -Jian Huang, -Hao Wu +John Joseph, +Helna Mary Baby, +Joselyn Rojas Quintero, +Devin Kenney, +Yohannes A Mebratu, +Eshant Bhatia, +Purna Shah, +Kabir Swain, +Dongtak Lee, +Shahdeep Kaur, +Xiang‐Ling Li, +John Mwangi, +Olivia Snapper, +Remya Nair, +Eli Agus, +Sruthi Ranganathan, +Julian Kage, +Jingjing Gao, +James N Luo, +Anthony Yu, +Dongsung Park, +Florian Douam, +Yohannes Tesfaigzi, +Jeffrey M Karp, +Nitin Joshi Research Article - A Full‐Process, Fine‐Grained, and Quantitative Rehabilitation Assessment Platform Enabled by On‐Skin Sensors and Multi‐Task Gait Transformer Model - 10.1002/adma.202408478 + Toward a Radically Simple Multi‐Modal Nasal Spray for Preventing Respiratory Infections + 10.1002/adma.202406348 Advanced Materials - 10.1002/adma.202408478 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408478 + 10.1002/adma.202406348 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406348 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408729 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406559 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408729 - A Peptide‐Drug Conjugate‐Based Nanoplatform for Immunometabolic Activation and In Situ Nerve Regeneration in Advanced‐Stage Alzheimer's Disease + 10.1002/adma.202406559 + β‐Ga2O3 Nanoribbon with Ultra‐High Solar‐Blind Ultraviolet Polarization Ratio Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A peptide‐drug conjugate‐based nanoplatform is designed to deliver hydroxychloroquine (HCQ) and all‐trans retinoic acid (ATRA) to microglia and astrocytes, respectively. The critical immune‐metabolic pathway in microglia is significantly activated to reverse the immune tolerance. Astrocytes are in situ trans‐differentiated into functional neurons. This nanoplatform significantly inhibits the progression of advanced‐stage Alzheimer’s Disease (AD). +Due to the anisotropy of the ultra‐wide bandgap semiconductor β‐Ga2O3, it can be prepared as a solar‐blind UV detector and is intrinsically sensitive to polarized light without the need of polarizers. This β‐Ga2O3‐based detector has an ultra‐high polarization ratio and is commercially viable. This suggests a new strategy for solar‐blind ultraviolet polarization detection and also provides promising solar‐blind optical communication. @@ -3025,46 +2913,49 @@ A peptide‐drug conjugate‐based nanoplatform is designed to deliver h Abstract -The formidable protection of physiological barriers and unclear pathogenic mechanisms impede drug development for Alzheimer's disease (AD). As defenders of the central nervous system, immune‐metabolism function, and stemness of glial cells remain dormant during degeneration, representing a significant challenge for simultaneously targeting and modulating. Here, a modular nanoplatform is presented composed of peptide‐drug conjugates and an inflammation‐responsive core. The nanoplatform is transported through the blood‐brain barrier via transcytosis and disassembles in the oxidative stress microenvironment upon intravenous administration. The released drug‐conjugated modules can specifically target and deliver hydroxychloroquine (HCQ) and all‐trans retinoic acid (ATRA) to microglia and astrocytes, respectively. The immune function of chronic tolerant microglia is activated by metabolic modulation, and reactive astrocytes trans‐differentiate into functional neurons. In a transgenic mouse model, nanoplatform reduces levels of toxic proteins and inflammation while increasing neuronal density. This results in the amelioration of learning and memory decline. The modular nanoplatform provides design principles for multi‐cellular targeting and combination nano‐therapy for inflammation‐related diseases. +Solar‐blind ultraviolet (UV) detection plays a critical role in imaging and communication due to its low‐noise background, high signal‐to‐noise ratio, and strong anti‐interference capabilities. Detecting the polarization state of UV light can enhance image information and expand the communication dimension. Although polarization detection is explored in visible and infrared light, and applied in fields such as astrophysics and submarine seismic wave detection, solar‐blind UV polarization detection remains largely unreported. This is primarily due to the challenge of creating UV polarizers with high transmittance, high extinction ratio, and strong resistance to UV radiation. In this study, it is discovered that the space symmetry breaking of the β‐Ga2O3’s b–c plane results in a significant optical absorption dichroic ratio. Leveraging β‐Ga2O3’s high solar‐blind UV response, a lensless solar‐blind UV polarization‐sensitive photodetector, circumventing the challenges associated with solar‐blind UV polarizers is designed. This photodetector exhibits an exceptionally high intrinsic polarization ratio under 254 nm linearly polarized light, approximately two orders of magnitude higher than other reported nanomaterial‐based polarization‐sensitive photodetectors. Additionally, it demonstrates significant advantages in solar‐blind UV imaging and light communication. This work introduces a novel strategy for solar‐blind ultraviolet polarization detection and offers a promising approach for solar‐blind light communication. - <img src="https://onlinelibrary.wiley.com/cms/asset/03fc188d-76d8-431e-b1b7-4d73140ba363/adma202408729-gra-0001-m.png" - alt="A Peptide-Drug Conjugate-Based Nanoplatform for Immunometabolic Activation and In Situ Nerve Regeneration in Advanced-Stage Alzheimer's Disease"/> -<p>A peptide-drug conjugate-based nanoplatform is designed to deliver hydroxychloroquine (HCQ) and all-trans retinoic acid (ATRA) to microglia and astrocytes, respectively. The critical immune-metabolic pathway in microglia is significantly activated to reverse the immune tolerance. Astrocytes are in situ trans-differentiated into functional neurons. This nanoplatform significantly inhibits the progression of advanced-stage Alzheimer’s Disease (AD). + <img src="https://onlinelibrary.wiley.com/cms/asset/2d7a2906-ab42-4839-9392-9af33dec5bb1/adma202406559-gra-0001-m.png" + alt="β-Ga2O3 Nanoribbon with Ultra-High Solar-Blind Ultraviolet Polarization Ratio"/> +<p>Due to the anisotropy of the ultra-wide bandgap semiconductor <i>β</i>-Ga<sub>2</sub>O<sub>3</sub>, it can be prepared as a solar-blind UV detector and is intrinsically sensitive to polarized light without the need of polarizers. This <i>β</i>-Ga<sub>2</sub>O<sub>3</sub>-based detector has an ultra-high polarization ratio and is commercially viable. This suggests a new strategy for solar-blind ultraviolet polarization detection and also provides promising solar-blind optical communication. </p> <br/> <h2>Abstract</h2> -<p>The formidable protection of physiological barriers and unclear pathogenic mechanisms impede drug development for Alzheimer's disease (AD). As defenders of the central nervous system, immune-metabolism function, and stemness of glial cells remain dormant during degeneration, representing a significant challenge for simultaneously targeting and modulating. Here, a modular nanoplatform is presented composed of peptide-drug conjugates and an inflammation-responsive core. The nanoplatform is transported through the blood-brain barrier via transcytosis and disassembles in the oxidative stress microenvironment upon intravenous administration. The released drug-conjugated modules can specifically target and deliver hydroxychloroquine (HCQ) and all-trans retinoic acid (ATRA) to microglia and astrocytes, respectively. The immune function of chronic tolerant microglia is activated by metabolic modulation, and reactive astrocytes trans-differentiate into functional neurons. In a transgenic mouse model, nanoplatform reduces levels of toxic proteins and inflammation while increasing neuronal density. This results in the amelioration of learning and memory decline. The modular nanoplatform provides design principles for multi-cellular targeting and combination nano-therapy for inflammation-related diseases.</p> +<p>Solar-blind ultraviolet (UV) detection plays a critical role in imaging and communication due to its low-noise background, high signal-to-noise ratio, and strong anti-interference capabilities. Detecting the polarization state of UV light can enhance image information and expand the communication dimension. Although polarization detection is explored in visible and infrared light, and applied in fields such as astrophysics and submarine seismic wave detection, solar-blind UV polarization detection remains largely unreported. This is primarily due to the challenge of creating UV polarizers with high transmittance, high extinction ratio, and strong resistance to UV radiation. In this study, it is discovered that the space symmetry breaking of the <i>β</i>-Ga<sub>2</sub>O<sub>3</sub>’s b–c plane results in a significant optical absorption dichroic ratio. Leveraging <i>β</i>-Ga<sub>2</sub>O<sub>3</sub>’s high solar-blind UV response, a lensless solar-blind UV polarization-sensitive photodetector, circumventing the challenges associated with solar-blind UV polarizers is designed. This photodetector exhibits an exceptionally high intrinsic polarization ratio under 254 nm linearly polarized light, approximately two orders of magnitude higher than other reported nanomaterial-based polarization-sensitive photodetectors. Additionally, it demonstrates significant advantages in solar-blind UV imaging and light communication. This work introduces a novel strategy for solar-blind ultraviolet polarization detection and offers a promising approach for solar-blind light communication.</p> -Peixin Liu, -Tongyu Zhang, -Yuxing Wu, -Qinjun Chen, -Tao Sun, -Chen Jiang +Kai Zhao, +Juehan Yang, +Pan Wang, +Ziqi Zhou, +Haoran Long, +Kaiyao Xin, +Can Liu, +Zheng Han, +Kaihui Liu, +Zhongming Wei Research Article - A Peptide‐Drug Conjugate‐Based Nanoplatform for Immunometabolic Activation and In Situ Nerve Regeneration in Advanced‐Stage Alzheimer's Disease - 10.1002/adma.202408729 + β‐Ga2O3 Nanoribbon with Ultra‐High Solar‐Blind Ultraviolet Polarization Ratio + 10.1002/adma.202406559 Advanced Materials - 10.1002/adma.202408729 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408729 + 10.1002/adma.202406559 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406559 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408774 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406611 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408774 - Fast and Efficient Fabrication of Functional Electronic Devices through Grayscale Digital Light Processing 3D Printing + 10.1002/adma.202406611 + Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities Advanced Materials, Volume 36, Issue 46, November 14, 2024. - -This study demonstrates the use of grayscale DLP 3D printing to fabricate polymeric composites with tailored conductivity. By manipulating light intensity and incorporating lithium ions, the process enables the creation of materials with conductivity differences exceeding three orders of magnitude, paving the way for low‐cost, rapid production of intricate electronic circuits and sensors. + The buckling of cylindrical shell structures upon depressurization is a well‐known phenomenon. If the shells are made of soft materials, the post‐buckling deformation can be fully recovered. Through a combination of experiments and simulations, the occurrence of a secondary instability in shells with a high buckling wave number is identified, which suddenly activates a coupled twisting‐folding deformation mode. This rich nonlinear behavior is harnessed to design soft robotic systems capable of executing sequential tasks with a single input signal. @@ -3074,48 +2965,46 @@ This study demonstrates the use of grayscale DLP 3D printing to fabricate polyme Abstract -Fabricating polymeric composites with desirable characteristics for electronic applications is a complex and costly process. Digital light processing (DLP) 3D printing emerges as a promising technique for manufacturing intricate structures. In this study, polymeric samples are fabricated with a conductivity difference exceeding three orders of magnitude in various portions of a part by employing grayscale DLP (g‐DLP) single‐vat single‐cure 3D printing deliberate resin design. This is realized through the manipulation of light intensity during the curing process. Specifically, the rational resin design with added lithium ions results in the polymer cured under the maximum UV‐light intensity exhibiting higher electrical resistance. Conversely, sections that are only partially cured retains uncured monomers, serving as a medium that facilitates ion mobility, consequently leading to higher conductivity. The versatility of g‐DLP allows precise control of light intensity in different regions during the printing process. This characteristic opens up possibilities for applications, notably the low‐cost, facile, and rapid production of complex electrical circuits and sensors. The utilization of this technique makes it feasible to fabricate materials with tailored conductivity and functionality, providing an innovative pathway to advance the accelerated and facile creation of sophisticated electronic devices. +The substantial deformation exhibited by hyperelastic cylindrical shells under pressurization makes them an ideal platform for programmable inflatable structures. If negative pressure is applied, the cylindrical shell will buckle, leading to a sequence of rich deformation modes, all of which are fully recoverable due to the hyperelastic material choice. While the initial buckling event under vacuum is well understood, here, the post‐buckling regime is explored and a region in the design space is identified in which a coupled twisting‐contraction deformation mode occurs; by carefully controlling the geometry of our homogeneous shells, the proportion of contraction versus twist can be controlled. Additionally, bending as a post‐buckling deformation mode can be unlocked by varying the thickness of our shells across the circumference. Since these soft shells can fully recover from substantial deformations caused by buckling, then these instability‐driven deformations are harnessed to build soft machines capable of a programmable sequence of movements with a single actuation input. - <img src="https://onlinelibrary.wiley.com/cms/asset/2b9f886c-6f95-4f72-89be-827172268279/adma202408774-gra-0001-m.png" - alt="Fast and Efficient Fabrication of Functional Electronic Devices through Grayscale Digital Light Processing 3D Printing"/> -<p>This study demonstrates the use of grayscale DLP 3D printing to fabricate polymeric composites with tailored conductivity. By manipulating light intensity and incorporating lithium ions, the process enables the creation of materials with conductivity differences exceeding three orders of magnitude, paving the way for low-cost, rapid production of intricate electronic circuits and sensors. + <img src="https://onlinelibrary.wiley.com/cms/asset/33d24a1a-c9c5-4c49-ad5e-dbf3f609dd5c/adma202406611-gra-0001-m.png" + alt="Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities"/><p>The buckling of cylindrical shell structures upon depressurization is a well-known phenomenon. If the shells are made of soft materials, the post-buckling deformation can be fully recovered. Through a combination of experiments and simulations, the occurrence of a secondary instability in shells with a high buckling wave number is identified, which suddenly activates a coupled twisting-folding deformation mode. This rich nonlinear behavior is harnessed to design soft robotic systems capable of executing sequential tasks with a single input signal. </p> <br/> <h2>Abstract</h2> -<p>Fabricating polymeric composites with desirable characteristics for electronic applications is a complex and costly process. Digital light processing (DLP) 3D printing emerges as a promising technique for manufacturing intricate structures. In this study, polymeric samples are fabricated with a conductivity difference exceeding three orders of magnitude in various portions of a part by employing grayscale DLP (g-DLP) single-vat single-cure 3D printing deliberate resin design. This is realized through the manipulation of light intensity during the curing process. Specifically, the rational resin design with added lithium ions results in the polymer cured under the maximum UV-light intensity exhibiting higher electrical resistance. Conversely, sections that are only partially cured retains uncured monomers, serving as a medium that facilitates ion mobility, consequently leading to higher conductivity. The versatility of g-DLP allows precise control of light intensity in different regions during the printing process. This characteristic opens up possibilities for applications, notably the low-cost, facile, and rapid production of complex electrical circuits and sensors. The utilization of this technique makes it feasible to fabricate materials with tailored conductivity and functionality, providing an innovative pathway to advance the accelerated and facile creation of sophisticated electronic devices.</p> +<p>The substantial deformation exhibited by hyperelastic cylindrical shells under pressurization makes them an ideal platform for programmable inflatable structures. If negative pressure is applied, the cylindrical shell will buckle, leading to a sequence of rich deformation modes, all of which are fully recoverable due to the hyperelastic material choice. While the initial buckling event under vacuum is well understood, here, the post-buckling regime is explored and a region in the design space is identified in which a coupled twisting-contraction deformation mode occurs; by carefully controlling the geometry of our homogeneous shells, the proportion of contraction versus twist can be controlled. Additionally, bending as a post-buckling deformation mode can be unlocked by varying the thickness of our shells across the circumference. Since these soft shells can fully recover from substantial deformations caused by buckling, then these instability-driven deformations are harnessed to build soft machines capable of a programmable sequence of movements with a single actuation input.</p> -Farzad Gholami, -Liang Yue, -Mingzhe Li, -Ayush Jain, -Akhlak Mahmood, -Marcus Fratarcangeli, -Rampi Ramprasad, -H. Jerry Qi +Yi Yang, +Helen Read, +Mohammed Sbai, +Ahmad Zareei, +Antonio Elia Forte, +David Melancon, +Katia Bertoldi Research Article - Fast and Efficient Fabrication of Functional Electronic Devices through Grayscale Digital Light Processing 3D Printing - 10.1002/adma.202408774 + Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities + 10.1002/adma.202406611 Advanced Materials - 10.1002/adma.202408774 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408774 + 10.1002/adma.202406611 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406611 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408988 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406706 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408988 - Enhanced Intramolecular Hole Transfer in Block Copolymer Enables >15% and Operational Stable Single‐Material–Organic Solar Cells + 10.1002/adma.202406706 + Ions‐induced Assembly of Perovskite Nanocomposites for Highly Efficient Light‐Emitting Diodes with EQE Exceeding 30% Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The impact of different synthetic protocols of block copolymer (BCP) is first investigated on the relevant photovoltaic properties. The more phase pure direct synthesis BCP exhibits enhanced intramolecular hole transfer, leading to a record efficiency of over 15% for single‐material–organic solar cells together with excellent long‐term operational stability. +This paper presents an ions‐induced crystallization method to synthesize perovskite dual‐phase nanocomposites of CsPbBr3 and Cs4PbBr6. This approach enlarges grain sizes, reduces trap density, and improves both light extraction efficiency and electrical characteristics. Consequently, green perovskite light‐emitting diodes with a maximum external quantum efficiencie exceeding 30% and a narrow full width at half‐maximum of 18 nm are achieved. @@ -3125,47 +3014,55 @@ The impact of different synthetic protocols of block copolymer (BCP) is first in Abstract -Recent studies on narrow bandgap all‐conjugated block copolymer (BCP) single‐material–organic solar cells (SMOSCs) have made unprecedented progress in power conversion efficiency (PCE); however, it still lacks understanding of the structure‐property relationship in these highly mixed materials. Herein, the impact of different synthetic protocols (direct synthesis (d‐BCP) versus sequential synthesis (s‐BCP)) is first investigated on the relevant photovoltaic properties. Targeting the same BCP, namely PBDB‐T‐b‐PYIT, it is found that the change in polymerization reaction leads to quite different optical and transport properties. The d‐BCP outputs a record‐high PCE of 15.02% for SMOSCs as well as enhanced operation stability under simulated 1‐sun illumination, which is significantly higher than that of s‐BCP (10.33%) and even close to its bulk heterojunction (BHJ) counterparts. Detailed transient absorption spectroscopy reveals ultrafast dynamics of charge transfer (CT) and exciton dissociation in BCP. In together with morphology characterization, it is revealed that the d‐BCP has more phase pure composition, enhanced molecular ordering, and higher intramolecular CT efficiency relative to those of s‐BCP. These findings gain insight into both the structure and carrier dynamic of BCP and demonstrate the possibility of achieving high‐efficiency and stable SMOSCs. +Metal halide perovskites, a cost‐effective class of semiconductos, hold great promise for display technologies that demand high‐efficiency, color‐pure light‐emitting diodes (LEDs). Early research on three‐dimensional (3D) perovskites showed low radiative efficiencies due to modest exciton binding energies. To inprove luminescence, reducing dimensionality or grain size has been a common approach. However, dividing the perovskite lattice into smaller units may hinder carrier transport, compromising electrical performance. Moreover, the increased surface area introduce additional surface trap states, leading to greater non‐radiative recombination. Here, an ions‐induced growth method is employed to assembe lattice‐anchored perovskite nanocomposites for efficient LEDs with high color purity. This approach enables the nanocomposite thin films, composed of 3D CsPbBr3 and its variant of zero‐dimensional (0D) Cs4PbBr6, to feature significant low trap‐assisted nonradiative recombination, enhanced light out‐coupling with a corrugated surface, and well‐balanced charge carrier transport. Based on the resultant 3D/0D perovskite nanocomposites, the perovskite LEDs (PeLEDs) achieving an remarkable external quantum efficiency of 31.0% at the emission peak of 521 nm with a narrow full width at half‐maximum of only 18 nm. This sets a new benchmark for color purity in high performance PeLED research, highlighting the significant advantage of this approach. - <img src="https://onlinelibrary.wiley.com/cms/asset/4a696f42-a308-4924-a37f-cb79e3f7b96b/adma202408988-gra-0001-m.png" - alt="Enhanced Intramolecular Hole Transfer in Block Copolymer Enables &gt;15% and Operational Stable Single-Material–Organic Solar Cells"/> -<p>The impact of different synthetic protocols of block copolymer (BCP) is first investigated on the relevant photovoltaic properties. The more phase pure direct synthesis BCP exhibits enhanced intramolecular hole transfer, leading to a record efficiency of over 15% for single-material–organic solar cells together with excellent long-term operational stability. + <img src="https://onlinelibrary.wiley.com/cms/asset/7d1faf85-53e4-45c7-9036-a853cd291528/adma202406706-gra-0001-m.png" + alt="Ions-induced Assembly of Perovskite Nanocomposites for Highly Efficient Light-Emitting Diodes with EQE Exceeding 30%"/> +<p>This paper presents an ions-induced crystallization method to synthesize perovskite dual-phase nanocomposites of CsPbBr<sub>3</sub> and Cs<sub>4</sub>PbBr<sub>6</sub>. This approach enlarges grain sizes, reduces trap density, and improves both light extraction efficiency and electrical characteristics. Consequently, green perovskite light-emitting diodes with a maximum external quantum efficiencie exceeding 30% and a narrow full width at half-maximum of 18 nm are achieved. </p> <br/> <h2>Abstract</h2> -<p>Recent studies on narrow bandgap all-conjugated block copolymer (BCP) single-material–organic solar cells (SMOSCs) have made unprecedented progress in power conversion efficiency (PCE); however, it still lacks understanding of the structure-property relationship in these highly mixed materials. Herein, the impact of different synthetic protocols (direct synthesis (<i>d</i>-BCP) versus sequential synthesis (<i>s</i>-BCP)) is first investigated on the relevant photovoltaic properties. Targeting the same BCP, namely PBDB-T-<i>b</i>-PYIT, it is found that the change in polymerization reaction leads to quite different optical and transport properties. The <i>d</i>-BCP outputs a record-high PCE of 15.02% for SMOSCs as well as enhanced operation stability under simulated 1-sun illumination, which is significantly higher than that of <i>s</i>-BCP (10.33%) and even close to its bulk heterojunction (BHJ) counterparts. Detailed transient absorption spectroscopy reveals ultrafast dynamics of charge transfer (CT) and exciton dissociation in BCP. In together with morphology characterization, it is revealed that the <i>d</i>-BCP has more phase pure composition, enhanced molecular ordering, and higher intramolecular CT efficiency relative to those of <i>s</i>-BCP. These findings gain insight into both the structure and carrier dynamic of BCP and demonstrate the possibility of achieving high-efficiency and stable SMOSCs.</p> +<p>Metal halide perovskites, a cost-effective class of semiconductos, hold great promise for display technologies that demand high-efficiency, color-pure light-emitting diodes (LEDs). Early research on three-dimensional (3D) perovskites showed low radiative efficiencies due to modest exciton binding energies. To inprove luminescence, reducing dimensionality or grain size has been a common approach. However, dividing the perovskite lattice into smaller units may hinder carrier transport, compromising electrical performance. Moreover, the increased surface area introduce additional surface trap states, leading to greater non-radiative recombination. Here, an ions-induced growth method is employed to assembe lattice-anchored perovskite nanocomposites for efficient LEDs with high color purity. This approach enables the nanocomposite thin films, composed of 3D CsPbBr<sub>3</sub> and its variant of zero-dimensional (0D) Cs<sub>4</sub>PbBr<sub>6</sub>, to feature significant low trap-assisted nonradiative recombination, enhanced light out-coupling with a corrugated surface, and well-balanced charge carrier transport. Based on the resultant 3D/0D perovskite nanocomposites, the perovskite LEDs (PeLEDs) achieving an remarkable external quantum efficiency of 31.0% at the emission peak of 521 nm with a narrow full width at half-maximum of only 18 nm. This sets a new benchmark for color purity in high performance PeLED research, highlighting the significant advantage of this approach.</p> -Bin Li, -Yuxin Kong, -Tao Li, -Hongxiang Li, -Haibin Zhao, -Pei Cheng, -Jianyu Yuan - - Research Article - Enhanced Intramolecular Hole Transfer in Block Copolymer Enables >15% and Operational Stable Single‐Material–Organic Solar Cells - 10.1002/adma.202408988 +Zhaohui Xing, +Guangrong Jin, +Qing Du, +Peiyuan Pang, +Tanghao Liu, +Yang Shen, +Dengliang Zhang, +Bufan Yu, +Yue Liang, +Dezhi Yang, +Jianxin Tang, +Lei Wang, +Guichuan Xing, +Jiangshan Chen, +Dongge Ma + + Research Article + Ions‐induced Assembly of Perovskite Nanocomposites for Highly Efficient Light‐Emitting Diodes with EQE Exceeding 30% + 10.1002/adma.202406706 Advanced Materials - 10.1002/adma.202408988 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408988 + 10.1002/adma.202406706 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406706 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409015 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406772 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409015 - Polypyridiniums with Inherent Autophagy‐Inducing Activity for Atherosclerosis Treatment by Intracellularly Co‐Delivering Two Antioxidant Enzymes + 10.1002/adma.202406772 + Giant Hall Switching by Surface‐State‐Mediated Spin‐Orbit Torque in a Hard Ferromagnetic Topological Insulator Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A series of polypyridiniums are proposed to effectively deliver two antioxidant enzymes into cytosolic of treated cells to down‐regulate lipopolysaccharide induced ROS. Moreover, the material itself can efficiently activate the autophagy in macrophages and inhibit foam cell formation. After being coated with neutrophil membranes, the polymer/protein complexes successfully halted the progression of atherosclerosis in ApoE‐/‐ mice upon intravenous injection. +Highly efficient current‐driven spin‐orbit torque (SOT) switching is observed in a hard ferromagnetic topological insulator (TI), V‐doped (Bi,Sb)2Te3 (VBST), with a record large switched anomalous Hall resistance of 9.2 kΩ by current. The SOT efficiency is significantly enhanced by Fermi level tuning, as VBST exhibits a transition from edge‐state‐mediated to surface‐state‐mediated transport. @@ -3175,50 +3072,61 @@ A series of polypyridiniums are proposed to effectively deliver two antioxidant Abstract -Atherosclerosis is a chronic inflammatory disease of the arterial intima and is becoming the leading cause of morbidity and mortality worldwide. There is considerable evidence that defective autophagy and overproduction of reactive oxygen species (ROS) are closely involved in the development and progression of atherosclerosis. Here, a polymer is developed with the inherent autophagy‐inducing activity to treat atherosclerosis by co‐delivering antioxidant enzymes. The lead material P5c screened from a library of polypyridiniums shows robust efficacy in cytosolic protein delivery, and efficiently delivers superoxide dismutase (SOD) and catalase (CAT) into macrophages to down‐regulate intracellular ROS. Moreover, P5c activates autophagy in macrophages and sufficiently inhibits foam cell formation. The P5c nanoparticle loaded with both SOD and CAT is further coated with neutrophil membranes to treat atherosclerosis in an ApoE−/− mice model. The treatment exhibits potent anti‐atherosclerosis effect via activating autophagy, decreasing the infiltration of senescent cells in atherosclerotic plaques, regulating the M2 polarization of macrophages, and restoring the structure and function of splenic corpuscles. The polymer offers a multifaceted approach to combat atherosclerosis, addressing both cellular dysfunction and the need for targeted protein delivery within affected cells. +Topological insulators (TI) and magnetic topological insulators (MTI) can apply highly efficient spin‐orbit torque (SOT) and manipulate the magnetization with their unique topological surface states (TSS) with ultrahigh efficiency. Here, efficient SOT switching of a hard MTI, V‐doped (Bi,Sb)2Te3 (VBST), with a large coercive field that can prevent the influence of an external magnetic field, is demonstrated. A giant switched anomalous Hall resistance of 9.2 kΩ is realized, among the largest of all SOT systems, which makes the Hall channel a good readout and eliminates the need to fabricate complicated magnetic tunnel junction (MTJ) structures. The SOT switching current density can be reduced to 2.8 × 105 A cm−2, indicating its high efficiency. Moreover, as the Fermi level is moved away from the Dirac point by both gate and composition tuning, VBST exhibits a transition from edge‐state‐mediated to surface‐state‐mediated transport, thus enhancing the SOT effective field to (1.56 ± 0.12) × 10−6 T A−1 cm2 and the interfacial charge‐to‐spin conversion efficiency to 3.9 ± 0.3 nm−1. The findings establish VBST as an extraordinary candidate for energy‐efficient magnetic memory devices. - <img src="https://onlinelibrary.wiley.com/cms/asset/62b6667c-2e4c-4c0a-a5b4-35b8de0a3f62/adma202409015-gra-0001-m.png" - alt="Polypyridiniums with Inherent Autophagy-Inducing Activity for Atherosclerosis Treatment by Intracellularly Co-Delivering Two Antioxidant Enzymes"/> -<p>A series of polypyridiniums are proposed to effectively deliver two antioxidant enzymes into cytosolic of treated cells to down-regulate lipopolysaccharide induced ROS. Moreover, the material itself can efficiently activate the autophagy in macrophages and inhibit foam cell formation. After being coated with neutrophil membranes, the polymer/protein complexes successfully halted the progression of atherosclerosis in ApoE<sup>-/-</sup> mice upon intravenous injection. + <img src="https://onlinelibrary.wiley.com/cms/asset/b5536829-d79c-4a54-99c9-08ccfb19309c/adma202406772-gra-0001-m.png" + alt="Giant Hall Switching by Surface-State-Mediated Spin-Orbit Torque in a Hard Ferromagnetic Topological Insulator"/> +<p>Highly efficient current-driven spin-orbit torque (SOT) switching is observed in a hard ferromagnetic topological insulator (TI), V-doped (Bi,Sb)<sub>2</sub>Te<sub>3</sub> (VBST), with a record large switched anomalous Hall resistance of 9.2 kΩ by current. The SOT efficiency is significantly enhanced by Fermi level tuning, as VBST exhibits a transition from edge-state-mediated to surface-state-mediated transport. </p> <br/> <h2>Abstract</h2> -<p>Atherosclerosis is a chronic inflammatory disease of the arterial intima and is becoming the leading cause of morbidity and mortality worldwide. There is considerable evidence that defective autophagy and overproduction of reactive oxygen species (ROS) are closely involved in the development and progression of atherosclerosis. Here, a polymer is developed with the inherent autophagy-inducing activity to treat atherosclerosis by co-delivering antioxidant enzymes. The lead material P5c screened from a library of polypyridiniums shows robust efficacy in cytosolic protein delivery, and efficiently delivers superoxide dismutase (SOD) and catalase (CAT) into macrophages to down-regulate intracellular ROS. Moreover, P5c activates autophagy in macrophages and sufficiently inhibits foam cell formation. The P5c nanoparticle loaded with both SOD and CAT is further coated with neutrophil membranes to treat atherosclerosis in an ApoE<sup>−/−</sup> mice model. The treatment exhibits potent anti-atherosclerosis effect via activating autophagy, decreasing the infiltration of senescent cells in atherosclerotic plaques, regulating the M2 polarization of macrophages, and restoring the structure and function of splenic corpuscles. The polymer offers a multifaceted approach to combat atherosclerosis, addressing both cellular dysfunction and the need for targeted protein delivery within affected cells.</p> +<p>Topological insulators (TI) and magnetic topological insulators (MTI) can apply highly efficient spin-orbit torque (SOT) and manipulate the magnetization with their unique topological surface states (TSS) with ultrahigh efficiency. Here, efficient SOT switching of a hard MTI, V-doped (Bi,Sb)<sub>2</sub>Te<sub>3</sub> (VBST), with a large coercive field that can prevent the influence of an external magnetic field, is demonstrated. A giant switched anomalous Hall resistance of 9.2 kΩ is realized, among the largest of all SOT systems, which makes the Hall channel a good readout and eliminates the need to fabricate complicated magnetic tunnel junction (MTJ) structures. The SOT switching current density can be reduced to 2.8 × 10<sup>5 </sup>A<sup> </sup>cm<sup>−2</sup>, indicating its high efficiency. Moreover, as the Fermi level is moved away from the Dirac point by both gate and composition tuning, VBST exhibits a transition from edge-state-mediated to surface-state-mediated transport, thus enhancing the SOT effective field to (1.56 ± 0.12) × 10<sup>−6 </sup>T<sup> </sup>A<sup>−1 </sup>cm<sup>2</sup> and the interfacial charge-to-spin conversion efficiency to 3.9 ± 0.3 nm<sup>−1</sup>. The findings establish VBST as an extraordinary candidate for energy-efficient magnetic memory devices.</p> -Mengxiao Liang, -Qian Wang, -Song Zhang, -Qi Lan, -Ruijue Wang, -Echuan Tan, -Lei Zhou, -Changping Wang, -Hui Wang, -Yiyun Cheng +Lixuan Tai, +Haoran He, +Su Kong Chong, +Huairuo Zhang, +Hanshen Huang, +Gang Qiu, +Yuxing Ren, +Yaochen Li, +Hung‐Yu Yang, +Ting‐Hsun Yang, +Xiang Dong, +Bingqian Dai, +Tao Qu, +Qingyuan Shu, +Quanjun Pan, +Peng Zhang, +Fei Xue, +Jie Li, +Albert V. Davydov, +Kang L. Wang Research Article - Polypyridiniums with Inherent Autophagy‐Inducing Activity for Atherosclerosis Treatment by Intracellularly Co‐Delivering Two Antioxidant Enzymes - 10.1002/adma.202409015 + Giant Hall Switching by Surface‐State‐Mediated Spin‐Orbit Torque in a Hard Ferromagnetic Topological Insulator + 10.1002/adma.202406772 Advanced Materials - 10.1002/adma.202409015 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409015 + 10.1002/adma.202406772 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406772 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409059 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407009 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409059 - Giant Capacitive Energy Storage in High‐Entropy Lead‐Free Ceramics with Temperature Self‐Check + 10.1002/adma.202407009 + Elastocaloric Heat Pump by Twist Induced Periodical Non‐Linear Stress for Low Hysteresis and High Carnot Efficiency Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Herein, octahedral tilt and cationic displacement are observed in high entropy (HE) BNT‐ based ceramics. On the basis of tape‐casting process and cold isostatic pressing, the optimal ceramics display a large Wrec (10.46 J cm−3) at 685 kV cm−1 and a high power density (332.88 MW cm−3). Importantly, Tm/Yb codoping endows the ceramics with fluorescent temperature self‐check feature. +Fiber twisting induces periodic non‐linear stress, leading to high elastocaloric performance and material COP. A novel elastocaloric heat pump is designed using this technique, incorporating a three‐port valve and a pump to separate the cooling and heating media, which results in low hysteresis, high efficiency, enhanced durability, and excellent cooling. + @@ -3228,59 +3136,53 @@ Herein, octahedral tilt and cationic displacement are observed in high entropy ( Abstract -Considering the large demand for electricity in the era of artificial intelligence and big data, there is an urgent need to explore novel energy storage media with higher energy density and intelligent temperature self‐check functions. High‐entropy (HE) ceramic capacitors are of great significance because of their excellent energy storage efficiency and high power density (PD). However, the contradiction between configurational entropy and polarization in traditional HE systems greatly restrains the increase in energy storage density. Herein, the contradiction is effectively solved by regulating the octahedral tilt and cationic displacement in ABO3‐type perovskite HE ceramics, i.e., (1‐x)[0.6(Bi0.47Na0.47Yb0.03Tm0.01)TiO3‐0.4(Ba0.5Sr0.5)TiO3]‐xSr(Zr0.5Hf0.5)O3 (BNYTT‐BST‐xSZH). Combining the tape‐casting process and cold isostatic pressing, the optimal BNYTT‐BST‐0.06SZH ceramic displays a large recoverable energy storage density (10.46 J cm−3) at 685 kV cm−1 and a high PD (332.88 MW cm−3). More importantly, due to Tm/Yb codoping, abnormal fluorescent negative thermal expansion and excellent real‐time temperature sensing are developed, thus the application of fault detection and warning in high‐voltage transmission line systems is conceptualized. This study provides an effective strategy for enhancing the polarization of energy‐storing HE ceramics and offers a promising material for overcoming the problems of insufficient capacitor density and thermal runaway in terminal communication. +Elastocaloric cooling is one of the most promising solid‐state cooling approaches to address the issues of energy shortage and global warming. However, the cooling efficiency and cycle life of this technology need to be improved, and the required driving force shall be reduced. Here, a novel elastocaloric heat pump by periodic non‐linear stress is developed by employing fiber twisting and separated cooling and heating media. The non‐linear stress generated by fiber twisting yields a hierarchical, rigid‐yet‐flexible architecture and a periodic entropy spatial distribution, which result in a low mechanical hysteresis work and a high cooling efficiency (a maximum material coefficient of performance (COP) of 30.8 and a maximum Carnot efficiency of 82%). The torsional non‐linear stress inhibits crack propagation and results in a highly extended cycle life (14752 cycles, more than ten times of fiber stretching). The heat pump exhibits a maximum average temperature span of 25.6 K, a maximum specific cooling power of 1850 W Kg−1, a maximum device COP of 19.5, and a maximum device power of 5.0 W, under each optimal condition. - <img src="https://onlinelibrary.wiley.com/cms/asset/c927c5ce-a2bf-445d-9e20-6350c3560329/adma202409059-gra-0001-m.png" - alt="Giant Capacitive Energy Storage in High-Entropy Lead-Free Ceramics with Temperature Self-Check"/> -<p>Herein, octahedral tilt and cationic displacement are observed in high entropy (HE) BNT- based ceramics. On the basis of tape-casting process and cold isostatic pressing, the optimal ceramics display a large <i>W</i> -<sub>rec</sub> (10.46 J cm<sup>−3</sup>) at 685 kV cm<sup>−1</sup> and a high power density (332.88 MW cm<sup>−3</sup>). Importantly, Tm/Yb codoping endows the ceramics with fluorescent temperature self-check feature. + <img src="https://onlinelibrary.wiley.com/cms/asset/72418722-ab2e-4dde-adbc-04d413f37578/adma202407009-gra-0001-m.png" + alt="Elastocaloric Heat Pump by Twist Induced Periodical Non-Linear Stress for Low Hysteresis and High Carnot Efficiency"/> +<p>Fiber twisting induces periodic non-linear stress, leading to high elastocaloric performance and material COP. A novel elastocaloric heat pump is designed using this technique, incorporating a three-port valve and a pump to separate the cooling and heating media, which results in low hysteresis, high efficiency, enhanced durability, and excellent cooling. </p> <br/> <h2>Abstract</h2> -<p>Considering the large demand for electricity in the era of artificial intelligence and big data, there is an urgent need to explore novel energy storage media with higher energy density and intelligent temperature self-check functions. High-entropy (HE) ceramic capacitors are of great significance because of their excellent energy storage efficiency and high power density (<i>P</i> -<sub>D</sub>). However, the contradiction between configurational entropy and polarization in traditional HE systems greatly restrains the increase in energy storage density. Herein, the contradiction is effectively solved by regulating the octahedral tilt and cationic displacement in ABO<sub>3</sub>-type perovskite HE ceramics, i.e., (1-<i>x</i>)[0.6(Bi<sub>0.47</sub>Na<sub>0.47</sub>Yb<sub>0.03</sub>Tm<sub>0.01</sub>)TiO<sub>3</sub>-0.4(Ba<sub>0.5</sub>Sr<sub>0.5</sub>)TiO<sub>3</sub>]-<i>x</i>Sr(Zr<sub>0.5</sub>Hf<sub>0.5</sub>)O<sub>3</sub> (BNYTT-BST-<i>x</i>SZH). Combining the tape-casting process and cold isostatic pressing, the optimal BNYTT-BST-0.06SZH ceramic displays a large recoverable energy storage density (10.46 J cm<sup>−3</sup>) at 685 kV cm<sup>−1</sup> and a high <i>P</i> -<sub>D</sub> (332.88 MW cm<sup>−3</sup>). More importantly, due to Tm/Yb codoping, abnormal fluorescent negative thermal expansion and excellent real-time temperature sensing are developed, thus the application of fault detection and warning in high-voltage transmission line systems is conceptualized. This study provides an effective strategy for enhancing the polarization of energy-storing HE ceramics and offers a promising material for overcoming the problems of insufficient capacitor density and thermal runaway in terminal communication.</p> +<p>Elastocaloric cooling is one of the most promising solid-state cooling approaches to address the issues of energy shortage and global warming. However, the cooling efficiency and cycle life of this technology need to be improved, and the required driving force shall be reduced. Here, a novel elastocaloric heat pump by periodic non-linear stress is developed by employing fiber twisting and separated cooling and heating media. The non-linear stress generated by fiber twisting yields a hierarchical, rigid-yet-flexible architecture and a periodic entropy spatial distribution, which result in a low mechanical hysteresis work and a high cooling efficiency (a maximum material coefficient of performance (<i>COP</i>) of 30.8 and a maximum Carnot efficiency of 82%). The torsional non-linear stress inhibits crack propagation and results in a highly extended cycle life (14752 cycles, more than ten times of fiber stretching). The heat pump exhibits a maximum average temperature span of 25.6 K, a maximum specific cooling power of 1850 W Kg<sup>−1</sup>, a maximum device <i>COP</i> of 19.5, and a maximum device power of 5.0 W, under each optimal condition.</p> -Xiangfu Zeng, -Jinfeng Lin, -Jie Shen, -Yan Chen, -Wei Xu, -Luomeng Tang, -Simin Wang, -Min Gao, -Chunlin Zhao, -Tengfei Lin, -Laihui Luo, -Chao Chen, -Baisheng Sa, -Cong Lin, -Xiao Wu, -Jiwei Zhai +Yicheng Xiao, +Guangkai Mei, +Danyang Feng, +Wubin Zhao, +Wenjin Guo, +Xueqi Leng, +Dong Qian, +Weiqiang Zhao, +Jie Bai, +Zongqian Wang, +Meifang Zhu, +Xiang Zhou, +Zunfeng Liu Research Article - Giant Capacitive Energy Storage in High‐Entropy Lead‐Free Ceramics with Temperature Self‐Check - 10.1002/adma.202409059 + Elastocaloric Heat Pump by Twist Induced Periodical Non‐Linear Stress for Low Hysteresis and High Carnot Efficiency + 10.1002/adma.202407009 Advanced Materials - 10.1002/adma.202409059 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409059 + 10.1002/adma.202407009 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407009 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409090 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407124 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409090 - Metal Halide Perovskite Nanocrystals‐Intermediated Hydrogel for Boosting the Biosensing Performance + 10.1002/adma.202407124 + A Perspective on Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Mn2+‐doped CsPbCl3/CsPb2Cl5 core/shell hetero perovskite nanocrystals with superior water stability are obtained via a trinity strategy by integrating Mn (II) substitution with CsPb2Cl5 inert shell and NH2‐PEG‐COOH coating. Hetero perovskite nanocrystals‐based hydrogel biosensor provides pesticide information on food products, achieving on‐site monitoring of chlorpyrifos at the nanogram per milliliter level. +This perspective covers the material design strategies for the Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals. It also highlights how lab‐scale catalysis can be translated to real‐time industrial level consumption of flue gas mixture by electrochemical catalysis. @@ -3290,47 +3192,42 @@ Mn2+‐doped CsPbCl3/CsPb2Cl5 core/shell hetero perovskite nanocrystals with Abstract -Metal‐halide perovskites have become attractive nanomaterials for advanced biosensors, yet the structural design remains challenging due to the trade‐off between environmental stability and sensing sensitivity. Herein, a trinity strategy is proposed to address this issue by integrating Mn (II) substitution with CsPb2Cl5 inert shell and NH2‐PEG‐COOH coating for designing Mn2+‐doped CsPbCl3/CsPb2Cl5 core/shell hetero perovskite nanocrystals (PMCP PNCs). The trinity strategy isolates the emissive Mn2+‐doped CsPbCl3 core from water and the Mn2+ d–d transition generates photoluminescence with a long lifetime, endowing the NH2‐PEG‐COOH capped Mn2+‐doped CsPbCl3/CsPb2Cl5 PNCs with robust water stability and oxygen‐sensitive property. Given the structural integration, photoluminescent hydrogel biosensors are designed by embedding the PMCP PNCs into the hydrogel system to deliver on‐site pesticide information on food products. Impressively, benefiting from the dual enzyme triggered‐responsive property of PMCP PNCs, the hydrogel biosensor is endowed with ultra‐high sensitivity toward chlorpyrifos pesticide at the nanogram per milliliter level. Such a robust PMCP PNCs‐based hydrogel sensor can provide accurate pesticide information while guiding the construction of photoluminescent biosensors for upcoming on‐site applications. +Electrochemical CO2 reduction reaction (eCO2RR) has been explored extensively for mitigation of noxious CO2 gas generating C1 and C2+ hydrocarbons and oxygenates as value‐added fuels and chemicals with remarkable selectivity. The source of CO2 being a pure CO2 feed, it does not fully satisfy the real‐time digestion of industrial exhausts. Besides the detrimental effect of noxious gas mixture leading to global warming, there is a huge capital investment in purifying the flue gas mixtures from industries. The presence of other impurity gases affects the eCO2RR mechanism and its activity and selectivity toward C2+ products dwindle drastically. Impurities like NOx, SOx, O2, N2, and halide ions present in flue gas mixture reduce the conversion and selectivity of eCO2RR significantly. Instead of wiping out these impurities via separation processes, new strategies from material chemistry and electrochemistry can open new avenues for turning foes to friends! In this perspective, the co‐electroreduction will vividly discussed and supporting role of different heteroatom‐containing impurity gases with CO2, generating highly stable C─N, C─S, C─X bonds, and highlight the existing limitations and providing probable solutions for attaining further success in this field and translating this to industrial exhaust streams. - <img src="https://onlinelibrary.wiley.com/cms/asset/e326666e-fa3e-4e5a-815d-2ea3219de4af/adma202409090-gra-0001-m.png" - alt="Metal Halide Perovskite Nanocrystals-Intermediated Hydrogel for Boosting the Biosensing Performance"/> -<p>Mn<sup>2+</sup>-doped CsPbCl<sub>3</sub>/CsPb<sub>2</sub>Cl<sub>5</sub> core/shell hetero perovskite nanocrystals with superior water stability are obtained via a trinity strategy by integrating Mn (II) substitution with CsPb<sub>2</sub>Cl<sub>5</sub> inert shell and NH<sub>2</sub>-PEG-COOH coating. Hetero perovskite nanocrystals-based hydrogel biosensor provides pesticide information on food products, achieving on-site monitoring of chlorpyrifos at the nanogram per milliliter level. + <img src="https://onlinelibrary.wiley.com/cms/asset/ba8f8b23-69f5-4966-b14c-2806f67bcbd9/adma202407124-gra-0001-m.png" + alt="A Perspective on Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals"/> +<p>This perspective covers the material design strategies for the Electrochemical Point Source Utilization of CO<sub>2</sub> and Other Flue Gas Components to Value Added Chemicals. It also highlights how lab-scale catalysis can be translated to real-time industrial level consumption of flue gas mixture by electrochemical catalysis. </p> <br/> <h2>Abstract</h2> -<p>Metal-halide perovskites have become attractive nanomaterials for advanced biosensors, yet the structural design remains challenging due to the trade-off between environmental stability and sensing sensitivity. Herein, a trinity strategy is proposed to address this issue by integrating Mn (II) substitution with CsPb<sub>2</sub>Cl<sub>5</sub> inert shell and NH<sub>2</sub>-PEG-COOH coating for designing Mn<sup>2+</sup>-doped CsPbCl<sub>3</sub>/CsPb<sub>2</sub>Cl<sub>5</sub> core/shell hetero perovskite nanocrystals (PMCP PNCs). The trinity strategy isolates the emissive Mn<sup>2+</sup>-doped CsPbCl<sub>3</sub> core from water and the Mn<sup>2+</sup> d–d transition generates photoluminescence with a long lifetime, endowing the NH<sub>2</sub>-PEG-COOH capped Mn<sup>2+</sup>-doped CsPbCl<sub>3</sub>/CsPb<sub>2</sub>Cl<sub>5</sub> PNCs with robust water stability and oxygen-sensitive property. Given the structural integration, photoluminescent hydrogel biosensors are designed by embedding the PMCP PNCs into the hydrogel system to deliver on-site pesticide information on food products. Impressively, benefiting from the dual enzyme triggered-responsive property of PMCP PNCs, the hydrogel biosensor is endowed with ultra-high sensitivity toward chlorpyrifos pesticide at the nanogram per milliliter level. Such a robust PMCP PNCs-based hydrogel sensor can provide accurate pesticide information while guiding the construction of photoluminescent biosensors for upcoming on-site applications.</p> +<p>Electrochemical CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR) has been explored extensively for mitigation of noxious CO<sub>2</sub> gas generating C<sub>1</sub> and C<sub>2+</sub> hydrocarbons and oxygenates as value-added fuels and chemicals with remarkable selectivity. The source of CO<sub>2</sub> being a pure CO<sub>2</sub> feed, it does not fully satisfy the real-time digestion of industrial exhausts. Besides the detrimental effect of noxious gas mixture leading to global warming, there is a huge capital investment in purifying the flue gas mixtures from industries. The presence of other impurity gases affects the eCO<sub>2</sub>RR mechanism and its activity and selectivity toward C<sub>2+</sub> products dwindle drastically. Impurities like NO<sub>x</sub>, SO<sub>x</sub>, O<sub>2</sub>, N<sub>2</sub>, and halide ions present in flue gas mixture reduce the conversion and selectivity of eCO<sub>2</sub>RR significantly. Instead of wiping out these impurities via separation processes, new strategies from material chemistry and electrochemistry can open new avenues for turning foes to friends! In this perspective, the co-electroreduction will vividly discussed and supporting role of different heteroatom-containing impurity gases with CO<sub>2</sub>, generating highly stable C─N, C─S, C─X bonds, and highlight the existing limitations and providing probable solutions for attaining further success in this field and translating this to industrial exhaust streams.</p> -Hongxia Li, -Yanan Hu, -Yan Zhang, -Hao Zhang, -Dong Yao, -Yuehe Lin, -Xu Yan +Soumi Mondal, +Sebastian C. Peter - Research Article - Metal Halide Perovskite Nanocrystals‐Intermediated Hydrogel for Boosting the Biosensing Performance - 10.1002/adma.202409090 + Perspective + A Perspective on Electrochemical Point Source Utilization of CO2 and Other Flue Gas Components to Value Added Chemicals + 10.1002/adma.202407124 Advanced Materials - 10.1002/adma.202409090 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409090 - Research Article + 10.1002/adma.202407124 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407124 + Perspective 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409297 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407305 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409297 - Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye‐Incorporated Photonic Crystal‐Based Sensor Array + 10.1002/adma.202407305 + Conjugated Polymer‐Based Photo‐Crosslinker for Efficient Photo‐Patterning of Polymer Semiconductors Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A colorimetric sensor array composed of dye‐incorporated colloidal photonic crystals is fabricated for detecting volatile organic compounds (VOCs). The overlap between the photonic bandgap edge and the absorption peak of the dye enhances color changes. The sensor array generates distinct color difference maps for acetaldehyde, acetone, and acetic acid, respectively, with the limit of detection as low as 0.02 ppm, without any data amplification. +A new conjugated polymer‐based photo‐crosslinker, PN3, with phenyl‐substituted azide groups in the side chains, is developed for efficient photo‐patterning of polymer semiconductors with superior performance, featuring a significantly low UV light exposure dose, high sensitivity (S), and high contrast (γ). @@ -3340,45 +3237,51 @@ A colorimetric sensor array composed of dye‐incorporated colloidal photoni Abstract -Chemoresponsive dyes offer the potential to selectively detect volatile organic compounds (VOCs) unique to certain disease states. Among different VOC sensing techniques, colorimetric sensing offers the advantage of facile recognition. However, it is often challenging to discern the color changes by the naked eye. Here, highly sensitive colorimetric VOC sensor arrays from dye‐incorporated colloidal photonic crystals (dye‐cPhCs) are reported. cPhCs are scalably fabricated on a 4‐inch wafer by spin‐coating of silica nanoparticles (NPs) dispersed in a photo‐cross‐linkable monomer, where the gradient shear flow along the film thickness creates densely‐packed square arrays of NPs in the top layers, whereas the bulk is quasi‐amorphous with larger periodicities. The broadened reflection peak allows for augmented dye absorption originating from the overlap between the photonic bandgap edge of the cPhC and the dye absorption peak, leading to a more noticeable color change upon exposure to VOCs. The sensor array generates distinct color difference maps for acetaldehyde, acetone, and acetic acid, respectively, without any data amplification. The limit of detection for acetaldehyde, acetone, and acetic acid is 1, 0.1, and 0.02 ppm, respectively. Moreover, VOC can be diagonalized by visually intuitive pattern recognition, and principal component analysis at reduced dimensionality is demonstrated. +Photo‐patterning of polymer semiconductors using photo‐crosslinkers has shown potential for organic circuit fabrication via solution processing techniques. However, the performance of patterning, including resolution (R), UV light exposure dose, sensitivity (S), and contrast (γ), remains unsatisfactory. In this study, a novel conjugated polymer based photo‐crosslinker (PN3, Figure 1a) is reported for the first time, which entails phenyl‐substituted azide groups in its side chains. Due to the potential π–π interactions between the conjugated backbone of PN3 and those of polymer semiconductors, PN3 exhibits superior miscibility with polymer semiconductors compared to the commonly used small molecule photo‐crosslinker 4Bx (Figure 1a). Consequently, photo‐patterning of polymer semiconductors with PN3 demonstrates improved performance with much lower UV light exposure dose, higher S and higher γ compared to 4Bx. By utilizing electron beam lithography, patterned arrays of polymer semiconductors with resolutions down to 500 nm and clearer edges are successfully fabricated using PN3. Furthermore, patterned arrays of PDPP4T, the p‐type semiconductor (Figure 1b), after being doped, can function as source‐drain electrodes for fabricating field‐effect transistors (FETs) with comparable charge mobility and significantly lower sub‐threshold swing value compared to those with gold electrodes. - <img src="https://onlinelibrary.wiley.com/cms/asset/77546715-3a1c-4fa9-8ca4-dbd251d0c660/adma202409297-gra-0001-m.png" - alt="Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye-Incorporated Photonic Crystal-Based Sensor Array"/> -<p>A colorimetric sensor array composed of dye-incorporated colloidal photonic crystals is fabricated for detecting volatile organic compounds (VOCs). The overlap between the photonic bandgap edge and the absorption peak of the dye enhances color changes. The sensor array generates distinct color difference maps for acetaldehyde, acetone, and acetic acid, respectively, with the limit of detection as low as 0.02 ppm, without any data amplification. + <img src="https://onlinelibrary.wiley.com/cms/asset/bc33a272-2dbf-4582-88e3-0a2bbd947c2e/adma202407305-gra-0001-m.png" + alt="Conjugated Polymer-Based Photo-Crosslinker for Efficient Photo-Patterning of Polymer Semiconductors"/> +<p>A new conjugated polymer-based photo-crosslinker, <b>PN3</b>, with phenyl-substituted azide groups in the side chains, is developed for efficient photo-patterning of polymer semiconductors with superior performance, featuring a significantly low UV light exposure dose, high sensitivity (<i>S</i>), and high contrast (<i>γ</i>). </p> <br/> <h2>Abstract</h2> -<p>Chemoresponsive dyes offer the potential to selectively detect volatile organic compounds (VOCs) unique to certain disease states. Among different VOC sensing techniques, colorimetric sensing offers the advantage of facile recognition. However, it is often challenging to discern the color changes by the naked eye. Here, highly sensitive colorimetric VOC sensor arrays from dye-incorporated colloidal photonic crystals (dye-cPhCs) are reported. cPhCs are scalably fabricated on a 4-inch wafer by spin-coating of silica nanoparticles (NPs) dispersed in a photo-cross-linkable monomer, where the gradient shear flow along the film thickness creates densely-packed square arrays of NPs in the top layers, whereas the bulk is quasi-amorphous with larger periodicities. The broadened reflection peak allows for augmented dye absorption originating from the overlap between the photonic bandgap edge of the cPhC and the dye absorption peak, leading to a more noticeable color change upon exposure to VOCs. The sensor array generates distinct color difference maps for acetaldehyde, acetone, and acetic acid, respectively, without any data amplification. The limit of detection for acetaldehyde, acetone, and acetic acid is 1, 0.1, and 0.02 ppm, respectively. Moreover, VOC can be diagonalized by visually intuitive pattern recognition, and principal component analysis at reduced dimensionality is demonstrated.</p> +<p>Photo-patterning of polymer semiconductors using photo-crosslinkers has shown potential for organic circuit fabrication via solution processing techniques. However, the performance of patterning, including resolution (<i>R</i>), UV light exposure dose, sensitivity (<i>S</i>), and contrast (<i>γ</i>), remains unsatisfactory. In this study, a novel conjugated polymer based photo-crosslinker (<b>PN3</b>, Figure 1a) is reported for the first time, which entails phenyl-substituted azide groups in its side chains. Due to the potential <i>π</i>–<i>π</i> interactions between the conjugated backbone of <b>PN3</b> and those of polymer semiconductors, <b>PN3</b> exhibits superior miscibility with polymer semiconductors compared to the commonly used small molecule photo-crosslinker <b>4Bx</b> (Figure 1a). Consequently, photo-patterning of polymer semiconductors with <b>PN3</b> demonstrates improved performance with much lower UV light exposure dose, higher <i>S</i> and higher <i>γ</i> compared to <b>4Bx</b>. By utilizing electron beam lithography, patterned arrays of polymer semiconductors with resolutions down to 500 nm and clearer edges are successfully fabricated using <b>PN3</b>. Furthermore, patterned arrays of <b>PDPP4T</b>, the <i>p</i>-type semiconductor (Figure 1b), after being doped, can function as source-drain electrodes for fabricating field-effect transistors (FETs) with comparable charge mobility and significantly lower sub-threshold swing value compared to those with gold electrodes.</p> -So Hee Nah, -Jong Bin Kim, -Hiu Ning Tiffany Chui, -Yeonjoon Suh, -Shu Yang +Xiang Xue, +Cheng Li, +Qi Zhou, +Xiaobo Yu, +Chenying Gao, +Kaiyuan Chenchai, +Junchao Liao, +Zhichun Shangguan, +Xisha Zhang, +Guanxin Zhang, +Deqing Zhang Research Article - Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye‐Incorporated Photonic Crystal‐Based Sensor Array - 10.1002/adma.202409297 + Conjugated Polymer‐Based Photo‐Crosslinker for Efficient Photo‐Patterning of Polymer Semiconductors + 10.1002/adma.202407305 Advanced Materials - 10.1002/adma.202409297 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409297 + 10.1002/adma.202407305 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407305 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409319 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407663 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409319 - Homogenizing Energy Landscape for Efficient and Spectrally Stable Blue Perovskite Light‐Emitting Diodes + 10.1002/adma.202407663 + Controlling the Relaxation Dynamics of Polymer Networks by Combining Associative and Dissociative Dynamic Covalent Bonds Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Dual modification on both bulk and interface is proposed to homogenize the energy landscape throughout the entire blue perovskite by comprehensively diminishing the low dimensional phases and reducing the halide defects. Resultantly, perovskite light emitting diodes with spectrally‐stable blue emission at 478 nm and a high external quantum efficiency of 21.9% are realized, representing a record in this type of devices. +The network topology and spatial structure of dynamic covalent polymer networks can be designed independently from their temporal structure and dynamic nature by the judicious combination of two distinctly different dynamic covalent chemistries. This enables improved extrusion‐based additive manufacturing, healing without creep and shape memory at time scales where the dissociative chemistry is activated and the associative chemistry remains inactive. @@ -3388,50 +3291,44 @@ Dual modification on both bulk and interface is proposed to homogenize the energ Abstract -Blue perovskite light‐emitting diodes (PeLEDs) have attracted enormous attention; however, their unsatisfactory device efficiency and spectral stability still remain great challenges. Unfavorable low‐dimensional phase distribution and defects with deeper energy levels usually cause energy disorder, substantially limiting the device's performance. Here, an additive‐interface optimization strategy is reported to tackle these issues, thus realizing efficient and spectrally stable blue PeLEDs. A new type of additive‐formamidinium tetrafluorosuccinate (FATFSA) is introduced into the quasi‐2D mixed halide perovskite accompanied by interface engineering, which effectively impedes the formation of undesired low‐dimensional phases with various bandgaps throughout the entire film, thereby boosting energy transfer process for accelerating radiative recombination; this strategy also diminishes the halide vacancies especially chloride‐related defects with deep energy level, thus reducing nonradiative energy loss for efficient radiative recombination. Benefitting from homogenized energy landscape throughout the entire perovskite emitting layer, PeLEDs with spectrally‐stable blue emission (478 nm) and champion external quantum efficiency (EQE) of 21.9% are realized, which represents a record value among this type of PeLEDs in the pure blue region. +Dynamic polymer networks offer a promising solution to key challenges in polymers such as recyclability, processability, and damage repair. However, the trade‐off between combining facile processability, fast self‐healing, and high creep resistance remains a major obstacle to implementation. To overcome this, two very distinct dynamic covalent chemistries, Diels–Alder and transesterification, is combined in a single network. The resulting dual dynamic networks offer an unprecedented set of properties and control over the relaxation times. The system decouples the relaxation dynamics of the network from the spatial motifs, and the tuning of the ratio between chemistries enables to control of the relaxation dynamics over six orders of magnitude. Taking advantage of this control, the composition and rheological behavior is optimized to drastically improve the resolution for extrusion‐based additive manufacturing of dynamic covalent networks. Additionally, two well‐defined and separated stress relaxation peaks are observed at compositions close to 50% of each dynamic chemistry, accentuating the double character of the system's relaxation dynamics. This atypical situation, enables to preparation of self‐healing materials with negligible creep, and with shape‐memory properties solely leveraging the two distinct relaxation dynamics, instead of the glass transition temperature or the melting point. - <img src="https://onlinelibrary.wiley.com/cms/asset/11ddf73c-d054-447a-9621-15fae9d42e61/adma202409319-gra-0001-m.png" - alt="Homogenizing Energy Landscape for Efficient and Spectrally Stable Blue Perovskite Light-Emitting Diodes"/> -<p>Dual modification on both bulk and interface is proposed to homogenize the energy landscape throughout the entire blue perovskite by comprehensively diminishing the low dimensional phases and reducing the halide defects. Resultantly, perovskite light emitting diodes with spectrally-stable blue emission at 478 nm and a high external quantum efficiency of 21.9% are realized, representing a record in this type of devices. + <img src="https://onlinelibrary.wiley.com/cms/asset/47ef48d8-5239-4320-b3a1-5659f82b6f54/adma202407663-gra-0001-m.png" + alt="Controlling the Relaxation Dynamics of Polymer Networks by Combining Associative and Dissociative Dynamic Covalent Bonds"/> +<p>The network topology and spatial structure of dynamic covalent polymer networks can be designed independently from their temporal structure and dynamic nature by the judicious combination of two distinctly different dynamic covalent chemistries. This enables improved extrusion-based additive manufacturing, healing without creep and shape memory at time scales where the dissociative chemistry is activated and the associative chemistry remains inactive. </p> <br/> <h2>Abstract</h2> -<p>Blue perovskite light-emitting diodes (PeLEDs) have attracted enormous attention; however, their unsatisfactory device efficiency and spectral stability still remain great challenges. Unfavorable low-dimensional phase distribution and defects with deeper energy levels usually cause energy disorder, substantially limiting the device's performance. Here, an additive-interface optimization strategy is reported to tackle these issues, thus realizing efficient and spectrally stable blue PeLEDs. A new type of additive-formamidinium tetrafluorosuccinate (FATFSA) is introduced into the quasi-2D mixed halide perovskite accompanied by interface engineering, which effectively impedes the formation of undesired low-dimensional phases with various bandgaps throughout the entire film, thereby boosting energy transfer process for accelerating radiative recombination; this strategy also diminishes the halide vacancies especially chloride-related defects with deep energy level, thus reducing nonradiative energy loss for efficient radiative recombination. Benefitting from homogenized energy landscape throughout the entire perovskite emitting layer, PeLEDs with spectrally-stable blue emission (478 nm) and champion external quantum efficiency (EQE) of 21.9% are realized, which represents a record value among this type of PeLEDs in the pure blue region.</p> +<p>Dynamic polymer networks offer a promising solution to key challenges in polymers such as recyclability, processability, and damage repair. However, the trade-off between combining facile processability, fast self-healing, and high creep resistance remains a major obstacle to implementation. To overcome this, two very distinct dynamic covalent chemistries, Diels–Alder and transesterification, is combined in a single network. The resulting dual dynamic networks offer an unprecedented set of properties and control over the relaxation times. The system decouples the relaxation dynamics of the network from the spatial motifs, and the tuning of the ratio between chemistries enables to control of the relaxation dynamics over six orders of magnitude. Taking advantage of this control, the composition and rheological behavior is optimized to drastically improve the resolution for extrusion-based additive manufacturing of dynamic covalent networks. Additionally, two well-defined and separated stress relaxation peaks are observed at compositions close to 50% of each dynamic chemistry, accentuating the double character of the system's relaxation dynamics. This atypical situation, enables to preparation of self-healing materials with negligible creep, and with shape-memory properties solely leveraging the two distinct relaxation dynamics, instead of the glass transition temperature or the melting point.</p> -Heng Qi, -Yu Tong, -Xuewen Zhang, -Hao Wang, -Lu Zhang, -Yali Chen, -Yibo Wang, -Jingzhi Shang, -Kun Wang, -Hongqiang Wang +Aleix Costa Cornellà, +Francesca Furia, +Guy Van Assche, +Joost Brancart Research Article - Homogenizing Energy Landscape for Efficient and Spectrally Stable Blue Perovskite Light‐Emitting Diodes - 10.1002/adma.202409319 + Controlling the Relaxation Dynamics of Polymer Networks by Combining Associative and Dissociative Dynamic Covalent Bonds + 10.1002/adma.202407663 Advanced Materials - 10.1002/adma.202409319 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409319 + 10.1002/adma.202407663 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407663 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409338 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408136 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409338 - Constructing Organic Phosphorescent Scintillators with Enhanced Triplet Exciton Utilization Through Multi‐Mode Radioluminescence for Efficient X‐Ray Imaging + 10.1002/adma.202408136 + Customized Corneal Cross‐Linking with Microneedle‐Mediated Riboflavin Delivery for Keratoconus Treatment Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A multimode radioluminescence process is developed by thermally activating the release of triplet excitons from organic phosphorescent scintillators. These scintillators achieve a maximum photoluminescence efficiency of 65.8% and a minimum X‐ray radiation detection limit of 110 nGy s−1, enabling efficient radiographic imaging with a spatial resolution of ≈10.0 lp mm−1. +Novel customized corneal cross‐linking (CXL) treatment, which utilizes microneedles for targeted riboflavin administration, not only achieves exceptional customized CXL effects comparable to the conventional epi‐off CXL protocol, but also improves visual function by flattening the corneal curvature within the treated zone, paving the way for customized CXL treatment of keratoconus and other corneal pathologies. @@ -3441,53 +3338,58 @@ A multimode radioluminescence process is developed by thermally activating the r Abstract -The development of organic phosphorescent scintillators with high exciton utilization efficiency has attracted significant attention but remains a difficult challenge because of the inherent spin‐forbidden feature of X‐ray‐induced triplet excitons. Herein, a design strategy is proposed to develop organic phosphorescent scintillators through thermally activated exciton release to convert stabilized spin‐forbidden triplet excitons to spin‐allowed singlet excitons, which enables singlet exciton‐dominated multi‐mode emission simultaneously from the lowest singlet, triplet, and stabilized triplet states. The resultant scintillators demonstrate a maximum photoluminescence efficiency of 65.8% and a minimum X‐ray radiation detection limit of 110 nGy s−1; this allows efficient radiography imaging with a spatial resolution of ≈10.0 lp mm−1. This study advances the fundamental understanding of exciton dynamics under X‐ray excitation, significantly broadening the practical use of phosphorescent materials for safety‐critical industries and medical diagnostics. +In this study, a novel customized corneal cross‐linking (CXL) treatment is explored that utilizes microneedles (MNs) for targeted riboflavin (RF) administration prior to the CXL procedure. Unlike the conventional “one‐size‐fits‐all” approach, this protocol offers an option for more precise and efficacious treatment. To simulate a customized corneal crosslinking technique, four distinct microneedle (MN) molds designs, including circular, semi‐circular, annular and butterfly shaped, are crafted for loading an optimized RF‐hyaluronic acid solution and for the subsequent fabrication of MN arrays with varying morphologies. These MNs can gently puncture the corneal epithelium while preserving the integrity of the underlying stromal layer. Following the application of these microneedles, RF solution is replenished to enhance the RF content within the stroma through the punctures created by the MNs, resulting in exceptional customized corneal cross‐linking effects that are comparable to the conventional epi‐off CXL protocol. Additionally, it flattened the corneal curvature within the treated zone and facilitated rapid postoperative recovery of corneal tissue. These findings suggest that the integration of customized microneedle RF delivery with corneal crosslinking technology represents a potential novel treatment modality, holding promise for the tailored treatment of corneal pathologies, and offering a more precise and efficient alternative to traditional methods. - <img src="https://onlinelibrary.wiley.com/cms/asset/d4da4703-ca0a-49c9-9d62-4eee9d620083/adma202409338-gra-0001-m.png" - alt="Constructing Organic Phosphorescent Scintillators with Enhanced Triplet Exciton Utilization Through Multi-Mode Radioluminescence for Efficient X-Ray Imaging"/> -<p>A multimode radioluminescence process is developed by thermally activating the release of triplet excitons from organic phosphorescent scintillators. These scintillators achieve a maximum photoluminescence efficiency of 65.8% and a minimum X-ray radiation detection limit of 110 nGy s<sup>−1</sup>, enabling efficient radiographic imaging with a spatial resolution of ≈10.0 lp mm<sup>−1</sup>. + <img src="https://onlinelibrary.wiley.com/cms/asset/4eca6f08-6644-4cce-83ac-d11b54fddaad/adma202408136-gra-0001-m.png" + alt="Customized Corneal Cross-Linking with Microneedle-Mediated Riboflavin Delivery for Keratoconus Treatment"/> +<p>Novel customized corneal cross-linking (CXL) treatment, which utilizes microneedles for targeted riboflavin administration, not only achieves exceptional customized CXL effects comparable to the conventional epi-off CXL protocol, but also improves visual function by flattening the corneal curvature within the treated zone, paving the way for customized CXL treatment of keratoconus and other corneal pathologies. </p> <br/> <h2>Abstract</h2> -<p>The development of organic phosphorescent scintillators with high exciton utilization efficiency has attracted significant attention but remains a difficult challenge because of the inherent spin-forbidden feature of X-ray-induced triplet excitons. Herein, a design strategy is proposed to develop organic phosphorescent scintillators through thermally activated exciton release to convert stabilized spin-forbidden triplet excitons to spin-allowed singlet excitons, which enables singlet exciton-dominated multi-mode emission simultaneously from the lowest singlet, triplet, and stabilized triplet states. The resultant scintillators demonstrate a maximum photoluminescence efficiency of 65.8% and a minimum X-ray radiation detection limit of 110 nGy s<sup>−1</sup>; this allows efficient radiography imaging with a spatial resolution of ≈10.0 lp mm<sup>−1</sup>. This study advances the fundamental understanding of exciton dynamics under X-ray excitation, significantly broadening the practical use of phosphorescent materials for safety-critical industries and medical diagnostics.</p> +<p>In this study, a novel customized corneal cross-linking (CXL) treatment is explored that utilizes microneedles (MNs) for targeted riboflavin (RF) administration prior to the CXL procedure. Unlike the conventional “one-size-fits-all” approach, this protocol offers an option for more precise and efficacious treatment. To simulate a customized corneal crosslinking technique, four distinct microneedle (MN) molds designs, including circular, semi-circular, annular and butterfly shaped, are crafted for loading an optimized RF-hyaluronic acid solution and for the subsequent fabrication of MN arrays with varying morphologies. These MNs can gently puncture the corneal epithelium while preserving the integrity of the underlying stromal layer. Following the application of these microneedles, RF solution is replenished to enhance the RF content within the stroma through the punctures created by the MNs, resulting in exceptional customized corneal cross-linking effects that are comparable to the conventional epi-off CXL protocol. Additionally, it flattened the corneal curvature within the treated zone and facilitated rapid postoperative recovery of corneal tissue. These findings suggest that the integration of customized microneedle RF delivery with corneal crosslinking technology represents a potential novel treatment modality, holding promise for the tailored treatment of corneal pathologies, and offering a more precise and efficient alternative to traditional methods.</p> -Huanhuan Li, -Yitong Liu, -Wei Zhao, -Hengyu Cao, -Xin Yan, -Shuman Zhang, -Xi Yan, -Hui Li, -Ye Tao, -Gaozhan Xie, -Wei Li, -Runfeng Chen, -Wei Huang +Mei Yang, +Hongxian Pan, +Tingting Chen, +Xin Chen, +Rui Ning, +Qianfang Ye, +Aodong Chen, +Jiawei Li, +Siheng Li, +Nan Zhao, +Yue Wu, +Xueyu Fu, +Keith M. Meek, +Lingxin Chen, +Xiaoying Wang, +Zhongxing Chen, +Xingtao Zhou, +Jinhai Huang Research Article - Constructing Organic Phosphorescent Scintillators with Enhanced Triplet Exciton Utilization Through Multi‐Mode Radioluminescence for Efficient X‐Ray Imaging - 10.1002/adma.202409338 + Customized Corneal Cross‐Linking with Microneedle‐Mediated Riboflavin Delivery for Keratoconus Treatment + 10.1002/adma.202408136 Advanced Materials - 10.1002/adma.202409338 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409338 + 10.1002/adma.202408136 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408136 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409592 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408268 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409592 - Confined Flash Printing and Synthesis of Stable Perovskite Nanofilms under Ambient Conditions + 10.1002/adma.202408268 + Upcycling the Spent Graphite Anode Into the Prelithiation Catalyst: A Separator Strategy Toward Anode‐Free Cell Prototyping Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A new method, confined flash printing, allows for the rapid synthesis of perovskite nanofilms under ambient conditions. This approach combines precursor transfer, synthesis, crystallization, and polymer protection in a single step using a laser. The method's simplicity and flexibility support the development of various perovskite materials and devices, including applications in biodetection. +Value‐added recycling of spent anode has become an urgent need for the circular battery manufacturing. In this work, Yao et al. developed an “integrated closed‐loop route” to upgrade the spent graphite into the prelithiation catalyst upon the fine tuning of the interlayer spacing and defect concentration, enabling customized prelithiation for the Li‐deficient electrodes. It fulfills both the sustainable supply chain and battery prototyping with higher energy efficiency. @@ -3497,51 +3399,55 @@ A new method, confined flash printing, allows for the rapid synthesis of perovsk Abstract -The fabrication of stable perovskite nanofilm patterns is important for the development of functional optical devices. However, current production approaches are limited by the requirement for strict inert gas protection and long processing times. Here, a confined flash printing synthesis method is presented to generate perovskite nanofilms under ambient conditions, combining precursor transfer, perovskite synthesis, crystallization, and polymer protection in a single step within milliseconds. A laser simultaneously prints and induces the flash synthesis, confined in a polymer nanofilm, under normal ambient conditions. Due to its simplicity and flexibility, the method enables the combination and screening of many different perovskite precursor materials on various substrates. Besides for the development of novel perovskite materials and devices, the nanofilms can be applied for biodetection. The unique H2O2‐responsive property of the ultrathin perovskite quantum dot film is applied for biomolecule detection based on oxidase‐catalyzed enzymatic reactions. +The substantial manufacturing of lithium‐ion batteries (LIBs) requires sustainable, circular, and decarbonized recycling strategies. While efforts are concentrated on extracting valuable metals from cathodes using intricate chemical process, the direct, efficient cathode regeneration remains a technological challenge. More urgently, the battery supply chain also requires the value‐added exploitation of retired anodes. Here, a “closed‐loop” approach is proposed to upcycle spent graphite into the prelithiation catalyst, namely the fewer‐layer graphene flakes (FGF), upon the exquisite tuning of interlayer spacing and defect concentration. Since the catalytic FGF mitigates the delithiation energy barrier from calcinated Li5FeO4 nanocrystalline, the composite layer of which cast on the polyolefin substrate thus enables a customized prelithiation capability (98% Li+ utilization) for the retired LiFePO4 recovery. Furthermore, the hydrophobic polymeric modification guarantees the moisture tolerance of Li5FeO4 agents, aligning with commercial battery manufacturing standards. The separator strategy well regulates the interfacial chemistry in the anode‐free pouch cell (LiFePO4||Cu), the prototype of which balances the robust cyclability, energy density up to 386.6 Wh kg−1 as well as the extreme power output of 1159.8 W kg−1. This study not only fulfills the sustainable supply chain with graphite upcycling, but also establishes a generic, viable protocol for the anode‐free cell prototyping. - <img src="https://onlinelibrary.wiley.com/cms/asset/002da7de-59ac-4b10-a1c5-44f3caca8d2f/adma202409592-gra-0001-m.png" - alt="Confined Flash Printing and Synthesis of Stable Perovskite Nanofilms under Ambient Conditions"/> -<p>A new method, confined flash printing, allows for the rapid synthesis of perovskite nanofilms under ambient conditions. This approach combines precursor transfer, synthesis, crystallization, and polymer protection in a single step using a laser. The method's simplicity and flexibility support the development of various perovskite materials and devices, including applications in biodetection. + <img src="https://onlinelibrary.wiley.com/cms/asset/301292ce-b6a5-4a86-8e24-accf8eddf179/adma202408268-gra-0001-m.png" + alt="Upcycling the Spent Graphite Anode Into the Prelithiation Catalyst: A Separator Strategy Toward Anode-Free Cell Prototyping"/> +<p>Value-added recycling of spent anode has become an urgent need for the circular battery manufacturing. In this work, Yao et al. developed an “integrated closed-loop route” to upgrade the spent graphite into the prelithiation catalyst upon the fine tuning of the interlayer spacing and defect concentration, enabling customized prelithiation for the Li-deficient electrodes. It fulfills both the sustainable supply chain and battery prototyping with higher energy efficiency. </p> <br/> <h2>Abstract</h2> -<p>The fabrication of stable perovskite nanofilm patterns is important for the development of functional optical devices. However, current production approaches are limited by the requirement for strict inert gas protection and long processing times. Here, a confined flash printing synthesis method is presented to generate perovskite nanofilms under ambient conditions, combining precursor transfer, perovskite synthesis, crystallization, and polymer protection in a single step within milliseconds. A laser simultaneously prints and induces the flash synthesis, confined in a polymer nanofilm, under normal ambient conditions. Due to its simplicity and flexibility, the method enables the combination and screening of many different perovskite precursor materials on various substrates. Besides for the development of novel perovskite materials and devices, the nanofilms can be applied for biodetection. The unique H<sub>2</sub>O<sub>2</sub>-responsive property of the ultrathin perovskite quantum dot film is applied for biomolecule detection based on oxidase-catalyzed enzymatic reactions.</p> +<p>The substantial manufacturing of lithium-ion batteries (LIBs) requires sustainable, circular, and decarbonized recycling strategies. While efforts are concentrated on extracting valuable metals from cathodes using intricate chemical process, the direct, efficient cathode regeneration remains a technological challenge. More urgently, the battery supply chain also requires the value-added exploitation of retired anodes. Here, a “closed-loop” approach is proposed to upcycle spent graphite into the prelithiation catalyst, namely the fewer-layer graphene flakes (FGF), upon the exquisite tuning of interlayer spacing and defect concentration. Since the catalytic FGF mitigates the delithiation energy barrier from calcinated Li<sub>5</sub>FeO<sub>4</sub> nanocrystalline, the composite layer of which cast on the polyolefin substrate thus enables a customized prelithiation capability (98% Li<sup>+</sup> utilization) for the retired LiFePO<sub>4</sub> recovery. Furthermore, the hydrophobic polymeric modification guarantees the moisture tolerance of Li<sub>5</sub>FeO<sub>4</sub> agents, aligning with commercial battery manufacturing standards. The separator strategy well regulates the interfacial chemistry in the anode-free pouch cell (LiFePO<sub>4</sub>||Cu), the prototype of which balances the robust cyclability, energy density up to 386.6 Wh kg<sup>−1</sup> as well as the extreme power output of 1159.8 W kg<sup>−1</sup>. This study not only fulfills the sustainable supply chain with graphite upcycling, but also establishes a generic, viable protocol for the anode-free cell prototyping.</p> -Yuxin Liu, -Tanja Knaus, -Zheng Wei, -Junfang Zhang, -Matteo Damian, -Sebastian Ronneberger, -Xingjun Zhu, -Peter H. Seeberger, -Hong Zhang, -Francesco G. Mutti, -Felix F. Loeffler +Ning Yao, +Fu Liu, +Ahu Shao, +Rongrong Xue, +Qiurong Jia, +Yuyao Liu, +Helin Wang, +Xin Wang, +Yaxin Zhang, +Min Zhang, +Zhiqiao Wang, +Yunsong Li, +Jiawen Tang, +Xiaoyu Tang, +Yue Ma Research Article - Confined Flash Printing and Synthesis of Stable Perovskite Nanofilms under Ambient Conditions - 10.1002/adma.202409592 + Upcycling the Spent Graphite Anode Into the Prelithiation Catalyst: A Separator Strategy Toward Anode‐Free Cell Prototyping + 10.1002/adma.202408268 Advanced Materials - 10.1002/adma.202409592 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409592 + 10.1002/adma.202408268 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408268 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409603 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408364 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409603 - Photochemical Control of Network Topology in PEG Hydrogels + 10.1002/adma.202408364 + Bioinspired Homonuclear Diatomic Iron Active Site Regulation for Efficient Antifouling Osmotic Energy Conversion Advanced Materials, Volume 36, Issue 46, November 14, 2024. -In this work, maleimide‐ and styrene‐functionalized poly(ethylene glycol) macromers are used to prepare photocrosslinked hydrogels along a continuum of network topologies, from step‐ to chain‐growth. This simple approach provides precise control over hydrogel nanostructure, decoupling gel modulus and diffusivity from the initial polymer content and presenting new opportunities for (bio)materials science and the study of soft matter physics. +Inspired by structural and functional models of natural cytochrome c oxidase (CcO), the conformations of the 2 hemes intrinsic to CcO can inspire the biomimetic active site regulation of nanozymes with powerful ROS generation capability for efficient antifouling osmotic energy conversion is demonstrated. The power density of bioinspired membranes reached 6.7 W m−2 and the antimicrobial performance increased 44.5‐fold. @@ -3551,60 +3457,51 @@ In this work, maleimide‐ and styrene‐functionalized poly(ethylene gl Abstract -Hydrogels are often synthesized through photoinitiated step‐, chain‐, and mixed‐mode polymerizations, generating diverse network topologies and resultant material properties that depend on the underlying network connectivity. While many photocrosslinking reactions are available, few afford controllable connectivity of the hydrogel network. Herein, a versatile photochemical strategy is introduced for tuning the structure of poly(ethylene glycol) (PEG) hydrogels using macromolecular monomers functionalized with maleimide and styrene moieties. Hydrogels are prepared along a gradient of topologies by varying the ratio of step‐growth (maleimide dimerization) to chain‐growth (maleimide‐styrene alternating copolymerization) network‐forming reactions. The initial PEG content and final network physical properties (e.g., modulus, swelling, diffusivity) are tailored in an independent manner, highlighting configurable gel mechanics and reactivity. These photochemical reactions allow high‐fidelity photopatterning and 3D printing and are compatible with 2D and 3D cell culture. Ultimately, this photopolymer chemistry allows facile control over network connectivity to achieve adjustable material properties for broad applications. +Membrane‐based reverse electrodialysis is globally recognized as a promising technology for harnessing osmotic energy. However, its practical application is greatly restricted by the poor anti‐fouling ability of existing membrane materials. Inspired by the structural and functional models of natural cytochrome c oxidases (CcO), the first use of atomically precise homonuclear diatomic iron composites as high‐performance osmotic energy conversion membranes with excellent anti‐fouling ability is demonstrated. Through rational tuning of the atomic configuration of the diatomic iron sites, the oxidase‐like activity can be precisely tailored, leading to the augmentation of ion throughput and anti‐fouling capacity. Composite membranes featuring direct Fe‐Fe motif configurations embedded within cellulose nanofibers (CNF/Fe‐DACs‐P) surpass state‐of‐the‐art CNF‐based membranes with power densities of ca. 6.7 W m−2 and a 44.5‐fold enhancement in antimicrobial performance. Combined, experimental characterization and density functional theory simulations reveal that homonuclear diatomic iron sites with metal‐metal interactions can achieve ideally balanced adsorption and desorption of intermediates, thus realizing superior oxidase‐like activity, enhanced ionic flux, and excellent antibacterial activity. - <img src="https://onlinelibrary.wiley.com/cms/asset/ea06b45f-38ea-42e9-8665-333cde1d9929/adma202409603-gra-0001-m.png" - alt="Photochemical Control of Network Topology in PEG Hydrogels"/> -<p>In this work, maleimide- and styrene-functionalized poly(ethylene glycol) macromers are used to prepare photocrosslinked hydrogels along a continuum of network topologies, from step- to chain-growth. This simple approach provides precise control over hydrogel nanostructure, decoupling gel modulus and diffusivity from the initial polymer content and presenting new opportunities for (bio)materials science and the study of soft matter physics. + <img src="https://onlinelibrary.wiley.com/cms/asset/212e6ab8-0d9c-4b3e-8a88-c13df16b0402/adma202408364-gra-0001-m.png" + alt="Bioinspired Homonuclear Diatomic Iron Active Site Regulation for Efficient Antifouling Osmotic Energy Conversion"/> +<p>Inspired by structural and functional models of natural cytochrome c oxidase (CcO), the conformations of the 2 hemes intrinsic to CcO can inspire the biomimetic active site regulation of nanozymes with powerful ROS generation capability for efficient antifouling osmotic energy conversion is demonstrated. The power density of bioinspired membranes reached 6.7 W m<sup>−2</sup> and the antimicrobial performance increased 44.5-fold. </p> <br/> <h2>Abstract</h2> -<p>Hydrogels are often synthesized through photoinitiated step-, chain-, and mixed-mode polymerizations, generating diverse network topologies and resultant material properties that depend on the underlying network connectivity. While many photocrosslinking reactions are available, few afford controllable connectivity of the hydrogel network. Herein, a versatile photochemical strategy is introduced for tuning the structure of poly(ethylene glycol) (PEG) hydrogels using macromolecular monomers functionalized with maleimide and styrene moieties. Hydrogels are prepared along a gradient of topologies by varying the ratio of step-growth (maleimide dimerization) to chain-growth (maleimide-styrene alternating copolymerization) network-forming reactions. The initial PEG content and final network physical properties (e.g., modulus, swelling, diffusivity) are tailored in an independent manner, highlighting configurable gel mechanics and reactivity. These photochemical reactions allow high-fidelity photopatterning and 3D printing and are compatible with 2D and 3D cell culture. Ultimately, this photopolymer chemistry allows facile control over network connectivity to achieve adjustable material properties for broad applications.</p> +<p>Membrane-based reverse electrodialysis is globally recognized as a promising technology for harnessing osmotic energy. However, its practical application is greatly restricted by the poor anti-fouling ability of existing membrane materials. Inspired by the structural and functional models of natural cytochrome <i>c</i> oxidases (C<i>c</i>O), the first use of atomically precise homonuclear diatomic iron composites as high-performance osmotic energy conversion membranes with excellent anti-fouling ability is demonstrated. Through rational tuning of the atomic configuration of the diatomic iron sites, the oxidase-like activity can be precisely tailored, leading to the augmentation of ion throughput and anti-fouling capacity. Composite membranes featuring direct Fe-Fe motif configurations embedded within cellulose nanofibers (CNF/Fe-DACs-P) surpass state-of-the-art CNF-based membranes with power densities of ca. 6.7 W m<sup>−2</sup> and a 44.5-fold enhancement in antimicrobial performance. Combined, experimental characterization and density functional theory simulations reveal that homonuclear diatomic iron sites with metal-metal interactions can achieve ideally balanced adsorption and desorption of intermediates, thus realizing superior oxidase-like activity, enhanced ionic flux, and excellent antibacterial activity.</p> -Bruce E. Kirkpatrick, -Grace K. Hach, -Benjamin R. Nelson, -Nathaniel P. Skillin, -Joshua S. Lee, -Lea Pearl Hibbard, -Abhishek P. Dhand, -Henry S. Grotheer, -Connor E. Miksch, -Violeta Salazar, -Tayler S. Hebner, -Sean P. Keyser, -Joshua T. Kamps, -Jasmine Sinha, -Laura J. Macdougall, -Benjamin D. Fairbanks, -Jason A. Burdick, -Timothy J. White, -Christopher N. Bowman, -Kristi S. Anseth +Zhe Li, +Donghai Wu, +Qingchen Wang, +Qixiang Zhang, +Peng Xu, +Fangning Liu, +Shibo Xi, +Dongwei Ma, +Yizhong Lu, +Lei Jiang, +Zhen Zhang Research Article - Photochemical Control of Network Topology in PEG Hydrogels - 10.1002/adma.202409603 + Bioinspired Homonuclear Diatomic Iron Active Site Regulation for Efficient Antifouling Osmotic Energy Conversion + 10.1002/adma.202408364 Advanced Materials - 10.1002/adma.202409603 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409603 + 10.1002/adma.202408364 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408364 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409606 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408367 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409606 - Microfiber Actuators With Hot‐Pressing‐Programmable Mechano‐Photothermal Responses for Electromagnetic Perception + 10.1002/adma.202408367 + Robust Growth of 2D Transition Metal Dichalcogenide Vertical Heterostructures via Ammonium‐Assisted CVD Strategy Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A hot‐pressing‐programmable microfiber‐film actuator is developed with mechano‐photothermal cooperativities and electromagnetic radiation perceptivity (sensitivity of 99.73% ± 0.15%). It demonstrates superior actuation response with mechanical/thermal/electrical stability, and realizes an amphibious robot with land–water adaptive locomotion for electromagnetic dynamic detection. This microstructure‐dominated electromagnetic‐perceptive actuator can inspire a new direction of environment‐interactive smart materials, and soft robots with multi‐scenario adaptivity and autonomous environment perceptivity. +This work demonstrates a universal strategy for robust growth of high‐quality transition metal dichalcogenide (TMD) vertical heterostructures and a novel design concept for the fabrication of high mobility and high responsivity photodetectors based on 2D TMD vertical heterostructures, which holds promise for the next‐generation photodetectors. @@ -3614,53 +3511,50 @@ A hot‐pressing‐programmable microfiber‐film actuator is develo Abstract -Electromagnetic radiation (EMR) is a ubiquitous harm and hard to detect dynamically in multiple scenarios. A mechano‐photothermal cooperative microfiber film (MFF) actuator is developed that can synchronously detect EMR with high reliability. The programmable actuation is deployed by a hot‐pressing methodology, achieving the MFF with moderate modulus (378 MPa) and superior toughness (87.26 MJ m−3) that ensure superior response (0.068 cm−1 s−1) and bending curvature (0.63 cm−1). A secondary hot‐pressing can further program the actuation behavior with black phosphorus local photothermal enhancement patterns to achieve 2D–3D transformable geometries. An amphibious robot with a land–water adaptive locomotion mechanism is designed by programming the MFFs. It can crawl on land and locomote on water with a velocity up to ≈1.8 mm s−1, and ≈2.39 cm s−1, respectively. Employing the conductive fabric layer of the actuator with electromagnetic induction effect, the amphibious robot can synchronously perceive environmental EMR with sensitivity up to 99.73% ± 0.15% during locomotion, with superior adaptability to EMR source intensity (0.1 to 3000 W) and distance (≈9 m) compared to a commercial EMR detector. This EMR detective microfiber actuator can inspire a new direction of environment‐interactive smart materials, and soft robots with multi‐scenario adaptivity and autonomous environment perceptivity. +Two dimension (2D) transition metal dichalcogenides (TMD) heterostructures have opened unparalleled prospects for next‐generation electronic and optoelectronic applications due to their atomic‐scale thickness and distinct physical properties. The chemical vapor deposition (CVD) method is the most feasible approach to prepare 2D TMD heterostructures. However, the synthesis of 2D vertical heterostructures faces competition between in‐plane and out‐of‐plane growth, which makes it difficult to precisely control the growth of vertical heterostructures. Here, a universal and controllable strategy is reported to grow various 2D TMD vertical heterostructures through an ammonium‐assisted CVD process. The ammonium‐assisted strategy shows excellent controllability and operational simplicity to prevent interlayer diffusion/alloying and thermal decomposition of the existed TMD templates. Ab initio simulations demonstrate that the reaction between NH4Cl and MoS2 leads to the formation of MoS3 clusters, promoting the nucleation and growth of 2D MoS2 on existed 2D WS2 layer, thereby leading to the growth of vertical heterostructure. The resulting 2D WSe2/WS2 vertical heterostructure photodetectors demonstrate an outstanding optoelectronic performance, which are comparable to the performances of photodetectors fabricated from mechanically exfoliated and stacked vertical heterostructures. The ammonium‐assisted strategy for robust growth of high‐quality vertical van der Waals heterostructures will facilitate fundamental physics investigations and device applications in electronics and optoelectronics. - <img src="https://onlinelibrary.wiley.com/cms/asset/d7f64130-6a69-47f6-825f-390275076a4e/adma202409606-gra-0001-m.png" - alt="Microfiber Actuators With Hot-Pressing-Programmable Mechano-Photothermal Responses for Electromagnetic Perception"/> -<p>A hot-pressing-programmable microfiber-film actuator is developed with mechano-photothermal cooperativities and electromagnetic radiation perceptivity (sensitivity of 99.73% ± 0.15%). It demonstrates superior actuation response with mechanical/thermal/electrical stability, and realizes an amphibious robot with land–water adaptive locomotion for electromagnetic dynamic detection. This microstructure-dominated electromagnetic-perceptive actuator can inspire a new direction of environment-interactive smart materials, and soft robots with multi-scenario adaptivity and autonomous environment perceptivity. + <img src="https://onlinelibrary.wiley.com/cms/asset/8cb88fe6-efd6-4f6a-9578-c3d066711f62/adma202408367-gra-0001-m.png" + alt="Robust Growth of 2D Transition Metal Dichalcogenide Vertical Heterostructures via Ammonium-Assisted CVD Strategy"/> +<p>This work demonstrates a universal strategy for robust growth of high-quality transition metal dichalcogenide (TMD) vertical heterostructures and a novel design concept for the fabrication of high mobility and high responsivity photodetectors based on 2D TMD vertical heterostructures, which holds promise for the next-generation photodetectors. </p> <br/> <h2>Abstract</h2> -<p>Electromagnetic radiation (EMR) is a ubiquitous harm and hard to detect dynamically in multiple scenarios. A mechano-photothermal cooperative microfiber film (MFF) actuator is developed that can synchronously detect EMR with high reliability. The programmable actuation is deployed by a hot-pressing methodology, achieving the MFF with moderate modulus (378 MPa) and superior toughness (87.26 MJ m<sup>−3</sup>) that ensure superior response (0.068 cm<sup>−1</sup> s<sup>−1</sup>) and bending curvature (0.63 cm<sup>−1</sup>). A secondary hot-pressing can further program the actuation behavior with black phosphorus local photothermal enhancement patterns to achieve 2D–3D transformable geometries. An amphibious robot with a land–water adaptive locomotion mechanism is designed by programming the MFFs. It can crawl on land and locomote on water with a velocity up to ≈1.8 mm s<sup>−1</sup>, and ≈2.39 cm s<sup>−1</sup>, respectively. Employing the conductive fabric layer of the actuator with electromagnetic induction effect, the amphibious robot can synchronously perceive environmental EMR with sensitivity up to 99.73% ± 0.15% during locomotion, with superior adaptability to EMR source intensity (0.1 to 3000 W) and distance (≈9 m) compared to a commercial EMR detector. This EMR detective microfiber actuator can inspire a new direction of environment-interactive smart materials, and soft robots with multi-scenario adaptivity and autonomous environment perceptivity.</p> +<p>Two dimension (2D) transition metal dichalcogenides (TMD) heterostructures have opened unparalleled prospects for next-generation electronic and optoelectronic applications due to their atomic-scale thickness and distinct physical properties. The chemical vapor deposition (CVD) method is the most feasible approach to prepare 2D TMD heterostructures. However, the synthesis of 2D vertical heterostructures faces competition between in-plane and out-of-plane growth, which makes it difficult to precisely control the growth of vertical heterostructures. Here, a universal and controllable strategy is reported to grow various 2D TMD vertical heterostructures through an ammonium-assisted CVD process. The ammonium-assisted strategy shows excellent controllability and operational simplicity to prevent interlayer diffusion/alloying and thermal decomposition of the existed TMD templates. Ab initio simulations demonstrate that the reaction between NH<sub>4</sub>Cl and MoS<sub>2</sub> leads to the formation of MoS<sub>3</sub> clusters, promoting the nucleation and growth of 2D MoS<sub>2</sub> on existed 2D WS<sub>2</sub> layer, thereby leading to the growth of vertical heterostructure. The resulting 2D WSe<sub>2</sub>/WS<sub>2</sub> vertical heterostructure photodetectors demonstrate an outstanding optoelectronic performance, which are comparable to the performances of photodetectors fabricated from mechanically exfoliated and stacked vertical heterostructures. The ammonium-assisted strategy for robust growth of high-quality vertical van der Waals heterostructures will facilitate fundamental physics investigations and device applications in electronics and optoelectronics.</p> -Mengjie Wu, -Xinran Zhou, -Jiwei Zhang, -Luyun Liu, -Shuang Wang, -Liming Zhu, -Zechang Ming, -Yufan Zhang, -Yong Xia, -Weikang Li, -Zijie Zhou, -Minghui Fan, -Jiaqing Xiong +Wei Li, +Qiuyin Qin, +Xin Li, +Ying Huangfu, +Dingyi Shen, +Jialing Liu, +Jia Li, +Bo Li, +Ruixia Wu, +Xidong Duan Research Article - Microfiber Actuators With Hot‐Pressing‐Programmable Mechano‐Photothermal Responses for Electromagnetic Perception - 10.1002/adma.202409606 + Robust Growth of 2D Transition Metal Dichalcogenide Vertical Heterostructures via Ammonium‐Assisted CVD Strategy + 10.1002/adma.202408367 Advanced Materials - 10.1002/adma.202409606 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409606 + 10.1002/adma.202408367 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408367 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409620 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408400 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409620 - From Simple Probe to Smart Composites: Water‐Soluble Pincer Complex With Multi‐Stimuli‐Responsive Luminescent Behaviors + 10.1002/adma.202408400 + Electric Field‐Manipulated Optical Chirality in Ferroelectric Vortex Domains Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A water‐soluble tripyridine Zn complex featuring a donor‐π‐acceptor (D‐π‐A) structure exhibited multi‐stimuli‐responsiveness to water, pH, and heat. Its composite with polyvinyl alcohol found versatile applications covering digital encryption, reversible writing, inkless printing, and fingerprint analysis. +The self‐assembly ferroelectric nanoislands with polar vortex domains and optical chirality, are designed and fabricated, leading to a reversible and nonvolatile on/off switching of optical chirality by electric fields. Such ferroelectric nanoislands, serving as discrete chiral units, can be integrated into ordered arrays and exhibit capabilities in chiral optical display functionalities. @@ -3670,44 +3564,56 @@ A water‐soluble tripyridine Zn complex featuring a donor‐π̴ Abstract -Water‐soluble smart materials with multi‐stimuli‐responsiveness and ultra‐long room‐temperature phosphorescence (RTP) have garnered broad attention. Herein, a water‐soluble terpyridine zinc complex (MeO‐Tpy‐Zn‐OAc), featuring a simple donor‐π‐acceptor (D‐π‐A) structure is presented, which responds to a variety of stimuli, including changes in solvents, pH, temperature, and the addition of amino acids. Notably, MeO‐Tpy‐Zn‐OAc functions as a fluorescence probe, capable of visually and selectively discriminating aspartate or histidine among other common amino acids in water. Additionally, when incorporated into polyvinyl alcohol (PVA) to form the composite MeO‐Tpy‐Zn‐OAc@PVA, the material exhibits reversible writing, photochromism, and a prolonged RTP with a 14 s afterglow. These unique properties enable the composite to be utilized in potential applications such as secure data encryption and inkless printing. +Manipulating optical chirality via electric fields has garnered considerable attention in the realm of both fundamental physics and practical applications. Chiral ferroelectrics, characterized by their inherent optical chirality and switchable spontaneous polarization, are emerging as a promising platform for electronic‐photonic integrated circuits applications. Unlike organics with chiral carbon centers, integrating chirality into technologically mature inorganic ferroelectrics has posed a long‐standing challenge. Here, the successful introduction of chirality is reported into self‐assembly La‐doped BiFeO3 nanoislands, which exhibit ferroelectric vortex domains. By employing synergistic experimental techniques with piezoresponse force microscopy and nonlinear optical second‐harmonic generation probes, a clear correlation between chirality and polarization configuration within these ferroelectric nanoislands is established. Furthermore, the deterministic control of ferroelectric vortex domains and chirality is demonstrated by applying electric fields, enabling reversible and nonvolatile generation and elimination of optically chiral signals. These findings significantly expand the repertoire of field‐controllable chiral systems and lay the groundwork for the development of innovative ferroelectric optoelectronic devices. - <img src="https://onlinelibrary.wiley.com/cms/asset/2203f91f-06c6-42e7-b6a7-12ff41bf7134/adma202409620-gra-0001-m.png" - alt="From Simple Probe to Smart Composites: Water-Soluble Pincer Complex With Multi-Stimuli-Responsive Luminescent Behaviors"/> -<p>A water-soluble tripyridine Zn complex featuring a donor-π-acceptor (D-π-A) structure exhibited multi-stimuli-responsiveness to water, pH, and heat. Its composite with polyvinyl alcohol found versatile applications covering digital encryption, reversible writing, inkless printing, and fingerprint analysis. + <img src="https://onlinelibrary.wiley.com/cms/asset/e3d55abf-c191-4489-b2f1-27a59f75392c/adma202408400-gra-0001-m.png" + alt="Electric Field-Manipulated Optical Chirality in Ferroelectric Vortex Domains"/> +<p>The self-assembly ferroelectric nanoislands with polar vortex domains and optical chirality, are designed and fabricated, leading to a reversible and nonvolatile on/off switching of optical chirality by electric fields. Such ferroelectric nanoislands, serving as discrete chiral units, can be integrated into ordered arrays and exhibit capabilities in chiral optical display functionalities. </p> <br/> <h2>Abstract</h2> -<p>Water-soluble smart materials with multi-stimuli-responsiveness and ultra-long room-temperature phosphorescence (RTP) have garnered broad attention. Herein, a water-soluble terpyridine zinc complex (<b>MeO-Tpy-Zn-OAc</b>), featuring a simple donor-π-acceptor (D-π-A) structure is presented, which responds to a variety of stimuli, including changes in solvents, pH, temperature, and the addition of amino acids. Notably, <b>MeO-Tpy-Zn-OAc</b> functions as a fluorescence probe, capable of visually and selectively discriminating aspartate or histidine among other common amino acids in water. Additionally, when incorporated into polyvinyl alcohol (PVA) to form the composite <b>MeO-Tpy-Zn-OAc</b>@PVA, the material exhibits reversible writing, photochromism, and a prolonged RTP with a 14 s afterglow. These unique properties enable the composite to be utilized in potential applications such as secure data encryption and inkless printing.</p> +<p>Manipulating optical chirality via electric fields has garnered considerable attention in the realm of both fundamental physics and practical applications. Chiral ferroelectrics, characterized by their inherent optical chirality and switchable spontaneous polarization, are emerging as a promising platform for electronic-photonic integrated circuits applications. Unlike organics with chiral carbon centers, integrating chirality into technologically mature inorganic ferroelectrics has posed a long-standing challenge. Here, the successful introduction of chirality is reported into self-assembly La-doped BiFeO<sub>3</sub> nanoislands, which exhibit ferroelectric vortex domains. By employing synergistic experimental techniques with piezoresponse force microscopy and nonlinear optical second-harmonic generation probes, a clear correlation between chirality and polarization configuration within these ferroelectric nanoislands is established. Furthermore, the deterministic control of ferroelectric vortex domains and chirality is demonstrated by applying electric fields, enabling reversible and nonvolatile generation and elimination of optically chiral signals. These findings significantly expand the repertoire of field-controllable chiral systems and lay the groundwork for the development of innovative ferroelectric optoelectronic devices.</p> -Lixin Duan, -Qingshu Zheng, -Yanlin Liang, -Tao Tu - - Research Article - From Simple Probe to Smart Composites: Water‐Soluble Pincer Complex With Multi‐Stimuli‐Responsive Luminescent Behaviors - 10.1002/adma.202409620 - Advanced Materials - 10.1002/adma.202409620 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409620 - Research Article - 36 - 46 - - - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409789 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 +Haojie Han, +Wei Li, +Qinghua Zhang, +Shiyu Tang, +Yue Wang, +Zongqi Xu, +Yiqun Liu, +Hetian Chen, +Jingkun Gu, +Jing Wang, +Di Yi, +Lin Gu, +Houbing Huang, +Ce‐Wen Nan, +Qian Li, +Jing Ma + + Research Article + Electric Field‐Manipulated Optical Chirality in Ferroelectric Vortex Domains + 10.1002/adma.202408400 + Advanced Materials + 10.1002/adma.202408400 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408400 + Research Article + 36 + 46 + + + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408476 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409789 - 4D Printing Hybrid Soft Robots Enabled by Shape‐Transformable Liquid Metal Nanoparticles + 10.1002/adma.202408476 + Mechanistic Understanding of the Underlying Energy Storage Mechanism of α‐MnO2‐based Pseudo‐Supercapacitors Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The integration of shape‐transformable liquid metal nanoparticles (LMNPs) is first unveiled into 3D printing to create hybrid soft robots with controlled mechanical properties and deformability. This method allows direct printing of one‐piece or assembled hybrid robots using a single LMNPs‐integrated ink recipe, enabling precise control of mechanical and shape memory properties for applications like grippers, bioinspired motors, and rehabilitation devices. +In this study, the pseudo‐capacitive reaction mechanism of manganese dioxide (α‐MnO2) nano‐supercapacitor is revealed in three ionic liquids by using in situ environmental transmission electron microscopy and further investigating the cycled product of macro‐supercapacitor. The underlying faradic reaction mechanisms of pseudo‐capacitance and superior performance are thoroughly elucidated through extensive experimental characterizations and theoretical analyses, providing insights into the selection of electrolytes in α‐MnO2‐based‐supercapacitors. @@ -3717,51 +3623,50 @@ The integration of shape‐transformable liquid metal nanoparticles (LMNPs) Abstract -In recent years, soft robotics has emerged as a rapidly expanding frontier research field that draws inspiration from the locomotion mechanisms of soft‐bodied creatures in nature to achieve smooth and complex motion for diverse applications. However, the fabrication of soft robots with hybrid structures remains challenging due to limitations in material selection and the complex, multi‐step processes involved in traditional manufacturing methods. Herein, a novel direct one‐step additive manufacturing (3D printing) approach is introduced for the fabrication of hybrid robots composed of soft and rigid components for sophisticated tasks. Inspired by the shape‐transformable liquid metal nanoparticles (LMNPs), a functional material toolkit with tuneable mechanical properties and deformability is developed by integrating differently shaped gallium‐based nanoparticles (GNPs) into the 3D printing polymers. Then the direct printing of assembled or one‐piece hybrid soft‐rigid robots is presented through a single recipe of GNPs‐integrated inks. This fabrication method enables precise control of the mechanical properties and shape memory properties within the hybrid structures of robot body with a customized structure design. Their capabilities are further demonstrated through the design and fabrication of hybrid robots as high‐precision gripper, bioinspired motor, and hand rehabilitation device. +Manganese dioxide (α‐MnO2) has attracted significant research interest in supercapacitors recently. However, the reaction mechanism of α‐MnO2 in supercapacitors remains unclear. Therefore, a nano‐supercapacitor using Environmental transmission electron microscopy (ETEM) is conducted and investigated the reaction mechanism of α‐MnO2 based on three ionic liquids (ILs). It found that in the aprotic ionic liquid (AIL) 1‐ethyl‐3‐methylimidazolium trifluoromethanesulfonate (EMIMOTF), α‐MnO2 nanowires (NWs) undergo an oxidation reaction due to the presence of an active proton at the second position (H2) of the imidazole ring. As a result, α‐MnO2 NWs undergo a phase transition and transform into Mn3O4, exhibiting pseudo‐capacitive properties. Furthermore, characterization of the macroscopic α‐MnO2 electrodes after cycling reveals that after the initial charging cycles, the dominant energy storage mechanism of the supercapacitor transitions from pseudo‐capacitance to a dual‐layer capacitance formed by the combination of Mn3O4 and unreacted α‐MnO2. Simultaneously, due to the coexistence of these two energy storage mechanisms, the specific capacitance of the supercapacitor in EMIMOTF electrolyte reaches up to 80 F g−1, and the cycle number reaches as high as 1000 cycles. The results are expected to provide insights into the selection of electrolytes in supercapacitors and offer a fundamental understanding of the internal reaction mechanisms in capacitors. - <img src="https://onlinelibrary.wiley.com/cms/asset/eba24e48-6051-4fbb-b144-1d31c6dc3db5/adma202409789-gra-0001-m.png" - alt="4D Printing Hybrid Soft Robots Enabled by Shape-Transformable Liquid Metal Nanoparticles"/> -<p>The integration of shape-transformable liquid metal nanoparticles (LMNPs) is first unveiled into 3D printing to create hybrid soft robots with controlled mechanical properties and deformability. This method allows direct printing of one-piece or assembled hybrid robots using a single LMNPs-integrated ink recipe, enabling precise control of mechanical and shape memory properties for applications like grippers, bioinspired motors, and rehabilitation devices. + <img src="https://onlinelibrary.wiley.com/cms/asset/9dc06df1-751f-44c9-8c95-ab7df7740eec/adma202408476-gra-0001-m.png" + alt="Mechanistic Understanding of the Underlying Energy Storage Mechanism of α-MnO2-based Pseudo-Supercapacitors"/> +<p>In this study, the pseudo-capacitive reaction mechanism of manganese dioxide (α-MnO<sub>2</sub>) nano-supercapacitor is revealed in three ionic liquids by using in situ environmental transmission electron microscopy and further investigating the cycled product of macro-supercapacitor. The underlying faradic reaction mechanisms of pseudo-capacitance and superior performance are thoroughly elucidated through extensive experimental characterizations and theoretical analyses, providing insights into the selection of electrolytes in α-MnO<sub>2</sub>-based-supercapacitors. </p> <br/> <h2>Abstract</h2> -<p>In recent years, soft robotics has emerged as a rapidly expanding frontier research field that draws inspiration from the locomotion mechanisms of soft-bodied creatures in nature to achieve smooth and complex motion for diverse applications. However, the fabrication of soft robots with hybrid structures remains challenging due to limitations in material selection and the complex, multi-step processes involved in traditional manufacturing methods. Herein, a novel direct one-step additive manufacturing (3D printing) approach is introduced for the fabrication of hybrid robots composed of soft and rigid components for sophisticated tasks. Inspired by the shape-transformable liquid metal nanoparticles (LMNPs), a functional material toolkit with tuneable mechanical properties and deformability is developed by integrating differently shaped gallium-based nanoparticles (GNPs) into the 3D printing polymers. Then the direct printing of assembled or one-piece hybrid soft-rigid robots is presented through a single recipe of GNPs-integrated inks. This fabrication method enables precise control of the mechanical properties and shape memory properties within the hybrid structures of robot body with a customized structure design. Their capabilities are further demonstrated through the design and fabrication of hybrid robots as high-precision gripper, bioinspired motor, and hand rehabilitation device.</p> +<p>Manganese dioxide (α-MnO<sub>2</sub>) has attracted significant research interest in supercapacitors recently. However, the reaction mechanism of α-MnO<sub>2</sub> in supercapacitors remains unclear. Therefore, a nano-supercapacitor using Environmental transmission electron microscopy (ETEM) is conducted and investigated the reaction mechanism of α-MnO<sub>2</sub> based on three ionic liquids (ILs). It found that in the aprotic ionic liquid (AIL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIMOTF), α-MnO<sub>2</sub> nanowires (NWs) undergo an oxidation reaction due to the presence of an active proton at the second position (H2) of the imidazole ring. As a result, α-MnO<sub>2</sub> NWs undergo a phase transition and transform into Mn<sub>3</sub>O<sub>4</sub>, exhibiting pseudo-capacitive properties. Furthermore, characterization of the macroscopic α-MnO<sub>2</sub> electrodes after cycling reveals that after the initial charging cycles, the dominant energy storage mechanism of the supercapacitor transitions from pseudo-capacitance to a dual-layer capacitance formed by the combination of Mn<sub>3</sub>O<sub>4</sub> and unreacted α-MnO<sub>2</sub>. Simultaneously, due to the coexistence of these two energy storage mechanisms, the specific capacitance of the supercapacitor in EMIMOTF electrolyte reaches up to 80 F g<sup>−1</sup>, and the cycle number reaches as high as 1000 cycles. The results are expected to provide insights into the selection of electrolytes in supercapacitors and offer a fundamental understanding of the internal reaction mechanisms in capacitors.</p> -Xumin Huang, -Liwen Zhang, -Jiangyu Hang, -Thomas Quinn, -Naufal Kabir Ahamed Nasar, -Yiliang Lin, -Chenyang Hu, -Xuan Pang, -Xuesi Chen, -Thomas P. Davis, -Ruirui Qiao +Lei Deng, +Zaifa Wang, +Hantao Cui, +Yunna Guo, +Zhangran Ye, +Hui Li, +Xinyu Zhang, +Peng Jia, +Qiaobao Zhang, +Liqiang Zhang Research Article - 4D Printing Hybrid Soft Robots Enabled by Shape‐Transformable Liquid Metal Nanoparticles - 10.1002/adma.202409789 + Mechanistic Understanding of the Underlying Energy Storage Mechanism of α‐MnO2‐based Pseudo‐Supercapacitors + 10.1002/adma.202408476 Advanced Materials - 10.1002/adma.202409789 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409789 + 10.1002/adma.202408476 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408476 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409810 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408478 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409810 - Bifunctionally Electrocatalytic Bromine Redox Reaction by Single‐Atom Catalysts for High‐Performance Zinc Batteries + 10.1002/adma.202408478 + A Full‐Process, Fine‐Grained, and Quantitative Rehabilitation Assessment Platform Enabled by On‐Skin Sensors and Multi‐Task Gait Transformer Model Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The mesoporous carbon framework with dispersed single iron atom coordinated with nitrogen atom (FeN5) moiety dispersed (FeSAC‐CMK) is developed as a conductive catalytic bromine host, which not only enhances the physicochemical adsorption of bromine species but also acts as a bifunctional electrocatalytic reactor to speed up redox kinetics of bromide/bromine (Br−/Br0) and free‐up1/3 unserviceable Br− locked by tribromide (Br3−) via conversing Br3−/Br− redox reaction to Br0/Br− redox reaction for high energy storage. +This work develops a full‐process, fine‐grained, and quantitative rehabilitation assessments platform (RAP) supported by on‐skin sensors and a multi‐task gait transformer model for patients with lower limb movement disorders. The RAP can perform multiple assessments including fall risk, walking ability, and rehabilitation progress, covering the whole process of rehabilitation and realizing objective and quantitative rehabilitation assessment. @@ -3771,49 +3676,51 @@ The mesoporous carbon framework with dispersed single iron atom coordinated with Abstract -Aqueous zinc‐bromine (Zn||Br2) batteries are regarded as one of the most promising energy storage devices due to their high safety, theoretical energy density, and low cost. However, the sluggish bromine redox kinetics and the formation of a soluble tribromide (Br3−) hinder their practical applications. Here, it is proposed dispersed single iron atom coordinated with nitrogen atoms (FeN5) in a mesoporous carbon framework (FeSAC‐CMK) as a conductive catalytic bromine host, which possesses porous structure and electrocatalytic functionality of FeN5 species for enhanced confinement and electrocatalytic effect. The active FeN5 species can fix the bromine (Br0) species to suppress the formation of Br3− effectively and bifunctionally catalyze the bromide (Br−)/Br° conversion. These free up 1/3 Br− locked by Br3− complexing agent for enhanced bromine utilization efficiency and conversion reversibility. Accordingly, the Zn||Br2 battery with FeSAC‐CMK delivers an impressive specific capacity of 344 mAh g−1 at 0.2 A g−1 and superior rate capability with 164 mAh g−1 achieved even at 20 A g−1, much higher than that of inactive CMK (262 mAh g−1 at 0.2 A g−1; 6 mAh g−1 at only 8 A g−1). Furthermore, the battery demonstrates excellent cycling performance of 88% capacity retention after 2000 cycles. +Rehabilitation of patients with lower limb movement disorders is a gradual process, which requires full‐process assessments to guide the implementation of rehabilitation plans. However, the current methods can only complete the assessment in one stage and lack objective and quantitative assessment strategies. Here, a full‐process, fine‐grained, and quantitative rehabilitation assessments platform (RAP) supported by on‐skin sensors and a multi‐task gait transformer (MG‐former) model for patients with lower limb movement disorders is developed. The signal quality and sensitivity of on‐skin sensor is improved by the synthesis of high‐performance triboelectric material and structure design. The MG‐former model can simultaneously perform multiple tasks including binary classification, multiclassification, and regression, corresponding to assessment of fall risk, walking ability, and rehabilitation progress, covering the whole rehabilitation cycle. The RAP can assess the walking ability of 23 hemiplegic patients, which has highly consistent results with the scores by the experienced physician. Furthermore, the MG‐former model outputs fine‐grained assessment results when performing regression task to track slight progress of patients that cannot be captured by conventional scales, facilitating adjustment of rehabilitation plans. This work provides an objective and quantitative platform, which is instructive for physicians and patients to implement effective strategy throughout the whole rehabilitation process. - <img src="https://onlinelibrary.wiley.com/cms/asset/14a3201e-caac-470b-8470-2d659f0bd77c/adma202409810-gra-0001-m.png" - alt="Bifunctionally Electrocatalytic Bromine Redox Reaction by Single-Atom Catalysts for High-Performance Zinc Batteries"/> -<p>The mesoporous carbon framework with dispersed single iron atom coordinated with nitrogen atom (FeN<sub>5</sub>) moiety dispersed (FeSAC-CMK) is developed as a conductive catalytic bromine host, which not only enhances the physicochemical adsorption of bromine species but also acts as a bifunctional electrocatalytic reactor to speed up redox kinetics of bromide/bromine (Br<sup>−</sup>/Br<sup>0</sup>) and free-up1/3 unserviceable Br<sup>−</sup> locked by tribromide (Br<sub>3</sub> -<sup>−</sup>) via conversing Br<sub>3</sub> -<sup>−</sup>/Br<sup>−</sup> redox reaction to Br<sup>0</sup>/Br<sup>−</sup> redox reaction for high energy storage. + <img src="https://onlinelibrary.wiley.com/cms/asset/c8bd47fe-ef61-4d43-8267-ba95e4bfc918/adma202408478-gra-0001-m.png" + alt="A Full-Process, Fine-Grained, and Quantitative Rehabilitation Assessment Platform Enabled by On-Skin Sensors and Multi-Task Gait Transformer Model"/> +<p>This work develops a full-process, fine-grained, and quantitative rehabilitation assessments platform (RAP) supported by on-skin sensors and a multi-task gait transformer model for patients with lower limb movement disorders. The RAP can perform multiple assessments including fall risk, walking ability, and rehabilitation progress, covering the whole process of rehabilitation and realizing objective and quantitative rehabilitation assessment. </p> <br/> <h2>Abstract</h2> -<p>Aqueous zinc-bromine (Zn||Br<sub>2</sub>) batteries are regarded as one of the most promising energy storage devices due to their high safety, theoretical energy density, and low cost. However, the sluggish bromine redox kinetics and the formation of a soluble tribromide (Br<sub>3</sub> -<sup>−</sup>) hinder their practical applications. Here, it is proposed dispersed single iron atom coordinated with nitrogen atoms (FeN<sub>5</sub>) in a mesoporous carbon framework (FeSAC-CMK) as a conductive catalytic bromine host, which possesses porous structure and electrocatalytic functionality of FeN<sub>5</sub> species for enhanced confinement and electrocatalytic effect. The active FeN<sub>5</sub> species can fix the bromine (Br<sup>0</sup>) species to suppress the formation of Br<sub>3</sub> -<sup>−</sup> effectively and bifunctionally catalyze the bromide (Br<sup>−</sup>)/Br° conversion. These free up 1/3 Br<sup>−</sup> locked by Br<sub>3</sub> -<sup>−</sup> complexing agent for enhanced bromine utilization efficiency and conversion reversibility. Accordingly, the Zn||Br<sub>2</sub> battery with FeSAC-CMK delivers an impressive specific capacity of 344 mAh g<sup>−1</sup> at 0.2 A g<sup>−1</sup> and superior rate capability with 164 mAh g<sup>−1</sup> achieved even at 20 A g<sup>−1</sup>, much higher than that of inactive CMK (262 mAh g<sup>−1</sup> at 0.2 A g<sup>−1</sup>; 6 mAh g<sup>−1</sup> at only 8 A g<sup>−1</sup>). Furthermore, the battery demonstrates excellent cycling performance of 88% capacity retention after 2000 cycles.</p> +<p>Rehabilitation of patients with lower limb movement disorders is a gradual process, which requires full-process assessments to guide the implementation of rehabilitation plans. However, the current methods can only complete the assessment in one stage and lack objective and quantitative assessment strategies. Here, a full-process, fine-grained, and quantitative rehabilitation assessments platform (RAP) supported by on-skin sensors and a multi-task gait transformer (MG-former) model for patients with lower limb movement disorders is developed. The signal quality and sensitivity of on-skin sensor is improved by the synthesis of high-performance triboelectric material and structure design. The MG-former model can simultaneously perform multiple tasks including binary classification, multiclassification, and regression, corresponding to assessment of fall risk, walking ability, and rehabilitation progress, covering the whole rehabilitation cycle. The RAP can assess the walking ability of 23 hemiplegic patients, which has highly consistent results with the scores by the experienced physician. Furthermore, the MG-former model outputs fine-grained assessment results when performing regression task to track slight progress of patients that cannot be captured by conventional scales, facilitating adjustment of rehabilitation plans. This work provides an objective and quantitative platform, which is instructive for physicians and patients to implement effective strategy throughout the whole rehabilitation process.</p> -Shengmei Chen, -Chao Peng, -Daming Zhu, -Chunyi Zhi +Zhixin Wang, +Xinrun He, +Tianzhao Bu, +Bo Pang, +Wei Guo, +Zhongyi Tu, +Zhiqiang Zhang, +Xiling Xiao, +Zhouping Yin, +Jian Huang, +Hao Wu Research Article - Bifunctionally Electrocatalytic Bromine Redox Reaction by Single‐Atom Catalysts for High‐Performance Zinc Batteries - 10.1002/adma.202409810 + A Full‐Process, Fine‐Grained, and Quantitative Rehabilitation Assessment Platform Enabled by On‐Skin Sensors and Multi‐Task Gait Transformer Model + 10.1002/adma.202408478 Advanced Materials - 10.1002/adma.202409810 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409810 + 10.1002/adma.202408478 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408478 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409906 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408729 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409906 - Molecular Engineering of Coordination Ligand for Multifunctional Sol–Gel Oxides + 10.1002/adma.202408729 + A Peptide‐Drug Conjugate‐Based Nanoplatform for Immunometabolic Activation and In Situ Nerve Regeneration in Advanced‐Stage Alzheimer's Disease Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A strategy to endow sol–gel oxide films with difficult‐to‐realize useful functionalities, such as direct photolithography, high dielectric strength, and high mobility by replacing the native ligand of sol–gel oxide with strategically designed/synthesized functional ligands is presented. This demonstrated a high‐performance solution‐processed all‐oxide patterning approach by controlling the functional ligands, facilitating a large‐area oxide TFT array with high reliability. +A peptide‐drug conjugate‐based nanoplatform is designed to deliver hydroxychloroquine (HCQ) and all‐trans retinoic acid (ATRA) to microglia and astrocytes, respectively. The critical immune‐metabolic pathway in microglia is significantly activated to reverse the immune tolerance. Astrocytes are in situ trans‐differentiated into functional neurons. This nanoplatform significantly inhibits the progression of advanced‐stage Alzheimer’s Disease (AD). @@ -3823,48 +3730,46 @@ A strategy to endow sol–gel oxide films with difficult‐to‐real Abstract -Here a ligand exchange strategy for synthesizing sol–gel oxides is demonstrated to achieve multifunctionality including direct photolithography, high dielectric strength, and high charge carrier mobility, which is challenging to obtain in such oxides. For this purpose, a series of bidentate ligands with azide termini and ethylene‐glycol bridges is synthesized, and these ligands are universally applicable to the synthesis of a variety of dielectric and semiconductor oxides. Optimized photolithography conditions yield a high‐quality ZrO2 dielectric film with a high dielectric constant and strength of ≈18 and ≈7 MV cm−1, respectively. Additionally, this strategy is applied to semiconductor oxides such as In2O3 and ZnO, and the all‐oxide‐patterned solution‐processed thin‐film transistor (TFT) demonstrates a high charge carrier mobility of ≈40 cm2 V−1 s−1. An oxide TFT array is fully photopatterned on a 4‐inch Si wafer; uniform performances are observed across these devices. This study suggests the possibility of realizing multifunctional oxides for application in advanced electronics using simple ligand exchange chemistry. +The formidable protection of physiological barriers and unclear pathogenic mechanisms impede drug development for Alzheimer's disease (AD). As defenders of the central nervous system, immune‐metabolism function, and stemness of glial cells remain dormant during degeneration, representing a significant challenge for simultaneously targeting and modulating. Here, a modular nanoplatform is presented composed of peptide‐drug conjugates and an inflammation‐responsive core. The nanoplatform is transported through the blood‐brain barrier via transcytosis and disassembles in the oxidative stress microenvironment upon intravenous administration. The released drug‐conjugated modules can specifically target and deliver hydroxychloroquine (HCQ) and all‐trans retinoic acid (ATRA) to microglia and astrocytes, respectively. The immune function of chronic tolerant microglia is activated by metabolic modulation, and reactive astrocytes trans‐differentiate into functional neurons. In a transgenic mouse model, nanoplatform reduces levels of toxic proteins and inflammation while increasing neuronal density. This results in the amelioration of learning and memory decline. The modular nanoplatform provides design principles for multi‐cellular targeting and combination nano‐therapy for inflammation‐related diseases. - <img src="https://onlinelibrary.wiley.com/cms/asset/5c80a198-7403-4cbf-a3be-825448d2497b/adma202409906-gra-0001-m.png" - alt="Molecular Engineering of Coordination Ligand for Multifunctional Sol–Gel Oxides"/> -<p>A strategy to endow sol–gel oxide films with difficult-to-realize useful functionalities, such as direct photolithography, high dielectric strength, and high mobility by replacing the native ligand of sol–gel oxide with strategically designed/synthesized functional ligands is presented. This demonstrated a high-performance solution-processed all-oxide patterning approach by controlling the functional ligands, facilitating a large-area oxide TFT array with high reliability. + <img src="https://onlinelibrary.wiley.com/cms/asset/03fc188d-76d8-431e-b1b7-4d73140ba363/adma202408729-gra-0001-m.png" + alt="A Peptide-Drug Conjugate-Based Nanoplatform for Immunometabolic Activation and In Situ Nerve Regeneration in Advanced-Stage Alzheimer's Disease"/> +<p>A peptide-drug conjugate-based nanoplatform is designed to deliver hydroxychloroquine (HCQ) and all-trans retinoic acid (ATRA) to microglia and astrocytes, respectively. The critical immune-metabolic pathway in microglia is significantly activated to reverse the immune tolerance. Astrocytes are in situ trans-differentiated into functional neurons. This nanoplatform significantly inhibits the progression of advanced-stage Alzheimer’s Disease (AD). </p> <br/> <h2>Abstract</h2> -<p>Here a ligand exchange strategy for synthesizing sol–gel oxides is demonstrated to achieve multifunctionality including direct photolithography, high dielectric strength, and high charge carrier mobility, which is challenging to obtain in such oxides. For this purpose, a series of bidentate ligands with azide termini and ethylene-glycol bridges is synthesized, and these ligands are universally applicable to the synthesis of a variety of dielectric and semiconductor oxides. Optimized photolithography conditions yield a high-quality ZrO<sub>2</sub> dielectric film with a high dielectric constant and strength of ≈18 and ≈7 MV cm<sup>−1</sup>, respectively. Additionally, this strategy is applied to semiconductor oxides such as In<sub>2</sub>O<sub>3</sub> and ZnO, and the all-oxide-patterned solution-processed thin-film transistor (TFT) demonstrates a high charge carrier mobility of ≈40 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup>. An oxide TFT array is fully photopatterned on a 4-inch Si wafer; uniform performances are observed across these devices. This study suggests the possibility of realizing multifunctional oxides for application in advanced electronics using simple ligand exchange chemistry.</p> +<p>The formidable protection of physiological barriers and unclear pathogenic mechanisms impede drug development for Alzheimer's disease (AD). As defenders of the central nervous system, immune-metabolism function, and stemness of glial cells remain dormant during degeneration, representing a significant challenge for simultaneously targeting and modulating. Here, a modular nanoplatform is presented composed of peptide-drug conjugates and an inflammation-responsive core. The nanoplatform is transported through the blood-brain barrier via transcytosis and disassembles in the oxidative stress microenvironment upon intravenous administration. The released drug-conjugated modules can specifically target and deliver hydroxychloroquine (HCQ) and all-trans retinoic acid (ATRA) to microglia and astrocytes, respectively. The immune function of chronic tolerant microglia is activated by metabolic modulation, and reactive astrocytes trans-differentiate into functional neurons. In a transgenic mouse model, nanoplatform reduces levels of toxic proteins and inflammation while increasing neuronal density. This results in the amelioration of learning and memory decline. The modular nanoplatform provides design principles for multi-cellular targeting and combination nano-therapy for inflammation-related diseases.</p> -Juhyeok Lee, -Syed Zahid Hassan, -Hye Ryun Sim, -Sangjun Lee, -Kyeong‐jun Jeong, -Jieun Kwon, -Chang Yun Son, -Dae Sung Chung +Peixin Liu, +Tongyu Zhang, +Yuxing Wu, +Qinjun Chen, +Tao Sun, +Chen Jiang Research Article - Molecular Engineering of Coordination Ligand for Multifunctional Sol–Gel Oxides - 10.1002/adma.202409906 + A Peptide‐Drug Conjugate‐Based Nanoplatform for Immunometabolic Activation and In Situ Nerve Regeneration in Advanced‐Stage Alzheimer's Disease + 10.1002/adma.202408729 Advanced Materials - 10.1002/adma.202409906 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409906 + 10.1002/adma.202408729 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408729 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409959 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408774 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409959 - Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2 + 10.1002/adma.202408774 + Fast and Efficient Fabrication of Functional Electronic Devices through Grayscale Digital Light Processing 3D Printing Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Partial oxidation of 2D van der Waals frameworks causes their aggregation in solution, while remaining colloidally stable. Strong inter‐sheet non‐covalent interactions give rise to intense, broad‐band visible light absorption. The absorption intensity, bandshape, and energy of this inter‐sheet absorption band is highly tunable by controlling solvent and framework identity. +This study demonstrates the use of grayscale DLP 3D printing to fabricate polymeric composites with tailored conductivity. By manipulating light intensity and incorporating lithium ions, the process enables the creation of materials with conductivity differences exceeding three orders of magnitude, paving the way for low‐cost, rapid production of intricate electronic circuits and sensors. @@ -3874,50 +3779,48 @@ Partial oxidation of 2D van der Waals frameworks causes their aggregation in sol Abstract -2D materials can be isolated as monolayer sheets when interlayer interactions involve weak van der Waals forces. These atomically thin structures enable novel topological physics and open chemical questions of how to tune the structure and properties of the sheets while maintaining them as isolated monolayers. Here, this work investigates 2D electroactive sheets that exfoliate in solution into colloidal nanosheets, but aggregate upon oxidation, giving rise to tunable interlayer charge transfer absorption and photoluminescence. This optical behavior resembles interlayer excitons, now intensely studied due to their long‐lived emission, but which remain difficult to tune through synthetic chemistry. Instead, the interlayer excitons of these framework sheets can be modulated through control of solvent, electrolyte, oxidation state, and the composition of the framework building blocks. Compared to other 2D materials, these framework sheets display the largest known interlayer binding strengths, attributable to specific orbital interactions between the sheets, and among the longest interlayer exciton lifetimes. Taken together, this study provides a microscopic basis for manipulating long‐range opto‐electronic behavior in van der Waals materials through molecular synthetic chemistry. +Fabricating polymeric composites with desirable characteristics for electronic applications is a complex and costly process. Digital light processing (DLP) 3D printing emerges as a promising technique for manufacturing intricate structures. In this study, polymeric samples are fabricated with a conductivity difference exceeding three orders of magnitude in various portions of a part by employing grayscale DLP (g‐DLP) single‐vat single‐cure 3D printing deliberate resin design. This is realized through the manipulation of light intensity during the curing process. Specifically, the rational resin design with added lithium ions results in the polymer cured under the maximum UV‐light intensity exhibiting higher electrical resistance. Conversely, sections that are only partially cured retains uncured monomers, serving as a medium that facilitates ion mobility, consequently leading to higher conductivity. The versatility of g‐DLP allows precise control of light intensity in different regions during the printing process. This characteristic opens up possibilities for applications, notably the low‐cost, facile, and rapid production of complex electrical circuits and sensors. The utilization of this technique makes it feasible to fabricate materials with tailored conductivity and functionality, providing an innovative pathway to advance the accelerated and facile creation of sophisticated electronic devices. - <img src="https://onlinelibrary.wiley.com/cms/asset/db341436-b229-45d9-afe2-b382e7aa901d/adma202409959-gra-0001-m.png" - alt="Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2"/> -<p>Partial oxidation of 2D van der Waals frameworks causes their aggregation in solution, while remaining colloidally stable. Strong inter-sheet non-covalent interactions give rise to intense, broad-band visible light absorption. The absorption intensity, bandshape, and energy of this inter-sheet absorption band is highly tunable by controlling solvent and framework identity. + <img src="https://onlinelibrary.wiley.com/cms/asset/2b9f886c-6f95-4f72-89be-827172268279/adma202408774-gra-0001-m.png" + alt="Fast and Efficient Fabrication of Functional Electronic Devices through Grayscale Digital Light Processing 3D Printing"/> +<p>This study demonstrates the use of grayscale DLP 3D printing to fabricate polymeric composites with tailored conductivity. By manipulating light intensity and incorporating lithium ions, the process enables the creation of materials with conductivity differences exceeding three orders of magnitude, paving the way for low-cost, rapid production of intricate electronic circuits and sensors. </p> <br/> <h2>Abstract</h2> -<p>2D materials can be isolated as monolayer sheets when interlayer interactions involve weak van der Waals forces. These atomically thin structures enable novel topological physics and open chemical questions of how to tune the structure and properties of the sheets while maintaining them as isolated monolayers. Here, this work investigates 2D electroactive sheets that exfoliate in solution into colloidal nanosheets, but aggregate upon oxidation, giving rise to tunable interlayer charge transfer absorption and photoluminescence. This optical behavior resembles interlayer excitons, now intensely studied due to their long-lived emission, but which remain difficult to tune through synthetic chemistry. Instead, the interlayer excitons of these framework sheets can be modulated through control of solvent, electrolyte, oxidation state, and the composition of the framework building blocks. Compared to other 2D materials, these framework sheets display the largest known interlayer binding strengths, attributable to specific orbital interactions between the sheets, and among the longest interlayer exciton lifetimes. Taken together, this study provides a microscopic basis for manipulating long-range opto-electronic behavior in van der Waals materials through molecular synthetic chemistry.</p> +<p>Fabricating polymeric composites with desirable characteristics for electronic applications is a complex and costly process. Digital light processing (DLP) 3D printing emerges as a promising technique for manufacturing intricate structures. In this study, polymeric samples are fabricated with a conductivity difference exceeding three orders of magnitude in various portions of a part by employing grayscale DLP (g-DLP) single-vat single-cure 3D printing deliberate resin design. This is realized through the manipulation of light intensity during the curing process. Specifically, the rational resin design with added lithium ions results in the polymer cured under the maximum UV-light intensity exhibiting higher electrical resistance. Conversely, sections that are only partially cured retains uncured monomers, serving as a medium that facilitates ion mobility, consequently leading to higher conductivity. The versatility of g-DLP allows precise control of light intensity in different regions during the printing process. This characteristic opens up possibilities for applications, notably the low-cost, facile, and rapid production of complex electrical circuits and sensors. The utilization of this technique makes it feasible to fabricate materials with tailored conductivity and functionality, providing an innovative pathway to advance the accelerated and facile creation of sophisticated electronic devices.</p> -Jacob McKenzie, -Doran L. Pennington, -Thomas Ericson, -Elana Cope, -Aaron J. Kaufman, -Anthony F. Cozzolino, -David C. Johnson, -Kentaro Kadota, -Christopher H. Hendon, -Carl K. Brozek +Farzad Gholami, +Liang Yue, +Mingzhe Li, +Ayush Jain, +Akhlak Mahmood, +Marcus Fratarcangeli, +Rampi Ramprasad, +H. Jerry Qi Research Article - Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2 - 10.1002/adma.202409959 + Fast and Efficient Fabrication of Functional Electronic Devices through Grayscale Digital Light Processing 3D Printing + 10.1002/adma.202408774 Advanced Materials - 10.1002/adma.202409959 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409959 + 10.1002/adma.202408774 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408774 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410007 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408988 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410007 - Flexible Neural Interface From Non‐Transient Silk Fibroin With Outstanding Conformality, Biocompatibility, and Bioelectric Conductivity + 10.1002/adma.202408988 + Enhanced Intramolecular Hole Transfer in Block Copolymer Enables >15% and Operational Stable Single‐Material–Organic Solar Cells Advanced Materials, Volume 36, Issue 46, November 14, 2024. -By precisely controlling the interactions between silk fibroin (SF) and poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), a robust and intertwined SF/PEDOT interface can be established. Leveraging this approach, a non‐transient SF‐based neural interface that possesses outstanding stability, conformality, biocompatibility, and bioelectric conductivity is developed. These features make it an ideal platform for the recording and monitoring of neural activities. +The impact of different synthetic protocols of block copolymer (BCP) is first investigated on the relevant photovoltaic properties. The more phase pure direct synthesis BCP exhibits enhanced intramolecular hole transfer, leading to a record efficiency of over 15% for single‐material–organic solar cells together with excellent long‐term operational stability. @@ -3927,50 +3830,47 @@ By precisely controlling the interactions between silk fibroin (SF) and poly(3,4 Abstract -Silk fibroin (SF) with good biocompatibility can enable an efficient and safe implementation of neural interfaces. However, it has been difficult to achieve a robust integration of patterned conducting materials (multichannel electrodes) on flexible SF film substrates due to the absence of some enduring interactions. In this study, a thermo‐assisted pattern‐transfer technique is demonstrated that can facilely transfer a layer of pre‐set poly(3,4‐ethylenedioxythiophene) (PEDOT) onto the flexible SF substrate through an interpenetrating network of 2 polymer chains, achieving a desired substrate/conductor intertwined interface with good flexibility (≈33 MPa), conductivity (386 S cm−1) and stability in liquid state over 4 months simultaneously. Importantly, this technique can be combined with ink‐jet printing to prepare a multichannel SF‐based neural interface for the electrocorticogram (ECoG) recording and inflammation remission in rat models. The SF‐based neural interface with satisfied tissue conformability, biocompatibility, and bioelectric conductivity is a promising ECoG acquisition tool, where the demonstrated approach can also be useful to develop other SF‐based flexible bioelectronics. +Recent studies on narrow bandgap all‐conjugated block copolymer (BCP) single‐material–organic solar cells (SMOSCs) have made unprecedented progress in power conversion efficiency (PCE); however, it still lacks understanding of the structure‐property relationship in these highly mixed materials. Herein, the impact of different synthetic protocols (direct synthesis (d‐BCP) versus sequential synthesis (s‐BCP)) is first investigated on the relevant photovoltaic properties. Targeting the same BCP, namely PBDB‐T‐b‐PYIT, it is found that the change in polymerization reaction leads to quite different optical and transport properties. The d‐BCP outputs a record‐high PCE of 15.02% for SMOSCs as well as enhanced operation stability under simulated 1‐sun illumination, which is significantly higher than that of s‐BCP (10.33%) and even close to its bulk heterojunction (BHJ) counterparts. Detailed transient absorption spectroscopy reveals ultrafast dynamics of charge transfer (CT) and exciton dissociation in BCP. In together with morphology characterization, it is revealed that the d‐BCP has more phase pure composition, enhanced molecular ordering, and higher intramolecular CT efficiency relative to those of s‐BCP. These findings gain insight into both the structure and carrier dynamic of BCP and demonstrate the possibility of achieving high‐efficiency and stable SMOSCs. - <img src="https://onlinelibrary.wiley.com/cms/asset/c1223cc9-0f38-4ac0-8599-34895fd6f6bf/adma202410007-gra-0001-m.png" - alt="Flexible Neural Interface From Non-Transient Silk Fibroin With Outstanding Conformality, Biocompatibility, and Bioelectric Conductivity"/> -<p>By precisely controlling the interactions between silk fibroin (SF) and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), a robust and intertwined SF/PEDOT interface can be established. Leveraging this approach, a non-transient SF-based neural interface that possesses outstanding stability, conformality, biocompatibility, and bioelectric conductivity is developed. These features make it an ideal platform for the recording and monitoring of neural activities. + <img src="https://onlinelibrary.wiley.com/cms/asset/4a696f42-a308-4924-a37f-cb79e3f7b96b/adma202408988-gra-0001-m.png" + alt="Enhanced Intramolecular Hole Transfer in Block Copolymer Enables &gt;15% and Operational Stable Single-Material–Organic Solar Cells"/> +<p>The impact of different synthetic protocols of block copolymer (BCP) is first investigated on the relevant photovoltaic properties. The more phase pure direct synthesis BCP exhibits enhanced intramolecular hole transfer, leading to a record efficiency of over 15% for single-material–organic solar cells together with excellent long-term operational stability. </p> <br/> <h2>Abstract</h2> -<p>Silk fibroin (SF) with good biocompatibility can enable an efficient and safe implementation of neural interfaces. However, it has been difficult to achieve a robust integration of patterned conducting materials (multichannel electrodes) on flexible SF film substrates due to the absence of some enduring interactions. In this study, a thermo-assisted pattern-transfer technique is demonstrated that can facilely transfer a layer of pre-set poly(3,4-ethylenedioxythiophene) (PEDOT) onto the flexible SF substrate through an interpenetrating network of 2 polymer chains, achieving a desired substrate/conductor intertwined interface with good flexibility (≈33 MPa), conductivity (386 S cm<sup>−1</sup>) and stability in liquid state over 4 months simultaneously. Importantly, this technique can be combined with ink-jet printing to prepare a multichannel SF-based neural interface for the electrocorticogram (ECoG) recording and inflammation remission in rat models. The SF-based neural interface with satisfied tissue conformability, biocompatibility, and bioelectric conductivity is a promising ECoG acquisition tool, where the demonstrated approach can also be useful to develop other SF-based flexible bioelectronics.</p> +<p>Recent studies on narrow bandgap all-conjugated block copolymer (BCP) single-material–organic solar cells (SMOSCs) have made unprecedented progress in power conversion efficiency (PCE); however, it still lacks understanding of the structure-property relationship in these highly mixed materials. Herein, the impact of different synthetic protocols (direct synthesis (<i>d</i>-BCP) versus sequential synthesis (<i>s</i>-BCP)) is first investigated on the relevant photovoltaic properties. Targeting the same BCP, namely PBDB-T-<i>b</i>-PYIT, it is found that the change in polymerization reaction leads to quite different optical and transport properties. The <i>d</i>-BCP outputs a record-high PCE of 15.02% for SMOSCs as well as enhanced operation stability under simulated 1-sun illumination, which is significantly higher than that of <i>s</i>-BCP (10.33%) and even close to its bulk heterojunction (BHJ) counterparts. Detailed transient absorption spectroscopy reveals ultrafast dynamics of charge transfer (CT) and exciton dissociation in BCP. In together with morphology characterization, it is revealed that the <i>d</i>-BCP has more phase pure composition, enhanced molecular ordering, and higher intramolecular CT efficiency relative to those of <i>s</i>-BCP. These findings gain insight into both the structure and carrier dynamic of BCP and demonstrate the possibility of achieving high-efficiency and stable SMOSCs.</p> -Zhanao Hu, -Yuqing Liang, -Suna Fan, -Qianqian Niu, -Jingjing Geng, -Qimei Huang, -Benjamin S. Hsiao, -Hao Chen, -Xiang Yao, -Yaopeng Zhang +Bin Li, +Yuxin Kong, +Tao Li, +Hongxiang Li, +Haibin Zhao, +Pei Cheng, +Jianyu Yuan Research Article - Flexible Neural Interface From Non‐Transient Silk Fibroin With Outstanding Conformality, Biocompatibility, and Bioelectric Conductivity - 10.1002/adma.202410007 + Enhanced Intramolecular Hole Transfer in Block Copolymer Enables >15% and Operational Stable Single‐Material–Organic Solar Cells + 10.1002/adma.202408988 Advanced Materials - 10.1002/adma.202410007 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410007 + 10.1002/adma.202408988 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408988 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410097 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409015 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410097 - Customization of 2D Atomic‐Molecular Heterojunction with Manipulatable Charge‐Transfer and Band Structure + 10.1002/adma.202409015 + Polypyridiniums with Inherent Autophagy‐Inducing Activity for Atherosclerosis Treatment by Intracellularly Co‐Delivering Two Antioxidant Enzymes Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A refined atomic‐molecular heterojunction strategy is developed featuring strong covalent bonds between organic molecule and 2D violet phosphorus atomic crystal, enabling enhanced charge‐transfer dynamics and customizable band structure regulation at the molecular level. Our research provides a low‐cost yet high‐efficiency regulatory approach to optimize device performance across diverse application domains. +A series of polypyridiniums are proposed to effectively deliver two antioxidant enzymes into cytosolic of treated cells to down‐regulate lipopolysaccharide induced ROS. Moreover, the material itself can efficiently activate the autophagy in macrophages and inhibit foam cell formation. After being coated with neutrophil membranes, the polymer/protein complexes successfully halted the progression of atherosclerosis in ApoE‐/‐ mice upon intravenous injection. @@ -3980,51 +3880,50 @@ A refined atomic‐molecular heterojunction strategy is developed featuring Abstract -Manipulating the properties of 2D materials through meticulously engineered artificial heterojunctions holds great promise for novel device applications. However, existing research on the crucial charge‐transfer interactions and energy profile regulation is predominantly focused on 2D van der Waals structures formed via weak van der Waals forces, limiting regulatory efficiency at high costs. Herein, a refined atomic‐molecular heterojunction strategy featuring strong covalent bonds between organic molecule and 2D violet phosphorus (VP) atomic crystal is developed, which enables enhanced charge‐transfer dynamics and customizable band structure regulation at the molecular level. Both experimentally and theoretically, it is demonstrated that grafting efficiency, charge redistribution, and energy gap regulation critically depend on organic electronegativity, providing a low‐cost yet high‐efficiency regulatory effect on a large scale. As a proof of concept, the novel VP‐molecular heterojunctions exhibit optimized performance in diverse application domains, presenting a general platform for future high‐performance device applications. +Atherosclerosis is a chronic inflammatory disease of the arterial intima and is becoming the leading cause of morbidity and mortality worldwide. There is considerable evidence that defective autophagy and overproduction of reactive oxygen species (ROS) are closely involved in the development and progression of atherosclerosis. Here, a polymer is developed with the inherent autophagy‐inducing activity to treat atherosclerosis by co‐delivering antioxidant enzymes. The lead material P5c screened from a library of polypyridiniums shows robust efficacy in cytosolic protein delivery, and efficiently delivers superoxide dismutase (SOD) and catalase (CAT) into macrophages to down‐regulate intracellular ROS. Moreover, P5c activates autophagy in macrophages and sufficiently inhibits foam cell formation. The P5c nanoparticle loaded with both SOD and CAT is further coated with neutrophil membranes to treat atherosclerosis in an ApoE−/− mice model. The treatment exhibits potent anti‐atherosclerosis effect via activating autophagy, decreasing the infiltration of senescent cells in atherosclerotic plaques, regulating the M2 polarization of macrophages, and restoring the structure and function of splenic corpuscles. The polymer offers a multifaceted approach to combat atherosclerosis, addressing both cellular dysfunction and the need for targeted protein delivery within affected cells. - <img src="https://onlinelibrary.wiley.com/cms/asset/777ec60e-13fe-434c-917a-db1f5641da85/adma202410097-gra-0001-m.png" - alt="Customization of 2D Atomic-Molecular Heterojunction with Manipulatable Charge-Transfer and Band Structure"/> -<p>A refined atomic-molecular heterojunction strategy is developed featuring strong covalent bonds between organic molecule and 2D violet phosphorus atomic crystal, enabling enhanced charge-transfer dynamics and customizable band structure regulation at the molecular level. Our research provides a low-cost yet high-efficiency regulatory approach to optimize device performance across diverse application domains. + <img src="https://onlinelibrary.wiley.com/cms/asset/62b6667c-2e4c-4c0a-a5b4-35b8de0a3f62/adma202409015-gra-0001-m.png" + alt="Polypyridiniums with Inherent Autophagy-Inducing Activity for Atherosclerosis Treatment by Intracellularly Co-Delivering Two Antioxidant Enzymes"/> +<p>A series of polypyridiniums are proposed to effectively deliver two antioxidant enzymes into cytosolic of treated cells to down-regulate lipopolysaccharide induced ROS. Moreover, the material itself can efficiently activate the autophagy in macrophages and inhibit foam cell formation. After being coated with neutrophil membranes, the polymer/protein complexes successfully halted the progression of atherosclerosis in ApoE<sup>-/-</sup> mice upon intravenous injection. </p> <br/> <h2>Abstract</h2> -<p>Manipulating the properties of 2D materials through meticulously engineered artificial heterojunctions holds great promise for novel device applications. However, existing research on the crucial charge-transfer interactions and energy profile regulation is predominantly focused on 2D van der Waals structures formed via weak van der Waals forces, limiting regulatory efficiency at high costs. Herein, a refined atomic-molecular heterojunction strategy featuring strong covalent bonds between organic molecule and 2D violet phosphorus (VP) atomic crystal is developed, which enables enhanced charge-transfer dynamics and customizable band structure regulation at the molecular level. Both experimentally and theoretically, it is demonstrated that grafting efficiency, charge redistribution, and energy gap regulation critically depend on organic electronegativity, providing a low-cost yet high-efficiency regulatory effect on a large scale. As a proof of concept, the novel VP-molecular heterojunctions exhibit optimized performance in diverse application domains, presenting a general platform for future high-performance device applications.</p> +<p>Atherosclerosis is a chronic inflammatory disease of the arterial intima and is becoming the leading cause of morbidity and mortality worldwide. There is considerable evidence that defective autophagy and overproduction of reactive oxygen species (ROS) are closely involved in the development and progression of atherosclerosis. Here, a polymer is developed with the inherent autophagy-inducing activity to treat atherosclerosis by co-delivering antioxidant enzymes. The lead material P5c screened from a library of polypyridiniums shows robust efficacy in cytosolic protein delivery, and efficiently delivers superoxide dismutase (SOD) and catalase (CAT) into macrophages to down-regulate intracellular ROS. Moreover, P5c activates autophagy in macrophages and sufficiently inhibits foam cell formation. The P5c nanoparticle loaded with both SOD and CAT is further coated with neutrophil membranes to treat atherosclerosis in an ApoE<sup>−/−</sup> mice model. The treatment exhibits potent anti-atherosclerosis effect via activating autophagy, decreasing the infiltration of senescent cells in atherosclerotic plaques, regulating the M2 polarization of macrophages, and restoring the structure and function of splenic corpuscles. The polymer offers a multifaceted approach to combat atherosclerosis, addressing both cellular dysfunction and the need for targeted protein delivery within affected cells.</p> -Weilin Chen, -An Chen, -Xue Liu, -Fan Shu, -Jianmin Zeng, -Jinying Zhang, -Hongbo Xu, -Gaoliang Peng, -Zhi Yang, -Jinjin Li, -Gang Liu +Mengxiao Liang, +Qian Wang, +Song Zhang, +Qi Lan, +Ruijue Wang, +Echuan Tan, +Lei Zhou, +Changping Wang, +Hui Wang, +Yiyun Cheng Research Article - Customization of 2D Atomic‐Molecular Heterojunction with Manipulatable Charge‐Transfer and Band Structure - 10.1002/adma.202410097 + Polypyridiniums with Inherent Autophagy‐Inducing Activity for Atherosclerosis Treatment by Intracellularly Co‐Delivering Two Antioxidant Enzymes + 10.1002/adma.202409015 Advanced Materials - 10.1002/adma.202410097 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410097 + 10.1002/adma.202409015 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409015 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410209 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409059 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410209 - Constructing a Janus Catholyte/Cathode Structure: A New Strategy for Stable Zn‐Organic Batteries + 10.1002/adma.202409059 + Giant Capacitive Energy Storage in High‐Entropy Lead‐Free Ceramics with Temperature Self‐Check Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Inspired by membrane‐less organelles in cells, a simple and versatile strategy is proposed—constructing a Janus catholyte/cathode structured electrode based on liquid‐liquid phase separation, in which redox‐active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte. +Herein, octahedral tilt and cationic displacement are observed in high entropy (HE) BNT‐ based ceramics. On the basis of tape‐casting process and cold isostatic pressing, the optimal ceramics display a large Wrec (10.46 J cm−3) at 685 kV cm−1 and a high power density (332.88 MW cm−3). Importantly, Tm/Yb codoping endows the ceramics with fluorescent temperature self‐check feature. @@ -4034,54 +3933,59 @@ Inspired by membrane‐less organelles in cells, a simple and versatile stra Abstract -Organic materials are promising candidates for the electrodes of aqueous zinc‐ion batteries due to their nonmetallic nature, environmental friendliness, and cost‐effectiveness. However, they often suffer from significant dissolution during the charge‐discharge process, which poses a major hurdle to their practical applications. Inspired by membrane‐less organelles in cells, a simple and versatile strategy is proposed—constructing a Janus catholyte/cathode structured electrode based on liquid‐liquid phase separation, in which redox‐active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte. The customization of phase separation systems by leveraging the hydrophobicity/hydrophilicity differences of various anions is successfully demonstrated. This approach allows for precise regulation of ion cluster/coordination structures, enabling the confinement of active substances while ensuring efficient ion transport. Consequently, the as‐constructed Zn||Janus catholyte/cathode cells exhibit superior reversible rate capacity (186 mA h g−1 at 5.0 A g−1) and remarkable cycling performance (retention of 72.5% after 12 000 cycles). The strategy in building Janus catholyte/cathode structured electrodes breaks free from the limitations imposed by traditional solid‐state electrodes, offering tremendous opportunities for exploring diverse advanced battery systems. +Considering the large demand for electricity in the era of artificial intelligence and big data, there is an urgent need to explore novel energy storage media with higher energy density and intelligent temperature self‐check functions. High‐entropy (HE) ceramic capacitors are of great significance because of their excellent energy storage efficiency and high power density (PD). However, the contradiction between configurational entropy and polarization in traditional HE systems greatly restrains the increase in energy storage density. Herein, the contradiction is effectively solved by regulating the octahedral tilt and cationic displacement in ABO3‐type perovskite HE ceramics, i.e., (1‐x)[0.6(Bi0.47Na0.47Yb0.03Tm0.01)TiO3‐0.4(Ba0.5Sr0.5)TiO3]‐xSr(Zr0.5Hf0.5)O3 (BNYTT‐BST‐xSZH). Combining the tape‐casting process and cold isostatic pressing, the optimal BNYTT‐BST‐0.06SZH ceramic displays a large recoverable energy storage density (10.46 J cm−3) at 685 kV cm−1 and a high PD (332.88 MW cm−3). More importantly, due to Tm/Yb codoping, abnormal fluorescent negative thermal expansion and excellent real‐time temperature sensing are developed, thus the application of fault detection and warning in high‐voltage transmission line systems is conceptualized. This study provides an effective strategy for enhancing the polarization of energy‐storing HE ceramics and offers a promising material for overcoming the problems of insufficient capacitor density and thermal runaway in terminal communication. - <img src="https://onlinelibrary.wiley.com/cms/asset/c85d831c-7fb9-4e87-8022-06f1f70e2e21/adma202410209-gra-0001-m.png" - alt="Constructing a Janus Catholyte/Cathode Structure: A New Strategy for Stable Zn-Organic Batteries"/> -<p>Inspired by membrane-less organelles in cells, a simple and versatile strategy is proposed—constructing a Janus catholyte/cathode structured electrode based on liquid-liquid phase separation, in which redox-active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte. + <img src="https://onlinelibrary.wiley.com/cms/asset/c927c5ce-a2bf-445d-9e20-6350c3560329/adma202409059-gra-0001-m.png" + alt="Giant Capacitive Energy Storage in High-Entropy Lead-Free Ceramics with Temperature Self-Check"/> +<p>Herein, octahedral tilt and cationic displacement are observed in high entropy (HE) BNT- based ceramics. On the basis of tape-casting process and cold isostatic pressing, the optimal ceramics display a large <i>W</i> +<sub>rec</sub> (10.46 J cm<sup>−3</sup>) at 685 kV cm<sup>−1</sup> and a high power density (332.88 MW cm<sup>−3</sup>). Importantly, Tm/Yb codoping endows the ceramics with fluorescent temperature self-check feature. </p> <br/> <h2>Abstract</h2> -<p>Organic materials are promising candidates for the electrodes of aqueous zinc-ion batteries due to their nonmetallic nature, environmental friendliness, and cost-effectiveness. However, they often suffer from significant dissolution during the charge-discharge process, which poses a major hurdle to their practical applications. Inspired by membrane-less organelles in cells, a simple and versatile strategy is proposed—constructing a Janus catholyte/cathode structured electrode based on liquid-liquid phase separation, in which redox-active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte. The customization of phase separation systems by leveraging the hydrophobicity/hydrophilicity differences of various anions is successfully demonstrated. This approach allows for precise regulation of ion cluster/coordination structures, enabling the confinement of active substances while ensuring efficient ion transport. Consequently, the as-constructed Zn||Janus catholyte/cathode cells exhibit superior reversible rate capacity (186 mA h g<sup>−1</sup> at 5.0 A g<sup>−1</sup>) and remarkable cycling performance (retention of 72.5% after 12 000 cycles). The strategy in building Janus catholyte/cathode structured electrodes breaks free from the limitations imposed by traditional solid-state electrodes, offering tremendous opportunities for exploring diverse advanced battery systems.</p> +<p>Considering the large demand for electricity in the era of artificial intelligence and big data, there is an urgent need to explore novel energy storage media with higher energy density and intelligent temperature self-check functions. High-entropy (HE) ceramic capacitors are of great significance because of their excellent energy storage efficiency and high power density (<i>P</i> +<sub>D</sub>). However, the contradiction between configurational entropy and polarization in traditional HE systems greatly restrains the increase in energy storage density. Herein, the contradiction is effectively solved by regulating the octahedral tilt and cationic displacement in ABO<sub>3</sub>-type perovskite HE ceramics, i.e., (1-<i>x</i>)[0.6(Bi<sub>0.47</sub>Na<sub>0.47</sub>Yb<sub>0.03</sub>Tm<sub>0.01</sub>)TiO<sub>3</sub>-0.4(Ba<sub>0.5</sub>Sr<sub>0.5</sub>)TiO<sub>3</sub>]-<i>x</i>Sr(Zr<sub>0.5</sub>Hf<sub>0.5</sub>)O<sub>3</sub> (BNYTT-BST-<i>x</i>SZH). Combining the tape-casting process and cold isostatic pressing, the optimal BNYTT-BST-0.06SZH ceramic displays a large recoverable energy storage density (10.46 J cm<sup>−3</sup>) at 685 kV cm<sup>−1</sup> and a high <i>P</i> +<sub>D</sub> (332.88 MW cm<sup>−3</sup>). More importantly, due to Tm/Yb codoping, abnormal fluorescent negative thermal expansion and excellent real-time temperature sensing are developed, thus the application of fault detection and warning in high-voltage transmission line systems is conceptualized. This study provides an effective strategy for enhancing the polarization of energy-storing HE ceramics and offers a promising material for overcoming the problems of insufficient capacitor density and thermal runaway in terminal communication.</p> -Hu Hong, -Yiqiao Wang, -Zhiquan Wei, -Xinru Yang, -Zhuoxi Wu, -Xun Guo, -Ao Chen, -Shaoce Zhang, -Shixun Wang, -Qing Li, -Shimei Li, -Dechao Zhang, -Qi Xiong, -Chunyi Zhi +Xiangfu Zeng, +Jinfeng Lin, +Jie Shen, +Yan Chen, +Wei Xu, +Luomeng Tang, +Simin Wang, +Min Gao, +Chunlin Zhao, +Tengfei Lin, +Laihui Luo, +Chao Chen, +Baisheng Sa, +Cong Lin, +Xiao Wu, +Jiwei Zhai Research Article - Constructing a Janus Catholyte/Cathode Structure: A New Strategy for Stable Zn‐Organic Batteries - 10.1002/adma.202410209 + Giant Capacitive Energy Storage in High‐Entropy Lead‐Free Ceramics with Temperature Self‐Check + 10.1002/adma.202409059 Advanced Materials - 10.1002/adma.202410209 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410209 + 10.1002/adma.202409059 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409059 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410324 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409090 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410324 - Programming Hydrogen Bonds for Reversible Elastic‐Plastic Phase Transition in a Conductive Stretchable Hydrogel Actuator with Rapid Ultra‐High‐Density Energy Conversion and Multiple Sensory Properties + 10.1002/adma.202409090 + Metal Halide Perovskite Nanocrystals‐Intermediated Hydrogel for Boosting the Biosensing Performance Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Inspired by the energy conversion of hairspring, an intelligent hydrogel is developed to achieve reversible transformation between elasticity and plasticity through precise regulation of hydrogen bonds, enabling efficient energy storage and release. The hydrogel exhibits exceptional drive rate, high energy density output, and diversified sensing capability. This groundbreaking innovation paves the way for novel designs of smart hydrogel actuators. +Mn2+‐doped CsPbCl3/CsPb2Cl5 core/shell hetero perovskite nanocrystals with superior water stability are obtained via a trinity strategy by integrating Mn (II) substitution with CsPb2Cl5 inert shell and NH2‐PEG‐COOH coating. Hetero perovskite nanocrystals‐based hydrogel biosensor provides pesticide information on food products, achieving on‐site monitoring of chlorpyrifos at the nanogram per milliliter level. @@ -4091,49 +3995,47 @@ Inspired by the energy conversion of hairspring, an intelligent hydrogel is deve Abstract -Smart hydrogels have recently garnered significant attention in the fields of actuators, human‐machine interaction, and soft robotics. However, when constructing large‐scale actuated systems, they usually exhibit limited actuation forces (≈2 kPa) and actuation speeds. Drawing inspiration from hairspring energy conversion mechanism, an elasticity‐plasticity‐controllable composite hydrogel (PCTA) with robust contraction capabilities is developed. By precisely manipulating intermolecular and intramolecular hydrogen‐bonding interactions, the material's elasticity and plasticity can be programmed to facilitate efficient energy storage and release. The proposed mechanism enables rapid generation of high contraction forces (900 kPa) at ultra‐high working densities (0.96 MJ m−3). Molecular dynamics simulations reveal that modifications in the number and nature of hydrogen bonds lead to a distinct elastic‐plastic transition in hydrogels. Furthermore, the conductive PCTA hydrogel exhibits multimodal sensing capabilities including stretchable strain sensing with a wide sensing range (1–200%), fast response time (180 ms), and excellent linearity of the output signal. Moreover, it demonstrates exceptional temperature and humidity sensing capabilities with high detection accuracy. The strong actuation power and real‐time sensory feedback from the composite hydrogels are expected to inspire novel flexible driving materials and intelligent sensing systems. +Metal‐halide perovskites have become attractive nanomaterials for advanced biosensors, yet the structural design remains challenging due to the trade‐off between environmental stability and sensing sensitivity. Herein, a trinity strategy is proposed to address this issue by integrating Mn (II) substitution with CsPb2Cl5 inert shell and NH2‐PEG‐COOH coating for designing Mn2+‐doped CsPbCl3/CsPb2Cl5 core/shell hetero perovskite nanocrystals (PMCP PNCs). The trinity strategy isolates the emissive Mn2+‐doped CsPbCl3 core from water and the Mn2+ d–d transition generates photoluminescence with a long lifetime, endowing the NH2‐PEG‐COOH capped Mn2+‐doped CsPbCl3/CsPb2Cl5 PNCs with robust water stability and oxygen‐sensitive property. Given the structural integration, photoluminescent hydrogel biosensors are designed by embedding the PMCP PNCs into the hydrogel system to deliver on‐site pesticide information on food products. Impressively, benefiting from the dual enzyme triggered‐responsive property of PMCP PNCs, the hydrogel biosensor is endowed with ultra‐high sensitivity toward chlorpyrifos pesticide at the nanogram per milliliter level. Such a robust PMCP PNCs‐based hydrogel sensor can provide accurate pesticide information while guiding the construction of photoluminescent biosensors for upcoming on‐site applications. - <img src="https://onlinelibrary.wiley.com/cms/asset/3103b334-4ffe-4ae8-9aaa-4d4880f320d2/adma202410324-gra-0001-m.png" - alt="Programming Hydrogen Bonds for Reversible Elastic-Plastic Phase Transition in a Conductive Stretchable Hydrogel Actuator with Rapid Ultra-High-Density Energy Conversion and Multiple Sensory Properties"/> -<p>Inspired by the energy conversion of hairspring, an intelligent hydrogel is developed to achieve reversible transformation between elasticity and plasticity through precise regulation of hydrogen bonds, enabling efficient energy storage and release. The hydrogel exhibits exceptional drive rate, high energy density output, and diversified sensing capability. This groundbreaking innovation paves the way for novel designs of smart hydrogel actuators. + <img src="https://onlinelibrary.wiley.com/cms/asset/e326666e-fa3e-4e5a-815d-2ea3219de4af/adma202409090-gra-0001-m.png" + alt="Metal Halide Perovskite Nanocrystals-Intermediated Hydrogel for Boosting the Biosensing Performance"/> +<p>Mn<sup>2+</sup>-doped CsPbCl<sub>3</sub>/CsPb<sub>2</sub>Cl<sub>5</sub> core/shell hetero perovskite nanocrystals with superior water stability are obtained via a trinity strategy by integrating Mn (II) substitution with CsPb<sub>2</sub>Cl<sub>5</sub> inert shell and NH<sub>2</sub>-PEG-COOH coating. Hetero perovskite nanocrystals-based hydrogel biosensor provides pesticide information on food products, achieving on-site monitoring of chlorpyrifos at the nanogram per milliliter level. </p> <br/> <h2>Abstract</h2> -<p>Smart hydrogels have recently garnered significant attention in the fields of actuators, human-machine interaction, and soft robotics. However, when constructing large-scale actuated systems, they usually exhibit limited actuation forces (≈2 kPa) and actuation speeds. Drawing inspiration from hairspring energy conversion mechanism, an elasticity-plasticity-controllable composite hydrogel (PCTA) with robust contraction capabilities is developed. By precisely manipulating intermolecular and intramolecular hydrogen-bonding interactions, the material's elasticity and plasticity can be programmed to facilitate efficient energy storage and release. The proposed mechanism enables rapid generation of high contraction forces (900 kPa) at ultra-high working densities (0.96 MJ m<sup>−3</sup>). Molecular dynamics simulations reveal that modifications in the number and nature of hydrogen bonds lead to a distinct elastic-plastic transition in hydrogels. Furthermore, the conductive PCTA hydrogel exhibits multimodal sensing capabilities including stretchable strain sensing with a wide sensing range (1–200%), fast response time (180 ms), and excellent linearity of the output signal. Moreover, it demonstrates exceptional temperature and humidity sensing capabilities with high detection accuracy. The strong actuation power and real-time sensory feedback from the composite hydrogels are expected to inspire novel flexible driving materials and intelligent sensing systems.</p> +<p>Metal-halide perovskites have become attractive nanomaterials for advanced biosensors, yet the structural design remains challenging due to the trade-off between environmental stability and sensing sensitivity. Herein, a trinity strategy is proposed to address this issue by integrating Mn (II) substitution with CsPb<sub>2</sub>Cl<sub>5</sub> inert shell and NH<sub>2</sub>-PEG-COOH coating for designing Mn<sup>2+</sup>-doped CsPbCl<sub>3</sub>/CsPb<sub>2</sub>Cl<sub>5</sub> core/shell hetero perovskite nanocrystals (PMCP PNCs). The trinity strategy isolates the emissive Mn<sup>2+</sup>-doped CsPbCl<sub>3</sub> core from water and the Mn<sup>2+</sup> d–d transition generates photoluminescence with a long lifetime, endowing the NH<sub>2</sub>-PEG-COOH capped Mn<sup>2+</sup>-doped CsPbCl<sub>3</sub>/CsPb<sub>2</sub>Cl<sub>5</sub> PNCs with robust water stability and oxygen-sensitive property. Given the structural integration, photoluminescent hydrogel biosensors are designed by embedding the PMCP PNCs into the hydrogel system to deliver on-site pesticide information on food products. Impressively, benefiting from the dual enzyme triggered-responsive property of PMCP PNCs, the hydrogel biosensor is endowed with ultra-high sensitivity toward chlorpyrifos pesticide at the nanogram per milliliter level. Such a robust PMCP PNCs-based hydrogel sensor can provide accurate pesticide information while guiding the construction of photoluminescent biosensors for upcoming on-site applications.</p> -Ping Guo, -Zhaoxin Zhang, -Chengnan Qian, -Ruofei Wang, -Lin Cheng, -Ye Tian, -Huaping Wu, -Shuze Zhu, -Aiping Liu +Hongxia Li, +Yanan Hu, +Yan Zhang, +Hao Zhang, +Dong Yao, +Yuehe Lin, +Xu Yan Research Article - Programming Hydrogen Bonds for Reversible Elastic‐Plastic Phase Transition in a Conductive Stretchable Hydrogel Actuator with Rapid Ultra‐High‐Density Energy Conversion and Multiple Sensory Properties - 10.1002/adma.202410324 + Metal Halide Perovskite Nanocrystals‐Intermediated Hydrogel for Boosting the Biosensing Performance + 10.1002/adma.202409090 Advanced Materials - 10.1002/adma.202410324 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410324 + 10.1002/adma.202409090 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409090 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410418 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409297 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410418 - Achieving Ultra‐Narrow‐Band Deep‐Red Electroluminescence By a Soliton‐type Dye Squaraine + 10.1002/adma.202409297 + Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye‐Incorporated Photonic Crystal‐Based Sensor Array Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Squaraine dyes typically exhibit narrow emission spectra due to their soliton‐like electronic structure characteristics. An organic light‐emitting diode based on soliton‐type squaraine dye is prepared, overcoming the luminescence quenching induced by dye aggregation. The deep‐red electroluminescence peak is located at 668 nm, with a full‐width at half‐maximum (FWHM) of only 0.10 eV. +A colorimetric sensor array composed of dye‐incorporated colloidal photonic crystals is fabricated for detecting volatile organic compounds (VOCs). The overlap between the photonic bandgap edge and the absorption peak of the dye enhances color changes. The sensor array generates distinct color difference maps for acetaldehyde, acetone, and acetic acid, respectively, with the limit of detection as low as 0.02 ppm, without any data amplification. @@ -4143,50 +4045,45 @@ Squaraine dyes typically exhibit narrow emission spectra due to their soliton Abstract -Due to the soliton‐like electronic structural characteristics, cyanine dyes typically exhibit spectral behaviors such as large molar extinction coefficients, narrow spectra, and high fluorescence efficiency. However, their extensive applications as emitters in electroluminescence are largely ignored due to their serious emission quenching in the aggregation state. Herein, it is reported a squaraine dye (a type of cyanine) SQPhEt. At different solution concentrations, the unusual decrease in full‐width at half‐maxima (FWHM) with increasing Stokes shift indicates the fluorescence quenching of SQPhEt in the aggregated state is because of the strong self‐absorption effect. A sensitized device structure can help to reduce the doping concentration of dye, which can effectively suppress self‐absorption. Benefitting from the large molar extinction coefficient of SQPhEt, even at low doping concentrations of 0.1 wt%, efficient Förster energy transfer can be achieved. The corresponding spin‐coating sensitized device based on SQPhEt as the dopant exhibits favorable deep‐red emission at 668 nm with a small FWHM of 0.10 eV. +Chemoresponsive dyes offer the potential to selectively detect volatile organic compounds (VOCs) unique to certain disease states. Among different VOC sensing techniques, colorimetric sensing offers the advantage of facile recognition. However, it is often challenging to discern the color changes by the naked eye. Here, highly sensitive colorimetric VOC sensor arrays from dye‐incorporated colloidal photonic crystals (dye‐cPhCs) are reported. cPhCs are scalably fabricated on a 4‐inch wafer by spin‐coating of silica nanoparticles (NPs) dispersed in a photo‐cross‐linkable monomer, where the gradient shear flow along the film thickness creates densely‐packed square arrays of NPs in the top layers, whereas the bulk is quasi‐amorphous with larger periodicities. The broadened reflection peak allows for augmented dye absorption originating from the overlap between the photonic bandgap edge of the cPhC and the dye absorption peak, leading to a more noticeable color change upon exposure to VOCs. The sensor array generates distinct color difference maps for acetaldehyde, acetone, and acetic acid, respectively, without any data amplification. The limit of detection for acetaldehyde, acetone, and acetic acid is 1, 0.1, and 0.02 ppm, respectively. Moreover, VOC can be diagonalized by visually intuitive pattern recognition, and principal component analysis at reduced dimensionality is demonstrated. - <img src="https://onlinelibrary.wiley.com/cms/asset/721d48bf-97ac-4021-b686-ef59f5b672cb/adma202410418-gra-0001-m.png" - alt="Achieving Ultra-Narrow-Band Deep-Red Electroluminescence By a Soliton-type Dye Squaraine"/> -<p>Squaraine dyes typically exhibit narrow emission spectra due to their soliton-like electronic structure characteristics. An organic light-emitting diode based on soliton-type squaraine dye is prepared, overcoming the luminescence quenching induced by dye aggregation. The deep-red electroluminescence peak is located at 668 nm, with a full-width at half-maximum (FWHM) of only 0.10 eV. + <img src="https://onlinelibrary.wiley.com/cms/asset/77546715-3a1c-4fa9-8ca4-dbd251d0c660/adma202409297-gra-0001-m.png" + alt="Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye-Incorporated Photonic Crystal-Based Sensor Array"/> +<p>A colorimetric sensor array composed of dye-incorporated colloidal photonic crystals is fabricated for detecting volatile organic compounds (VOCs). The overlap between the photonic bandgap edge and the absorption peak of the dye enhances color changes. The sensor array generates distinct color difference maps for acetaldehyde, acetone, and acetic acid, respectively, with the limit of detection as low as 0.02 ppm, without any data amplification. </p> <br/> <h2>Abstract</h2> -<p>Due to the soliton-like electronic structural characteristics, cyanine dyes typically exhibit spectral behaviors such as large molar extinction coefficients, narrow spectra, and high fluorescence efficiency. However, their extensive applications as emitters in electroluminescence are largely ignored due to their serious emission quenching in the aggregation state. Herein, it is reported a squaraine dye (a type of cyanine) SQPhEt. At different solution concentrations, the unusual decrease in full-width at half-maxima (FWHM) with increasing Stokes shift indicates the fluorescence quenching of SQPhEt in the aggregated state is because of the strong self-absorption effect. A sensitized device structure can help to reduce the doping concentration of dye, which can effectively suppress self-absorption. Benefitting from the large molar extinction coefficient of SQPhEt, even at low doping concentrations of 0.1 wt%, efficient Förster energy transfer can be achieved. The corresponding spin-coating sensitized device based on SQPhEt as the dopant exhibits favorable deep-red emission at 668 nm with a small FWHM of 0.10 eV.</p> +<p>Chemoresponsive dyes offer the potential to selectively detect volatile organic compounds (VOCs) unique to certain disease states. Among different VOC sensing techniques, colorimetric sensing offers the advantage of facile recognition. However, it is often challenging to discern the color changes by the naked eye. Here, highly sensitive colorimetric VOC sensor arrays from dye-incorporated colloidal photonic crystals (dye-cPhCs) are reported. cPhCs are scalably fabricated on a 4-inch wafer by spin-coating of silica nanoparticles (NPs) dispersed in a photo-cross-linkable monomer, where the gradient shear flow along the film thickness creates densely-packed square arrays of NPs in the top layers, whereas the bulk is quasi-amorphous with larger periodicities. The broadened reflection peak allows for augmented dye absorption originating from the overlap between the photonic bandgap edge of the cPhC and the dye absorption peak, leading to a more noticeable color change upon exposure to VOCs. The sensor array generates distinct color difference maps for acetaldehyde, acetone, and acetic acid, respectively, without any data amplification. The limit of detection for acetaldehyde, acetone, and acetic acid is 1, 0.1, and 0.02 ppm, respectively. Moreover, VOC can be diagonalized by visually intuitive pattern recognition, and principal component analysis at reduced dimensionality is demonstrated.</p> -Wenle Tan, -Yue Yu, -Tianyuan Shi, -Lveting Zhang, -Hanlin Gan, -Bohan Wang, -Ganlin Liu, -Mingke Li, -Lei Ying, -Yuguang Ma +So Hee Nah, +Jong Bin Kim, +Hiu Ning Tiffany Chui, +Yeonjoon Suh, +Shu Yang Research Article - Achieving Ultra‐Narrow‐Band Deep‐Red Electroluminescence By a Soliton‐type Dye Squaraine - 10.1002/adma.202410418 + Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye‐Incorporated Photonic Crystal‐Based Sensor Array + 10.1002/adma.202409297 Advanced Materials - 10.1002/adma.202410418 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410418 + 10.1002/adma.202409297 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409297 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410422 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409319 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410422 - Unveiling the Cation Dependence in Alkaline Hydrogen Evolution by Differently‐Charged Ruthenium/Molybdenum Sulfide Hybrids + 10.1002/adma.202409319 + Homogenizing Energy Landscape for Efficient and Spectrally Stable Blue Perovskite Light‐Emitting Diodes Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Alkaline hydrogen evolution kinetics via water reduction limits the water electrolysis efficiency and depends on both catalyst structures and electrolyte cations. Herein, by hybridizing metallic Ru with differently‐charged MoSx clusters, the interrelated effect of metal valence and charged support for the cation‐dependent hydrogen evolution activity is demonstrated, in which the metal valence determines the water activation capability and the support determines the cation accumulation. +Dual modification on both bulk and interface is proposed to homogenize the energy landscape throughout the entire blue perovskite by comprehensively diminishing the low dimensional phases and reducing the halide defects. Resultantly, perovskite light emitting diodes with spectrally‐stable blue emission at 478 nm and a high external quantum efficiency of 21.9% are realized, representing a record in this type of devices. @@ -4196,48 +4093,50 @@ Alkaline hydrogen evolution kinetics via water reduction limits the water electr Abstract -The sluggish kinetics of hydrogen evolution reaction (HER) via water reduction limits the efficiency of alkaline water electrolysis. The HER kinetics is not only intimately related to the catalyst surface structure but also relevant to the cation identity of the electrolyte. The cation dependence also relies on the surface electronic structure and applied potential, but this interrelated effect and its underlying mechanism awaits elucidation. Herein, differently‐charged molybdenum sulfide (MoSx) cluster supports ([Mo3S13]2− and [Mo3S7]4+) are utilized to hybridize with the identical metallic Ru centers. The specific electrostatic interaction between MoSx clusters and Ru precursors induces different Ru valences of the hybrids, with a higher valence state for Ru/Mo3S13 endowing a higher activity. The Ru/Mo3S13 and Ru/Mo3S7 exhibited drastically‐different cation dependence, in which the charged support determines the local accumulation of cations and resulting water structures. The more negatively‐charged Mo3S13 support induces the facile accumulation of cations, especially for less‐hydrated K+ cations. The water activation capability by Ru valences and cation accumulation from the support effect in‐together determine the cation‐dependent alkaline HER activity. This work not only enriches the understanding about the cation‐dependent HER mechanism but also shines a light on the rational optimization strategy of electrode/electrolyte interfaces. +Blue perovskite light‐emitting diodes (PeLEDs) have attracted enormous attention; however, their unsatisfactory device efficiency and spectral stability still remain great challenges. Unfavorable low‐dimensional phase distribution and defects with deeper energy levels usually cause energy disorder, substantially limiting the device's performance. Here, an additive‐interface optimization strategy is reported to tackle these issues, thus realizing efficient and spectrally stable blue PeLEDs. A new type of additive‐formamidinium tetrafluorosuccinate (FATFSA) is introduced into the quasi‐2D mixed halide perovskite accompanied by interface engineering, which effectively impedes the formation of undesired low‐dimensional phases with various bandgaps throughout the entire film, thereby boosting energy transfer process for accelerating radiative recombination; this strategy also diminishes the halide vacancies especially chloride‐related defects with deep energy level, thus reducing nonradiative energy loss for efficient radiative recombination. Benefitting from homogenized energy landscape throughout the entire perovskite emitting layer, PeLEDs with spectrally‐stable blue emission (478 nm) and champion external quantum efficiency (EQE) of 21.9% are realized, which represents a record value among this type of PeLEDs in the pure blue region. - <img src="https://onlinelibrary.wiley.com/cms/asset/f2a30e94-9acf-4d11-9f46-3d752bab69ea/adma202410422-gra-0001-m.png" - alt="Unveiling the Cation Dependence in Alkaline Hydrogen Evolution by Differently-Charged Ruthenium/Molybdenum Sulfide Hybrids"/> -<p>Alkaline hydrogen evolution kinetics via water reduction limits the water electrolysis efficiency and depends on both catalyst structures and electrolyte cations. Herein, by hybridizing metallic Ru with differently-charged MoSx clusters, the interrelated effect of metal valence and charged support for the cation-dependent hydrogen evolution activity is demonstrated, in which the metal valence determines the water activation capability and the support determines the cation accumulation. + <img src="https://onlinelibrary.wiley.com/cms/asset/11ddf73c-d054-447a-9621-15fae9d42e61/adma202409319-gra-0001-m.png" + alt="Homogenizing Energy Landscape for Efficient and Spectrally Stable Blue Perovskite Light-Emitting Diodes"/> +<p>Dual modification on both bulk and interface is proposed to homogenize the energy landscape throughout the entire blue perovskite by comprehensively diminishing the low dimensional phases and reducing the halide defects. Resultantly, perovskite light emitting diodes with spectrally-stable blue emission at 478 nm and a high external quantum efficiency of 21.9% are realized, representing a record in this type of devices. </p> <br/> <h2>Abstract</h2> -<p>The sluggish kinetics of hydrogen evolution reaction (HER) via water reduction limits the efficiency of alkaline water electrolysis. The HER kinetics is not only intimately related to the catalyst surface structure but also relevant to the cation identity of the electrolyte. The cation dependence also relies on the surface electronic structure and applied potential, but this interrelated effect and its underlying mechanism awaits elucidation. Herein, differently-charged molybdenum sulfide (MoS<sub>x</sub>) cluster supports ([Mo<sub>3</sub>S<sub>13</sub>]<sup>2−</sup> and [Mo<sub>3</sub>S<sub>7</sub>]<sup>4+</sup>) are utilized to hybridize with the identical metallic Ru centers. The specific electrostatic interaction between MoS<sub>x</sub> clusters and Ru precursors induces different Ru valences of the hybrids, with a higher valence state for Ru/Mo<sub>3</sub>S<sub>13</sub> endowing a higher activity. The Ru/Mo<sub>3</sub>S<sub>13</sub> and Ru/Mo<sub>3</sub>S<sub>7</sub> exhibited drastically-different cation dependence, in which the charged support determines the local accumulation of cations and resulting water structures. The more negatively-charged Mo<sub>3</sub>S<sub>13</sub> support induces the facile accumulation of cations, especially for less-hydrated K<sup>+</sup> cations. The water activation capability by Ru valences and cation accumulation from the support effect in-together determine the cation-dependent alkaline HER activity. This work not only enriches the understanding about the cation-dependent HER mechanism but also shines a light on the rational optimization strategy of electrode/electrolyte interfaces.</p> +<p>Blue perovskite light-emitting diodes (PeLEDs) have attracted enormous attention; however, their unsatisfactory device efficiency and spectral stability still remain great challenges. Unfavorable low-dimensional phase distribution and defects with deeper energy levels usually cause energy disorder, substantially limiting the device's performance. Here, an additive-interface optimization strategy is reported to tackle these issues, thus realizing efficient and spectrally stable blue PeLEDs. A new type of additive-formamidinium tetrafluorosuccinate (FATFSA) is introduced into the quasi-2D mixed halide perovskite accompanied by interface engineering, which effectively impedes the formation of undesired low-dimensional phases with various bandgaps throughout the entire film, thereby boosting energy transfer process for accelerating radiative recombination; this strategy also diminishes the halide vacancies especially chloride-related defects with deep energy level, thus reducing nonradiative energy loss for efficient radiative recombination. Benefitting from homogenized energy landscape throughout the entire perovskite emitting layer, PeLEDs with spectrally-stable blue emission (478 nm) and champion external quantum efficiency (EQE) of 21.9% are realized, which represents a record value among this type of PeLEDs in the pure blue region.</p> -Shaoyan Wang, -Tao Jiang, -Yaming Hao, -Jianxiang Wu, -Can Lei, -Zhe Chen, -Wei Du, -Ming Gong +Heng Qi, +Yu Tong, +Xuewen Zhang, +Hao Wang, +Lu Zhang, +Yali Chen, +Yibo Wang, +Jingzhi Shang, +Kun Wang, +Hongqiang Wang Research Article - Unveiling the Cation Dependence in Alkaline Hydrogen Evolution by Differently‐Charged Ruthenium/Molybdenum Sulfide Hybrids - 10.1002/adma.202410422 + Homogenizing Energy Landscape for Efficient and Spectrally Stable Blue Perovskite Light‐Emitting Diodes + 10.1002/adma.202409319 Advanced Materials - 10.1002/adma.202410422 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410422 + 10.1002/adma.202409319 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409319 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410441 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409338 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410441 - Spatial Control of Nickel Vacancies in Colloidal NiMgO Nanocrystals for Efficient and Stable All‐inorganic Quantum Dot Light‐Emitting Diodes + 10.1002/adma.202409338 + Constructing Organic Phosphorescent Scintillators with Enhanced Triplet Exciton Utilization Through Multi‐Mode Radioluminescence for Efficient X‐Ray Imaging Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Colloidal NiMgO nanocrystals with spatially controlled Mg are introduced as hole‐transport materials for all‐inorganic quantum dot light‐emitting diodes. This novel approach enhances device performance, achieving a peak external quantum efficiency of 16.4%, a peak luminance of 269 455 cd m−2, and a half‐life of 462 690 h at 100 nit, paving the way for more efficient and stable next‐generation displays. +A multimode radioluminescence process is developed by thermally activating the release of triplet excitons from organic phosphorescent scintillators. These scintillators achieve a maximum photoluminescence efficiency of 65.8% and a minimum X‐ray radiation detection limit of 110 nGy s−1, enabling efficient radiographic imaging with a spatial resolution of ≈10.0 lp mm−1. @@ -4247,56 +4146,53 @@ Colloidal NiMgO nanocrystals with spatially controlled Mg are introduced as hole Abstract -Colloidal quantum dot (QD)–based light‐emitting diodes (QD‐LEDs) have reached the pinnacle of quantum efficiency and are now being actively developed for next‐generation displays and brighter light sources. Previous research has suggested utilizing inorganic hole‐transport layers (HTLs) to explore brighter and more stable QD‐LEDs. However, the performance metrics of such QD‐LEDs with inorganic HTLs generally lag behind those of organic‐inorganic hybrid QD‐LEDs employing organic HTLs. In this study, colloidal NiMgO nanocrystals (NCs) with spatially controlled Mg are introduced as HTLs for realizing efficient and stable all‐inorganic QD‐LEDs. During the co‐condensation of Ni and Mg precursors to produce valence band‐lowered NiMgO NCs, incorporating ≈2% Mg into the NiO lattice creates additional Ni vacancies (VNi) within and on the NCs, influencing the hole concentration and mobility of the NiMgO NC films. Passivating the VNi exposed on the surface with magnesium hydroxide allows for tuning the electrical properties of the NiMgO NCs relative to those of an electron transport layer, allowing for a balanced charge supply and suppressed negative charging of the QDs. Optimized all‐inorganic QD‐LEDs employing NiMgO NCs achieved a peak external quantum efficiency of 16.4%, peak luminance of 269 455 cd m⁻2, and a half‐life of 462 690 h at 100 nit. +The development of organic phosphorescent scintillators with high exciton utilization efficiency has attracted significant attention but remains a difficult challenge because of the inherent spin‐forbidden feature of X‐ray‐induced triplet excitons. Herein, a design strategy is proposed to develop organic phosphorescent scintillators through thermally activated exciton release to convert stabilized spin‐forbidden triplet excitons to spin‐allowed singlet excitons, which enables singlet exciton‐dominated multi‐mode emission simultaneously from the lowest singlet, triplet, and stabilized triplet states. The resultant scintillators demonstrate a maximum photoluminescence efficiency of 65.8% and a minimum X‐ray radiation detection limit of 110 nGy s−1; this allows efficient radiography imaging with a spatial resolution of ≈10.0 lp mm−1. This study advances the fundamental understanding of exciton dynamics under X‐ray excitation, significantly broadening the practical use of phosphorescent materials for safety‐critical industries and medical diagnostics. - <img src="https://onlinelibrary.wiley.com/cms/asset/5f32287c-1abd-4365-ac53-18b5eb0f7d09/adma202410441-gra-0001-m.png" - alt="Spatial Control of Nickel Vacancies in Colloidal NiMgO Nanocrystals for Efficient and Stable All-inorganic Quantum Dot Light-Emitting Diodes"/> -<p>Colloidal NiMgO nanocrystals with spatially controlled Mg are introduced as hole-transport materials for all-inorganic quantum dot light-emitting diodes. This novel approach enhances device performance, achieving a peak external quantum efficiency of 16.4%, a peak luminance of 269 455 cd m<sup>−</sup> -<sup>2</sup>, and a half-life of 462 690 h at 100 nit, paving the way for more efficient and stable next-generation displays. + <img src="https://onlinelibrary.wiley.com/cms/asset/d4da4703-ca0a-49c9-9d62-4eee9d620083/adma202409338-gra-0001-m.png" + alt="Constructing Organic Phosphorescent Scintillators with Enhanced Triplet Exciton Utilization Through Multi-Mode Radioluminescence for Efficient X-Ray Imaging"/> +<p>A multimode radioluminescence process is developed by thermally activating the release of triplet excitons from organic phosphorescent scintillators. These scintillators achieve a maximum photoluminescence efficiency of 65.8% and a minimum X-ray radiation detection limit of 110 nGy s<sup>−1</sup>, enabling efficient radiographic imaging with a spatial resolution of ≈10.0 lp mm<sup>−1</sup>. </p> <br/> <h2>Abstract</h2> -<p>Colloidal quantum dot (QD)–based light-emitting diodes (QD-LEDs) have reached the pinnacle of quantum efficiency and are now being actively developed for next-generation displays and brighter light sources. Previous research has suggested utilizing inorganic hole-transport layers (HTLs) to explore brighter and more stable QD-LEDs. However, the performance metrics of such QD-LEDs with inorganic HTLs generally lag behind those of organic-inorganic hybrid QD-LEDs employing organic HTLs. In this study, colloidal NiMgO nanocrystals (NCs) with spatially controlled Mg are introduced as HTLs for realizing efficient and stable all-inorganic QD-LEDs. During the co-condensation of Ni and Mg precursors to produce valence band-lowered NiMgO NCs, incorporating ≈2% Mg into the NiO lattice creates additional Ni vacancies (V<sub>Ni</sub>) within and on the NCs, influencing the hole concentration and mobility of the NiMgO NC films. Passivating the V<sub>Ni</sub> exposed on the surface with magnesium hydroxide allows for tuning the electrical properties of the NiMgO NCs relative to those of an electron transport layer, allowing for a balanced charge supply and suppressed negative charging of the QDs. Optimized all-inorganic QD-LEDs employing NiMgO NCs achieved a peak external quantum efficiency of 16.4%, peak luminance of 269 455 cd m⁻<sup>2</sup>, and a half-life of 462 690 h at 100 nit.</p> +<p>The development of organic phosphorescent scintillators with high exciton utilization efficiency has attracted significant attention but remains a difficult challenge because of the inherent spin-forbidden feature of X-ray-induced triplet excitons. Herein, a design strategy is proposed to develop organic phosphorescent scintillators through thermally activated exciton release to convert stabilized spin-forbidden triplet excitons to spin-allowed singlet excitons, which enables singlet exciton-dominated multi-mode emission simultaneously from the lowest singlet, triplet, and stabilized triplet states. The resultant scintillators demonstrate a maximum photoluminescence efficiency of 65.8% and a minimum X-ray radiation detection limit of 110 nGy s<sup>−1</sup>; this allows efficient radiography imaging with a spatial resolution of ≈10.0 lp mm<sup>−1</sup>. This study advances the fundamental understanding of exciton dynamics under X-ray excitation, significantly broadening the practical use of phosphorescent materials for safety-critical industries and medical diagnostics.</p> -Woon Ho Jung, -Byong Jae Kim, -Mahnmin Choi, -Hyeonjun Lee, -Hyunjin Cho, -Yong Woo Kwon, -Yeongho Choi, -Hyo Geun Lee, -Jinha Yoon, -Keeyong Lee, -Sang Ho Oh, -Seong‐Yong Cho, -Doh C. Lee, -Sohee Jeong, -Jaehoon Lim +Huanhuan Li, +Yitong Liu, +Wei Zhao, +Hengyu Cao, +Xin Yan, +Shuman Zhang, +Xi Yan, +Hui Li, +Ye Tao, +Gaozhan Xie, +Wei Li, +Runfeng Chen, +Wei Huang Research Article - Spatial Control of Nickel Vacancies in Colloidal NiMgO Nanocrystals for Efficient and Stable All‐inorganic Quantum Dot Light‐Emitting Diodes - 10.1002/adma.202410441 + Constructing Organic Phosphorescent Scintillators with Enhanced Triplet Exciton Utilization Through Multi‐Mode Radioluminescence for Efficient X‐Ray Imaging + 10.1002/adma.202409338 Advanced Materials - 10.1002/adma.202410441 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410441 + 10.1002/adma.202409338 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409338 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410469 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409592 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410469 - Low‐Symmetry Van der Waals Dielectric GaInS3 Triggered 2D MoS2 Giant Anisotropy via Symmetry Engineering + 10.1002/adma.202409592 + Confined Flash Printing and Synthesis of Stable Perovskite Nanofilms under Ambient Conditions Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The low‐symmetry dielectrics GaInS3 sparks MoS2 obvious anisotropy, at the inface of MoS2/GaInS3 heterojunction. The anisotropic optical responses are confirmed through polarized Raman and PL spectra. Under dual‐gate modulation, MoS2 FET demonstrates highly adjustable anisotropic conductivity up to 106. Remarkably, the GaInS3‐gated MoS2 photodetector exhibits a large dichroic ratio (≈167), which greatly promotes its application in polarized photodetection. +A new method, confined flash printing, allows for the rapid synthesis of perovskite nanofilms under ambient conditions. This approach combines precursor transfer, synthesis, crystallization, and polymer protection in a single step using a laser. The method's simplicity and flexibility support the development of various perovskite materials and devices, including applications in biodetection. @@ -4306,50 +4202,51 @@ The low‐symmetry dielectrics GaInS3 sparks MoS2 obvious anisotropy, at the Abstract -Low‐symmetry structures in van der Waals materials have facilitated the advancement of anisotropic electronic and optoelectronic devices. However, the intrinsic low symmetry structure exhibits a small adjustable anisotropy ratio (1–10), which hinders its further assembly and processing into high‐performance devices. Here, a novel 2D anisotropic dielectric, GaInS3 (GIS), which induces isotropic MoS2 to exhibit significant anisotropic optical and electrical responses is demonstrated. With the excellent gate modulation ability of 2D GIS (dielectric constant k ∼12), MoS2 field effect transistor (FET) shows an adjustable conductance ratio from isotropic to anisotropic under dual‐gate modulation, up to 106. Theoretical calculations indicate that anisotropy originates from lattice mismatch‐induced charge density deformation at the interface. Moreover, the MoS2/GIS photodetector demonstrates high responsivity (≈4750 A W−1) and a large dichroic ratio (≈167). The anisotropic van der Waals dielectric GIS paves the way for the development of 2D transition metal dichalcogenides (TMDCs) in the fields of anisotropic photonics, electronics, and optoelectronics. +The fabrication of stable perovskite nanofilm patterns is important for the development of functional optical devices. However, current production approaches are limited by the requirement for strict inert gas protection and long processing times. Here, a confined flash printing synthesis method is presented to generate perovskite nanofilms under ambient conditions, combining precursor transfer, perovskite synthesis, crystallization, and polymer protection in a single step within milliseconds. A laser simultaneously prints and induces the flash synthesis, confined in a polymer nanofilm, under normal ambient conditions. Due to its simplicity and flexibility, the method enables the combination and screening of many different perovskite precursor materials on various substrates. Besides for the development of novel perovskite materials and devices, the nanofilms can be applied for biodetection. The unique H2O2‐responsive property of the ultrathin perovskite quantum dot film is applied for biomolecule detection based on oxidase‐catalyzed enzymatic reactions. - <img src="https://onlinelibrary.wiley.com/cms/asset/ad0e5e01-1a08-4e7f-9412-ef74dfa89e5b/adma202410469-gra-0001-m.png" - alt="Low-Symmetry Van der Waals Dielectric GaInS3 Triggered 2D MoS2 Giant Anisotropy via Symmetry Engineering"/> -<p>The low-symmetry dielectrics GaInS<sub>3</sub> sparks MoS<sub>2</sub> obvious anisotropy, at the inface of MoS<sub>2</sub>/GaInS<sub>3</sub> heterojunction. The anisotropic optical responses are confirmed through polarized Raman and PL spectra. Under dual-gate modulation, MoS<sub>2</sub> FET demonstrates highly adjustable anisotropic conductivity up to 10<sup>6</sup>. Remarkably, the GaInS<sub>3</sub>-gated MoS<sub>2</sub> photodetector exhibits a large dichroic ratio (≈167), which greatly promotes its application in polarized photodetection. + <img src="https://onlinelibrary.wiley.com/cms/asset/002da7de-59ac-4b10-a1c5-44f3caca8d2f/adma202409592-gra-0001-m.png" + alt="Confined Flash Printing and Synthesis of Stable Perovskite Nanofilms under Ambient Conditions"/> +<p>A new method, confined flash printing, allows for the rapid synthesis of perovskite nanofilms under ambient conditions. This approach combines precursor transfer, synthesis, crystallization, and polymer protection in a single step using a laser. The method's simplicity and flexibility support the development of various perovskite materials and devices, including applications in biodetection. </p> <br/> <h2>Abstract</h2> -<p>Low-symmetry structures in van der Waals materials have facilitated the advancement of anisotropic electronic and optoelectronic devices. However, the intrinsic low symmetry structure exhibits a small adjustable anisotropy ratio (1–10), which hinders its further assembly and processing into high-performance devices. Here, a novel 2D anisotropic dielectric, GaInS<sub>3</sub> (GIS), which induces isotropic MoS<sub>2</sub> to exhibit significant anisotropic optical and electrical responses is demonstrated. With the excellent gate modulation ability of 2D GIS (dielectric constant <i>k</i> ∼12), MoS<sub>2</sub> field effect transistor (FET) shows an adjustable conductance ratio from isotropic to anisotropic under dual-gate modulation, up to 10<sup>6</sup>. Theoretical calculations indicate that anisotropy originates from lattice mismatch-induced charge density deformation at the interface. Moreover, the MoS<sub>2</sub>/GIS photodetector demonstrates high responsivity (≈4750 A W<sup>−1</sup>) and a large dichroic ratio (≈167). The anisotropic van der Waals dielectric GIS paves the way for the development of 2D transition metal dichalcogenides (TMDCs) in the fields of anisotropic photonics, electronics, and optoelectronics.</p> +<p>The fabrication of stable perovskite nanofilm patterns is important for the development of functional optical devices. However, current production approaches are limited by the requirement for strict inert gas protection and long processing times. Here, a confined flash printing synthesis method is presented to generate perovskite nanofilms under ambient conditions, combining precursor transfer, perovskite synthesis, crystallization, and polymer protection in a single step within milliseconds. A laser simultaneously prints and induces the flash synthesis, confined in a polymer nanofilm, under normal ambient conditions. Due to its simplicity and flexibility, the method enables the combination and screening of many different perovskite precursor materials on various substrates. Besides for the development of novel perovskite materials and devices, the nanofilms can be applied for biodetection. The unique H<sub>2</sub>O<sub>2</sub>-responsive property of the ultrathin perovskite quantum dot film is applied for biomolecule detection based on oxidase-catalyzed enzymatic reactions.</p> -Zongdong Sun, -Jie Liu, -Yongshan Xu, -Xiong Xiong, -Yuan Li, -Meihui Wang, -Kailang Liu, -Huiqiao Li, -Yanqing Wu, -Tianyou Zhai +Yuxin Liu, +Tanja Knaus, +Zheng Wei, +Junfang Zhang, +Matteo Damian, +Sebastian Ronneberger, +Xingjun Zhu, +Peter H. Seeberger, +Hong Zhang, +Francesco G. Mutti, +Felix F. Loeffler Research Article - Low‐Symmetry Van der Waals Dielectric GaInS3 Triggered 2D MoS2 Giant Anisotropy via Symmetry Engineering - 10.1002/adma.202410469 + Confined Flash Printing and Synthesis of Stable Perovskite Nanofilms under Ambient Conditions + 10.1002/adma.202409592 Advanced Materials - 10.1002/adma.202410469 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410469 + 10.1002/adma.202409592 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409592 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410537 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409603 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410537 - WS2 Moiré Superlattices Supporting Au Nanoclusters and Isolated Ru to Boost Hydrogen Production + 10.1002/adma.202409603 + Photochemical Control of Network Topology in PEG Hydrogels Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Maximizing the catalytic activity of single‐atom and nanocluster catalysts is essential for their industrial application in water‐alkali electrolyzers. A bilayer WS2 moiré superlattices are reported that support Au nanoclusters and Ru single atoms (Ru1/Aun‐2LWS2) to enhance hydrogen evolution reaction (HER). Experiments and theories indicate that the improved HER activity stems from strong metal–support interactions in Ru1/Aun‐2LWS2, promoting charge redistribution in the catalyst. +In this work, maleimide‐ and styrene‐functionalized poly(ethylene glycol) macromers are used to prepare photocrosslinked hydrogels along a continuum of network topologies, from step‐ to chain‐growth. This simple approach provides precise control over hydrogel nanostructure, decoupling gel modulus and diffusivity from the initial polymer content and presenting new opportunities for (bio)materials science and the study of soft matter physics. @@ -4359,54 +4256,60 @@ Maximizing the catalytic activity of single‐atom and nanocluster catalysts Abstract -Maximizing the catalytic activity of single‐atom and nanocluster catalysts through the modulation of the interaction between these components and the corresponding supports is crucial but challenging. Herein, guided by theoretical calculations, a nanoporous bilayer WS2 Moiré superlattices (MSLs) supported Au nanoclusters (NCs) adjacent to Ru single atoms (SAs) (Ru1/Aun‐2LWS2) is developed for alkaline hydrogen evolution reaction (HER) for the first time. Theoretical analysis suggests that the induced robust electronic metal–support interaction effect in Ru1/Aun‐2LWS2 is prone to promote the charge redistribution among Ru SAs, Au NCs, and WS2 MSLs support, which is beneficial to reduce the energy barrier for water adsorption and thus promoting the subsequent H2 formation. As feedback, the well‐designed Ru1/Aun‐2LWS2 electrocatalyst exhibits outstanding HER performance with high activity (η10 = 19 mV), low Tafel slope (35 mV dec−1), and excellent long‐term stability. Further, in situ, experimental studies reveal that the reconstruction of Ru SAs/NCs with S vacancies in Ru1/Aun‐2LWS2 structure acts as the main catalytically active center, while high‐valence Au NCs are responsible for activating and stabilizing Ru sites to prevent the dissolution and deactivation of active sites. This work offers guidelines for the rational design of high‐performance atomic‐scale electrocatalysts. +Hydrogels are often synthesized through photoinitiated step‐, chain‐, and mixed‐mode polymerizations, generating diverse network topologies and resultant material properties that depend on the underlying network connectivity. While many photocrosslinking reactions are available, few afford controllable connectivity of the hydrogel network. Herein, a versatile photochemical strategy is introduced for tuning the structure of poly(ethylene glycol) (PEG) hydrogels using macromolecular monomers functionalized with maleimide and styrene moieties. Hydrogels are prepared along a gradient of topologies by varying the ratio of step‐growth (maleimide dimerization) to chain‐growth (maleimide‐styrene alternating copolymerization) network‐forming reactions. The initial PEG content and final network physical properties (e.g., modulus, swelling, diffusivity) are tailored in an independent manner, highlighting configurable gel mechanics and reactivity. These photochemical reactions allow high‐fidelity photopatterning and 3D printing and are compatible with 2D and 3D cell culture. Ultimately, this photopolymer chemistry allows facile control over network connectivity to achieve adjustable material properties for broad applications. - <img src="https://onlinelibrary.wiley.com/cms/asset/55b7e8ce-5f16-429a-9b15-075d0ef3cbfd/adma202410537-gra-0001-m.png" - alt="WS2 Moiré Superlattices Supporting Au Nanoclusters and Isolated Ru to Boost Hydrogen Production"/> -<p>Maximizing the catalytic activity of single-atom and nanocluster catalysts is essential for their industrial application in water-alkali electrolyzers. A bilayer WS<sub>2</sub> moiré superlattices are reported that support Au nanoclusters and Ru single atoms (Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub>) to enhance hydrogen evolution reaction (HER). Experiments and theories indicate that the improved HER activity stems from strong metal–support interactions in Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub>, promoting charge redistribution in the catalyst. + <img src="https://onlinelibrary.wiley.com/cms/asset/ea06b45f-38ea-42e9-8665-333cde1d9929/adma202409603-gra-0001-m.png" + alt="Photochemical Control of Network Topology in PEG Hydrogels"/> +<p>In this work, maleimide- and styrene-functionalized poly(ethylene glycol) macromers are used to prepare photocrosslinked hydrogels along a continuum of network topologies, from step- to chain-growth. This simple approach provides precise control over hydrogel nanostructure, decoupling gel modulus and diffusivity from the initial polymer content and presenting new opportunities for (bio)materials science and the study of soft matter physics. </p> <br/> <h2>Abstract</h2> -<p>Maximizing the catalytic activity of single-atom and nanocluster catalysts through the modulation of the interaction between these components and the corresponding supports is crucial but challenging. Herein, guided by theoretical calculations, a nanoporous bilayer WS<sub>2</sub> Moiré superlattices (MSLs) supported Au nanoclusters (NCs) adjacent to Ru single atoms (SAs) (Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub>) is developed for alkaline hydrogen evolution reaction (HER) for the first time. Theoretical analysis suggests that the induced robust electronic metal–support interaction effect in Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub> is prone to promote the charge redistribution among Ru SAs, Au NCs, and WS<sub>2</sub> MSLs support, which is beneficial to reduce the energy barrier for water adsorption and thus promoting the subsequent H<sub>2</sub> formation. As feedback, the well-designed Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub> electrocatalyst exhibits outstanding HER performance with high activity (<i>η</i> -<sub>10</sub> = 19 mV), low Tafel slope (35 mV dec<sup>−1</sup>), and excellent long-term stability. Further, in situ, experimental studies reveal that the reconstruction of Ru SAs/NCs with S vacancies in Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub> structure acts as the main catalytically active center, while high-valence Au NCs are responsible for activating and stabilizing Ru sites to prevent the dissolution and deactivation of active sites. This work offers guidelines for the rational design of high-performance atomic-scale electrocatalysts.</p> +<p>Hydrogels are often synthesized through photoinitiated step-, chain-, and mixed-mode polymerizations, generating diverse network topologies and resultant material properties that depend on the underlying network connectivity. While many photocrosslinking reactions are available, few afford controllable connectivity of the hydrogel network. Herein, a versatile photochemical strategy is introduced for tuning the structure of poly(ethylene glycol) (PEG) hydrogels using macromolecular monomers functionalized with maleimide and styrene moieties. Hydrogels are prepared along a gradient of topologies by varying the ratio of step-growth (maleimide dimerization) to chain-growth (maleimide-styrene alternating copolymerization) network-forming reactions. The initial PEG content and final network physical properties (e.g., modulus, swelling, diffusivity) are tailored in an independent manner, highlighting configurable gel mechanics and reactivity. These photochemical reactions allow high-fidelity photopatterning and 3D printing and are compatible with 2D and 3D cell culture. Ultimately, this photopolymer chemistry allows facile control over network connectivity to achieve adjustable material properties for broad applications.</p> -Dechao Chen, -Tianyu Gao, -Zengxi Wei, -Mengjia Wang, -Yingfei Ma, -Dongdong Xiao, -Changsheng Cao, -Cheng‐You Lee, -Pan Liu, -Dengchao Wang, -Shuangliang Zhao, -Hsiao‐Tsu Wang, -Lili Han +Bruce E. Kirkpatrick, +Grace K. Hach, +Benjamin R. Nelson, +Nathaniel P. Skillin, +Joshua S. Lee, +Lea Pearl Hibbard, +Abhishek P. Dhand, +Henry S. Grotheer, +Connor E. Miksch, +Violeta Salazar, +Tayler S. Hebner, +Sean P. Keyser, +Joshua T. Kamps, +Jasmine Sinha, +Laura J. Macdougall, +Benjamin D. Fairbanks, +Jason A. Burdick, +Timothy J. White, +Christopher N. Bowman, +Kristi S. Anseth Research Article - WS2 Moiré Superlattices Supporting Au Nanoclusters and Isolated Ru to Boost Hydrogen Production - 10.1002/adma.202410537 + Photochemical Control of Network Topology in PEG Hydrogels + 10.1002/adma.202409603 Advanced Materials - 10.1002/adma.202410537 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410537 + 10.1002/adma.202409603 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409603 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410568 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409606 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410568 - Hybrid Anapole Induced Chirality in Metasurfaces + 10.1002/adma.202409606 + Microfiber Actuators With Hot‐Pressing‐Programmable Mechano‐Photothermal Responses for Electromagnetic Perception Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This work presents the design of an asymmetric H‐shaped metasurface that induces hybrid anapole (HA) for achieving chiro‐optical responses. By breaking the structural symmetry, the metasurface supports both first‐order and pseudo higher‐order HA, leading to enhanced circular dichroism and polarization control. These results provide valuable insights into the fundamental study of anapole physics and have significant implications for nanophotonics applications. +A hot‐pressing‐programmable microfiber‐film actuator is developed with mechano‐photothermal cooperativities and electromagnetic radiation perceptivity (sensitivity of 99.73% ± 0.15%). It demonstrates superior actuation response with mechanical/thermal/electrical stability, and realizes an amphibious robot with land–water adaptive locomotion for electromagnetic dynamic detection. This microstructure‐dominated electromagnetic‐perceptive actuator can inspire a new direction of environment‐interactive smart materials, and soft robots with multi‐scenario adaptivity and autonomous environment perceptivity. @@ -4416,43 +4319,53 @@ This work presents the design of an asymmetric H‐shaped metasurface that i Abstract -The interaction between light and matter, particularly chirality, plays a pivotal role in modern science and technology. Typically, metasurfaces achieve chiro‐optical effects by coupling electric and magnetic dipoles in specific orientations. In this work, the design and optimization of an asymmetric H‐shaped metasurface is explored to induce hybrid anapole (HA) for optical activity. When the symmetry of the metasurface structure is disrupted, the design can simultaneously excite first‐order and pseudo high‐order HA under illumination with a specific circular polarization, both occurring within the same spectral regime. This results in high reflection for one circular polarization and a significant reduction in reflection for the orthogonal polarization, thereby exhibiting exceptional chiro‐optical activity. Moreover, the HA‐based chiral metasurface demonstrates strong polarization control capabilities, as verified by Stokes parameter analysis, revealing high birefringence and a pronounced dependence on the incident polarization angle. These results provide valuable insights for the design and optimization of HA metasurfaces for advanced optical applications and polarization control, paving the way for new developments in chiral nanophotonics. +Electromagnetic radiation (EMR) is a ubiquitous harm and hard to detect dynamically in multiple scenarios. A mechano‐photothermal cooperative microfiber film (MFF) actuator is developed that can synchronously detect EMR with high reliability. The programmable actuation is deployed by a hot‐pressing methodology, achieving the MFF with moderate modulus (378 MPa) and superior toughness (87.26 MJ m−3) that ensure superior response (0.068 cm−1 s−1) and bending curvature (0.63 cm−1). A secondary hot‐pressing can further program the actuation behavior with black phosphorus local photothermal enhancement patterns to achieve 2D–3D transformable geometries. An amphibious robot with a land–water adaptive locomotion mechanism is designed by programming the MFFs. It can crawl on land and locomote on water with a velocity up to ≈1.8 mm s−1, and ≈2.39 cm s−1, respectively. Employing the conductive fabric layer of the actuator with electromagnetic induction effect, the amphibious robot can synchronously perceive environmental EMR with sensitivity up to 99.73% ± 0.15% during locomotion, with superior adaptability to EMR source intensity (0.1 to 3000 W) and distance (≈9 m) compared to a commercial EMR detector. This EMR detective microfiber actuator can inspire a new direction of environment‐interactive smart materials, and soft robots with multi‐scenario adaptivity and autonomous environment perceptivity. - <img src="https://onlinelibrary.wiley.com/cms/asset/b0270839-3c8d-460b-88d4-28f0efef4797/adma202410568-gra-0001-m.png" - alt="Hybrid Anapole Induced Chirality in Metasurfaces"/> -<p>This work presents the design of an asymmetric H-shaped metasurface that induces hybrid anapole (HA) for achieving chiro-optical responses. By breaking the structural symmetry, the metasurface supports both first-order and pseudo higher-order HA, leading to enhanced circular dichroism and polarization control. These results provide valuable insights into the fundamental study of anapole physics and have significant implications for nanophotonics applications. + <img src="https://onlinelibrary.wiley.com/cms/asset/d7f64130-6a69-47f6-825f-390275076a4e/adma202409606-gra-0001-m.png" + alt="Microfiber Actuators With Hot-Pressing-Programmable Mechano-Photothermal Responses for Electromagnetic Perception"/> +<p>A hot-pressing-programmable microfiber-film actuator is developed with mechano-photothermal cooperativities and electromagnetic radiation perceptivity (sensitivity of 99.73% ± 0.15%). It demonstrates superior actuation response with mechanical/thermal/electrical stability, and realizes an amphibious robot with land–water adaptive locomotion for electromagnetic dynamic detection. This microstructure-dominated electromagnetic-perceptive actuator can inspire a new direction of environment-interactive smart materials, and soft robots with multi-scenario adaptivity and autonomous environment perceptivity. </p> <br/> <h2>Abstract</h2> -<p>The interaction between light and matter, particularly chirality, plays a pivotal role in modern science and technology. Typically, metasurfaces achieve chiro-optical effects by coupling electric and magnetic dipoles in specific orientations. In this work, the design and optimization of an asymmetric H-shaped metasurface is explored to induce hybrid anapole (HA) for optical activity. When the symmetry of the metasurface structure is disrupted, the design can simultaneously excite first-order and pseudo high-order HA under illumination with a specific circular polarization, both occurring within the same spectral regime. This results in high reflection for one circular polarization and a significant reduction in reflection for the orthogonal polarization, thereby exhibiting exceptional chiro-optical activity. Moreover, the HA-based chiral metasurface demonstrates strong polarization control capabilities, as verified by Stokes parameter analysis, revealing high birefringence and a pronounced dependence on the incident polarization angle. These results provide valuable insights for the design and optimization of HA metasurfaces for advanced optical applications and polarization control, paving the way for new developments in chiral nanophotonics.</p> +<p>Electromagnetic radiation (EMR) is a ubiquitous harm and hard to detect dynamically in multiple scenarios. A mechano-photothermal cooperative microfiber film (MFF) actuator is developed that can synchronously detect EMR with high reliability. The programmable actuation is deployed by a hot-pressing methodology, achieving the MFF with moderate modulus (378 MPa) and superior toughness (87.26 MJ m<sup>−3</sup>) that ensure superior response (0.068 cm<sup>−1</sup> s<sup>−1</sup>) and bending curvature (0.63 cm<sup>−1</sup>). A secondary hot-pressing can further program the actuation behavior with black phosphorus local photothermal enhancement patterns to achieve 2D–3D transformable geometries. An amphibious robot with a land–water adaptive locomotion mechanism is designed by programming the MFFs. It can crawl on land and locomote on water with a velocity up to ≈1.8 mm s<sup>−1</sup>, and ≈2.39 cm s<sup>−1</sup>, respectively. Employing the conductive fabric layer of the actuator with electromagnetic induction effect, the amphibious robot can synchronously perceive environmental EMR with sensitivity up to 99.73% ± 0.15% during locomotion, with superior adaptability to EMR source intensity (0.1 to 3000 W) and distance (≈9 m) compared to a commercial EMR detector. This EMR detective microfiber actuator can inspire a new direction of environment-interactive smart materials, and soft robots with multi-scenario adaptivity and autonomous environment perceptivity.</p> -Amir Hassanfiroozi, -Yen Cheng Lu, -Pin Chieh Wu +Mengjie Wu, +Xinran Zhou, +Jiwei Zhang, +Luyun Liu, +Shuang Wang, +Liming Zhu, +Zechang Ming, +Yufan Zhang, +Yong Xia, +Weikang Li, +Zijie Zhou, +Minghui Fan, +Jiaqing Xiong Research Article - Hybrid Anapole Induced Chirality in Metasurfaces - 10.1002/adma.202410568 + Microfiber Actuators With Hot‐Pressing‐Programmable Mechano‐Photothermal Responses for Electromagnetic Perception + 10.1002/adma.202409606 Advanced Materials - 10.1002/adma.202410568 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410568 + 10.1002/adma.202409606 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409606 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410815 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409620 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410815 - On‐Chip Synthesis of Quasi‐2D Semimetals from Multi‐Layer Chalcogenides + 10.1002/adma.202409620 + From Simple Probe to Smart Composites: Water‐Soluble Pincer Complex With Multi‐Stimuli‐Responsive Luminescent Behaviors Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This work presents a generalizable approach for the on‐chip synthesis of non‐layered, nanometer‐thick, quasi‐2D semimetals from multi‐layer chalcogenides. In the exemplary case, sub‐20 nm semiconducting InSe with nickel deposited on top are subjected to a low‐temperature annealing step. This process enables a controlled transformation of the layered InSe into non‐layered, crystalline Kagome‐semimetal Ni3In2Se2 via reaction with the laterally diffusing nickel. +A water‐soluble tripyridine Zn complex featuring a donor‐π‐acceptor (D‐π‐A) structure exhibited multi‐stimuli‐responsiveness to water, pH, and heat. Its composite with polyvinyl alcohol found versatile applications covering digital encryption, reversible writing, inkless printing, and fingerprint analysis. @@ -4462,52 +4375,44 @@ This work presents a generalizable approach for the on‐chip synthesis of n Abstract -Reducing the dimensions of materials from three to two, or quasi‐two, provides a fertile platform for exploring emergent quantum phenomena and developing next‐generation electronic devices. However, growing high‐quality, ultrathin, quasi2D materials in a templated fashion on an arbitrary substrate is challenging. Here, the study demonstrates a simple and reproducible on‐chip approach for synthesizing non‐layered, nanometer‐thick, quasi‐2D semimetals. In one implementation, this method starts with thin semiconducting InSe flakes of below 20 nm in thickness with nickel deposited on top, followed by a low‐temperature annealing step that results in a controlled transformation of the layered InSe to a non‐layered, crystalline semimetal via reaction with the laterally diffusing nickel. Atomic resolution microscopy reveals the transformed semimetal to be Ni3In2Se2 with a Kagome‐lattice structure. Moreover, it is demonstrated that this synthesis method is generalizable by transforming 2D layered chalcogenides such as SnS and SnSe employing Ni and Co to non‐layered semimetals, paving the way for engineering novel types of devices. +Water‐soluble smart materials with multi‐stimuli‐responsiveness and ultra‐long room‐temperature phosphorescence (RTP) have garnered broad attention. Herein, a water‐soluble terpyridine zinc complex (MeO‐Tpy‐Zn‐OAc), featuring a simple donor‐π‐acceptor (D‐π‐A) structure is presented, which responds to a variety of stimuli, including changes in solvents, pH, temperature, and the addition of amino acids. Notably, MeO‐Tpy‐Zn‐OAc functions as a fluorescence probe, capable of visually and selectively discriminating aspartate or histidine among other common amino acids in water. Additionally, when incorporated into polyvinyl alcohol (PVA) to form the composite MeO‐Tpy‐Zn‐OAc@PVA, the material exhibits reversible writing, photochromism, and a prolonged RTP with a 14 s afterglow. These unique properties enable the composite to be utilized in potential applications such as secure data encryption and inkless printing. - <img src="https://onlinelibrary.wiley.com/cms/asset/eae44bf1-f226-4712-a099-6e0bcb101b89/adma202410815-gra-0001-m.png" - alt="On-Chip Synthesis of Quasi-2D Semimetals from Multi-Layer Chalcogenides"/> -<p>This work presents a generalizable approach for the on-chip synthesis of non-layered, nanometer-thick, quasi-2D semimetals from multi-layer chalcogenides. In the exemplary case, sub-20 nm semiconducting InSe with nickel deposited on top are subjected to a low-temperature annealing step. This process enables a controlled transformation of the layered InSe into non-layered, crystalline Kagome-semimetal Ni<sub>3</sub>In<sub>2</sub>Se<sub>2</sub> via reaction with the laterally diffusing nickel. + <img src="https://onlinelibrary.wiley.com/cms/asset/2203f91f-06c6-42e7-b6a7-12ff41bf7134/adma202409620-gra-0001-m.png" + alt="From Simple Probe to Smart Composites: Water-Soluble Pincer Complex With Multi-Stimuli-Responsive Luminescent Behaviors"/> +<p>A water-soluble tripyridine Zn complex featuring a donor-π-acceptor (D-π-A) structure exhibited multi-stimuli-responsiveness to water, pH, and heat. Its composite with polyvinyl alcohol found versatile applications covering digital encryption, reversible writing, inkless printing, and fingerprint analysis. </p> <br/> <h2>Abstract</h2> -<p>Reducing the dimensions of materials from three to two, or quasi-two, provides a fertile platform for exploring emergent quantum phenomena and developing next-generation electronic devices. However, growing high-quality, ultrathin, quasi2D materials in a templated fashion on an arbitrary substrate is challenging. Here, the study demonstrates a simple and reproducible on-chip approach for synthesizing non-layered, nanometer-thick, quasi-2D semimetals. In one implementation, this method starts with thin semiconducting InSe flakes of below 20 nm in thickness with nickel deposited on top, followed by a low-temperature annealing step that results in a controlled transformation of the layered InSe to a non-layered, crystalline semimetal via reaction with the laterally diffusing nickel. Atomic resolution microscopy reveals the transformed semimetal to be Ni<sub>3</sub>In<sub>2</sub>Se<sub>2</sub> with a Kagome-lattice structure. Moreover, it is demonstrated that this synthesis method is generalizable by transforming 2D layered chalcogenides such as SnS and SnSe employing Ni and Co to non-layered semimetals, paving the way for engineering novel types of devices.</p> +<p>Water-soluble smart materials with multi-stimuli-responsiveness and ultra-long room-temperature phosphorescence (RTP) have garnered broad attention. Herein, a water-soluble terpyridine zinc complex (<b>MeO-Tpy-Zn-OAc</b>), featuring a simple donor-π-acceptor (D-π-A) structure is presented, which responds to a variety of stimuli, including changes in solvents, pH, temperature, and the addition of amino acids. Notably, <b>MeO-Tpy-Zn-OAc</b> functions as a fluorescence probe, capable of visually and selectively discriminating aspartate or histidine among other common amino acids in water. Additionally, when incorporated into polyvinyl alcohol (PVA) to form the composite <b>MeO-Tpy-Zn-OAc</b>@PVA, the material exhibits reversible writing, photochromism, and a prolonged RTP with a 14 s afterglow. These unique properties enable the composite to be utilized in potential applications such as secure data encryption and inkless printing.</p> -Jun Cai, -Huairuo Zhang, -Yuanqiu Tan, -Zheng Sun, -Peng Wu, -Rahul Tripathi, -Sergiy Krylyuk, -Caleb Suhy, -Jing Kong, -Albert V. Davydov, -Zhihong Chen, -Joerg Appenzeller +Lixin Duan, +Qingshu Zheng, +Yanlin Liang, +Tao Tu Research Article - On‐Chip Synthesis of Quasi‐2D Semimetals from Multi‐Layer Chalcogenides - 10.1002/adma.202410815 + From Simple Probe to Smart Composites: Water‐Soluble Pincer Complex With Multi‐Stimuli‐Responsive Luminescent Behaviors + 10.1002/adma.202409620 Advanced Materials - 10.1002/adma.202410815 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410815 + 10.1002/adma.202409620 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409620 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411004 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409789 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202411004 - Grain Boundary Filling Empowers (002)‐Textured Zn Metal Anodes with Superior Stability + 10.1002/adma.202409789 + 4D Printing Hybrid Soft Robots Enabled by Shape‐Transformable Liquid Metal Nanoparticles Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Grain boundary wetting strategy is demonstrated to completely fill the Zn grain boundaries, while simultaneously converting the initial random‐textured Zn into a single (002)‐textured Zn. Using In as the boundary filler, the as‐received intercrystalline‐modified (002)‐textured Zn (IM(002) Zn) ensures homogeneous epitaxial Zn deposition and significantly mitigates the intergranular issues, resulting in excellent reversibility in various battery configurations. +The integration of shape‐transformable liquid metal nanoparticles (LMNPs) is first unveiled into 3D printing to create hybrid soft robots with controlled mechanical properties and deformability. This method allows direct printing of one‐piece or assembled hybrid robots using a single LMNPs‐integrated ink recipe, enabling precise control of mechanical and shape memory properties for applications like grippers, bioinspired motors, and rehabilitation devices. @@ -4517,54 +4422,51 @@ Grain boundary wetting strategy is demonstrated to completely fill the Zn grain Abstract -Aqueous Zn battery is promising for grid‐level energy storage due to its high safety and low cost, but dendrite growth and side reactions at the Zn metal anode hinder its development. Designing Zn with (002) orientation improves the stability of the Zn anode, yet grain boundaries remain susceptible to corrosion and dendrite growth. Addressing these intergranular issues is crucial for enhancing the electrochemical performance of (002)‐textured Zn. Here, a strategy based on grain boundary wetting to fill intergranular regions and mitigate these issues is reported. By systematically investigating boundary fillers and filling conditions, In metal is chosen as the filler, and one‐step annealing is used to synergistically convert commercial Zn foils into single (002)‐textured Zn while filling In into the boundaries. The inter‐crystalline‐modified (002)‐textured Zn (IM(002) Zn) effectively inhibits corrosion and dendrite growth, resulting in excellent stability in batteries. This work offers new insights into Zn anode protection and the development of high‐energy Zn batteries. +In recent years, soft robotics has emerged as a rapidly expanding frontier research field that draws inspiration from the locomotion mechanisms of soft‐bodied creatures in nature to achieve smooth and complex motion for diverse applications. However, the fabrication of soft robots with hybrid structures remains challenging due to limitations in material selection and the complex, multi‐step processes involved in traditional manufacturing methods. Herein, a novel direct one‐step additive manufacturing (3D printing) approach is introduced for the fabrication of hybrid robots composed of soft and rigid components for sophisticated tasks. Inspired by the shape‐transformable liquid metal nanoparticles (LMNPs), a functional material toolkit with tuneable mechanical properties and deformability is developed by integrating differently shaped gallium‐based nanoparticles (GNPs) into the 3D printing polymers. Then the direct printing of assembled or one‐piece hybrid soft‐rigid robots is presented through a single recipe of GNPs‐integrated inks. This fabrication method enables precise control of the mechanical properties and shape memory properties within the hybrid structures of robot body with a customized structure design. Their capabilities are further demonstrated through the design and fabrication of hybrid robots as high‐precision gripper, bioinspired motor, and hand rehabilitation device. - <img src="https://onlinelibrary.wiley.com/cms/asset/2d9431e8-6f56-428c-b5c9-34ab525bfa37/adma202411004-gra-0001-m.png" - alt="Grain Boundary Filling Empowers (002)-Textured Zn Metal Anodes with Superior Stability"/> -<p>Grain boundary wetting strategy is demonstrated to completely fill the Zn grain boundaries, while simultaneously converting the initial random-textured Zn into a single (002)-textured Zn. Using In as the boundary filler, the as-received intercrystalline-modified (002)-textured Zn (IM(002) Zn) ensures homogeneous epitaxial Zn deposition and significantly mitigates the intergranular issues, resulting in excellent reversibility in various battery configurations. + <img src="https://onlinelibrary.wiley.com/cms/asset/eba24e48-6051-4fbb-b144-1d31c6dc3db5/adma202409789-gra-0001-m.png" + alt="4D Printing Hybrid Soft Robots Enabled by Shape-Transformable Liquid Metal Nanoparticles"/> +<p>The integration of shape-transformable liquid metal nanoparticles (LMNPs) is first unveiled into 3D printing to create hybrid soft robots with controlled mechanical properties and deformability. This method allows direct printing of one-piece or assembled hybrid robots using a single LMNPs-integrated ink recipe, enabling precise control of mechanical and shape memory properties for applications like grippers, bioinspired motors, and rehabilitation devices. </p> <br/> <h2>Abstract</h2> -<p>Aqueous Zn battery is promising for grid-level energy storage due to its high safety and low cost, but dendrite growth and side reactions at the Zn metal anode hinder its development. Designing Zn with (002) orientation improves the stability of the Zn anode, yet grain boundaries remain susceptible to corrosion and dendrite growth. Addressing these intergranular issues is crucial for enhancing the electrochemical performance of (002)-textured Zn. Here, a strategy based on grain boundary wetting to fill intergranular regions and mitigate these issues is reported. By systematically investigating boundary fillers and filling conditions, In metal is chosen as the filler, and one-step annealing is used to synergistically convert commercial Zn foils into single (002)-textured Zn while filling In into the boundaries. The inter-crystalline-modified (002)-textured Zn (IM(002) Zn) effectively inhibits corrosion and dendrite growth, resulting in excellent stability in batteries. This work offers new insights into Zn anode protection and the development of high-energy Zn batteries.</p> +<p>In recent years, soft robotics has emerged as a rapidly expanding frontier research field that draws inspiration from the locomotion mechanisms of soft-bodied creatures in nature to achieve smooth and complex motion for diverse applications. However, the fabrication of soft robots with hybrid structures remains challenging due to limitations in material selection and the complex, multi-step processes involved in traditional manufacturing methods. Herein, a novel direct one-step additive manufacturing (3D printing) approach is introduced for the fabrication of hybrid robots composed of soft and rigid components for sophisticated tasks. Inspired by the shape-transformable liquid metal nanoparticles (LMNPs), a functional material toolkit with tuneable mechanical properties and deformability is developed by integrating differently shaped gallium-based nanoparticles (GNPs) into the 3D printing polymers. Then the direct printing of assembled or one-piece hybrid soft-rigid robots is presented through a single recipe of GNPs-integrated inks. This fabrication method enables precise control of the mechanical properties and shape memory properties within the hybrid structures of robot body with a customized structure design. Their capabilities are further demonstrated through the design and fabrication of hybrid robots as high-precision gripper, bioinspired motor, and hand rehabilitation device.</p> -Zibo Chen, -Yizhou Wang, -Qiang Wu, -Cheng Wang, -Qian He, -Tao Hu, -Xuran Han, -Jialu Chen, -Yu Zhang, -Jianyu Chen, -Lijun Yang, -Xuebin Wang, -Yanwen Ma, -Jin Zhao - - Research Article - Grain Boundary Filling Empowers (002)‐Textured Zn Metal Anodes with Superior Stability - 10.1002/adma.202411004 - Advanced Materials - 10.1002/adma.202411004 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411004 - Research Article +Xumin Huang, +Liwen Zhang, +Jiangyu Hang, +Thomas Quinn, +Naufal Kabir Ahamed Nasar, +Yiliang Lin, +Chenyang Hu, +Xuan Pang, +Xuesi Chen, +Thomas P. Davis, +Ruirui Qiao + + Research Article + 4D Printing Hybrid Soft Robots Enabled by Shape‐Transformable Liquid Metal Nanoparticles + 10.1002/adma.202409789 + Advanced Materials + 10.1002/adma.202409789 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409789 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411479 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409810 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202411479 - Additive‐Free Gelation of Graphene Oxide Dispersions via Mild Thermal Annealing: Implications for 3D Printing and Supercapacitor Applications + 10.1002/adma.202409810 + Bifunctionally Electrocatalytic Bromine Redox Reaction by Single‐Atom Catalysts for High‐Performance Zinc Batteries Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A mild thermal annealing (MTA) process transforms graphene oxide (GO) into an additive‐free gel, significantly enhancing its rheological properties. SAXS experiments reveal the microstructural changes during MTA. The graphitic domains developed through MTA promote hydrophobic attractions, inducing a network structure. Through 3D‐printing and electrochemical experiments, MTA demonstrates potential as an optimal gelation method for GO. +The mesoporous carbon framework with dispersed single iron atom coordinated with nitrogen atom (FeN5) moiety dispersed (FeSAC‐CMK) is developed as a conductive catalytic bromine host, which not only enhances the physicochemical adsorption of bromine species but also acts as a bifunctional electrocatalytic reactor to speed up redox kinetics of bromide/bromine (Br−/Br0) and free‐up1/3 unserviceable Br− locked by tribromide (Br3−) via conversing Br3−/Br− redox reaction to Br0/Br− redox reaction for high energy storage. @@ -4574,46 +4476,49 @@ A mild thermal annealing (MTA) process transforms graphene oxide (GO) into an ad Abstract -Herein, a mild thermal annealing (MTA) process is presented for additive‐free gelation of graphene oxide (GO) dispersions. This process transitions the GO from a nematic liquid crystal phase to a random network structure, significantly enhancing its rheological properties by order of magnitude. This transition is facilitated by the diffusion of functional groups on the GO surface, which induces hydrophobic attractions, leading to a stable network structure. Employing rheo‐SAXS experiments, detailed insights are provided into the microstructural changes of GO gel under shear stress, establishing a direct correlation between its rheological behavior and microstructure. The distinctive properties of MTA‐processed inks are illustrated, seamlessly integrating with 3D printing, to yield a highly porous lattice structure that demonstrates promising potential as a supercapacitor electrode. The MTA process, an additive‐free approach to gelation, maintains the inherent dispersion properties of GO while offering scalability. Thus, this method brings significant economic and environmental advantages compared to conventional gelation techniques. The findings not only advance the fundamental understanding of 2D colloidal network gels but also increase the potential of GO for a wide range of applications, from gas and liquid absorbers to electrodes for energy storage and conversion, and biomedical fields. +Aqueous zinc‐bromine (Zn||Br2) batteries are regarded as one of the most promising energy storage devices due to their high safety, theoretical energy density, and low cost. However, the sluggish bromine redox kinetics and the formation of a soluble tribromide (Br3−) hinder their practical applications. Here, it is proposed dispersed single iron atom coordinated with nitrogen atoms (FeN5) in a mesoporous carbon framework (FeSAC‐CMK) as a conductive catalytic bromine host, which possesses porous structure and electrocatalytic functionality of FeN5 species for enhanced confinement and electrocatalytic effect. The active FeN5 species can fix the bromine (Br0) species to suppress the formation of Br3− effectively and bifunctionally catalyze the bromide (Br−)/Br° conversion. These free up 1/3 Br− locked by Br3− complexing agent for enhanced bromine utilization efficiency and conversion reversibility. Accordingly, the Zn||Br2 battery with FeSAC‐CMK delivers an impressive specific capacity of 344 mAh g−1 at 0.2 A g−1 and superior rate capability with 164 mAh g−1 achieved even at 20 A g−1, much higher than that of inactive CMK (262 mAh g−1 at 0.2 A g−1; 6 mAh g−1 at only 8 A g−1). Furthermore, the battery demonstrates excellent cycling performance of 88% capacity retention after 2000 cycles. - <img src="https://onlinelibrary.wiley.com/cms/asset/90b23329-2ad3-4325-9f46-3f8efd43c462/adma202411479-gra-0001-m.png" - alt="Additive-Free Gelation of Graphene Oxide Dispersions via Mild Thermal Annealing: Implications for 3D Printing and Supercapacitor Applications"/> -<p>A mild thermal annealing (MTA) process transforms graphene oxide (GO) into an additive-free gel, significantly enhancing its rheological properties. SAXS experiments reveal the microstructural changes during MTA. The graphitic domains developed through MTA promote hydrophobic attractions, inducing a network structure. Through 3D-printing and electrochemical experiments, MTA demonstrates potential as an optimal gelation method for GO. + <img src="https://onlinelibrary.wiley.com/cms/asset/14a3201e-caac-470b-8470-2d659f0bd77c/adma202409810-gra-0001-m.png" + alt="Bifunctionally Electrocatalytic Bromine Redox Reaction by Single-Atom Catalysts for High-Performance Zinc Batteries"/> +<p>The mesoporous carbon framework with dispersed single iron atom coordinated with nitrogen atom (FeN<sub>5</sub>) moiety dispersed (FeSAC-CMK) is developed as a conductive catalytic bromine host, which not only enhances the physicochemical adsorption of bromine species but also acts as a bifunctional electrocatalytic reactor to speed up redox kinetics of bromide/bromine (Br<sup>−</sup>/Br<sup>0</sup>) and free-up1/3 unserviceable Br<sup>−</sup> locked by tribromide (Br<sub>3</sub> +<sup>−</sup>) via conversing Br<sub>3</sub> +<sup>−</sup>/Br<sup>−</sup> redox reaction to Br<sup>0</sup>/Br<sup>−</sup> redox reaction for high energy storage. </p> <br/> <h2>Abstract</h2> -<p>Herein, a mild thermal annealing (MTA) process is presented for additive-free gelation of graphene oxide (GO) dispersions. This process transitions the GO from a nematic liquid crystal phase to a random network structure, significantly enhancing its rheological properties by order of magnitude. This transition is facilitated by the diffusion of functional groups on the GO surface, which induces hydrophobic attractions, leading to a stable network structure. Employing rheo-SAXS experiments, detailed insights are provided into the microstructural changes of GO gel under shear stress, establishing a direct correlation between its rheological behavior and microstructure. The distinctive properties of MTA-processed inks are illustrated, seamlessly integrating with 3D printing, to yield a highly porous lattice structure that demonstrates promising potential as a supercapacitor electrode. The MTA process, an additive-free approach to gelation, maintains the inherent dispersion properties of GO while offering scalability. Thus, this method brings significant economic and environmental advantages compared to conventional gelation techniques. The findings not only advance the fundamental understanding of 2D colloidal network gels but also increase the potential of GO for a wide range of applications, from gas and liquid absorbers to electrodes for energy storage and conversion, and biomedical fields.</p> +<p>Aqueous zinc-bromine (Zn||Br<sub>2</sub>) batteries are regarded as one of the most promising energy storage devices due to their high safety, theoretical energy density, and low cost. However, the sluggish bromine redox kinetics and the formation of a soluble tribromide (Br<sub>3</sub> +<sup>−</sup>) hinder their practical applications. Here, it is proposed dispersed single iron atom coordinated with nitrogen atoms (FeN<sub>5</sub>) in a mesoporous carbon framework (FeSAC-CMK) as a conductive catalytic bromine host, which possesses porous structure and electrocatalytic functionality of FeN<sub>5</sub> species for enhanced confinement and electrocatalytic effect. The active FeN<sub>5</sub> species can fix the bromine (Br<sup>0</sup>) species to suppress the formation of Br<sub>3</sub> +<sup>−</sup> effectively and bifunctionally catalyze the bromide (Br<sup>−</sup>)/Br° conversion. These free up 1/3 Br<sup>−</sup> locked by Br<sub>3</sub> +<sup>−</sup> complexing agent for enhanced bromine utilization efficiency and conversion reversibility. Accordingly, the Zn||Br<sub>2</sub> battery with FeSAC-CMK delivers an impressive specific capacity of 344 mAh g<sup>−1</sup> at 0.2 A g<sup>−1</sup> and superior rate capability with 164 mAh g<sup>−1</sup> achieved even at 20 A g<sup>−1</sup>, much higher than that of inactive CMK (262 mAh g<sup>−1</sup> at 0.2 A g<sup>−1</sup>; 6 mAh g<sup>−1</sup> at only 8 A g<sup>−1</sup>). Furthermore, the battery demonstrates excellent cycling performance of 88% capacity retention after 2000 cycles.</p> -Geon Woong Kim, -Seonghyun Lee, -Guksung Kim, -Howon Lee, -Kyu Tae Lee, -So Youn Kim +Shengmei Chen, +Chao Peng, +Daming Zhu, +Chunyi Zhi Research Article - Additive‐Free Gelation of Graphene Oxide Dispersions via Mild Thermal Annealing: Implications for 3D Printing and Supercapacitor Applications - 10.1002/adma.202411479 + Bifunctionally Electrocatalytic Bromine Redox Reaction by Single‐Atom Catalysts for High‐Performance Zinc Batteries + 10.1002/adma.202409810 Advanced Materials - 10.1002/adma.202411479 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411479 + 10.1002/adma.202409810 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409810 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411587 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409906 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202411587 - Sustainable Nanofibril Interfaces for Strain‐Resilient and Multimodal Porous Bioelectronics + 10.1002/adma.202409906 + Molecular Engineering of Coordination Ligand for Multifunctional Sol–Gel Oxides Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Porous, soft bioelectronics are breathable and offer long‐term biocompatibility, but face challenges in stability under stretching and sweat management. This study uses cellulose nanofibrils (CNF) as interfaces to improve strain resilience and printing quality on porous substrates. In addition, CNF‐based microfluidics enables continuous sweat monitoring, resulting in a multimodal bioelectronic system for tracking energy metabolism and consumption. +A strategy to endow sol–gel oxide films with difficult‐to‐realize useful functionalities, such as direct photolithography, high dielectric strength, and high mobility by replacing the native ligand of sol–gel oxide with strategically designed/synthesized functional ligands is presented. This demonstrated a high‐performance solution‐processed all‐oxide patterning approach by controlling the functional ligands, facilitating a large‐area oxide TFT array with high reliability. @@ -4623,52 +4528,48 @@ Porous, soft bioelectronics are breathable and offer long‐term biocompatib Abstract -Porous soft bioelectronics have attracted significant attention due to their high breathability, long‐term biocompatibility, and other unique features inaccessible in nonporous counterparts. However, fabricating high‐quality multimodal bioelectronic components that operate stably under strain on porous substrates, along with integrating microfluidics for sweat management, remains challenging. In this study, cellulose nanofibrils (CNF) are explored, biomass‐derived sustainable biomaterials, as nanofibril interfaces with unprecedented interfacial robustness to enable high‐quality printing of strain‐resilient bioelectronics on porous substrates by reducing surface roughness and creating mechanical heterogeneity. Also, CNF‐based microfluidics can provide continuous sweat collection and refreshment, crucial for accurate biochemical sensing. Building upon these advancements, a multimodal porous wearable bioelectronic system is further developed capable of simultaneously detecting electrocardiograms and glucose and beta‐hydroxybutyrate in sweat for monitoring energy metabolism and consumption. This work introduces novel strategies for fabricating high‐quality, strain‐resilient porous bioelectronics with customizable multimodalities to meet arising personalized healthcare needs. +Here a ligand exchange strategy for synthesizing sol–gel oxides is demonstrated to achieve multifunctionality including direct photolithography, high dielectric strength, and high charge carrier mobility, which is challenging to obtain in such oxides. For this purpose, a series of bidentate ligands with azide termini and ethylene‐glycol bridges is synthesized, and these ligands are universally applicable to the synthesis of a variety of dielectric and semiconductor oxides. Optimized photolithography conditions yield a high‐quality ZrO2 dielectric film with a high dielectric constant and strength of ≈18 and ≈7 MV cm−1, respectively. Additionally, this strategy is applied to semiconductor oxides such as In2O3 and ZnO, and the all‐oxide‐patterned solution‐processed thin‐film transistor (TFT) demonstrates a high charge carrier mobility of ≈40 cm2 V−1 s−1. An oxide TFT array is fully photopatterned on a 4‐inch Si wafer; uniform performances are observed across these devices. This study suggests the possibility of realizing multifunctional oxides for application in advanced electronics using simple ligand exchange chemistry. - <img src="https://onlinelibrary.wiley.com/cms/asset/a954db35-9f00-4471-af2d-306741f25720/adma202411587-gra-0001-m.png" - alt="Sustainable Nanofibril Interfaces for Strain-Resilient and Multimodal Porous Bioelectronics"/> -<p>Porous, soft bioelectronics are breathable and offer long-term biocompatibility, but face challenges in stability under stretching and sweat management. This study uses cellulose nanofibrils (CNF) as interfaces to improve strain resilience and printing quality on porous substrates. In addition, CNF-based microfluidics enables continuous sweat monitoring, resulting in a multimodal bioelectronic system for tracking energy metabolism and consumption. + <img src="https://onlinelibrary.wiley.com/cms/asset/5c80a198-7403-4cbf-a3be-825448d2497b/adma202409906-gra-0001-m.png" + alt="Molecular Engineering of Coordination Ligand for Multifunctional Sol–Gel Oxides"/> +<p>A strategy to endow sol–gel oxide films with difficult-to-realize useful functionalities, such as direct photolithography, high dielectric strength, and high mobility by replacing the native ligand of sol–gel oxide with strategically designed/synthesized functional ligands is presented. This demonstrated a high-performance solution-processed all-oxide patterning approach by controlling the functional ligands, facilitating a large-area oxide TFT array with high reliability. </p> <br/> <h2>Abstract</h2> -<p>Porous soft bioelectronics have attracted significant attention due to their high breathability, long-term biocompatibility, and other unique features inaccessible in nonporous counterparts. However, fabricating high-quality multimodal bioelectronic components that operate stably under strain on porous substrates, along with integrating microfluidics for sweat management, remains challenging. In this study, cellulose nanofibrils (CNF) are explored, biomass-derived sustainable biomaterials, as nanofibril interfaces with unprecedented interfacial robustness to enable high-quality printing of strain-resilient bioelectronics on porous substrates by reducing surface roughness and creating mechanical heterogeneity. Also, CNF-based microfluidics can provide continuous sweat collection and refreshment, crucial for accurate biochemical sensing. Building upon these advancements, a multimodal porous wearable bioelectronic system is further developed capable of simultaneously detecting electrocardiograms and glucose and beta-hydroxybutyrate in sweat for monitoring energy metabolism and consumption. This work introduces novel strategies for fabricating high-quality, strain-resilient porous bioelectronics with customizable multimodalities to meet arising personalized healthcare needs.</p> +<p>Here a ligand exchange strategy for synthesizing sol–gel oxides is demonstrated to achieve multifunctionality including direct photolithography, high dielectric strength, and high charge carrier mobility, which is challenging to obtain in such oxides. For this purpose, a series of bidentate ligands with azide termini and ethylene-glycol bridges is synthesized, and these ligands are universally applicable to the synthesis of a variety of dielectric and semiconductor oxides. Optimized photolithography conditions yield a high-quality ZrO<sub>2</sub> dielectric film with a high dielectric constant and strength of ≈18 and ≈7 MV cm<sup>−1</sup>, respectively. Additionally, this strategy is applied to semiconductor oxides such as In<sub>2</sub>O<sub>3</sub> and ZnO, and the all-oxide-patterned solution-processed thin-film transistor (TFT) demonstrates a high charge carrier mobility of ≈40 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup>. An oxide TFT array is fully photopatterned on a 4-inch Si wafer; uniform performances are observed across these devices. This study suggests the possibility of realizing multifunctional oxides for application in advanced electronics using simple ligand exchange chemistry.</p> -Ganggang Zhao, -Zehua Chen, -Shaoyun Wang, -Sicheng Chen, -Feng Zhang, -Syed Muntazir Andrabi, -Yadong Xu, -Qunle Ouyang, -Milton Eric Busquets Rosas, -Xiaoyan Qian, -Jingwei Xie, -Zheng Yan +Juhyeok Lee, +Syed Zahid Hassan, +Hye Ryun Sim, +Sangjun Lee, +Kyeong‐jun Jeong, +Jieun Kwon, +Chang Yun Son, +Dae Sung Chung Research Article - Sustainable Nanofibril Interfaces for Strain‐Resilient and Multimodal Porous Bioelectronics - 10.1002/adma.202411587 + Molecular Engineering of Coordination Ligand for Multifunctional Sol–Gel Oxides + 10.1002/adma.202409906 Advanced Materials - 10.1002/adma.202411587 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411587 + 10.1002/adma.202409906 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409906 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411942 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409959 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202411942 - Unlocking Efficient Alkaline Hydrogen Evolution Through Ru–Sn Dual Metal Sites and a Novel Hydroxyl Spillover Effect + 10.1002/adma.202409959 + Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2 Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A Ru–Sn/SnO2 NS electrocatalyst, with optimized Ru–Sn sites for water dissociation and hydrogen adsorption and SnO2‐induced unique hydroxyl spillover, enhances the alkaline hydrogen evolution by accelerating hydroxyl transfer and protecting active sites. +Partial oxidation of 2D van der Waals frameworks causes their aggregation in solution, while remaining colloidally stable. Strong inter‐sheet non‐covalent interactions give rise to intense, broad‐band visible light absorption. The absorption intensity, bandshape, and energy of this inter‐sheet absorption band is highly tunable by controlling solvent and framework identity. @@ -4678,45 +4579,50 @@ A Ru–Sn/SnO2 NS electrocatalyst, with optimized Ru–Sn sites for wate Abstract -Alkaline hydrogen evolution reaction (HER) has great potential in practical hydrogen production but is still limited by the lack of active and stable electrocatalysts. Herein, the efficient water dissociation process, fast transfer of adsorbed hydroxyl and optimized hydrogen adsorption are first achieved on a cooperative electrocatalyst, named as Ru–Sn/SnO2 NS, in which the Ru–Sn dual metal sites and SnO2 heterojunction are constructed based on porous Ru nanosheet. The density functional theory (DFT) calculations and in situ infrared spectra suggest that Ru–Sn dual sites can optimize the water dissociation process and hydrogen adsorption, while the existence of SnO2 can induce the unique hydroxyl spillover effect, accelerating the hydroxyl transfer process and avoiding the poison of active sites. As results, Ru–Sn/SnO2 NS display remarkable alkaline HER performance with an extremely low overpotential (12 mV at 10 mA cm−2) and robust stability (650 h), much superior to those of Ru NS (27 mV at 10 mA cm−2 with 90 h stability) and Ru–Sn NS (16 mV at 10 mA cm−2 with 120 h stability). The work sheds new light on designing of efficient alkaline HER electrocatalyst. +2D materials can be isolated as monolayer sheets when interlayer interactions involve weak van der Waals forces. These atomically thin structures enable novel topological physics and open chemical questions of how to tune the structure and properties of the sheets while maintaining them as isolated monolayers. Here, this work investigates 2D electroactive sheets that exfoliate in solution into colloidal nanosheets, but aggregate upon oxidation, giving rise to tunable interlayer charge transfer absorption and photoluminescence. This optical behavior resembles interlayer excitons, now intensely studied due to their long‐lived emission, but which remain difficult to tune through synthetic chemistry. Instead, the interlayer excitons of these framework sheets can be modulated through control of solvent, electrolyte, oxidation state, and the composition of the framework building blocks. Compared to other 2D materials, these framework sheets display the largest known interlayer binding strengths, attributable to specific orbital interactions between the sheets, and among the longest interlayer exciton lifetimes. Taken together, this study provides a microscopic basis for manipulating long‐range opto‐electronic behavior in van der Waals materials through molecular synthetic chemistry. - <img src="https://onlinelibrary.wiley.com/cms/asset/7937731e-f737-4bc6-8f77-e9e11d2292cc/adma202411942-gra-0001-m.png" - alt="Unlocking Efficient Alkaline Hydrogen Evolution Through Ru–Sn Dual Metal Sites and a Novel Hydroxyl Spillover Effect"/> -<p>A Ru–Sn/SnO<sub>2</sub> NS electrocatalyst, with optimized Ru–Sn sites for water dissociation and hydrogen adsorption and SnO<sub>2</sub>-induced unique hydroxyl spillover, enhances the alkaline hydrogen evolution by accelerating hydroxyl transfer and protecting active sites. + <img src="https://onlinelibrary.wiley.com/cms/asset/db341436-b229-45d9-afe2-b382e7aa901d/adma202409959-gra-0001-m.png" + alt="Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2"/> +<p>Partial oxidation of 2D van der Waals frameworks causes their aggregation in solution, while remaining colloidally stable. Strong inter-sheet non-covalent interactions give rise to intense, broad-band visible light absorption. The absorption intensity, bandshape, and energy of this inter-sheet absorption band is highly tunable by controlling solvent and framework identity. </p> <br/> <h2>Abstract</h2> -<p>Alkaline hydrogen evolution reaction (HER) has great potential in practical hydrogen production but is still limited by the lack of active and stable electrocatalysts. Herein, the efficient water dissociation process, fast transfer of adsorbed hydroxyl and optimized hydrogen adsorption are first achieved on a cooperative electrocatalyst, named as Ru–Sn/SnO<sub>2</sub> NS, in which the Ru–Sn dual metal sites and SnO<sub>2</sub> heterojunction are constructed based on porous Ru nanosheet. The density functional theory (DFT) calculations and in situ infrared spectra suggest that Ru–Sn dual sites can optimize the water dissociation process and hydrogen adsorption, while the existence of SnO<sub>2</sub> can induce the unique hydroxyl spillover effect, accelerating the hydroxyl transfer process and avoiding the poison of active sites. As results, Ru–Sn/SnO<sub>2</sub> NS display remarkable alkaline HER performance with an extremely low overpotential (12 mV at 10 mA cm<sup>−2</sup>) and robust stability (650 h), much superior to those of Ru NS (27 mV at 10 mA cm<sup>−2</sup> with 90 h stability) and Ru–Sn NS (16 mV at 10 mA cm<sup>−2</sup> with 120 h stability). The work sheds new light on designing of efficient alkaline HER electrocatalyst.</p> +<p>2D materials can be isolated as monolayer sheets when interlayer interactions involve weak van der Waals forces. These atomically thin structures enable novel topological physics and open chemical questions of how to tune the structure and properties of the sheets while maintaining them as isolated monolayers. Here, this work investigates 2D electroactive sheets that exfoliate in solution into colloidal nanosheets, but aggregate upon oxidation, giving rise to tunable interlayer charge transfer absorption and photoluminescence. This optical behavior resembles interlayer excitons, now intensely studied due to their long-lived emission, but which remain difficult to tune through synthetic chemistry. Instead, the interlayer excitons of these framework sheets can be modulated through control of solvent, electrolyte, oxidation state, and the composition of the framework building blocks. Compared to other 2D materials, these framework sheets display the largest known interlayer binding strengths, attributable to specific orbital interactions between the sheets, and among the longest interlayer exciton lifetimes. Taken together, this study provides a microscopic basis for manipulating long-range opto-electronic behavior in van der Waals materials through molecular synthetic chemistry.</p> -Zhen‐Tong Yan, -Shi Tao, -Juan Wang, -Xiu‐Li Lu, -Tong‐Bu Lu +Jacob McKenzie, +Doran L. Pennington, +Thomas Ericson, +Elana Cope, +Aaron J. Kaufman, +Anthony F. Cozzolino, +David C. Johnson, +Kentaro Kadota, +Christopher H. Hendon, +Carl K. Brozek Research Article - Unlocking Efficient Alkaline Hydrogen Evolution Through Ru–Sn Dual Metal Sites and a Novel Hydroxyl Spillover Effect - 10.1002/adma.202411942 + Tunable Interlayer Interactions in Exfoliated 2D van der Waals Framework Fe(SCN)2(Pyrazine)2 + 10.1002/adma.202409959 Advanced Materials - 10.1002/adma.202411942 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411942 + 10.1002/adma.202409959 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409959 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411968 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410007 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202411968 - Multi‐Functional Silole Hole Transport Layer for Efficient and Stable Lead–Tin Perovskite and Tandem Solar Cells + 10.1002/adma.202410007 + Flexible Neural Interface From Non‐Transient Silk Fibroin With Outstanding Conformality, Biocompatibility, and Bioelectric Conductivity Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The traditional hole transport material (HTM) PEDOT: PSS is a bottleneck for long‐term stability in Sn–Pb perovskite solar cells (PSCs). This work offers an alternative means toward efficient and stable Sn–Pb PSCs using a new multi‐functional HTM Silole‐COOH, demonstrating 23.2%‐efficient single‐junction Sn–Pb PSCs, 25.8%‐efficient all‐perovskite tandems while avoiding the stability concerns associated with PEDOT: PSS. +By precisely controlling the interactions between silk fibroin (SF) and poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), a robust and intertwined SF/PEDOT interface can be established. Leveraging this approach, a non‐transient SF‐based neural interface that possesses outstanding stability, conformality, biocompatibility, and bioelectric conductivity is developed. These features make it an ideal platform for the recording and monitoring of neural activities. @@ -4726,56 +4632,50 @@ The traditional hole transport material (HTM) PEDOT: PSS is a bottleneck for lon Abstract -Despite high theoretical efficiencies and rapid improvements in performance, high‐efficiency ≈1.2 eV mixed Sn–Pb perovskite solar cells (PSCs) generally rely on poly(3,4‐ethylenedioxythiophene) polystyrenesulfonate (PEDOT: PSS) as the hole transport layer (HTL); a material that is considered to be a bottleneck for long‐term stability due to its acidity and hygroscopic nature. Seeking to replace PEDOT: PSS with an alternative HTL with improved atmospheric and thermal stability, herein, a silole derivative (Silole‐COOH) tuned with optimal electronic properties and efficient carrier transport by incorporating a carboxyl functional group is designed, which results in an optimal band alignment for hole extraction from Sn–Pb perovskites and robust air and thermal stability. Thin films composed of the Silole‐COOH exhibit superior conductivity and carrier mobility compared to PEDOT: PSS, in addition to reduced nonradiative quasi‐Fermi‐level splitting losses at the HTL/perovskite interface and improved quality of Sn–Pb perovskite. Replacement of PEDOT: PSS with Silole‐COOH leads to 23.2%‐efficient single‐junction Sn–Pb PSCs, 25.8%‐efficient all‐perovskite tandems, and long operating stability in ambient air. +Silk fibroin (SF) with good biocompatibility can enable an efficient and safe implementation of neural interfaces. However, it has been difficult to achieve a robust integration of patterned conducting materials (multichannel electrodes) on flexible SF film substrates due to the absence of some enduring interactions. In this study, a thermo‐assisted pattern‐transfer technique is demonstrated that can facilely transfer a layer of pre‐set poly(3,4‐ethylenedioxythiophene) (PEDOT) onto the flexible SF substrate through an interpenetrating network of 2 polymer chains, achieving a desired substrate/conductor intertwined interface with good flexibility (≈33 MPa), conductivity (386 S cm−1) and stability in liquid state over 4 months simultaneously. Importantly, this technique can be combined with ink‐jet printing to prepare a multichannel SF‐based neural interface for the electrocorticogram (ECoG) recording and inflammation remission in rat models. The SF‐based neural interface with satisfied tissue conformability, biocompatibility, and bioelectric conductivity is a promising ECoG acquisition tool, where the demonstrated approach can also be useful to develop other SF‐based flexible bioelectronics. - <img src="https://onlinelibrary.wiley.com/cms/asset/29b89e4f-fec0-410b-b88b-b9fcfe60e8f4/adma202411968-gra-0001-m.png" - alt="Multi-Functional Silole Hole Transport Layer for Efficient and Stable Lead–Tin Perovskite and Tandem Solar Cells"/> -<p>The traditional hole transport material (HTM) PEDOT: PSS is a bottleneck for long-term stability in Sn–Pb perovskite solar cells (PSCs). This work offers an alternative means toward efficient and stable Sn–Pb PSCs using a new multi-functional HTM Silole-COOH, demonstrating 23.2%-efficient single-junction Sn–Pb PSCs, 25.8%-efficient all-perovskite tandems while avoiding the stability concerns associated with PEDOT: PSS. + <img src="https://onlinelibrary.wiley.com/cms/asset/c1223cc9-0f38-4ac0-8599-34895fd6f6bf/adma202410007-gra-0001-m.png" + alt="Flexible Neural Interface From Non-Transient Silk Fibroin With Outstanding Conformality, Biocompatibility, and Bioelectric Conductivity"/> +<p>By precisely controlling the interactions between silk fibroin (SF) and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), a robust and intertwined SF/PEDOT interface can be established. Leveraging this approach, a non-transient SF-based neural interface that possesses outstanding stability, conformality, biocompatibility, and bioelectric conductivity is developed. These features make it an ideal platform for the recording and monitoring of neural activities. </p> <br/> <h2>Abstract</h2> -<p>Despite high theoretical efficiencies and rapid improvements in performance, high-efficiency ≈1.2 eV mixed Sn–Pb perovskite solar cells (PSCs) generally rely on poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT: PSS) as the hole transport layer (HTL); a material that is considered to be a bottleneck for long-term stability due to its acidity and hygroscopic nature. Seeking to replace PEDOT: PSS with an alternative HTL with improved atmospheric and thermal stability, herein, a silole derivative (Silole-COOH) tuned with optimal electronic properties and efficient carrier transport by incorporating a carboxyl functional group is designed, which results in an optimal band alignment for hole extraction from Sn–Pb perovskites and robust air and thermal stability. Thin films composed of the Silole-COOH exhibit superior conductivity and carrier mobility compared to PEDOT: PSS, in addition to reduced nonradiative quasi-Fermi-level splitting losses at the HTL/perovskite interface and improved quality of Sn–Pb perovskite. Replacement of PEDOT: PSS with Silole-COOH leads to 23.2%-efficient single-junction Sn–Pb PSCs, 25.8%-efficient all-perovskite tandems, and long operating stability in ambient air.</p> +<p>Silk fibroin (SF) with good biocompatibility can enable an efficient and safe implementation of neural interfaces. However, it has been difficult to achieve a robust integration of patterned conducting materials (multichannel electrodes) on flexible SF film substrates due to the absence of some enduring interactions. In this study, a thermo-assisted pattern-transfer technique is demonstrated that can facilely transfer a layer of pre-set poly(3,4-ethylenedioxythiophene) (PEDOT) onto the flexible SF substrate through an interpenetrating network of 2 polymer chains, achieving a desired substrate/conductor intertwined interface with good flexibility (≈33 MPa), conductivity (386 S cm<sup>−1</sup>) and stability in liquid state over 4 months simultaneously. Importantly, this technique can be combined with ink-jet printing to prepare a multichannel SF-based neural interface for the electrocorticogram (ECoG) recording and inflammation remission in rat models. The SF-based neural interface with satisfied tissue conformability, biocompatibility, and bioelectric conductivity is a promising ECoG acquisition tool, where the demonstrated approach can also be useful to develop other SF-based flexible bioelectronics.</p> -Yuanjing Cai, -Aidan Maxwell, -Chongwen Li, -Eui Dae Jung, -Lewei Zeng, -Boran Kumral, -Peter Serles, -Zhan'ao Tan, -Runnan Yu, -Salvatore Boccia, -Mingxing Chen, -Cheng Jiang, -Dongcheng Chen, -Yanjiang Liu, -Zaiwei Wang, -Luke Grater +Zhanao Hu, +Yuqing Liang, +Suna Fan, +Qianqian Niu, +Jingjing Geng, +Qimei Huang, +Benjamin S. Hsiao, +Hao Chen, +Xiang Yao, +Yaopeng Zhang Research Article - Multi‐Functional Silole Hole Transport Layer for Efficient and Stable Lead–Tin Perovskite and Tandem Solar Cells - 10.1002/adma.202411968 + Flexible Neural Interface From Non‐Transient Silk Fibroin With Outstanding Conformality, Biocompatibility, and Bioelectric Conductivity + 10.1002/adma.202410007 Advanced Materials - 10.1002/adma.202411968 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411968 + 10.1002/adma.202410007 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410007 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403626 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410097 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202403626 - Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface + 10.1002/adma.202410097 + Customization of 2D Atomic‐Molecular Heterojunction with Manipulatable Charge‐Transfer and Band Structure Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This study clarifies methane electro‐oxidation process on ceria surfaces using Sm‐doped ceria (SDC) model thin‐film electrochemical cells, integrating impedance spectroscopy, operando X‐ray photoelectron spectroscopy, and DFT calculations. It presents definitive answers regarding ceria's electrocatalytic activity and reaction rate‐limiting steps, significantly contributing to the advancement of efficient, carbon‐neutral fuel utilization in high‐temperature solid oxide fuel cells. +A refined atomic‐molecular heterojunction strategy is developed featuring strong covalent bonds between organic molecule and 2D violet phosphorus atomic crystal, enabling enhanced charge‐transfer dynamics and customizable band structure regulation at the molecular level. Our research provides a low‐cost yet high‐efficiency regulatory approach to optimize device performance across diverse application domains. @@ -4785,51 +4685,51 @@ This study clarifies methane electro‐oxidation process on ceria surfaces u Abstract -Solid oxide fuel cells (SOFCs) stand out in sustainable energy systems for their unique ability to efficiently utilize hydrocarbon fuels, particularly those from carbon‐neutral sources. CeO2−δ (ceria) based oxides embedded in SOFCs are recognized for their critical role in managing hydrocarbon activation and carbon coking. However, even for the simplest hydrocarbon molecule, CH4, the mechanism of electrochemical oxidation at the ceria/gas interface is not well understood and the capability of ceria to electrochemically oxidize methane remains a topic of debate. This lack of clarity stems from the intricate design of standard metal/oxide composite electrodes and the complex nature of electrode reactions involving multiple chemical and electrochemical steps. This study presents a Sm‐doped ceria thin‐film model cell that selectively monitors CH4 direct‐electro‐oxidation on the ceria surface. Using impedance spectroscopy, operando X‐ray photoelectron spectroscopy, and density functional theory, it is unveiled that ceria surfaces facilitate C─H bond cleavage and that H2O formation is key in determining the overall reaction rate at the electrode. These insights effectively address the longstanding debate regarding the direct utilization of CH4 in SOFCs. Moreover, these findings pave the way for an optimized electrode design strategy, essential for developing high‐performance, environmentally sustainable fuel cells. +Manipulating the properties of 2D materials through meticulously engineered artificial heterojunctions holds great promise for novel device applications. However, existing research on the crucial charge‐transfer interactions and energy profile regulation is predominantly focused on 2D van der Waals structures formed via weak van der Waals forces, limiting regulatory efficiency at high costs. Herein, a refined atomic‐molecular heterojunction strategy featuring strong covalent bonds between organic molecule and 2D violet phosphorus (VP) atomic crystal is developed, which enables enhanced charge‐transfer dynamics and customizable band structure regulation at the molecular level. Both experimentally and theoretically, it is demonstrated that grafting efficiency, charge redistribution, and energy gap regulation critically depend on organic electronegativity, providing a low‐cost yet high‐efficiency regulatory effect on a large scale. As a proof of concept, the novel VP‐molecular heterojunctions exhibit optimized performance in diverse application domains, presenting a general platform for future high‐performance device applications. - <img src="https://onlinelibrary.wiley.com/cms/asset/7d22a316-fd6f-4fa1-a4f5-f06e0c35acbe/adma202403626-gra-0001-m.png" - alt="Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface"/> -<p>This study clarifies methane electro-oxidation process on ceria surfaces using Sm-doped ceria (SDC) model thin-film electrochemical cells, integrating impedance spectroscopy, operando X-ray photoelectron spectroscopy, and DFT calculations. It presents definitive answers regarding ceria's electrocatalytic activity and reaction rate-limiting steps, significantly contributing to the advancement of efficient, carbon-neutral fuel utilization in high-temperature solid oxide fuel cells. + <img src="https://onlinelibrary.wiley.com/cms/asset/777ec60e-13fe-434c-917a-db1f5641da85/adma202410097-gra-0001-m.png" + alt="Customization of 2D Atomic-Molecular Heterojunction with Manipulatable Charge-Transfer and Band Structure"/> +<p>A refined atomic-molecular heterojunction strategy is developed featuring strong covalent bonds between organic molecule and 2D violet phosphorus atomic crystal, enabling enhanced charge-transfer dynamics and customizable band structure regulation at the molecular level. Our research provides a low-cost yet high-efficiency regulatory approach to optimize device performance across diverse application domains. </p> <br/> <h2>Abstract</h2> -<p>Solid oxide fuel cells (SOFCs) stand out in sustainable energy systems for their unique ability to efficiently utilize hydrocarbon fuels, particularly those from carbon-neutral sources. CeO<sub>2−δ</sub> (ceria) based oxides embedded in SOFCs are recognized for their critical role in managing hydrocarbon activation and carbon coking. However, even for the simplest hydrocarbon molecule, CH<sub>4</sub>, the mechanism of electrochemical oxidation at the ceria/gas interface is not well understood and the capability of ceria to electrochemically oxidize methane remains a topic of debate. This lack of clarity stems from the intricate design of standard metal/oxide composite electrodes and the complex nature of electrode reactions involving multiple chemical and electrochemical steps. This study presents a Sm-doped ceria thin-film model cell that selectively monitors CH<sub>4</sub> direct-electro-oxidation on the ceria surface. Using impedance spectroscopy, operando X-ray photoelectron spectroscopy, and density functional theory, it is unveiled that ceria surfaces facilitate C─H bond cleavage and that H<sub>2</sub>O formation is key in determining the overall reaction rate at the electrode. These insights effectively address the longstanding debate regarding the direct utilization of CH<sub>4</sub> in SOFCs. Moreover, these findings pave the way for an optimized electrode design strategy, essential for developing high-performance, environmentally sustainable fuel cells.</p> +<p>Manipulating the properties of 2D materials through meticulously engineered artificial heterojunctions holds great promise for novel device applications. However, existing research on the crucial charge-transfer interactions and energy profile regulation is predominantly focused on 2D van der Waals structures formed via weak van der Waals forces, limiting regulatory efficiency at high costs. Herein, a refined atomic-molecular heterojunction strategy featuring strong covalent bonds between organic molecule and 2D violet phosphorus (VP) atomic crystal is developed, which enables enhanced charge-transfer dynamics and customizable band structure regulation at the molecular level. Both experimentally and theoretically, it is demonstrated that grafting efficiency, charge redistribution, and energy gap regulation critically depend on organic electronegativity, providing a low-cost yet high-efficiency regulatory effect on a large scale. As a proof of concept, the novel VP-molecular heterojunctions exhibit optimized performance in diverse application domains, presenting a general platform for future high-performance device applications.</p> -Yoonseok Choi, -Hyunwoo Ha, -Jinwook Kim, -Han Gil Seo, -Hyuk Choi, -Beomgyun Jeong, -JeongDo Yoo, -Ethan J. Crumlin, -Graeme Henkelman, -Hyun You Kim, -WooChul Jung +Weilin Chen, +An Chen, +Xue Liu, +Fan Shu, +Jianmin Zeng, +Jinying Zhang, +Hongbo Xu, +Gaoliang Peng, +Zhi Yang, +Jinjin Li, +Gang Liu Research Article - Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface - 10.1002/adma.202403626 + Customization of 2D Atomic‐Molecular Heterojunction with Manipulatable Charge‐Transfer and Band Structure + 10.1002/adma.202410097 Advanced Materials - 10.1002/adma.202403626 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403626 + 10.1002/adma.202410097 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410097 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403728 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410209 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202403728 - Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics + 10.1002/adma.202410209 + Constructing a Janus Catholyte/Cathode Structure: A New Strategy for Stable Zn‐Organic Batteries Advanced Materials, Volume 36, Issue 46, November 14, 2024. -An optimal approach without the need for additional catalysts or solvents for the upcycling of poly(ethylene terephthalate) (PET) waste is reported. Specifically, bio‐based hydrogenated dimer acids are found to directly convert PET bottles into biodegradable copolyesters suitable for agricultural mulch films. This work provides an environmentally friendly and cost‐effective strategy for the large‐scale upgrading and reprocessing of PET waste. +Inspired by membrane‐less organelles in cells, a simple and versatile strategy is proposed—constructing a Janus catholyte/cathode structured electrode based on liquid‐liquid phase separation, in which redox‐active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte. @@ -4839,45 +4739,54 @@ An optimal approach without the need for additional catalysts or solvents for th Abstract -Poly(ethylene terephthalate) (PET) is an important polymer with annual output second only to polyethylene. Due to its low biodegradability, a large amount of PET is recycled for sustainable development. However, current strategies for PET recycling are limited by low added value or small product scale. It is urgent to make a breakthrough on the principle of PET macromolecular reaction and efficiently prepare products with high added value and wide applications. Here, the catalyst‐ and solvent‐free synthesis of biodegradable plastics are reported through novel carboxyl‐ester transesterification between PET waste and bio‐based hydrogenated dimer acid (HDA), which can directly substitute some terephthalic acid (TPA) units in PET chain by HDA unit. This macromolecular reaction can be facilely carried out on current equipment in the polyester industry without any additional catalyst and solvent, thus enabling low‐cost and large‐scale production. Furthermore, the product semi‐bio‐based copolyester shows excellent mechanical properties, regulable flexibility and good biodegradability, which is expected to substitute poly(butylene adipate‐co‐terephthalate) (PBAT) plastic as high value‐added biodegradable materials. This work provides an environmental‐friendly and economic strategy for the large‐scale upcycling of PET waste. +Organic materials are promising candidates for the electrodes of aqueous zinc‐ion batteries due to their nonmetallic nature, environmental friendliness, and cost‐effectiveness. However, they often suffer from significant dissolution during the charge‐discharge process, which poses a major hurdle to their practical applications. Inspired by membrane‐less organelles in cells, a simple and versatile strategy is proposed—constructing a Janus catholyte/cathode structured electrode based on liquid‐liquid phase separation, in which redox‐active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte. The customization of phase separation systems by leveraging the hydrophobicity/hydrophilicity differences of various anions is successfully demonstrated. This approach allows for precise regulation of ion cluster/coordination structures, enabling the confinement of active substances while ensuring efficient ion transport. Consequently, the as‐constructed Zn||Janus catholyte/cathode cells exhibit superior reversible rate capacity (186 mA h g−1 at 5.0 A g−1) and remarkable cycling performance (retention of 72.5% after 12 000 cycles). The strategy in building Janus catholyte/cathode structured electrodes breaks free from the limitations imposed by traditional solid‐state electrodes, offering tremendous opportunities for exploring diverse advanced battery systems. - <img src="https://onlinelibrary.wiley.com/cms/asset/908da09f-f571-4b03-afdc-e0291bea3808/adma202403728-gra-0001-m.png" - alt="Catalyst- and Solvent-Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics"/> -<p>An optimal approach without the need for additional catalysts or solvents for the upcycling of poly(ethylene terephthalate) (PET) waste is reported. Specifically, bio-based hydrogenated dimer acids are found to directly convert PET bottles into biodegradable copolyesters suitable for agricultural mulch films. This work provides an environmentally friendly and cost-effective strategy for the large-scale upgrading and reprocessing of PET waste. + <img src="https://onlinelibrary.wiley.com/cms/asset/c85d831c-7fb9-4e87-8022-06f1f70e2e21/adma202410209-gra-0001-m.png" + alt="Constructing a Janus Catholyte/Cathode Structure: A New Strategy for Stable Zn-Organic Batteries"/> +<p>Inspired by membrane-less organelles in cells, a simple and versatile strategy is proposed—constructing a Janus catholyte/cathode structured electrode based on liquid-liquid phase separation, in which redox-active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte. </p> <br/> <h2>Abstract</h2> -<p>Poly(ethylene terephthalate) (PET) is an important polymer with annual output second only to polyethylene. Due to its low biodegradability, a large amount of PET is recycled for sustainable development. However, current strategies for PET recycling are limited by low added value or small product scale. It is urgent to make a breakthrough on the principle of PET macromolecular reaction and efficiently prepare products with high added value and wide applications. Here, the catalyst- and solvent-free synthesis of biodegradable plastics are reported through novel carboxyl-ester transesterification between PET waste and bio-based hydrogenated dimer acid (HDA), which can directly substitute some terephthalic acid (TPA) units in PET chain by HDA unit. This macromolecular reaction can be facilely carried out on current equipment in the polyester industry without any additional catalyst and solvent, thus enabling low-cost and large-scale production. Furthermore, the product semi-bio-based copolyester shows excellent mechanical properties, regulable flexibility and good biodegradability, which is expected to substitute poly(butylene adipate-<i>co</i>-terephthalate) (PBAT) plastic as high value-added biodegradable materials. This work provides an environmental-friendly and economic strategy for the large-scale upcycling of PET waste.</p> +<p>Organic materials are promising candidates for the electrodes of aqueous zinc-ion batteries due to their nonmetallic nature, environmental friendliness, and cost-effectiveness. However, they often suffer from significant dissolution during the charge-discharge process, which poses a major hurdle to their practical applications. Inspired by membrane-less organelles in cells, a simple and versatile strategy is proposed—constructing a Janus catholyte/cathode structured electrode based on liquid-liquid phase separation, in which redox-active organic molecules are confined in the liquid state within the activated carbon, thereby eliminating the volume effect and preventing their diffusion into the electrolyte. The customization of phase separation systems by leveraging the hydrophobicity/hydrophilicity differences of various anions is successfully demonstrated. This approach allows for precise regulation of ion cluster/coordination structures, enabling the confinement of active substances while ensuring efficient ion transport. Consequently, the as-constructed Zn||Janus catholyte/cathode cells exhibit superior reversible rate capacity (186 mA h g<sup>−1</sup> at 5.0 A g<sup>−1</sup>) and remarkable cycling performance (retention of 72.5% after 12 000 cycles). The strategy in building Janus catholyte/cathode structured electrodes breaks free from the limitations imposed by traditional solid-state electrodes, offering tremendous opportunities for exploring diverse advanced battery systems.</p> -Tianxiang Fang, -Weipo Jiang, -Tengfei Zheng, -Xuxia Yao, -Weipu Zhu +Hu Hong, +Yiqiao Wang, +Zhiquan Wei, +Xinru Yang, +Zhuoxi Wu, +Xun Guo, +Ao Chen, +Shaoce Zhang, +Shixun Wang, +Qing Li, +Shimei Li, +Dechao Zhang, +Qi Xiong, +Chunyi Zhi Research Article - Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics - 10.1002/adma.202403728 + Constructing a Janus Catholyte/Cathode Structure: A New Strategy for Stable Zn‐Organic Batteries + 10.1002/adma.202410209 Advanced Materials - 10.1002/adma.202403728 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202403728 + 10.1002/adma.202410209 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410209 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407437 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410324 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202407437 - Real Topological Phonons in 3D Carbon Allotropes + 10.1002/adma.202410324 + Programming Hydrogen Bonds for Reversible Elastic‐Plastic Phase Transition in a Conductive Stretchable Hydrogel Actuator with Rapid Ultra‐High‐Density Energy Conversion and Multiple Sensory Properties Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The findings indicate that among the 1661 3D carbon allotropes in the Samara Carbon Allotrope Database (SACADA), 79 possess a phononic real Chern insulating (PRCI) state, 2 possess a phononic real nodal line (PRNL) state, 12 possess a phononic real Dirac point (PRDP) state, and 10 possess a phononic real triple‐point pair (PRTPP) state, respectively. The real topology of PRCI, PRNL, PRDP, and PRTTP states in 3D carbon allotropes is manifested in the second‐order phononic hinge states. +Inspired by the energy conversion of hairspring, an intelligent hydrogel is developed to achieve reversible transformation between elasticity and plasticity through precise regulation of hydrogen bonds, enabling efficient energy storage and release. The hydrogel exhibits exceptional drive rate, high energy density output, and diversified sensing capability. This groundbreaking innovation paves the way for novel designs of smart hydrogel actuators. @@ -4887,49 +4796,49 @@ The findings indicate that among the 1661 3D carbon allotropes in the Samara Car Abstract -There has been a significant focus on real topological systems that enjoy space‐time inversion symmetry and lack spin‐orbit coupling. While the theoretical classification of the real topology has been established, more progress has yet to be made in the materials realization of real topological phononic states in 3D. To address this crucial issue, high‐throughput computing is performed to inspect the real topology in the phonon spectrums of the 3D carbon allotropes. Among 1661 carbon allotropes listed in the Samara Carbon Allotrope Database (SACADA), 79 candidates host a phononic real Chern insulating (PRCI) state, 2 candidates host a phononic real nodal line (PRNL) state, 12 candidates host a phononic real Dirac point (PRDP) state, and 10 candidates host a phononic real triple‐point pair (PRTPP) state. The PRCI, PRNL, PRTPP, and PRDP states of 27‐SG. 166‐pcu‐h, 1081‐SG. 194‐42T13‐CA, 52‐SG. 141‐gis, and 132‐SG. 191‐3,4T157 are exhibited as illustrative examples, and the second‐order phononic hinge modes are explored. This study broadens the understanding of 3D topological phonons and expands the material candidates with phononic hinge modes and phononic real topology. +Smart hydrogels have recently garnered significant attention in the fields of actuators, human‐machine interaction, and soft robotics. However, when constructing large‐scale actuated systems, they usually exhibit limited actuation forces (≈2 kPa) and actuation speeds. Drawing inspiration from hairspring energy conversion mechanism, an elasticity‐plasticity‐controllable composite hydrogel (PCTA) with robust contraction capabilities is developed. By precisely manipulating intermolecular and intramolecular hydrogen‐bonding interactions, the material's elasticity and plasticity can be programmed to facilitate efficient energy storage and release. The proposed mechanism enables rapid generation of high contraction forces (900 kPa) at ultra‐high working densities (0.96 MJ m−3). Molecular dynamics simulations reveal that modifications in the number and nature of hydrogen bonds lead to a distinct elastic‐plastic transition in hydrogels. Furthermore, the conductive PCTA hydrogel exhibits multimodal sensing capabilities including stretchable strain sensing with a wide sensing range (1–200%), fast response time (180 ms), and excellent linearity of the output signal. Moreover, it demonstrates exceptional temperature and humidity sensing capabilities with high detection accuracy. The strong actuation power and real‐time sensory feedback from the composite hydrogels are expected to inspire novel flexible driving materials and intelligent sensing systems. - <img src="https://onlinelibrary.wiley.com/cms/asset/746bcfc9-a33f-483d-993c-6cc47210462b/adma202407437-gra-0001-m.png" - alt="Real Topological Phonons in 3D Carbon Allotropes"/> -<p>The findings indicate that among the 1661 3D carbon allotropes in the Samara Carbon Allotrope Database (SACADA), 79 possess a phononic real Chern insulating (PRCI) state, 2 possess a phononic real nodal line (PRNL) state, 12 possess a phononic real Dirac point (PRDP) state, and 10 possess a phononic real triple-point pair (PRTPP) state, respectively. The real topology of PRCI, PRNL, PRDP, and PRTTP states in 3D carbon allotropes is manifested in the second-order phononic hinge states. + <img src="https://onlinelibrary.wiley.com/cms/asset/3103b334-4ffe-4ae8-9aaa-4d4880f320d2/adma202410324-gra-0001-m.png" + alt="Programming Hydrogen Bonds for Reversible Elastic-Plastic Phase Transition in a Conductive Stretchable Hydrogel Actuator with Rapid Ultra-High-Density Energy Conversion and Multiple Sensory Properties"/> +<p>Inspired by the energy conversion of hairspring, an intelligent hydrogel is developed to achieve reversible transformation between elasticity and plasticity through precise regulation of hydrogen bonds, enabling efficient energy storage and release. The hydrogel exhibits exceptional drive rate, high energy density output, and diversified sensing capability. This groundbreaking innovation paves the way for novel designs of smart hydrogel actuators. </p> <br/> <h2>Abstract</h2> -<p>There has been a significant focus on real topological systems that enjoy space-time inversion symmetry and lack spin-orbit coupling. While the theoretical classification of the real topology has been established, more progress has yet to be made in the materials realization of real topological phononic states in 3D. To address this crucial issue, high-throughput computing is performed to inspect the real topology in the phonon spectrums of the 3D carbon allotropes. Among 1661 carbon allotropes listed in the Samara Carbon Allotrope Database (SACADA), 79 candidates host a phononic real Chern insulating (PRCI) state, 2 candidates host a phononic real nodal line (PRNL) state, 12 candidates host a phononic real Dirac point (PRDP) state, and 10 candidates host a phononic real triple-point pair (PRTPP) state. The PRCI, PRNL, PRTPP, and PRDP states of 27-SG. 166-pcu-h, 1081-SG. 194-4<sup>2</sup>T13-CA, 52-SG. 141-gis, and 132-SG. 191-3,4T157 are exhibited as illustrative examples, and the second-order phononic hinge modes are explored. This study broadens the understanding of 3D topological phonons and expands the material candidates with phononic hinge modes and phononic real topology.</p> +<p>Smart hydrogels have recently garnered significant attention in the fields of actuators, human-machine interaction, and soft robotics. However, when constructing large-scale actuated systems, they usually exhibit limited actuation forces (≈2 kPa) and actuation speeds. Drawing inspiration from hairspring energy conversion mechanism, an elasticity-plasticity-controllable composite hydrogel (PCTA) with robust contraction capabilities is developed. By precisely manipulating intermolecular and intramolecular hydrogen-bonding interactions, the material's elasticity and plasticity can be programmed to facilitate efficient energy storage and release. The proposed mechanism enables rapid generation of high contraction forces (900 kPa) at ultra-high working densities (0.96 MJ m<sup>−3</sup>). Molecular dynamics simulations reveal that modifications in the number and nature of hydrogen bonds lead to a distinct elastic-plastic transition in hydrogels. Furthermore, the conductive PCTA hydrogel exhibits multimodal sensing capabilities including stretchable strain sensing with a wide sensing range (1–200%), fast response time (180 ms), and excellent linearity of the output signal. Moreover, it demonstrates exceptional temperature and humidity sensing capabilities with high detection accuracy. The strong actuation power and real-time sensory feedback from the composite hydrogels are expected to inspire novel flexible driving materials and intelligent sensing systems.</p> -Xiaotian Wang, -Jingbo Bai, -Jianhua Wang, -Zhenxiang Cheng, -Shifeng Qian, -Wenhong Wang, -Gang Zhang, -Zhi‐Ming Yu, -Yugui Yao +Ping Guo, +Zhaoxin Zhang, +Chengnan Qian, +Ruofei Wang, +Lin Cheng, +Ye Tian, +Huaping Wu, +Shuze Zhu, +Aiping Liu Research Article - Real Topological Phonons in 3D Carbon Allotropes - 10.1002/adma.202407437 + Programming Hydrogen Bonds for Reversible Elastic‐Plastic Phase Transition in a Conductive Stretchable Hydrogel Actuator with Rapid Ultra‐High‐Density Energy Conversion and Multiple Sensory Properties + 10.1002/adma.202410324 Advanced Materials - 10.1002/adma.202407437 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407437 + 10.1002/adma.202410324 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410324 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408448 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410418 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202408448 - Solution‐Processed Micro‐Nanostructured Electron Transport Layer via Bubble‐Assisted Assembly for Efficient Perovskite Photovoltaics + 10.1002/adma.202410418 + Achieving Ultra‐Narrow‐Band Deep‐Red Electroluminescence By a Soliton‐type Dye Squaraine Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The unbalanced diffusion lengths of photogenerated electrons and holes in formamidine (FA)‐based perovskite materials facilitate the charge recombination. Here, ordered SnO2 micro‐nanoarrays are constructed by a bubble‐assisted printing method and serve as “speedway” for electron transport in perovskite photovoltaics. Perovskite layers embedded with SnO2 arrays result in reduced charge recombination and improved power conversion efficiency in perovskite solar cells. +Squaraine dyes typically exhibit narrow emission spectra due to their soliton‐like electronic structure characteristics. An organic light‐emitting diode based on soliton‐type squaraine dye is prepared, overcoming the luminescence quenching induced by dye aggregation. The deep‐red electroluminescence peak is located at 668 nm, with a full‐width at half‐maximum (FWHM) of only 0.10 eV. @@ -4939,53 +4848,50 @@ The unbalanced diffusion lengths of photogenerated electrons and holes in formam Abstract -Organic–inorganic halide perovskite solar cells (PSCs) have attracted significant attention in photovoltaic research, owing to their superior optoelectronic properties and cost‐effective manufacturing techniques. However, the unbalanced charge carrier diffusion length in perovskite materials leads to the recombination of photogenerated electrons and holes. The inefficient charge carrier collecting process severely affects the power conversion efficiency (PCE) of the PSCs. Herein, a solution‐processed SnO2 array electron transport layer with precisely tunable micro‐nanostructures is fabricated via a bubble‐template‐assisted approach, serving as both electron transport layers and scaffolds for the perovskite layer. Due to the optimized electron transporting pathway and enlarged perovskite grain size, the PSCs achieve a PCE of 25.35% (25.07% certificated PCE). +Due to the soliton‐like electronic structural characteristics, cyanine dyes typically exhibit spectral behaviors such as large molar extinction coefficients, narrow spectra, and high fluorescence efficiency. However, their extensive applications as emitters in electroluminescence are largely ignored due to their serious emission quenching in the aggregation state. Herein, it is reported a squaraine dye (a type of cyanine) SQPhEt. At different solution concentrations, the unusual decrease in full‐width at half‐maxima (FWHM) with increasing Stokes shift indicates the fluorescence quenching of SQPhEt in the aggregated state is because of the strong self‐absorption effect. A sensitized device structure can help to reduce the doping concentration of dye, which can effectively suppress self‐absorption. Benefitting from the large molar extinction coefficient of SQPhEt, even at low doping concentrations of 0.1 wt%, efficient Förster energy transfer can be achieved. The corresponding spin‐coating sensitized device based on SQPhEt as the dopant exhibits favorable deep‐red emission at 668 nm with a small FWHM of 0.10 eV. - <img src="https://onlinelibrary.wiley.com/cms/asset/d4d15568-be05-4ab0-83a1-fc418e2398b2/adma202408448-gra-0001-m.png" - alt="Solution-Processed Micro-Nanostructured Electron Transport Layer via Bubble-Assisted Assembly for Efficient Perovskite Photovoltaics"/> -<p>The unbalanced diffusion lengths of photogenerated electrons and holes in formamidine (FA)-based perovskite materials facilitate the charge recombination. Here, ordered SnO<sub>2</sub> micro-nanoarrays are constructed by a bubble-assisted printing method and serve as “speedway” for electron transport in perovskite photovoltaics. Perovskite layers embedded with SnO<sub>2</sub> arrays result in reduced charge recombination and improved power conversion efficiency in perovskite solar cells. + <img src="https://onlinelibrary.wiley.com/cms/asset/721d48bf-97ac-4021-b686-ef59f5b672cb/adma202410418-gra-0001-m.png" + alt="Achieving Ultra-Narrow-Band Deep-Red Electroluminescence By a Soliton-type Dye Squaraine"/> +<p>Squaraine dyes typically exhibit narrow emission spectra due to their soliton-like electronic structure characteristics. An organic light-emitting diode based on soliton-type squaraine dye is prepared, overcoming the luminescence quenching induced by dye aggregation. The deep-red electroluminescence peak is located at 668 nm, with a full-width at half-maximum (FWHM) of only 0.10 eV. </p> <br/> <h2>Abstract</h2> -<p>Organic–inorganic halide perovskite solar cells (PSCs) have attracted significant attention in photovoltaic research, owing to their superior optoelectronic properties and cost-effective manufacturing techniques. However, the unbalanced charge carrier diffusion length in perovskite materials leads to the recombination of photogenerated electrons and holes. The inefficient charge carrier collecting process severely affects the power conversion efficiency (PCE) of the PSCs. Herein, a solution-processed SnO<sub>2</sub> array electron transport layer with precisely tunable micro-nanostructures is fabricated via a bubble-template-assisted approach, serving as both electron transport layers and scaffolds for the perovskite layer. Due to the optimized electron transporting pathway and enlarged perovskite grain size, the PSCs achieve a PCE of 25.35% (25.07% certificated PCE).</p> +<p>Due to the soliton-like electronic structural characteristics, cyanine dyes typically exhibit spectral behaviors such as large molar extinction coefficients, narrow spectra, and high fluorescence efficiency. However, their extensive applications as emitters in electroluminescence are largely ignored due to their serious emission quenching in the aggregation state. Herein, it is reported a squaraine dye (a type of cyanine) SQPhEt. At different solution concentrations, the unusual decrease in full-width at half-maxima (FWHM) with increasing Stokes shift indicates the fluorescence quenching of SQPhEt in the aggregated state is because of the strong self-absorption effect. A sensitized device structure can help to reduce the doping concentration of dye, which can effectively suppress self-absorption. Benefitting from the large molar extinction coefficient of SQPhEt, even at low doping concentrations of 0.1 wt%, efficient Förster energy transfer can be achieved. The corresponding spin-coating sensitized device based on SQPhEt as the dopant exhibits favorable deep-red emission at 668 nm with a small FWHM of 0.10 eV.</p> -Yongrui Yang, -Fanyi Min, -Yiyang Wang, -Lutong Guo, -Haoran Long, -Zhiyuan Qu, -Kun Zhang, -Yang Wang, -Juehan Yang, -Yu Chen, -Lei Meng, -Yali Qiao, -Yanlin Song +Wenle Tan, +Yue Yu, +Tianyuan Shi, +Lveting Zhang, +Hanlin Gan, +Bohan Wang, +Ganlin Liu, +Mingke Li, +Lei Ying, +Yuguang Ma Research Article - Solution‐Processed Micro‐Nanostructured Electron Transport Layer via Bubble‐Assisted Assembly for Efficient Perovskite Photovoltaics - 10.1002/adma.202408448 + Achieving Ultra‐Narrow‐Band Deep‐Red Electroluminescence By a Soliton‐type Dye Squaraine + 10.1002/adma.202410418 Advanced Materials - 10.1002/adma.202408448 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408448 + 10.1002/adma.202410418 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410418 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409142 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410422 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409142 - Untethered & Stiffness‐Tunable Ferromagnetic Liquid Robots for Cleaning Thrombus in Complex Blood Vessels + 10.1002/adma.202410422 + Unveiling the Cation Dependence in Alkaline Hydrogen Evolution by Differently‐Charged Ruthenium/Molybdenum Sulfide Hybrids Advanced Materials, Volume 36, Issue 46, November 14, 2024. -In this study, a ferromagnetic liquid robot (FMLR) with tunable modulus (0.1–2018 Pa) applied to thrombus removal in complex blood vessels is developed. Besides, in medical robotic applications, FMLR can be used in telerobotic neurointerventional. This study introduces an efficient approach for thrombus elimination, broadening the utilization of FMLRs within the realm of clinical medicine. +Alkaline hydrogen evolution kinetics via water reduction limits the water electrolysis efficiency and depends on both catalyst structures and electrolyte cations. Herein, by hybridizing metallic Ru with differently‐charged MoSx clusters, the interrelated effect of metal valence and charged support for the cation‐dependent hydrogen evolution activity is demonstrated, in which the metal valence determines the water activation capability and the support determines the cation accumulation. @@ -4995,50 +4901,48 @@ In this study, a ferromagnetic liquid robot (FMLR) with tunable modulus (0.1R Abstract -Thrombosis is a significant threat to human health. However, the existing clinical treatment methods have limitations. Magnetic soft matter is used in the biomedical field for years, and ferromagnetic liquids exhibit tunable stiffness and on‐demand movement advantages under magnetic fields. In this study, a ferromagnetic liquid robot (FMLR) is developed and applied it to thrombus removal in complex blood vessels. The FMLR consisted of Fe3O4 magnetic nanoparticles and dimethyl silicone oil. The FMLR can pass through a narrow complex maze through shape deformation by tailoring the intensity and direction of the external magnetic field. Finite element simulation analysis is used to validate the mechanism of controllable FMLR movements. Importantly, the storage modulus of FMLR can be tuned from 0.1 to 2018 Pa by varying the external magnetic intensity, ensuring its effectiveness in removing rigid and stubborn thrombi present on the vascular walls. Toward medical robotic applications, FMLR can be used in telerobotic neurointerventional. Experiments demonstrating the capability of FMLR to remove thrombi in the ear veins of rabbits are conducted. This study introduces an efficient approach for thrombus elimination, broadening the utilization of FMLRs within the realm of clinical medicine. +The sluggish kinetics of hydrogen evolution reaction (HER) via water reduction limits the efficiency of alkaline water electrolysis. The HER kinetics is not only intimately related to the catalyst surface structure but also relevant to the cation identity of the electrolyte. The cation dependence also relies on the surface electronic structure and applied potential, but this interrelated effect and its underlying mechanism awaits elucidation. Herein, differently‐charged molybdenum sulfide (MoSx) cluster supports ([Mo3S13]2− and [Mo3S7]4+) are utilized to hybridize with the identical metallic Ru centers. The specific electrostatic interaction between MoSx clusters and Ru precursors induces different Ru valences of the hybrids, with a higher valence state for Ru/Mo3S13 endowing a higher activity. The Ru/Mo3S13 and Ru/Mo3S7 exhibited drastically‐different cation dependence, in which the charged support determines the local accumulation of cations and resulting water structures. The more negatively‐charged Mo3S13 support induces the facile accumulation of cations, especially for less‐hydrated K+ cations. The water activation capability by Ru valences and cation accumulation from the support effect in‐together determine the cation‐dependent alkaline HER activity. This work not only enriches the understanding about the cation‐dependent HER mechanism but also shines a light on the rational optimization strategy of electrode/electrolyte interfaces. - <img src="https://onlinelibrary.wiley.com/cms/asset/2d226df9-9bce-4bdf-8fb0-15a9978876f0/adma202409142-gra-0001-m.png" - alt="Untethered &amp; Stiffness-Tunable Ferromagnetic Liquid Robots for Cleaning Thrombus in Complex Blood Vessels"/> -<p>In this study, a ferromagnetic liquid robot (FMLR) with tunable modulus (0.1–2018 Pa) applied to thrombus removal in complex blood vessels is developed. Besides, in medical robotic applications, FMLR can be used in telerobotic neurointerventional. This study introduces an efficient approach for thrombus elimination, broadening the utilization of FMLRs within the realm of clinical medicine. + <img src="https://onlinelibrary.wiley.com/cms/asset/f2a30e94-9acf-4d11-9f46-3d752bab69ea/adma202410422-gra-0001-m.png" + alt="Unveiling the Cation Dependence in Alkaline Hydrogen Evolution by Differently-Charged Ruthenium/Molybdenum Sulfide Hybrids"/> +<p>Alkaline hydrogen evolution kinetics via water reduction limits the water electrolysis efficiency and depends on both catalyst structures and electrolyte cations. Herein, by hybridizing metallic Ru with differently-charged MoSx clusters, the interrelated effect of metal valence and charged support for the cation-dependent hydrogen evolution activity is demonstrated, in which the metal valence determines the water activation capability and the support determines the cation accumulation. </p> <br/> <h2>Abstract</h2> -<p>Thrombosis is a significant threat to human health. However, the existing clinical treatment methods have limitations. Magnetic soft matter is used in the biomedical field for years, and ferromagnetic liquids exhibit tunable stiffness and on-demand movement advantages under magnetic fields. In this study, a ferromagnetic liquid robot (FMLR) is developed and applied it to thrombus removal in complex blood vessels. The FMLR consisted of Fe<sub>3</sub>O<sub>4</sub> magnetic nanoparticles and dimethyl silicone oil. The FMLR can pass through a narrow complex maze through shape deformation by tailoring the intensity and direction of the external magnetic field. Finite element simulation analysis is used to validate the mechanism of controllable FMLR movements. Importantly, the storage modulus of FMLR can be tuned from 0.1 to 2018 Pa by varying the external magnetic intensity, ensuring its effectiveness in removing rigid and stubborn thrombi present on the vascular walls. Toward medical robotic applications, FMLR can be used in telerobotic neurointerventional. Experiments demonstrating the capability of FMLR to remove thrombi in the ear veins of rabbits are conducted. This study introduces an efficient approach for thrombus elimination, broadening the utilization of FMLRs within the realm of clinical medicine.</p> +<p>The sluggish kinetics of hydrogen evolution reaction (HER) via water reduction limits the efficiency of alkaline water electrolysis. The HER kinetics is not only intimately related to the catalyst surface structure but also relevant to the cation identity of the electrolyte. The cation dependence also relies on the surface electronic structure and applied potential, but this interrelated effect and its underlying mechanism awaits elucidation. Herein, differently-charged molybdenum sulfide (MoS<sub>x</sub>) cluster supports ([Mo<sub>3</sub>S<sub>13</sub>]<sup>2−</sup> and [Mo<sub>3</sub>S<sub>7</sub>]<sup>4+</sup>) are utilized to hybridize with the identical metallic Ru centers. The specific electrostatic interaction between MoS<sub>x</sub> clusters and Ru precursors induces different Ru valences of the hybrids, with a higher valence state for Ru/Mo<sub>3</sub>S<sub>13</sub> endowing a higher activity. The Ru/Mo<sub>3</sub>S<sub>13</sub> and Ru/Mo<sub>3</sub>S<sub>7</sub> exhibited drastically-different cation dependence, in which the charged support determines the local accumulation of cations and resulting water structures. The more negatively-charged Mo<sub>3</sub>S<sub>13</sub> support induces the facile accumulation of cations, especially for less-hydrated K<sup>+</sup> cations. The water activation capability by Ru valences and cation accumulation from the support effect in-together determine the cation-dependent alkaline HER activity. This work not only enriches the understanding about the cation-dependent HER mechanism but also shines a light on the rational optimization strategy of electrode/electrolyte interfaces.</p> -Zhuofan Li, -Shanfei Zhang, -Qi Wang, -Yizhuo Xu, -Yike Li, -Xiaojun Chen, -Peng Chen, -Dezhi Chen, -Yunsong Shi, -Bin Su +Shaoyan Wang, +Tao Jiang, +Yaming Hao, +Jianxiang Wu, +Can Lei, +Zhe Chen, +Wei Du, +Ming Gong Research Article - Untethered & Stiffness‐Tunable Ferromagnetic Liquid Robots for Cleaning Thrombus in Complex Blood Vessels - 10.1002/adma.202409142 + Unveiling the Cation Dependence in Alkaline Hydrogen Evolution by Differently‐Charged Ruthenium/Molybdenum Sulfide Hybrids + 10.1002/adma.202410422 Advanced Materials - 10.1002/adma.202409142 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409142 + 10.1002/adma.202410422 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410422 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409175 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410441 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409175 - Universal Ensemble‐Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures + 10.1002/adma.202410441 + Spatial Control of Nickel Vacancies in Colloidal NiMgO Nanocrystals for Efficient and Stable All‐inorganic Quantum Dot Light‐Emitting Diodes Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This paper introduces GNNOpt, an equivariant graph‐neural‐network architecture incorporating universal embedding with automatic optimization. GNNOpt allows for precise prediction of optical spectra based exclusively on crystal structures and can be up to a million times faster than traditional first‐principles calculations. Consequently, GNNOpt can significantly speed up the development of photovoltaic and quantum materials. +Colloidal NiMgO nanocrystals with spatially controlled Mg are introduced as hole‐transport materials for all‐inorganic quantum dot light‐emitting diodes. This novel approach enhances device performance, achieving a peak external quantum efficiency of 16.4%, a peak luminance of 269 455 cd m−2, and a half‐life of 462 690 h at 100 nit, paving the way for more efficient and stable next‐generation displays. @@ -5048,44 +4952,56 @@ This paper introduces GNNOpt, an equivariant graph‐neural‐network ar Abstract -Optical properties in solids, such as refractive index and absorption, hold vast applications ranging from solar panels to sensors, photodetectors, and transparent displays. However, first‐principles computation of optical properties from crystal structures is a complex task due to the high convergence criteria and computational cost. Recent progress in machine learning shows promise in predicting material properties, yet predicting optical properties from crystal structures remains challenging due to the lack of efficient atomic embeddings. Here, Graph Neural Network for Optical spectra prediction (GNNOpt) is introduced, an equivariant graph‐neural‐network architecture featuring universal embedding with automatic optimization. This enables high‐quality optical predictions with a dataset of only 944 materials. GNNOpt predicts all optical properties based on the Kramers‐Krönig relations, including absorption coefficient, complex dielectric function, complex refractive index, and reflectance. The trained model is applied to screen photovoltaic materials based on spectroscopic limited maximum efficiency and search for quantum materials based on quantum weight. First‐principles calculations validate the efficacy of the GNNOpt model, demonstrating excellent agreement in predicting the optical spectra of unseen materials. The discovery of new quantum materials with high predicted quantum weight, such as SiOs, which host exotic quasiparticles with multifold nontrivial topology, demonstrates the potential of GNNOpt in predicting optical properties across a broad range of materials and applications. +Colloidal quantum dot (QD)–based light‐emitting diodes (QD‐LEDs) have reached the pinnacle of quantum efficiency and are now being actively developed for next‐generation displays and brighter light sources. Previous research has suggested utilizing inorganic hole‐transport layers (HTLs) to explore brighter and more stable QD‐LEDs. However, the performance metrics of such QD‐LEDs with inorganic HTLs generally lag behind those of organic‐inorganic hybrid QD‐LEDs employing organic HTLs. In this study, colloidal NiMgO nanocrystals (NCs) with spatially controlled Mg are introduced as HTLs for realizing efficient and stable all‐inorganic QD‐LEDs. During the co‐condensation of Ni and Mg precursors to produce valence band‐lowered NiMgO NCs, incorporating ≈2% Mg into the NiO lattice creates additional Ni vacancies (VNi) within and on the NCs, influencing the hole concentration and mobility of the NiMgO NC films. Passivating the VNi exposed on the surface with magnesium hydroxide allows for tuning the electrical properties of the NiMgO NCs relative to those of an electron transport layer, allowing for a balanced charge supply and suppressed negative charging of the QDs. Optimized all‐inorganic QD‐LEDs employing NiMgO NCs achieved a peak external quantum efficiency of 16.4%, peak luminance of 269 455 cd m⁻2, and a half‐life of 462 690 h at 100 nit. - <img src="https://onlinelibrary.wiley.com/cms/asset/66e3de52-7fa6-4fed-b932-5a91397248bf/adma202409175-gra-0001-m.png" - alt="Universal Ensemble-Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures"/> -<p>This paper introduces GNNOpt, an equivariant graph-neural-network architecture incorporating universal embedding with automatic optimization. GNNOpt allows for precise prediction of optical spectra based exclusively on crystal structures and can be up to a million times faster than traditional first-principles calculations. Consequently, GNNOpt can significantly speed up the development of photovoltaic and quantum materials. + <img src="https://onlinelibrary.wiley.com/cms/asset/5f32287c-1abd-4365-ac53-18b5eb0f7d09/adma202410441-gra-0001-m.png" + alt="Spatial Control of Nickel Vacancies in Colloidal NiMgO Nanocrystals for Efficient and Stable All-inorganic Quantum Dot Light-Emitting Diodes"/> +<p>Colloidal NiMgO nanocrystals with spatially controlled Mg are introduced as hole-transport materials for all-inorganic quantum dot light-emitting diodes. This novel approach enhances device performance, achieving a peak external quantum efficiency of 16.4%, a peak luminance of 269 455 cd m<sup>−</sup> +<sup>2</sup>, and a half-life of 462 690 h at 100 nit, paving the way for more efficient and stable next-generation displays. </p> <br/> <h2>Abstract</h2> -<p>Optical properties in solids, such as refractive index and absorption, hold vast applications ranging from solar panels to sensors, photodetectors, and transparent displays. However, first-principles computation of optical properties from crystal structures is a complex task due to the high convergence criteria and computational cost. Recent progress in machine learning shows promise in predicting material properties, yet predicting optical properties from crystal structures remains challenging due to the lack of efficient atomic embeddings. Here, Graph Neural Network for Optical spectra prediction (GNNOpt) is introduced, an equivariant graph-neural-network architecture featuring universal embedding with automatic optimization. This enables high-quality optical predictions with a dataset of only 944 materials. GNNOpt predicts all optical properties based on the Kramers-Krönig relations, including absorption coefficient, complex dielectric function, complex refractive index, and reflectance. The trained model is applied to screen photovoltaic materials based on spectroscopic limited maximum efficiency and search for quantum materials based on quantum weight. First-principles calculations validate the efficacy of the GNNOpt model, demonstrating excellent agreement in predicting the optical spectra of unseen materials. The discovery of new quantum materials with high predicted quantum weight, such as SiOs, which host exotic quasiparticles with multifold nontrivial topology, demonstrates the potential of GNNOpt in predicting optical properties across a broad range of materials and applications.</p> +<p>Colloidal quantum dot (QD)–based light-emitting diodes (QD-LEDs) have reached the pinnacle of quantum efficiency and are now being actively developed for next-generation displays and brighter light sources. Previous research has suggested utilizing inorganic hole-transport layers (HTLs) to explore brighter and more stable QD-LEDs. However, the performance metrics of such QD-LEDs with inorganic HTLs generally lag behind those of organic-inorganic hybrid QD-LEDs employing organic HTLs. In this study, colloidal NiMgO nanocrystals (NCs) with spatially controlled Mg are introduced as HTLs for realizing efficient and stable all-inorganic QD-LEDs. During the co-condensation of Ni and Mg precursors to produce valence band-lowered NiMgO NCs, incorporating ≈2% Mg into the NiO lattice creates additional Ni vacancies (V<sub>Ni</sub>) within and on the NCs, influencing the hole concentration and mobility of the NiMgO NC films. Passivating the V<sub>Ni</sub> exposed on the surface with magnesium hydroxide allows for tuning the electrical properties of the NiMgO NCs relative to those of an electron transport layer, allowing for a balanced charge supply and suppressed negative charging of the QDs. Optimized all-inorganic QD-LEDs employing NiMgO NCs achieved a peak external quantum efficiency of 16.4%, peak luminance of 269 455 cd m⁻<sup>2</sup>, and a half-life of 462 690 h at 100 nit.</p> -Nguyen Tuan Hung, -Ryotaro Okabe, -Abhijatmedhi Chotrattanapituk, -Mingda Li +Woon Ho Jung, +Byong Jae Kim, +Mahnmin Choi, +Hyeonjun Lee, +Hyunjin Cho, +Yong Woo Kwon, +Yeongho Choi, +Hyo Geun Lee, +Jinha Yoon, +Keeyong Lee, +Sang Ho Oh, +Seong‐Yong Cho, +Doh C. Lee, +Sohee Jeong, +Jaehoon Lim Research Article - Universal Ensemble‐Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures - 10.1002/adma.202409175 + Spatial Control of Nickel Vacancies in Colloidal NiMgO Nanocrystals for Efficient and Stable All‐inorganic Quantum Dot Light‐Emitting Diodes + 10.1002/adma.202410441 Advanced Materials - 10.1002/adma.202409175 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409175 + 10.1002/adma.202410441 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410441 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410669 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410469 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410669 - Innovative In Situ Passivation Strategy for High‐Efficiency Sb2(S,Se)3 Solar Cells + 10.1002/adma.202410469 + Low‐Symmetry Van der Waals Dielectric GaInS3 Triggered 2D MoS2 Giant Anisotropy via Symmetry Engineering Advanced Materials, Volume 36, Issue 46, November 14, 2024. -10.81%‐efficiency Sb2(S,Se)3 solar cell is achieved using an in situ passivation technique, which involves incorporating sodium selenosulfate to the precursor solution, effectively passivates deep‐level intrinsic defects, enhances film quality, and reduces non‐radiative recombination. +The low‐symmetry dielectrics GaInS3 sparks MoS2 obvious anisotropy, at the inface of MoS2/GaInS3 heterojunction. The anisotropic optical responses are confirmed through polarized Raman and PL spectra. Under dual‐gate modulation, MoS2 FET demonstrates highly adjustable anisotropic conductivity up to 106. Remarkably, the GaInS3‐gated MoS2 photodetector exhibits a large dichroic ratio (≈167), which greatly promotes its application in polarized photodetection. @@ -5095,51 +5011,50 @@ Mingda Li Abstract -An effective defect passivation strategy is crucial for enhancing the performance of antimony selenosulfide (Sb2(S,Se)3) solar cells, as it significantly influences charge transport and extraction efficiency. Herein, a convenient and novel in situ passivation (ISP) technique is successfully introduced to enhance the performance of Sb2(S,Se)3 solar cells, achieving a champion efficiency of 10.81%, which is among the highest recorded for Sb2(S,Se)3 solar cells to date. The first principles calculations and the experimental data reveal that incorporating sodium selenosulfate in the ISP strategy effectively functions as an in situ selenization, effectively passivating deep‐level cation antisite SbSe defect within the Sb2(S,Se)3 films and significantly suppressing non‐radiative recombination in the devices. Space‐charge‐limited current (SCLC), photoluminescence (PL), and transient absorption spectroscopy (TAS) measurements verify the high quality of the passivated films, showing fewer traps and defects. Moreover, the ISP strategy improved the overall quality of the Sb2(S,Se)3 films, and fine‐tuned the energy levels, thereby facilitating enhanced carrier transport. This study thus provides a straightforward and effective method for passivating deep‐level defects in Sb2(S,Se)3 solar cells. +Low‐symmetry structures in van der Waals materials have facilitated the advancement of anisotropic electronic and optoelectronic devices. However, the intrinsic low symmetry structure exhibits a small adjustable anisotropy ratio (1–10), which hinders its further assembly and processing into high‐performance devices. Here, a novel 2D anisotropic dielectric, GaInS3 (GIS), which induces isotropic MoS2 to exhibit significant anisotropic optical and electrical responses is demonstrated. With the excellent gate modulation ability of 2D GIS (dielectric constant k ∼12), MoS2 field effect transistor (FET) shows an adjustable conductance ratio from isotropic to anisotropic under dual‐gate modulation, up to 106. Theoretical calculations indicate that anisotropy originates from lattice mismatch‐induced charge density deformation at the interface. Moreover, the MoS2/GIS photodetector demonstrates high responsivity (≈4750 A W−1) and a large dichroic ratio (≈167). The anisotropic van der Waals dielectric GIS paves the way for the development of 2D transition metal dichalcogenides (TMDCs) in the fields of anisotropic photonics, electronics, and optoelectronics. - <img src="https://onlinelibrary.wiley.com/cms/asset/a159347a-126b-4446-89bd-159795f0ef3e/adma202410669-gra-0001-m.png" - alt="Innovative In Situ Passivation Strategy for High-Efficiency Sb2(S,Se)3 Solar Cells"/> -<p>10.81%-efficiency Sb<sub>2</sub>(S,Se)<sub>3</sub> solar cell is achieved using an in situ passivation technique, which involves incorporating sodium selenosulfate to the precursor solution, effectively passivates deep-level intrinsic defects, enhances film quality, and reduces non-radiative recombination. + <img src="https://onlinelibrary.wiley.com/cms/asset/ad0e5e01-1a08-4e7f-9412-ef74dfa89e5b/adma202410469-gra-0001-m.png" + alt="Low-Symmetry Van der Waals Dielectric GaInS3 Triggered 2D MoS2 Giant Anisotropy via Symmetry Engineering"/> +<p>The low-symmetry dielectrics GaInS<sub>3</sub> sparks MoS<sub>2</sub> obvious anisotropy, at the inface of MoS<sub>2</sub>/GaInS<sub>3</sub> heterojunction. The anisotropic optical responses are confirmed through polarized Raman and PL spectra. Under dual-gate modulation, MoS<sub>2</sub> FET demonstrates highly adjustable anisotropic conductivity up to 10<sup>6</sup>. Remarkably, the GaInS<sub>3</sub>-gated MoS<sub>2</sub> photodetector exhibits a large dichroic ratio (≈167), which greatly promotes its application in polarized photodetection. </p> <br/> <h2>Abstract</h2> -<p>An effective defect passivation strategy is crucial for enhancing the performance of antimony selenosulfide (Sb<sub>2</sub>(S,Se)<sub>3</sub>) solar cells, as it significantly influences charge transport and extraction efficiency. Herein, a convenient and novel in situ passivation (ISP) technique is successfully introduced to enhance the performance of Sb<sub>2</sub>(S,Se)<sub>3</sub> solar cells, achieving a champion efficiency of 10.81%, which is among the highest recorded for Sb<sub>2</sub>(S,Se)<sub>3</sub> solar cells to date. The first principles calculations and the experimental data reveal that incorporating sodium selenosulfate in the ISP strategy effectively functions as an in situ selenization, effectively passivating deep-level cation antisite Sb<sub>Se</sub> defect within the Sb<sub>2</sub>(S,Se)<sub>3</sub> films and significantly suppressing non-radiative recombination in the devices. Space-charge-limited current (SCLC), photoluminescence (PL), and transient absorption spectroscopy (TAS) measurements verify the high quality of the passivated films, showing fewer traps and defects. Moreover, the ISP strategy improved the overall quality of the Sb<sub>2</sub>(S,Se)<sub>3</sub> films, and fine-tuned the energy levels, thereby facilitating enhanced carrier transport. This study thus provides a straightforward and effective method for passivating deep-level defects in Sb<sub>2</sub>(S,Se)<sub>3</sub> solar cells.</p> +<p>Low-symmetry structures in van der Waals materials have facilitated the advancement of anisotropic electronic and optoelectronic devices. However, the intrinsic low symmetry structure exhibits a small adjustable anisotropy ratio (1–10), which hinders its further assembly and processing into high-performance devices. Here, a novel 2D anisotropic dielectric, GaInS<sub>3</sub> (GIS), which induces isotropic MoS<sub>2</sub> to exhibit significant anisotropic optical and electrical responses is demonstrated. With the excellent gate modulation ability of 2D GIS (dielectric constant <i>k</i> ∼12), MoS<sub>2</sub> field effect transistor (FET) shows an adjustable conductance ratio from isotropic to anisotropic under dual-gate modulation, up to 10<sup>6</sup>. Theoretical calculations indicate that anisotropy originates from lattice mismatch-induced charge density deformation at the interface. Moreover, the MoS<sub>2</sub>/GIS photodetector demonstrates high responsivity (≈4750 A W<sup>−1</sup>) and a large dichroic ratio (≈167). The anisotropic van der Waals dielectric GIS paves the way for the development of 2D transition metal dichalcogenides (TMDCs) in the fields of anisotropic photonics, electronics, and optoelectronics.</p> -Yuqi Zhao, -Wentao Xu, -Jing Wen, -Xiaomin Wang, -Xueling Chen, -Bo Che, -Haolin Wang, -Junbo Gong, -Tao Chen, -Xudong Xiao, -Jianmin Li - - Research Article - Innovative In Situ Passivation Strategy for High‐Efficiency Sb2(S,Se)3 Solar Cells - 10.1002/adma.202410669 - Advanced Materials - 10.1002/adma.202410669 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410669 - Research Article +Zongdong Sun, +Jie Liu, +Yongshan Xu, +Xiong Xiong, +Yuan Li, +Meihui Wang, +Kailang Liu, +Huiqiao Li, +Yanqing Wu, +Tianyou Zhai + + Research Article + Low‐Symmetry Van der Waals Dielectric GaInS3 Triggered 2D MoS2 Giant Anisotropy via Symmetry Engineering + 10.1002/adma.202410469 + Advanced Materials + 10.1002/adma.202410469 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410469 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410947 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410537 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410947 - De‐Passivation and Surface Crystal Plane Reconstruction via Chemical Polishing for Highly Reversible Zinc Anodes + 10.1002/adma.202410537 + WS2 Moiré Superlattices Supporting Au Nanoclusters and Isolated Ru to Boost Hydrogen Production Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The chemically polished Zn metal anode (CP‐Zn), achieved through a facile immersion method, effectively removes passivation layers and selectively exposes (002) crystal planes. This process ensures uniform zinc deposition and improved cell stability, demonstrated by over 4600 hours of stable cycling in symmetric cells and high capacity retention in full cells. +Maximizing the catalytic activity of single‐atom and nanocluster catalysts is essential for their industrial application in water‐alkali electrolyzers. A bilayer WS2 moiré superlattices are reported that support Au nanoclusters and Ru single atoms (Ru1/Aun‐2LWS2) to enhance hydrogen evolution reaction (HER). Experiments and theories indicate that the improved HER activity stems from strong metal–support interactions in Ru1/Aun‐2LWS2, promoting charge redistribution in the catalyst. @@ -5149,74 +5064,54 @@ The chemically polished Zn metal anode (CP‐Zn), achieved through a facile Abstract -Despite the widespread adoption of Zn anodes for aqueous energy storage, the presence of an inherent passivation layer and the polycrystalline interface of commercial Zn foil consistently lead to non‐uniform electrodeposition, undermining stability and practicality. Herein, the study introduces a chemically polished Zn metal anode (CP‐Zn) fabricated via a simple immersion method. This “chemically polishing” process can effectively remove the interfacial passivation layer (de‐passivation), providing ample active sites for plating/stripping and ensuring the uniformly distributed electric field and Zn2+ ion flux. Additionally, selective etching during chemical polishing exposes more (002) crystal planes, promoting homogeneous and smooth zinc deposition while suppressing related side reactions. Demonstrated by CP‐Zn anode, the symmetric cell exhibits stable cycling over 4600 h at 1 mA cm−2 and 240 h at 50% depth of discharge (DOD), with a CP‐Zn||VO2 full cell maintaining ≈75.3% capacity retention over 1000 cycles at 3 A g−1. This chemically polishing strategy presents a promising avenue for advancing the commercialization of aqueous zinc‐ion batteries. +Maximizing the catalytic activity of single‐atom and nanocluster catalysts through the modulation of the interaction between these components and the corresponding supports is crucial but challenging. Herein, guided by theoretical calculations, a nanoporous bilayer WS2 Moiré superlattices (MSLs) supported Au nanoclusters (NCs) adjacent to Ru single atoms (SAs) (Ru1/Aun‐2LWS2) is developed for alkaline hydrogen evolution reaction (HER) for the first time. Theoretical analysis suggests that the induced robust electronic metal–support interaction effect in Ru1/Aun‐2LWS2 is prone to promote the charge redistribution among Ru SAs, Au NCs, and WS2 MSLs support, which is beneficial to reduce the energy barrier for water adsorption and thus promoting the subsequent H2 formation. As feedback, the well‐designed Ru1/Aun‐2LWS2 electrocatalyst exhibits outstanding HER performance with high activity (η10 = 19 mV), low Tafel slope (35 mV dec−1), and excellent long‐term stability. Further, in situ, experimental studies reveal that the reconstruction of Ru SAs/NCs with S vacancies in Ru1/Aun‐2LWS2 structure acts as the main catalytically active center, while high‐valence Au NCs are responsible for activating and stabilizing Ru sites to prevent the dissolution and deactivation of active sites. This work offers guidelines for the rational design of high‐performance atomic‐scale electrocatalysts. - <img src="https://onlinelibrary.wiley.com/cms/asset/63ba616d-bf3e-4006-890e-bee9204e7129/adma202410947-gra-0001-m.png" - alt="De-Passivation and Surface Crystal Plane Reconstruction via Chemical Polishing for Highly Reversible Zinc Anodes"/> -<p>The chemically polished Zn metal anode (CP-Zn), achieved through a facile immersion method, effectively removes passivation layers and selectively exposes (002) crystal planes. This process ensures uniform zinc deposition and improved cell stability, demonstrated by over 4600 hours of stable cycling in symmetric cells and high capacity retention in full cells. + <img src="https://onlinelibrary.wiley.com/cms/asset/55b7e8ce-5f16-429a-9b15-075d0ef3cbfd/adma202410537-gra-0001-m.png" + alt="WS2 Moiré Superlattices Supporting Au Nanoclusters and Isolated Ru to Boost Hydrogen Production"/> +<p>Maximizing the catalytic activity of single-atom and nanocluster catalysts is essential for their industrial application in water-alkali electrolyzers. A bilayer WS<sub>2</sub> moiré superlattices are reported that support Au nanoclusters and Ru single atoms (Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub>) to enhance hydrogen evolution reaction (HER). Experiments and theories indicate that the improved HER activity stems from strong metal–support interactions in Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub>, promoting charge redistribution in the catalyst. </p> <br/> <h2>Abstract</h2> -<p>Despite the widespread adoption of Zn anodes for aqueous energy storage, the presence of an inherent passivation layer and the polycrystalline interface of commercial Zn foil consistently lead to non-uniform electrodeposition, undermining stability and practicality. Herein, the study introduces a chemically polished Zn metal anode (CP-Zn) fabricated via a simple immersion method. This “chemically polishing” process can effectively remove the interfacial passivation layer (de-passivation), providing ample active sites for plating/stripping and ensuring the uniformly distributed electric field and Zn<sup>2+</sup> ion flux. Additionally, selective etching during chemical polishing exposes more (002) crystal planes, promoting homogeneous and smooth zinc deposition while suppressing related side reactions. Demonstrated by CP-Zn anode, the symmetric cell exhibits stable cycling over 4600 h at 1 mA cm<sup>−2</sup> and 240 h at 50% depth of discharge (DOD), with a CP-Zn||VO<sub>2</sub> full cell maintaining ≈75.3% capacity retention over 1000 cycles at 3 A g<sup>−1</sup>. This chemically polishing strategy presents a promising avenue for advancing the commercialization of aqueous zinc-ion batteries.</p> +<p>Maximizing the catalytic activity of single-atom and nanocluster catalysts through the modulation of the interaction between these components and the corresponding supports is crucial but challenging. Herein, guided by theoretical calculations, a nanoporous bilayer WS<sub>2</sub> Moiré superlattices (MSLs) supported Au nanoclusters (NCs) adjacent to Ru single atoms (SAs) (Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub>) is developed for alkaline hydrogen evolution reaction (HER) for the first time. Theoretical analysis suggests that the induced robust electronic metal–support interaction effect in Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub> is prone to promote the charge redistribution among Ru SAs, Au NCs, and WS<sub>2</sub> MSLs support, which is beneficial to reduce the energy barrier for water adsorption and thus promoting the subsequent H<sub>2</sub> formation. As feedback, the well-designed Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub> electrocatalyst exhibits outstanding HER performance with high activity (<i>η</i> +<sub>10</sub> = 19 mV), low Tafel slope (35 mV dec<sup>−1</sup>), and excellent long-term stability. Further, in situ, experimental studies reveal that the reconstruction of Ru SAs/NCs with S vacancies in Ru<sub>1</sub>/Au<sub>n</sub>-2LWS<sub>2</sub> structure acts as the main catalytically active center, while high-valence Au NCs are responsible for activating and stabilizing Ru sites to prevent the dissolution and deactivation of active sites. This work offers guidelines for the rational design of high-performance atomic-scale electrocatalysts.</p> -Jin Cao, -Xu Wang, -Shangshu Qian, -Dongdong Zhang, -Ding Luo, -Lulu Zhang, -Jiaqian Qin, -Xinyu Zhang, -Xuelin Yang, -Jun Lu +Dechao Chen, +Tianyu Gao, +Zengxi Wei, +Mengjia Wang, +Yingfei Ma, +Dongdong Xiao, +Changsheng Cao, +Cheng‐You Lee, +Pan Liu, +Dengchao Wang, +Shuangliang Zhao, +Hsiao‐Tsu Wang, +Lili Han Research Article - De‐Passivation and Surface Crystal Plane Reconstruction via Chemical Polishing for Highly Reversible Zinc Anodes - 10.1002/adma.202410947 + WS2 Moiré Superlattices Supporting Au Nanoclusters and Isolated Ru to Boost Hydrogen Production + 10.1002/adma.202410537 Advanced Materials - 10.1002/adma.202410947 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410947 + 10.1002/adma.202410537 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410537 Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470366 - Thu, 14 Nov 2024 22:16:54 -0800 - 2024-11-14T10:16:54-08:00 - Wiley: Advanced Materials: Table of Contents - Fri, 01 Nov 2024 00:00:00 -0700 - Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470366 - Masthead: (Adv. Mater. 46/2024) - Advanced Materials, Volume 36, Issue 46, November 14, 2024. - - - - Masthead - Masthead: (Adv. Mater. 46/2024) - 10.1002/adma.202470366 - Advanced Materials - 10.1002/adma.202470366 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470366 - Masthead - 36 - 46 - - - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470364 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410568 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470364 - Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics (Adv. Mater. 46/2024) + 10.1002/adma.202410568 + Hybrid Anapole Induced Chirality in Metasurfaces Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Upcycling of Plastics -In the article number 2403728, Weipu Zhu and co‐workers report an optimal approach without additional catalysts and solvents for the upcycling of poly(ethylene terephthalate) (PET) waste. Specifically, bio‐based hydrogenated dimer acids are found to directly convert PET bottles into biodegradable copolyesters suitable for agricultural mulch films. This work provides an environmentally friendly and cost‐effective strategy for the large‐scale upcycling of PET waste. +This work presents the design of an asymmetric H‐shaped metasurface that induces hybrid anapole (HA) for achieving chiro‐optical responses. By breaking the structural symmetry, the metasurface supports both first‐order and pseudo higher‐order HA, leading to enhanced circular dichroism and polarization control. These results provide valuable insights into the fundamental study of anapole physics and have significant implications for nanophotonics applications. @@ -5224,45 +5119,45 @@ In the article number 2403728, Weipu Zhu and co‐workers report an optimal + +Abstract +The interaction between light and matter, particularly chirality, plays a pivotal role in modern science and technology. Typically, metasurfaces achieve chiro‐optical effects by coupling electric and magnetic dipoles in specific orientations. In this work, the design and optimization of an asymmetric H‐shaped metasurface is explored to induce hybrid anapole (HA) for optical activity. When the symmetry of the metasurface structure is disrupted, the design can simultaneously excite first‐order and pseudo high‐order HA under illumination with a specific circular polarization, both occurring within the same spectral regime. This results in high reflection for one circular polarization and a significant reduction in reflection for the orthogonal polarization, thereby exhibiting exceptional chiro‐optical activity. Moreover, the HA‐based chiral metasurface demonstrates strong polarization control capabilities, as verified by Stokes parameter analysis, revealing high birefringence and a pronounced dependence on the incident polarization angle. These results provide valuable insights for the design and optimization of HA metasurfaces for advanced optical applications and polarization control, paving the way for new developments in chiral nanophotonics. - <img src="https://onlinelibrary.wiley.com/cms/asset/31a80b18-ba8a-4093-bab6-fc13532c217a/adma202470364-gra-0001-m.png" - alt="Catalyst- and Solvent-Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics (Adv. Mater. 46/2024)"/> -<p><b>Upcycling of Plastics</b></p> -<p>In the article number <a href="https://doi.org/10.1002/adma.202403728">2403728</a>, Weipu Zhu and co-workers report an optimal approach without additional catalysts and solvents for the upcycling of poly(ethylene terephthalate) (PET) waste. Specifically, bio-based hydrogenated dimer acids are found to directly convert PET bottles into biodegradable copolyesters suitable for agricultural mulch films. This work provides an environmentally friendly and cost-effective strategy for the large-scale upcycling of PET waste. + <img src="https://onlinelibrary.wiley.com/cms/asset/b0270839-3c8d-460b-88d4-28f0efef4797/adma202410568-gra-0001-m.png" + alt="Hybrid Anapole Induced Chirality in Metasurfaces"/> +<p>This work presents the design of an asymmetric H-shaped metasurface that induces hybrid anapole (HA) for achieving chiro-optical responses. By breaking the structural symmetry, the metasurface supports both first-order and pseudo higher-order HA, leading to enhanced circular dichroism and polarization control. These results provide valuable insights into the fundamental study of anapole physics and have significant implications for nanophotonics applications. </p> <br/> - +<h2>Abstract</h2> +<p>The interaction between light and matter, particularly chirality, plays a pivotal role in modern science and technology. Typically, metasurfaces achieve chiro-optical effects by coupling electric and magnetic dipoles in specific orientations. In this work, the design and optimization of an asymmetric H-shaped metasurface is explored to induce hybrid anapole (HA) for optical activity. When the symmetry of the metasurface structure is disrupted, the design can simultaneously excite first-order and pseudo high-order HA under illumination with a specific circular polarization, both occurring within the same spectral regime. This results in high reflection for one circular polarization and a significant reduction in reflection for the orthogonal polarization, thereby exhibiting exceptional chiro-optical activity. Moreover, the HA-based chiral metasurface demonstrates strong polarization control capabilities, as verified by Stokes parameter analysis, revealing high birefringence and a pronounced dependence on the incident polarization angle. These results provide valuable insights for the design and optimization of HA metasurfaces for advanced optical applications and polarization control, paving the way for new developments in chiral nanophotonics.</p> -Tianxiang Fang, -Weipo Jiang, -Tengfei Zheng, -Xuxia Yao, -Weipu Zhu +Amir Hassanfiroozi, +Yen Cheng Lu, +Pin Chieh Wu - Cover Picture - Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics (Adv. Mater. 46/2024) - 10.1002/adma.202470364 + Research Article + Hybrid Anapole Induced Chirality in Metasurfaces + 10.1002/adma.202410568 Advanced Materials - 10.1002/adma.202470364 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470364 - Cover Picture + 10.1002/adma.202410568 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410568 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470365 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410815 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470365 - Multi‐Functional Biomaterial for the Treatment and Prevention of Central Line‐Associated Bloodstream Infections (Adv. Mater. 46/2024) + 10.1002/adma.202410815 + On‐Chip Synthesis of Quasi‐2D Semimetals from Multi‐Layer Chalcogenides Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Injectable Multi‐Functional Biomaterial -Catheter infections represent a major worldwide public health problem with no viable solution. In article number 2405805, Rahmi Oklu and co‐workers show that an injectable biomaterial can both prevent and treat catheter infections and promote healing of the catheter entry site. Image credit to Mike Austin, internalart.com +This work presents a generalizable approach for the on‐chip synthesis of non‐layered, nanometer‐thick, quasi‐2D semimetals from multi‐layer chalcogenides. In the exemplary case, sub‐20 nm semiconducting InSe with nickel deposited on top are subjected to a low‐temperature annealing step. This process enables a controlled transformation of the layered InSe into non‐layered, crystalline Kagome‐semimetal Ni3In2Se2 via reaction with the laterally diffusing nickel. @@ -5270,47 +5165,55 @@ Catheter infections represent a major worldwide public health problem with no vi + +Abstract +Reducing the dimensions of materials from three to two, or quasi‐two, provides a fertile platform for exploring emergent quantum phenomena and developing next‐generation electronic devices. However, growing high‐quality, ultrathin, quasi2D materials in a templated fashion on an arbitrary substrate is challenging. Here, the study demonstrates a simple and reproducible on‐chip approach for synthesizing non‐layered, nanometer‐thick, quasi‐2D semimetals. In one implementation, this method starts with thin semiconducting InSe flakes of below 20 nm in thickness with nickel deposited on top, followed by a low‐temperature annealing step that results in a controlled transformation of the layered InSe to a non‐layered, crystalline semimetal via reaction with the laterally diffusing nickel. Atomic resolution microscopy reveals the transformed semimetal to be Ni3In2Se2 with a Kagome‐lattice structure. Moreover, it is demonstrated that this synthesis method is generalizable by transforming 2D layered chalcogenides such as SnS and SnSe employing Ni and Co to non‐layered semimetals, paving the way for engineering novel types of devices. - <img src="https://onlinelibrary.wiley.com/cms/asset/0be385eb-2773-43ca-867f-0be1416f92f8/adma202470365-gra-0001-m.png" - alt="Multi-Functional Biomaterial for the Treatment and Prevention of Central Line-Associated Bloodstream Infections (Adv. Mater. 46/2024)"/> -<p><b>Injectable Multi-Functional Biomaterial</b></p> -<p>Catheter infections represent a major worldwide public health problem with no viable solution. In article number <a href="https://doi.org/10.1002/adma.202405805">2405805</a>, Rahmi Oklu and co-workers show that an injectable biomaterial can both prevent and treat catheter infections and promote healing of the catheter entry site. Image credit to Mike Austin, internalart.com + <img src="https://onlinelibrary.wiley.com/cms/asset/eae44bf1-f226-4712-a099-6e0bcb101b89/adma202410815-gra-0001-m.png" + alt="On-Chip Synthesis of Quasi-2D Semimetals from Multi-Layer Chalcogenides"/> +<p>This work presents a generalizable approach for the on-chip synthesis of non-layered, nanometer-thick, quasi-2D semimetals from multi-layer chalcogenides. In the exemplary case, sub-20 nm semiconducting InSe with nickel deposited on top are subjected to a low-temperature annealing step. This process enables a controlled transformation of the layered InSe into non-layered, crystalline Kagome-semimetal Ni<sub>3</sub>In<sub>2</sub>Se<sub>2</sub> via reaction with the laterally diffusing nickel. </p> <br/> - +<h2>Abstract</h2> +<p>Reducing the dimensions of materials from three to two, or quasi-two, provides a fertile platform for exploring emergent quantum phenomena and developing next-generation electronic devices. However, growing high-quality, ultrathin, quasi2D materials in a templated fashion on an arbitrary substrate is challenging. Here, the study demonstrates a simple and reproducible on-chip approach for synthesizing non-layered, nanometer-thick, quasi-2D semimetals. In one implementation, this method starts with thin semiconducting InSe flakes of below 20 nm in thickness with nickel deposited on top, followed by a low-temperature annealing step that results in a controlled transformation of the layered InSe to a non-layered, crystalline semimetal via reaction with the laterally diffusing nickel. Atomic resolution microscopy reveals the transformed semimetal to be Ni<sub>3</sub>In<sub>2</sub>Se<sub>2</sub> with a Kagome-lattice structure. Moreover, it is demonstrated that this synthesis method is generalizable by transforming 2D layered chalcogenides such as SnS and SnSe employing Ni and Co to non-layered semimetals, paving the way for engineering novel types of devices.</p> -Jinjoo Kim, -Hyeongseop Keum, -Hassan Albadawi, -Zefu Zhang, -Erin H. Graf, -Enes Cevik, -Rahmi Oklu +Jun Cai, +Huairuo Zhang, +Yuanqiu Tan, +Zheng Sun, +Peng Wu, +Rahul Tripathi, +Sergiy Krylyuk, +Caleb Suhy, +Jing Kong, +Albert V. Davydov, +Zhihong Chen, +Joerg Appenzeller - Inside Front Cover - Multi‐Functional Biomaterial for the Treatment and Prevention of Central Line‐Associated Bloodstream Infections (Adv. Mater. 46/2024) - 10.1002/adma.202470365 + Research Article + On‐Chip Synthesis of Quasi‐2D Semimetals from Multi‐Layer Chalcogenides + 10.1002/adma.202410815 Advanced Materials - 10.1002/adma.202470365 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470365 - Inside Front Cover + 10.1002/adma.202410815 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410815 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470367 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411004 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470367 - Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye‐Incorporated Photonic Crystal‐Based Sensor Array (Adv. Mater. 46/2024) + 10.1002/adma.202411004 + Grain Boundary Filling Empowers (002)‐Textured Zn Metal Anodes with Superior Stability Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Volatile Organic Compounds -In article number 2409297, Shu Yang and co‐workers present an innovative approach to enhance volatile organic compound (VOC) sensing by integrating dyes with colloidal photonic crystals. The broadened reflection peak allows for augmented dye absorption originating from the overlap between the photonic bandgap edge and the dye absorption peak, leading to a more noticeable color change discernible to the naked eye, eliminating the need for signal amplification. +Grain boundary wetting strategy is demonstrated to completely fill the Zn grain boundaries, while simultaneously converting the initial random‐textured Zn into a single (002)‐textured Zn. Using In as the boundary filler, the as‐received intercrystalline‐modified (002)‐textured Zn (IM(002) Zn) ensures homogeneous epitaxial Zn deposition and significantly mitigates the intergranular issues, resulting in excellent reversibility in various battery configurations. + @@ -5318,45 +5221,55 @@ In article number 2409297, Shu Yang and co‐workers present an innovative a +Abstract +Aqueous Zn battery is promising for grid‐level energy storage due to its high safety and low cost, but dendrite growth and side reactions at the Zn metal anode hinder its development. Designing Zn with (002) orientation improves the stability of the Zn anode, yet grain boundaries remain susceptible to corrosion and dendrite growth. Addressing these intergranular issues is crucial for enhancing the electrochemical performance of (002)‐textured Zn. Here, a strategy based on grain boundary wetting to fill intergranular regions and mitigate these issues is reported. By systematically investigating boundary fillers and filling conditions, In metal is chosen as the filler, and one‐step annealing is used to synergistically convert commercial Zn foils into single (002)‐textured Zn while filling In into the boundaries. The inter‐crystalline‐modified (002)‐textured Zn (IM(002) Zn) effectively inhibits corrosion and dendrite growth, resulting in excellent stability in batteries. This work offers new insights into Zn anode protection and the development of high‐energy Zn batteries. - <img src="https://onlinelibrary.wiley.com/cms/asset/16e10b02-a66c-4abc-ac7e-5f0434b3e15a/adma202470367-gra-0001-m.png" - alt="Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye-Incorporated Photonic Crystal-Based Sensor Array (Adv. Mater. 46/2024)"/> -<p><b>Volatile Organic Compounds</b></p> -<p>In article number <a href="https://doi.org/10.1002/adma.202409297">2409297</a>, Shu Yang and co-workers present an innovative approach to enhance volatile organic compound (VOC) sensing by integrating dyes with colloidal photonic crystals. The broadened reflection peak allows for augmented dye absorption originating from the overlap between the photonic bandgap edge and the dye absorption peak, leading to a more noticeable color change discernible to the naked eye, eliminating the need for signal amplification. + <img src="https://onlinelibrary.wiley.com/cms/asset/2d9431e8-6f56-428c-b5c9-34ab525bfa37/adma202411004-gra-0001-m.png" + alt="Grain Boundary Filling Empowers (002)-Textured Zn Metal Anodes with Superior Stability"/> +<p>Grain boundary wetting strategy is demonstrated to completely fill the Zn grain boundaries, while simultaneously converting the initial random-textured Zn into a single (002)-textured Zn. Using In as the boundary filler, the as-received intercrystalline-modified (002)-textured Zn (IM(002) Zn) ensures homogeneous epitaxial Zn deposition and significantly mitigates the intergranular issues, resulting in excellent reversibility in various battery configurations. </p> <br/> - +<h2>Abstract</h2> +<p>Aqueous Zn battery is promising for grid-level energy storage due to its high safety and low cost, but dendrite growth and side reactions at the Zn metal anode hinder its development. Designing Zn with (002) orientation improves the stability of the Zn anode, yet grain boundaries remain susceptible to corrosion and dendrite growth. Addressing these intergranular issues is crucial for enhancing the electrochemical performance of (002)-textured Zn. Here, a strategy based on grain boundary wetting to fill intergranular regions and mitigate these issues is reported. By systematically investigating boundary fillers and filling conditions, In metal is chosen as the filler, and one-step annealing is used to synergistically convert commercial Zn foils into single (002)-textured Zn while filling In into the boundaries. The inter-crystalline-modified (002)-textured Zn (IM(002) Zn) effectively inhibits corrosion and dendrite growth, resulting in excellent stability in batteries. This work offers new insights into Zn anode protection and the development of high-energy Zn batteries.</p> -So Hee Nah, -Jong Bin Kim, -Hiu Ning Tiffany Chui, -Yeonjoon Suh, -Shu Yang +Zibo Chen, +Yizhou Wang, +Qiang Wu, +Cheng Wang, +Qian He, +Tao Hu, +Xuran Han, +Jialu Chen, +Yu Zhang, +Jianyu Chen, +Lijun Yang, +Xuebin Wang, +Yanwen Ma, +Jin Zhao - Frontispiece - Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye‐Incorporated Photonic Crystal‐Based Sensor Array (Adv. Mater. 46/2024) - 10.1002/adma.202470367 + Research Article + Grain Boundary Filling Empowers (002)‐Textured Zn Metal Anodes with Superior Stability + 10.1002/adma.202411004 Advanced Materials - 10.1002/adma.202470367 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470367 - Frontispiece + 10.1002/adma.202411004 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411004 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470368 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411479 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470368 - Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities (Adv. Mater. 46/2024) + 10.1002/adma.202411479 + Additive‐Free Gelation of Graphene Oxide Dispersions via Mild Thermal Annealing: Implications for 3D Printing and Supercapacitor Applications Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Programmable Instabilities -The article number 2406611 by David Melancon, Katia Bertoldi, and co‐workers focuses on the highly nonlinear response of elastomeric cylindrical shells during depressurization. Instability‐driven deformations are harnessed to build soft machines capable of a programmable sequence of movements with a single actuation input. +A mild thermal annealing (MTA) process transforms graphene oxide (GO) into an additive‐free gel, significantly enhancing its rheological properties. SAXS experiments reveal the microstructural changes during MTA. The graphitic domains developed through MTA promote hydrophobic attractions, inducing a network structure. Through 3D‐printing and electrochemical experiments, MTA demonstrates potential as an optimal gelation method for GO. @@ -5364,90 +5277,104 @@ The article number 2406611 by David Melancon, Katia Bertoldi, and co‐worke - - <img src="https://onlinelibrary.wiley.com/cms/asset/cf027c89-642d-45e0-b277-d039c3af3130/adma202470368-gra-0001-m.png" - alt="Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities (Adv. Mater. 46/2024)"/> -<p><b>Programmable Instabilities</b></p> -<p>The article number <a href="https://doi.org/10.1002/adma.202406611">2406611</a> by David Melancon, Katia Bertoldi, and co-workers focuses on the highly nonlinear response of elastomeric cylindrical shells during depressurization. Instability-driven deformations are harnessed to build soft machines capable of a programmable sequence of movements with a single actuation input. -</p> -<br/> - +Abstract +Herein, a mild thermal annealing (MTA) process is presented for additive‐free gelation of graphene oxide (GO) dispersions. This process transitions the GO from a nematic liquid crystal phase to a random network structure, significantly enhancing its rheological properties by order of magnitude. This transition is facilitated by the diffusion of functional groups on the GO surface, which induces hydrophobic attractions, leading to a stable network structure. Employing rheo‐SAXS experiments, detailed insights are provided into the microstructural changes of GO gel under shear stress, establishing a direct correlation between its rheological behavior and microstructure. The distinctive properties of MTA‐processed inks are illustrated, seamlessly integrating with 3D printing, to yield a highly porous lattice structure that demonstrates promising potential as a supercapacitor electrode. The MTA process, an additive‐free approach to gelation, maintains the inherent dispersion properties of GO while offering scalability. Thus, this method brings significant economic and environmental advantages compared to conventional gelation techniques. The findings not only advance the fundamental understanding of 2D colloidal network gels but also increase the potential of GO for a wide range of applications, from gas and liquid absorbers to electrodes for energy storage and conversion, and biomedical fields. + + <img src="https://onlinelibrary.wiley.com/cms/asset/90b23329-2ad3-4325-9f46-3f8efd43c462/adma202411479-gra-0001-m.png" + alt="Additive-Free Gelation of Graphene Oxide Dispersions via Mild Thermal Annealing: Implications for 3D Printing and Supercapacitor Applications"/> +<p>A mild thermal annealing (MTA) process transforms graphene oxide (GO) into an additive-free gel, significantly enhancing its rheological properties. SAXS experiments reveal the microstructural changes during MTA. The graphitic domains developed through MTA promote hydrophobic attractions, inducing a network structure. Through 3D-printing and electrochemical experiments, MTA demonstrates potential as an optimal gelation method for GO. + +</p> +<br/> +<h2>Abstract</h2> +<p>Herein, a mild thermal annealing (MTA) process is presented for additive-free gelation of graphene oxide (GO) dispersions. This process transitions the GO from a nematic liquid crystal phase to a random network structure, significantly enhancing its rheological properties by order of magnitude. This transition is facilitated by the diffusion of functional groups on the GO surface, which induces hydrophobic attractions, leading to a stable network structure. Employing rheo-SAXS experiments, detailed insights are provided into the microstructural changes of GO gel under shear stress, establishing a direct correlation between its rheological behavior and microstructure. The distinctive properties of MTA-processed inks are illustrated, seamlessly integrating with 3D printing, to yield a highly porous lattice structure that demonstrates promising potential as a supercapacitor electrode. The MTA process, an additive-free approach to gelation, maintains the inherent dispersion properties of GO while offering scalability. Thus, this method brings significant economic and environmental advantages compared to conventional gelation techniques. The findings not only advance the fundamental understanding of 2D colloidal network gels but also increase the potential of GO for a wide range of applications, from gas and liquid absorbers to electrodes for energy storage and conversion, and biomedical fields.</p> -Yi Yang, -Helen Read, -Mohammed Sbai, -Ahmad Zareei, -Antonio Elia Forte, -David Melancon, -Katia Bertoldi +Geon Woong Kim, +Seonghyun Lee, +Guksung Kim, +Howon Lee, +Kyu Tae Lee, +So Youn Kim - Frontispiece - Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities (Adv. Mater. 46/2024) - 10.1002/adma.202470368 + Research Article + Additive‐Free Gelation of Graphene Oxide Dispersions via Mild Thermal Annealing: Implications for 3D Printing and Supercapacitor Applications + 10.1002/adma.202411479 Advanced Materials - 10.1002/adma.202470368 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470368 - Frontispiece + 10.1002/adma.202411479 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411479 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470369 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411587 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470369 - Universal Ensemble‐Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures (Adv. Mater. 46/2024) + 10.1002/adma.202411587 + Sustainable Nanofibril Interfaces for Strain‐Resilient and Multimodal Porous Bioelectronics Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Universal Ensemble‐Embedding Graph‐Neural Network -In article number 2409175, Nguyen Tuan Hung, Mingda Li, and co‐workers present a graph‐neural network architecture featuring universal embedding to predict the optical properties of materials from only crystal structures. The model performs a highly precise optical prediction at the quantum simulation level, making it suitable for various applications, from solar cells to quantum materials. +Porous, soft bioelectronics are breathable and offer long‐term biocompatibility, but face challenges in stability under stretching and sweat management. This study uses cellulose nanofibrils (CNF) as interfaces to improve strain resilience and printing quality on porous substrates. In addition, CNF‐based microfluidics enables continuous sweat monitoring, resulting in a multimodal bioelectronic system for tracking energy metabolism and consumption. + + +Abstract +Porous soft bioelectronics have attracted significant attention due to their high breathability, long‐term biocompatibility, and other unique features inaccessible in nonporous counterparts. However, fabricating high‐quality multimodal bioelectronic components that operate stably under strain on porous substrates, along with integrating microfluidics for sweat management, remains challenging. In this study, cellulose nanofibrils (CNF) are explored, biomass‐derived sustainable biomaterials, as nanofibril interfaces with unprecedented interfacial robustness to enable high‐quality printing of strain‐resilient bioelectronics on porous substrates by reducing surface roughness and creating mechanical heterogeneity. Also, CNF‐based microfluidics can provide continuous sweat collection and refreshment, crucial for accurate biochemical sensing. Building upon these advancements, a multimodal porous wearable bioelectronic system is further developed capable of simultaneously detecting electrocardiograms and glucose and beta‐hydroxybutyrate in sweat for monitoring energy metabolism and consumption. This work introduces novel strategies for fabricating high‐quality, strain‐resilient porous bioelectronics with customizable multimodalities to meet arising personalized healthcare needs. - <img src="https://onlinelibrary.wiley.com/cms/asset/694b422e-efd9-4b7d-9f7d-359e6ad094ea/adma202470369-gra-0001-m.png" - alt="Universal Ensemble-Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures (Adv. Mater. 46/2024)"/> -<p><b>Universal Ensemble-Embedding Graph-Neural Network</b></p> -<p>In article number <a href="https://doi.org/10.1002/adma.202409175">2409175</a>, Nguyen Tuan Hung, Mingda Li, and co-workers present a graph-neural network architecture featuring universal embedding to predict the optical properties of materials from only crystal structures. The model performs a highly precise optical prediction at the quantum simulation level, making it suitable for various applications, from solar cells to quantum materials. + <img src="https://onlinelibrary.wiley.com/cms/asset/a954db35-9f00-4471-af2d-306741f25720/adma202411587-gra-0001-m.png" + alt="Sustainable Nanofibril Interfaces for Strain-Resilient and Multimodal Porous Bioelectronics"/> +<p>Porous, soft bioelectronics are breathable and offer long-term biocompatibility, but face challenges in stability under stretching and sweat management. This study uses cellulose nanofibrils (CNF) as interfaces to improve strain resilience and printing quality on porous substrates. In addition, CNF-based microfluidics enables continuous sweat monitoring, resulting in a multimodal bioelectronic system for tracking energy metabolism and consumption. + </p> <br/> - +<h2>Abstract</h2> +<p>Porous soft bioelectronics have attracted significant attention due to their high breathability, long-term biocompatibility, and other unique features inaccessible in nonporous counterparts. However, fabricating high-quality multimodal bioelectronic components that operate stably under strain on porous substrates, along with integrating microfluidics for sweat management, remains challenging. In this study, cellulose nanofibrils (CNF) are explored, biomass-derived sustainable biomaterials, as nanofibril interfaces with unprecedented interfacial robustness to enable high-quality printing of strain-resilient bioelectronics on porous substrates by reducing surface roughness and creating mechanical heterogeneity. Also, CNF-based microfluidics can provide continuous sweat collection and refreshment, crucial for accurate biochemical sensing. Building upon these advancements, a multimodal porous wearable bioelectronic system is further developed capable of simultaneously detecting electrocardiograms and glucose and beta-hydroxybutyrate in sweat for monitoring energy metabolism and consumption. This work introduces novel strategies for fabricating high-quality, strain-resilient porous bioelectronics with customizable multimodalities to meet arising personalized healthcare needs.</p> -Nguyen Tuan Hung, -Ryotaro Okabe, -Abhijatmedhi Chotrattanapituk, -Mingda Li +Ganggang Zhao, +Zehua Chen, +Shaoyun Wang, +Sicheng Chen, +Feng Zhang, +Syed Muntazir Andrabi, +Yadong Xu, +Qunle Ouyang, +Milton Eric Busquets Rosas, +Xiaoyan Qian, +Jingwei Xie, +Zheng Yan - Frontispiece - Universal Ensemble‐Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures (Adv. Mater. 46/2024) - 10.1002/adma.202470369 + Research Article + Sustainable Nanofibril Interfaces for Strain‐Resilient and Multimodal Porous Bioelectronics + 10.1002/adma.202411587 Advanced Materials - 10.1002/adma.202470369 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470369 - Frontispiece + 10.1002/adma.202411587 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411587 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470370 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411942 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470370 - Customized Corneal Cross‐Linking with Microneedle‐Mediated Riboflavin Delivery for Keratoconus Treatment (Adv. Mater. 46/2024) + 10.1002/adma.202411942 + Unlocking Efficient Alkaline Hydrogen Evolution Through Ru–Sn Dual Metal Sites and a Novel Hydroxyl Spillover Effect Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Customized Corneal Cross‐Linking -ln article number 2408136, Zhongxing Chen, Xingtao Zhou, Jinhai Huang, and co‐workers introduce an innovative customized corneal cross‐linking (CXL) therapy employing microneedles (MNs) for precise riboflavin (RF) delivery achieves notable CXL effects comparable to conventional epi‐off CXL protocol and enhances visual function by flattening the corneal curvature in the treated zone. The frontispiece metaphorically represents the customized CXL process as being skillfully manipulated by magicians, highlighting the precision and efficacy of using MNs to deliver RF directly into the stroma and reinforce specific corneal zone. +A Ru–Sn/SnO2 NS electrocatalyst, with optimized Ru–Sn sites for water dissociation and hydrogen adsorption and SnO2‐induced unique hydroxyl spillover, enhances the alkaline hydrogen evolution by accelerating hydroxyl transfer and protecting active sites. + @@ -5455,58 +5382,46 @@ ln article number 2408136, Zhongxing Chen, Xingtao Zhou, Jinhai Huang, and co +Abstract +Alkaline hydrogen evolution reaction (HER) has great potential in practical hydrogen production but is still limited by the lack of active and stable electrocatalysts. Herein, the efficient water dissociation process, fast transfer of adsorbed hydroxyl and optimized hydrogen adsorption are first achieved on a cooperative electrocatalyst, named as Ru–Sn/SnO2 NS, in which the Ru–Sn dual metal sites and SnO2 heterojunction are constructed based on porous Ru nanosheet. The density functional theory (DFT) calculations and in situ infrared spectra suggest that Ru–Sn dual sites can optimize the water dissociation process and hydrogen adsorption, while the existence of SnO2 can induce the unique hydroxyl spillover effect, accelerating the hydroxyl transfer process and avoiding the poison of active sites. As results, Ru–Sn/SnO2 NS display remarkable alkaline HER performance with an extremely low overpotential (12 mV at 10 mA cm−2) and robust stability (650 h), much superior to those of Ru NS (27 mV at 10 mA cm−2 with 90 h stability) and Ru–Sn NS (16 mV at 10 mA cm−2 with 120 h stability). The work sheds new light on designing of efficient alkaline HER electrocatalyst. - <img src="https://onlinelibrary.wiley.com/cms/asset/96666f2c-52e5-4e3f-ab67-6a65b79373b3/adma202470370-gra-0001-m.png" - alt="Customized Corneal Cross-Linking with Microneedle-Mediated Riboflavin Delivery for Keratoconus Treatment (Adv. Mater. 46/2024)"/> -<p><b>Customized Corneal Cross-Linking</b></p> -<p>ln article number <a href="https://doi.org/10.1002/adma.202408136">2408136</a>, Zhongxing Chen, Xingtao Zhou, Jinhai Huang, and co-workers introduce an innovative customized corneal cross-linking (CXL) therapy employing microneedles (MNs) for precise riboflavin (RF) delivery achieves notable CXL effects comparable to conventional epi-off CXL protocol and enhances visual function by flattening the corneal curvature in the treated zone. The frontispiece metaphorically represents the customized CXL process as being skillfully manipulated by magicians, highlighting the precision and efficacy of using MNs to deliver RF directly into the stroma and reinforce specific corneal zone. + <img src="https://onlinelibrary.wiley.com/cms/asset/7937731e-f737-4bc6-8f77-e9e11d2292cc/adma202411942-gra-0001-m.png" + alt="Unlocking Efficient Alkaline Hydrogen Evolution Through Ru–Sn Dual Metal Sites and a Novel Hydroxyl Spillover Effect"/> +<p>A Ru–Sn/SnO<sub>2</sub> NS electrocatalyst, with optimized Ru–Sn sites for water dissociation and hydrogen adsorption and SnO<sub>2</sub>-induced unique hydroxyl spillover, enhances the alkaline hydrogen evolution by accelerating hydroxyl transfer and protecting active sites. </p> <br/> - +<h2>Abstract</h2> +<p>Alkaline hydrogen evolution reaction (HER) has great potential in practical hydrogen production but is still limited by the lack of active and stable electrocatalysts. Herein, the efficient water dissociation process, fast transfer of adsorbed hydroxyl and optimized hydrogen adsorption are first achieved on a cooperative electrocatalyst, named as Ru–Sn/SnO<sub>2</sub> NS, in which the Ru–Sn dual metal sites and SnO<sub>2</sub> heterojunction are constructed based on porous Ru nanosheet. The density functional theory (DFT) calculations and in situ infrared spectra suggest that Ru–Sn dual sites can optimize the water dissociation process and hydrogen adsorption, while the existence of SnO<sub>2</sub> can induce the unique hydroxyl spillover effect, accelerating the hydroxyl transfer process and avoiding the poison of active sites. As results, Ru–Sn/SnO<sub>2</sub> NS display remarkable alkaline HER performance with an extremely low overpotential (12 mV at 10 mA cm<sup>−2</sup>) and robust stability (650 h), much superior to those of Ru NS (27 mV at 10 mA cm<sup>−2</sup> with 90 h stability) and Ru–Sn NS (16 mV at 10 mA cm<sup>−2</sup> with 120 h stability). The work sheds new light on designing of efficient alkaline HER electrocatalyst.</p> -Mei Yang, -Hongxian Pan, -Tingting Chen, -Xin Chen, -Rui Ning, -Qianfang Ye, -Aodong Chen, -Jiawei Li, -Siheng Li, -Nan Zhao, -Yue Wu, -Xueyu Fu, -Keith M. Meek, -Lingxin Chen, -Xiaoying Wang, -Zhongxing Chen, -Xingtao Zhou, -Jinhai Huang +Zhen‐Tong Yan, +Shi Tao, +Juan Wang, +Xiu‐Li Lu, +Tong‐Bu Lu - Frontispiece - Customized Corneal Cross‐Linking with Microneedle‐Mediated Riboflavin Delivery for Keratoconus Treatment (Adv. Mater. 46/2024) - 10.1002/adma.202470370 + Research Article + Unlocking Efficient Alkaline Hydrogen Evolution Through Ru–Sn Dual Metal Sites and a Novel Hydroxyl Spillover Effect + 10.1002/adma.202411942 Advanced Materials - 10.1002/adma.202470370 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470370 - Frontispiece + 10.1002/adma.202411942 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411942 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470371 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411968 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470371 - Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles (Adv. Mater. 46/2024) + 10.1002/adma.202411968 + Multi‐Functional Silole Hole Transport Layer for Efficient and Stable Lead–Tin Perovskite and Tandem Solar Cells Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Microscopic Structures in Living Tumor Characterized by Magnetic Nanoparticles -The article number 2404766 by Satoshi Ot and co‐workers delves into the magnetic relaxation response of magnetic nanoparticles within tumors, unraveling insights into cancer cell distribution, stromal components, and vascularization. The intricate world of tumor microstructures is described by the combination of the non‐biological samples. Measuring magnetic relaxation time and analyzing tumor structures paves the way for non‐invasive cancer diagnostics and therapeutics using magnetic nanoparticles. +The traditional hole transport material (HTM) PEDOT: PSS is a bottleneck for long‐term stability in Sn–Pb perovskite solar cells (PSCs). This work offers an alternative means toward efficient and stable Sn–Pb PSCs using a new multi‐functional HTM Silole‐COOH, demonstrating 23.2%‐efficient single‐junction Sn–Pb PSCs, 25.8%‐efficient all‐perovskite tandems while avoiding the stability concerns associated with PEDOT: PSS. @@ -5514,48 +5429,58 @@ The article number 2404766 by Satoshi Ot and co‐workers delves into the ma + +Abstract +Despite high theoretical efficiencies and rapid improvements in performance, high‐efficiency ≈1.2 eV mixed Sn–Pb perovskite solar cells (PSCs) generally rely on poly(3,4‐ethylenedioxythiophene) polystyrenesulfonate (PEDOT: PSS) as the hole transport layer (HTL); a material that is considered to be a bottleneck for long‐term stability due to its acidity and hygroscopic nature. Seeking to replace PEDOT: PSS with an alternative HTL with improved atmospheric and thermal stability, herein, a silole derivative (Silole‐COOH) tuned with optimal electronic properties and efficient carrier transport by incorporating a carboxyl functional group is designed, which results in an optimal band alignment for hole extraction from Sn–Pb perovskites and robust air and thermal stability. Thin films composed of the Silole‐COOH exhibit superior conductivity and carrier mobility compared to PEDOT: PSS, in addition to reduced nonradiative quasi‐Fermi‐level splitting losses at the HTL/perovskite interface and improved quality of Sn–Pb perovskite. Replacement of PEDOT: PSS with Silole‐COOH leads to 23.2%‐efficient single‐junction Sn–Pb PSCs, 25.8%‐efficient all‐perovskite tandems, and long operating stability in ambient air. - <img src="https://onlinelibrary.wiley.com/cms/asset/dd3e8a01-9289-495c-bca2-4b9796d3df89/adma202470371-gra-0001-m.png" - alt="Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles (Adv. Mater. 46/2024)"/> -<p><b>Microscopic Structures in Living Tumor Characterized by Magnetic Nanoparticles</b></p> -<p>The article number <a href="https://doi.org/10.1002/adma.202404766">2404766</a> by Satoshi Ot and co-workers delves into the magnetic relaxation response of magnetic nanoparticles within tumors, unraveling insights into cancer cell distribution, stromal components, and vascularization. The intricate world of tumor microstructures is described by the combination of the non-biological samples. Measuring magnetic relaxation time and analyzing tumor structures paves the way for non-invasive cancer diagnostics and therapeutics using magnetic nanoparticles. + <img src="https://onlinelibrary.wiley.com/cms/asset/29b89e4f-fec0-410b-b88b-b9fcfe60e8f4/adma202411968-gra-0001-m.png" + alt="Multi-Functional Silole Hole Transport Layer for Efficient and Stable Lead–Tin Perovskite and Tandem Solar Cells"/> +<p>The traditional hole transport material (HTM) PEDOT: PSS is a bottleneck for long-term stability in Sn–Pb perovskite solar cells (PSCs). This work offers an alternative means toward efficient and stable Sn–Pb PSCs using a new multi-functional HTM Silole-COOH, demonstrating 23.2%-efficient single-junction Sn–Pb PSCs, 25.8%-efficient all-perovskite tandems while avoiding the stability concerns associated with PEDOT: PSS. </p> <br/> - +<h2>Abstract</h2> +<p>Despite high theoretical efficiencies and rapid improvements in performance, high-efficiency ≈1.2 eV mixed Sn–Pb perovskite solar cells (PSCs) generally rely on poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT: PSS) as the hole transport layer (HTL); a material that is considered to be a bottleneck for long-term stability due to its acidity and hygroscopic nature. Seeking to replace PEDOT: PSS with an alternative HTL with improved atmospheric and thermal stability, herein, a silole derivative (Silole-COOH) tuned with optimal electronic properties and efficient carrier transport by incorporating a carboxyl functional group is designed, which results in an optimal band alignment for hole extraction from Sn–Pb perovskites and robust air and thermal stability. Thin films composed of the Silole-COOH exhibit superior conductivity and carrier mobility compared to PEDOT: PSS, in addition to reduced nonradiative quasi-Fermi-level splitting losses at the HTL/perovskite interface and improved quality of Sn–Pb perovskite. Replacement of PEDOT: PSS with Silole-COOH leads to 23.2%-efficient single-junction Sn–Pb PSCs, 25.8%-efficient all-perovskite tandems, and long operating stability in ambient air.</p> -Satoshi Ota, -Hiroki Kosaka, -Keita Honda, -Kota Hoshino, -Haruki Goto, -Masato Futagawa, -Yasushi Takemura, -Kosuke Shimizu +Yuanjing Cai, +Aidan Maxwell, +Chongwen Li, +Eui Dae Jung, +Lewei Zeng, +Boran Kumral, +Peter Serles, +Zhan'ao Tan, +Runnan Yu, +Salvatore Boccia, +Mingxing Chen, +Cheng Jiang, +Dongcheng Chen, +Yanjiang Liu, +Zaiwei Wang, +Luke Grater - Inside Back Cover - Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles (Adv. Mater. 46/2024) - 10.1002/adma.202470371 + Research Article + Multi‐Functional Silole Hole Transport Layer for Efficient and Stable Lead–Tin Perovskite and Tandem Solar Cells + 10.1002/adma.202411968 Advanced Materials - 10.1002/adma.202470371 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470371 - Inside Back Cover + 10.1002/adma.202411968 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411968 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470372 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403626 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202470372 - Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface (Adv. Mater. 46/2024) + 10.1002/adma.202403626 + Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Methane Electrooxidation -The cover illustration represents the electrochemical oxidation of methane on ceria‐based electrodes. The concept uses an ‘infinite staircase’ to depict the challenge of water molecule production relative to carbon dioxide production ‐ a key finding of the article number 2403626 by Hyun You Kim, WooChul Jung, and co‐workers. For example, water molecules are portrayed as struggling and slowly ascending the stairs, while carbon dioxide molecules are shown energetically and rapidly moving upward. +This study clarifies methane electro‐oxidation process on ceria surfaces using Sm‐doped ceria (SDC) model thin‐film electrochemical cells, integrating impedance spectroscopy, operando X‐ray photoelectron spectroscopy, and DFT calculations. It presents definitive answers regarding ceria's electrocatalytic activity and reaction rate‐limiting steps, significantly contributing to the advancement of efficient, carbon‐neutral fuel utilization in high‐temperature solid oxide fuel cells. @@ -5563,15 +5488,18 @@ The cover illustration represents the electrochemical oxidation of methane on ce + +Abstract +Solid oxide fuel cells (SOFCs) stand out in sustainable energy systems for their unique ability to efficiently utilize hydrocarbon fuels, particularly those from carbon‐neutral sources. CeO2−δ (ceria) based oxides embedded in SOFCs are recognized for their critical role in managing hydrocarbon activation and carbon coking. However, even for the simplest hydrocarbon molecule, CH4, the mechanism of electrochemical oxidation at the ceria/gas interface is not well understood and the capability of ceria to electrochemically oxidize methane remains a topic of debate. This lack of clarity stems from the intricate design of standard metal/oxide composite electrodes and the complex nature of electrode reactions involving multiple chemical and electrochemical steps. This study presents a Sm‐doped ceria thin‐film model cell that selectively monitors CH4 direct‐electro‐oxidation on the ceria surface. Using impedance spectroscopy, operando X‐ray photoelectron spectroscopy, and density functional theory, it is unveiled that ceria surfaces facilitate C─H bond cleavage and that H2O formation is key in determining the overall reaction rate at the electrode. These insights effectively address the longstanding debate regarding the direct utilization of CH4 in SOFCs. Moreover, these findings pave the way for an optimized electrode design strategy, essential for developing high‐performance, environmentally sustainable fuel cells. - <img src="https://onlinelibrary.wiley.com/cms/asset/a75719bd-3208-4a25-a3f9-e215e6f81559/adma202470372-gra-0001-m.png" - alt="Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface (Adv. Mater. 46/2024)"/> -<p><b>Methane Electrooxidation</b></p> -<p>The cover illustration represents the electrochemical oxidation of methane on ceria-based electrodes. The concept uses an ‘infinite staircase’ to depict the challenge of water molecule production relative to carbon dioxide production - a key finding of the article number <a href="https://doi.org/10.1002/adma.202403626">2403626</a> by Hyun You Kim, WooChul Jung, and co-workers. For example, water molecules are portrayed as struggling and slowly ascending the stairs, while carbon dioxide molecules are shown energetically and rapidly moving upward. + <img src="https://onlinelibrary.wiley.com/cms/asset/7d22a316-fd6f-4fa1-a4f5-f06e0c35acbe/adma202403626-gra-0001-m.png" + alt="Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface"/> +<p>This study clarifies methane electro-oxidation process on ceria surfaces using Sm-doped ceria (SDC) model thin-film electrochemical cells, integrating impedance spectroscopy, operando X-ray photoelectron spectroscopy, and DFT calculations. It presents definitive answers regarding ceria's electrocatalytic activity and reaction rate-limiting steps, significantly contributing to the advancement of efficient, carbon-neutral fuel utilization in high-temperature solid oxide fuel cells. </p> <br/> - +<h2>Abstract</h2> +<p>Solid oxide fuel cells (SOFCs) stand out in sustainable energy systems for their unique ability to efficiently utilize hydrocarbon fuels, particularly those from carbon-neutral sources. CeO<sub>2−δ</sub> (ceria) based oxides embedded in SOFCs are recognized for their critical role in managing hydrocarbon activation and carbon coking. However, even for the simplest hydrocarbon molecule, CH<sub>4</sub>, the mechanism of electrochemical oxidation at the ceria/gas interface is not well understood and the capability of ceria to electrochemically oxidize methane remains a topic of debate. This lack of clarity stems from the intricate design of standard metal/oxide composite electrodes and the complex nature of electrode reactions involving multiple chemical and electrochemical steps. This study presents a Sm-doped ceria thin-film model cell that selectively monitors CH<sub>4</sub> direct-electro-oxidation on the ceria surface. Using impedance spectroscopy, operando X-ray photoelectron spectroscopy, and density functional theory, it is unveiled that ceria surfaces facilitate C─H bond cleavage and that H<sub>2</sub>O formation is key in determining the overall reaction rate at the electrode. These insights effectively address the longstanding debate regarding the direct utilization of CH<sub>4</sub> in SOFCs. Moreover, these findings pave the way for an optimized electrode design strategy, essential for developing high-performance, environmentally sustainable fuel cells.</p> Yoonseok Choi, Hyunwoo Ha, @@ -5585,28 +5513,28 @@ Graeme Henkelman, Hyun You Kim, WooChul Jung - Back Cover - Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface (Adv. Mater. 46/2024) - 10.1002/adma.202470372 + Research Article + Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface + 10.1002/adma.202403626 Advanced Materials - 10.1002/adma.202470372 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202470372 - Back Cover + 10.1002/adma.202403626 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403626 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409663 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403728 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202409663 - Nanosonosensitizer Optimization for Enhanced Sonodynamic Disease Treatment + 10.1002/adma.202403728 + Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The review summarizes, discusses, and highlights the latest optimization strategies for nanosonosensitizers in sonodynamic therapy, emphasizing their high potential for treating tumors, bacterial infections, atherosclerosis, and autoimmune disorders. This review also discusses the biosafety and biocompatibility of these nanosonosensitizers for guaranteeing the clinical translation, which further provides an overview of facing challenges and emerging opportunities in nanosonosensitizer‐enabled sonodynamic therapy, aiming to promote its clinical implementation. +An optimal approach without the need for additional catalysts or solvents for the upcycling of poly(ethylene terephthalate) (PET) waste is reported. Specifically, bio‐based hydrogenated dimer acids are found to directly convert PET bottles into biodegradable copolyesters suitable for agricultural mulch films. This work provides an environmentally friendly and cost‐effective strategy for the large‐scale upgrading and reprocessing of PET waste. @@ -5616,48 +5544,45 @@ The review summarizes, discusses, and highlights the latest optimization strateg Abstract -Low‐intensity ultrasound‐mediated sonodynamic therapy (SDT), which, by design, integrates sonosensitizers and molecular oxygen to generate therapeutic substances (e.g., toxic hydroxyl radicals, superoxide anions, or singlet oxygen) at disease sites, has shown enormous potential for the effective treatment of a variety of diseases. Nanoscale sonosensitizers play a crucial role in the SDT process because their structural, compositional, physicochemical, and biological characteristics are key determinants of therapeutic efficacy. In particular, advances in materials science and nanotechnology have invigorated a series of optimization strategies for augmenting the therapeutic efficacy of nanosonosensitizers. This comprehensive review systematically summarizes, discusses, and highlights state‐of‐the‐art studies on the current achievements of nanosonosensitizer optimization in enhanced sonodynamic disease treatment, with an emphasis on the general design principles of nanosonosensitizers and their optimization strategies, mainly including organic and inorganic nanosonosensitizers. Additionally, recent advancements in optimized nanosonosensitizers for therapeutic applications aimed at treating various diseases, such as cancer, bacterial infections, atherosclerosis, and autoimmune diseases, are clarified in detail. Furthermore, the biological effects of the improved nanosonosensitizers for versatile SDT applications are thoroughly discussed. The review concludes by highlighting the current challenges and future opportunities in this rapidly evolving research field to expedite its practical clinical translation and application. +Poly(ethylene terephthalate) (PET) is an important polymer with annual output second only to polyethylene. Due to its low biodegradability, a large amount of PET is recycled for sustainable development. However, current strategies for PET recycling are limited by low added value or small product scale. It is urgent to make a breakthrough on the principle of PET macromolecular reaction and efficiently prepare products with high added value and wide applications. Here, the catalyst‐ and solvent‐free synthesis of biodegradable plastics are reported through novel carboxyl‐ester transesterification between PET waste and bio‐based hydrogenated dimer acid (HDA), which can directly substitute some terephthalic acid (TPA) units in PET chain by HDA unit. This macromolecular reaction can be facilely carried out on current equipment in the polyester industry without any additional catalyst and solvent, thus enabling low‐cost and large‐scale production. Furthermore, the product semi‐bio‐based copolyester shows excellent mechanical properties, regulable flexibility and good biodegradability, which is expected to substitute poly(butylene adipate‐co‐terephthalate) (PBAT) plastic as high value‐added biodegradable materials. This work provides an environmental‐friendly and economic strategy for the large‐scale upcycling of PET waste. - <img src="https://onlinelibrary.wiley.com/cms/asset/65f009b8-456e-44dd-b34e-8d5bd9e1b16d/adma202409663-gra-0001-m.png" - alt="Nanosonosensitizer Optimization for Enhanced Sonodynamic Disease Treatment"/> -<p>The review summarizes, discusses, and highlights the latest optimization strategies for nanosonosensitizers in sonodynamic therapy, emphasizing their high potential for treating tumors, bacterial infections, atherosclerosis, and autoimmune disorders. This review also discusses the biosafety and biocompatibility of these nanosonosensitizers for guaranteeing the clinical translation, which further provides an overview of facing challenges and emerging opportunities in nanosonosensitizer-enabled sonodynamic therapy, aiming to promote its clinical implementation. + <img src="https://onlinelibrary.wiley.com/cms/asset/908da09f-f571-4b03-afdc-e0291bea3808/adma202403728-gra-0001-m.png" + alt="Catalyst- and Solvent-Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics"/> +<p>An optimal approach without the need for additional catalysts or solvents for the upcycling of poly(ethylene terephthalate) (PET) waste is reported. Specifically, bio-based hydrogenated dimer acids are found to directly convert PET bottles into biodegradable copolyesters suitable for agricultural mulch films. This work provides an environmentally friendly and cost-effective strategy for the large-scale upgrading and reprocessing of PET waste. </p> <br/> <h2>Abstract</h2> -<p>Low-intensity ultrasound-mediated sonodynamic therapy (SDT), which, by design, integrates sonosensitizers and molecular oxygen to generate therapeutic substances (e.g., toxic hydroxyl radicals, superoxide anions, or singlet oxygen) at disease sites, has shown enormous potential for the effective treatment of a variety of diseases. Nanoscale sonosensitizers play a crucial role in the SDT process because their structural, compositional, physicochemical, and biological characteristics are key determinants of therapeutic efficacy. In particular, advances in materials science and nanotechnology have invigorated a series of optimization strategies for augmenting the therapeutic efficacy of nanosonosensitizers. This comprehensive review systematically summarizes, discusses, and highlights state-of-the-art studies on the current achievements of nanosonosensitizer optimization in enhanced sonodynamic disease treatment, with an emphasis on the general design principles of nanosonosensitizers and their optimization strategies, mainly including organic and inorganic nanosonosensitizers. Additionally, recent advancements in optimized nanosonosensitizers for therapeutic applications aimed at treating various diseases, such as cancer, bacterial infections, atherosclerosis, and autoimmune diseases, are clarified in detail. Furthermore, the biological effects of the improved nanosonosensitizers for versatile SDT applications are thoroughly discussed. The review concludes by highlighting the current challenges and future opportunities in this rapidly evolving research field to expedite its practical clinical translation and application.</p> +<p>Poly(ethylene terephthalate) (PET) is an important polymer with annual output second only to polyethylene. Due to its low biodegradability, a large amount of PET is recycled for sustainable development. However, current strategies for PET recycling are limited by low added value or small product scale. It is urgent to make a breakthrough on the principle of PET macromolecular reaction and efficiently prepare products with high added value and wide applications. Here, the catalyst- and solvent-free synthesis of biodegradable plastics are reported through novel carboxyl-ester transesterification between PET waste and bio-based hydrogenated dimer acid (HDA), which can directly substitute some terephthalic acid (TPA) units in PET chain by HDA unit. This macromolecular reaction can be facilely carried out on current equipment in the polyester industry without any additional catalyst and solvent, thus enabling low-cost and large-scale production. Furthermore, the product semi-bio-based copolyester shows excellent mechanical properties, regulable flexibility and good biodegradability, which is expected to substitute poly(butylene adipate-<i>co</i>-terephthalate) (PBAT) plastic as high value-added biodegradable materials. This work provides an environmental-friendly and economic strategy for the large-scale upcycling of PET waste.</p> -Min Zhang, -Dandan Sun, -Hui Huang, -Dayan Yang, -Xinran Song, -Wei Feng, -Xiangxiang Jing, -Yu Chen +Tianxiang Fang, +Weipo Jiang, +Tengfei Zheng, +Xuxia Yao, +Weipu Zhu - Review - Nanosonosensitizer Optimization for Enhanced Sonodynamic Disease Treatment - 10.1002/adma.202409663 + Research Article + Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics + 10.1002/adma.202403728 Advanced Materials - 10.1002/adma.202409663 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202409663 - Review + 10.1002/adma.202403728 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202403728 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410704 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407437 Thu, 14 Nov 2024 22:16:54 -0800 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents Fri, 01 Nov 2024 00:00:00 -0700 Fri, 01 Nov 2024 00:00:00 -0700 - 10.1002/adma.202410704 - Routes to Bidirectional Cathodes for Reversible Aprotic Alkali Metal–CO2 Batteries + 10.1002/adma.202407437 + Real Topological Phonons in 3D Carbon Allotropes Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This review summarizes the CO2 conversion reaction mechanisms and the “engineering strategies from internal catalyst to the external environment–cathode properties–CO2 conversion reaction kinetics and mechanisms–batteries performance” relationship through calculation and experiment results, to provide routes to bidirectional cathodes for reversible aprotic alkali metal–CO2 batteries and other gas batteries. +The findings indicate that among the 1661 3D carbon allotropes in the Samara Carbon Allotrope Database (SACADA), 79 possess a phononic real Chern insulating (PRCI) state, 2 possess a phononic real nodal line (PRNL) state, 12 possess a phononic real Dirac point (PRDP) state, and 10 possess a phononic real triple‐point pair (PRTPP) state, respectively. The real topology of PRCI, PRNL, PRDP, and PRTTP states in 3D carbon allotropes is manifested in the second‐order phononic hinge states. @@ -5667,49 +5592,49 @@ This review summarizes the CO2 conversion reaction mechanisms and the “eng Abstract -Aprotic alkali metal–CO2 batteries (AAMCBs) have garnered significant interest owing to fixing CO2 and providing large energy storage capacity. The practical implementation of AAMCBs is constrained by the sluggish kinetics of the CO2 reduction reaction (CO2RR) and the CO2 evolution reaction (CO2ER). Because the CO2ER and CO2RR take place on the cathode, which connects the internal catalyst with the external environment. Building a bidirectional cathode with excellent CO2ER and CO2RR kinetics by optimizing the cathode's internal catalyst and environment has attracted most of the attention to improving the electrochemical performance of AAMCBs. However, there remains a lack of comprehensive understanding. This review aims to give a route to bidirectional cathodes for reversible AAMCBs, by systematically discussing engineering strategies of both the internal catalyst (atomic, nanoscopic, and macroscopic levels) and the external environment (photo, photo‐thermal, and force field). The CO2ER and CO2RR mechanisms and the “engineering strategies from internal catalyst to the external environment–cathode properties–CO2RR and CO2ER kinetics and mechanisms–batteries performance” relationship are elucidated by combining computational and experimental approaches. This review establishes a fundamental understanding for designing bidirectional cathodes and gives a route for developing reversible AAMCBs and similar metal–gas battery systems. +There has been a significant focus on real topological systems that enjoy space‐time inversion symmetry and lack spin‐orbit coupling. While the theoretical classification of the real topology has been established, more progress has yet to be made in the materials realization of real topological phononic states in 3D. To address this crucial issue, high‐throughput computing is performed to inspect the real topology in the phonon spectrums of the 3D carbon allotropes. Among 1661 carbon allotropes listed in the Samara Carbon Allotrope Database (SACADA), 79 candidates host a phononic real Chern insulating (PRCI) state, 2 candidates host a phononic real nodal line (PRNL) state, 12 candidates host a phononic real Dirac point (PRDP) state, and 10 candidates host a phononic real triple‐point pair (PRTPP) state. The PRCI, PRNL, PRTPP, and PRDP states of 27‐SG. 166‐pcu‐h, 1081‐SG. 194‐42T13‐CA, 52‐SG. 141‐gis, and 132‐SG. 191‐3,4T157 are exhibited as illustrative examples, and the second‐order phononic hinge modes are explored. This study broadens the understanding of 3D topological phonons and expands the material candidates with phononic hinge modes and phononic real topology. - <img src="https://onlinelibrary.wiley.com/cms/asset/a177e1a8-5c7d-408a-a3fe-b7064896370c/adma202410704-gra-0001-m.png" - alt="Routes to Bidirectional Cathodes for Reversible Aprotic Alkali Metal–CO2 Batteries"/> -<p>This review summarizes the CO<sub>2</sub> conversion reaction mechanisms and the “engineering strategies from internal catalyst to the external environment–cathode properties–CO<sub>2</sub> conversion reaction kinetics and mechanisms–batteries performance” relationship through calculation and experiment results, to provide routes to bidirectional cathodes for reversible aprotic alkali metal–CO<sub>2</sub> batteries and other gas batteries. + <img src="https://onlinelibrary.wiley.com/cms/asset/746bcfc9-a33f-483d-993c-6cc47210462b/adma202407437-gra-0001-m.png" + alt="Real Topological Phonons in 3D Carbon Allotropes"/> +<p>The findings indicate that among the 1661 3D carbon allotropes in the Samara Carbon Allotrope Database (SACADA), 79 possess a phononic real Chern insulating (PRCI) state, 2 possess a phononic real nodal line (PRNL) state, 12 possess a phononic real Dirac point (PRDP) state, and 10 possess a phononic real triple-point pair (PRTPP) state, respectively. The real topology of PRCI, PRNL, PRDP, and PRTTP states in 3D carbon allotropes is manifested in the second-order phononic hinge states. </p> <br/> <h2>Abstract</h2> -<p>Aprotic alkali metal–CO<sub>2</sub> batteries (AAMCBs) have garnered significant interest owing to fixing CO<sub>2</sub> and providing large energy storage capacity. The practical implementation of AAMCBs is constrained by the sluggish kinetics of the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) and the CO<sub>2</sub> evolution reaction (CO<sub>2</sub>ER). Because the CO<sub>2</sub>ER and CO<sub>2</sub>RR take place on the cathode, which connects the internal catalyst with the external environment. Building a bidirectional cathode with excellent CO<sub>2</sub>ER and CO<sub>2</sub>RR kinetics by optimizing the cathode's internal catalyst and environment has attracted most of the attention to improving the electrochemical performance of AAMCBs. However, there remains a lack of comprehensive understanding. This review aims to give a route to bidirectional cathodes for reversible AAMCBs, by systematically discussing engineering strategies of both the internal catalyst (atomic, nanoscopic, and macroscopic levels) and the external environment (photo, photo-thermal, and force field). The CO<sub>2</sub>ER and CO<sub>2</sub>RR mechanisms and the “engineering strategies from internal catalyst to the external environment–cathode properties–CO<sub>2</sub>RR and CO<sub>2</sub>ER kinetics and mechanisms–batteries performance” relationship are elucidated by combining computational and experimental approaches. This review establishes a fundamental understanding for designing bidirectional cathodes and gives a route for developing reversible AAMCBs and similar metal–gas battery systems.</p> +<p>There has been a significant focus on real topological systems that enjoy space-time inversion symmetry and lack spin-orbit coupling. While the theoretical classification of the real topology has been established, more progress has yet to be made in the materials realization of real topological phononic states in 3D. To address this crucial issue, high-throughput computing is performed to inspect the real topology in the phonon spectrums of the 3D carbon allotropes. Among 1661 carbon allotropes listed in the Samara Carbon Allotrope Database (SACADA), 79 candidates host a phononic real Chern insulating (PRCI) state, 2 candidates host a phononic real nodal line (PRNL) state, 12 candidates host a phononic real Dirac point (PRDP) state, and 10 candidates host a phononic real triple-point pair (PRTPP) state. The PRCI, PRNL, PRTPP, and PRDP states of 27-SG. 166-pcu-h, 1081-SG. 194-4<sup>2</sup>T13-CA, 52-SG. 141-gis, and 132-SG. 191-3,4T157 are exhibited as illustrative examples, and the second-order phononic hinge modes are explored. This study broadens the understanding of 3D topological phonons and expands the material candidates with phononic hinge modes and phononic real topology.</p> -Yihao Cheng, -Yuxuan Wang, -Biao Chen, -Xiaopeng Han, -Fang He, -Chunnian He, -Wenbin Hu, -Guangmin Zhou, -Naiqin Zhao +Xiaotian Wang, +Jingbo Bai, +Jianhua Wang, +Zhenxiang Cheng, +Shifeng Qian, +Wenhong Wang, +Gang Zhang, +Zhi‐Ming Yu, +Yugui Yao - Review - Routes to Bidirectional Cathodes for Reversible Aprotic Alkali Metal–CO2 Batteries - 10.1002/adma.202410704 + Research Article + Real Topological Phonons in 3D Carbon Allotropes + 10.1002/adma.202407437 Advanced Materials - 10.1002/adma.202410704 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410704 - Review + 10.1002/adma.202407437 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407437 + Research Article 36 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411449 - Thu, 14 Nov 2024 21:20:48 -0800 - 2024-11-14T09:20:48-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408448 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202411449 - Plasticizer Design Principle of “Like Dissolves Like”: Semiconductor Fluid Plasticized Stretchable Fully π‐Conjugated Polymers Films for Uniform Large‐Area and Flexible Deep‐Blue Polymer Light‐Emitting Diodes - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202408448 + Solution‐Processed Micro‐Nanostructured Electron Transport Layer via Bubble‐Assisted Assembly for Efficient Perovskite Photovoltaics + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -“Like Dissolves Like” design principle is established to prepare semiconductor fluid plasticizers for the preparation of intrinsically stretchable FπCPs films in flexible electronics. Model matched nonpolar M1 plasticizer is achieved to obtain stretchable PFO blended films. Plasticized PFO film presents an efficient, narrowband and stable deep‐blue emission, uniform morphology, and excellent intrinsic stretchability for the fabrication of deep‐blue FPLEDs. +The unbalanced diffusion lengths of photogenerated electrons and holes in formamidine (FA)‐based perovskite materials facilitate the charge recombination. Here, ordered SnO2 micro‐nanoarrays are constructed by a bubble‐assisted printing method and serve as “speedway” for electron transport in perovskite photovoltaics. Perovskite layers embedded with SnO2 arrays result in reduced charge recombination and improved power conversion efficiency in perovskite solar cells. @@ -5719,50 +5644,53 @@ Naiqin Zhao Abstract -Physical blending of fully π‐conjugated polymers (FπCPs) is an effective strategy to achieve intrinsically stretchable films for the fabrication of flexible optoelectronic devices, but easily causes phase separation, nonuniform morphology and uncontrollable photo‐electronic processing. This may cause low efficiency, unstable and nonuniform emission, and poor color purity, which are undesirable for deep‐blue flexible polymer light‐emitting diodes (FPLEDs). Herein, a “Like Dissolves Like” design principle to prepare semiconductor fluid plasticizers (SFPs) is established and intrinsically stretchable FπCPs films via external plasticization for high‐performance deep‐blue FPLEDs are developed. Three fundamental requirements are proposed, “similar conjugated skeleton, similar molecular polarity, and similar electronic structures,” to prepare model‐matched nonpolar M1 and polar M2 plasticizers for poly(9,9‐dioctylfluorene) (PFO). Large‐area plasticized PFO films exhibit an efficient, narrowband, and stable ultra‐deep‐blue electroluminescence (FWHM < 40 nm, CIE: 0.12, 0.04), uniform morphology, and excellent intrinsic stretchability (fracture strain >20% and crack‐onset strain >120%). Efficient and uniform deep‐blue FPLEDs based on stretchable PFO films are fabricated with a high brightness of ≈3000 cd cm−2. Finally, blended PFO films exhibit outstanding stretch‐deformation cycling stability of their deep‐blue electroluminescent behavior, confirming the effectiveness of the “Like Dissolves Like” principle to design matched SFPs for stretchable FπCP films in flexible electronics. +Organic–inorganic halide perovskite solar cells (PSCs) have attracted significant attention in photovoltaic research, owing to their superior optoelectronic properties and cost‐effective manufacturing techniques. However, the unbalanced charge carrier diffusion length in perovskite materials leads to the recombination of photogenerated electrons and holes. The inefficient charge carrier collecting process severely affects the power conversion efficiency (PCE) of the PSCs. Herein, a solution‐processed SnO2 array electron transport layer with precisely tunable micro‐nanostructures is fabricated via a bubble‐template‐assisted approach, serving as both electron transport layers and scaffolds for the perovskite layer. Due to the optimized electron transporting pathway and enlarged perovskite grain size, the PSCs achieve a PCE of 25.35% (25.07% certificated PCE). - <img src="https://onlinelibrary.wiley.com/cms/asset/44e73300-920b-4add-b0fd-b1965db367c9/adma202411449-gra-0001-m.png" - alt="Plasticizer Design Principle of “Like Dissolves Like”: Semiconductor Fluid Plasticized Stretchable Fully π-Conjugated Polymers Films for Uniform Large-Area and Flexible Deep-Blue Polymer Light-Emitting Diodes"/> -<p>“Like Dissolves Like” design principle is established to prepare semiconductor fluid plasticizers for the preparation of intrinsically stretchable FπCPs films in flexible electronics. Model matched nonpolar M1 plasticizer is achieved to obtain stretchable PFO blended films. Plasticized PFO film presents an efficient, narrowband and stable deep-blue emission, uniform morphology, and excellent intrinsic stretchability for the fabrication of deep-blue FPLEDs. + <img src="https://onlinelibrary.wiley.com/cms/asset/d4d15568-be05-4ab0-83a1-fc418e2398b2/adma202408448-gra-0001-m.png" + alt="Solution-Processed Micro-Nanostructured Electron Transport Layer via Bubble-Assisted Assembly for Efficient Perovskite Photovoltaics"/> +<p>The unbalanced diffusion lengths of photogenerated electrons and holes in formamidine (FA)-based perovskite materials facilitate the charge recombination. Here, ordered SnO<sub>2</sub> micro-nanoarrays are constructed by a bubble-assisted printing method and serve as “speedway” for electron transport in perovskite photovoltaics. Perovskite layers embedded with SnO<sub>2</sub> arrays result in reduced charge recombination and improved power conversion efficiency in perovskite solar cells. </p> <br/> <h2>Abstract</h2> -<p>Physical blending of fully π-conjugated polymers (FπCPs) is an effective strategy to achieve intrinsically stretchable films for the fabrication of flexible optoelectronic devices, but easily causes phase separation, nonuniform morphology and uncontrollable photo-electronic processing. This may cause low efficiency, unstable and nonuniform emission, and poor color purity, which are undesirable for deep-blue flexible polymer light-emitting diodes (FPLEDs). Herein, a “Like Dissolves Like” design principle to prepare semiconductor fluid plasticizers (SFPs) is established and intrinsically stretchable FπCPs films via external plasticization for high-performance deep-blue FPLEDs are developed. Three fundamental requirements are proposed, “similar conjugated skeleton, similar molecular polarity, and similar electronic structures,” to prepare model-matched nonpolar M1 and polar M2 plasticizers for poly(9,9-dioctylfluorene) (PFO). Large-area plasticized PFO films exhibit an efficient, narrowband, and stable ultra-deep-blue electroluminescence (FWHM &lt; 40 nm, CIE: 0.12, 0.04), uniform morphology, and excellent intrinsic stretchability (fracture strain &gt;20% and crack-onset strain &gt;120%). Efficient and uniform deep-blue FPLEDs based on stretchable PFO films are fabricated with a high brightness of ≈3000 cd cm<sup>−2</sup>. Finally, blended PFO films exhibit outstanding stretch-deformation cycling stability of their deep-blue electroluminescent behavior, confirming the effectiveness of the “Like Dissolves Like” principle to design matched SFPs for stretchable FπCP films in flexible electronics.</p> +<p>Organic–inorganic halide perovskite solar cells (PSCs) have attracted significant attention in photovoltaic research, owing to their superior optoelectronic properties and cost-effective manufacturing techniques. However, the unbalanced charge carrier diffusion length in perovskite materials leads to the recombination of photogenerated electrons and holes. The inefficient charge carrier collecting process severely affects the power conversion efficiency (PCE) of the PSCs. Herein, a solution-processed SnO<sub>2</sub> array electron transport layer with precisely tunable micro-nanostructures is fabricated via a bubble-template-assisted approach, serving as both electron transport layers and scaffolds for the perovskite layer. Due to the optimized electron transporting pathway and enlarged perovskite grain size, the PSCs achieve a PCE of 25.35% (25.07% certificated PCE).</p> -Jingyao Ma, -Man Xu, -Zhiqiang Zhuo, -Kuande Wang, -Qianyi Li, -Hao Li, -Quanyou Feng, -Wenyu Chen, -Ningning Yu, -Mengyuan Li, -Linghai Xie, -Jinyi Lin +Yongrui Yang, +Fanyi Min, +Yiyang Wang, +Lutong Guo, +Haoran Long, +Zhiyuan Qu, +Kun Zhang, +Yang Wang, +Juehan Yang, +Yu Chen, +Lei Meng, +Yali Qiao, +Yanlin Song Research Article - Plasticizer Design Principle of “Like Dissolves Like”: Semiconductor Fluid Plasticized Stretchable Fully π‐Conjugated Polymers Films for Uniform Large‐Area and Flexible Deep‐Blue Polymer Light‐Emitting Diodes - 10.1002/adma.202411449 + Solution‐Processed Micro‐Nanostructured Electron Transport Layer via Bubble‐Assisted Assembly for Efficient Perovskite Photovoltaics + 10.1002/adma.202408448 Advanced Materials - 10.1002/adma.202411449 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411449 + 10.1002/adma.202408448 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408448 Research Article + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407156 - Thu, 14 Nov 2024 21:20:20 -0800 - 2024-11-14T09:20:20-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409142 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202407156 - Biocooperative Regenerative Materials by Harnessing Blood‐Clotting and Peptide Self‐Assembly - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202409142 + Untethered & Stiffness‐Tunable Ferromagnetic Liquid Robots for Cleaning Thrombus in Complex Blood Vessels + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Nature has evolved to repair small fractures by leveraging the cellular and molecular components of regenerative hematoma (RH). This study introduces a biocooperative material approach that enables the use of key endogenous molecules and processes to engineer living regenerative biomaterials with tuneable structural and biological properties. in vitro and in vivo validation is demonstrated. +In this study, a ferromagnetic liquid robot (FMLR) with tunable modulus (0.1–2018 Pa) applied to thrombus removal in complex blood vessels is developed. Besides, in medical robotic applications, FMLR can be used in telerobotic neurointerventional. This study introduces an efficient approach for thrombus elimination, broadening the utilization of FMLRs within the realm of clinical medicine. @@ -5772,49 +5700,50 @@ Nature has evolved to repair small fractures by leveraging the cellular and mole Abstract -The immune system has evolved to heal small ruptures and fractures with remarkable efficacy through regulation of the regenerative hematoma (RH); a rich and dynamic environment that coordinates numerous molecular and cellular processes to achieve complete repair. Here, a biocooperative approach that harnesses endogenous molecules and natural healing to engineer personalized regenerative materials is presented. Peptide amphiphiles (PAs) are co‐assembled with blood components during coagulation to engineer a living material that exhibits key compositional and structural properties of the RH. By exploiting non‐selective and selective PA‐blood interactions, the material can be immediately manipulated, mechanically‐tuned, and 3D printed. The material preserves normal platelet behavior, generates and provides a continuous source of growth factors, and promotes in vitro growth of mesenchymal stromal cells, endothelial cells, and fibroblasts. Furthermore, using a personalized autologous approach to convert whole blood into PA‐blood gel implants, bone regeneration is shown in a critical‐sized rat calvarial defect. This study provides proof‐of‐concept for a biocooperative approach that goes beyond biomimicry by using mechanisms that Nature has evolved to heal as tools to engineer accessible, personalized, and regenerative biomaterials that can be readily formed at point of use. +Thrombosis is a significant threat to human health. However, the existing clinical treatment methods have limitations. Magnetic soft matter is used in the biomedical field for years, and ferromagnetic liquids exhibit tunable stiffness and on‐demand movement advantages under magnetic fields. In this study, a ferromagnetic liquid robot (FMLR) is developed and applied it to thrombus removal in complex blood vessels. The FMLR consisted of Fe3O4 magnetic nanoparticles and dimethyl silicone oil. The FMLR can pass through a narrow complex maze through shape deformation by tailoring the intensity and direction of the external magnetic field. Finite element simulation analysis is used to validate the mechanism of controllable FMLR movements. Importantly, the storage modulus of FMLR can be tuned from 0.1 to 2018 Pa by varying the external magnetic intensity, ensuring its effectiveness in removing rigid and stubborn thrombi present on the vascular walls. Toward medical robotic applications, FMLR can be used in telerobotic neurointerventional. Experiments demonstrating the capability of FMLR to remove thrombi in the ear veins of rabbits are conducted. This study introduces an efficient approach for thrombus elimination, broadening the utilization of FMLRs within the realm of clinical medicine. - <img src="https://onlinelibrary.wiley.com/cms/asset/5d347ea1-7a79-419e-8cba-3d5a99599cfc/adma202407156-gra-0001-m.png" - alt="Biocooperative Regenerative Materials by Harnessing Blood-Clotting and Peptide Self-Assembly"/> -<p>Nature has evolved to repair small fractures by leveraging the cellular and molecular components of regenerative hematoma (RH). This study introduces a biocooperative material approach that enables the use of key endogenous molecules and processes to engineer living regenerative biomaterials with tuneable structural and biological properties. in vitro and in vivo validation is demonstrated. + <img src="https://onlinelibrary.wiley.com/cms/asset/2d226df9-9bce-4bdf-8fb0-15a9978876f0/adma202409142-gra-0001-m.png" + alt="Untethered &amp; Stiffness-Tunable Ferromagnetic Liquid Robots for Cleaning Thrombus in Complex Blood Vessels"/> +<p>In this study, a ferromagnetic liquid robot (FMLR) with tunable modulus (0.1–2018 Pa) applied to thrombus removal in complex blood vessels is developed. Besides, in medical robotic applications, FMLR can be used in telerobotic neurointerventional. This study introduces an efficient approach for thrombus elimination, broadening the utilization of FMLRs within the realm of clinical medicine. </p> <br/> <h2>Abstract</h2> -<p>The immune system has evolved to heal small ruptures and fractures with remarkable efficacy through regulation of the regenerative hematoma (RH); a rich and dynamic environment that coordinates numerous molecular and cellular processes to achieve complete repair. Here, a biocooperative approach that harnesses endogenous molecules and natural healing to engineer personalized regenerative materials is presented. Peptide amphiphiles (PAs) are co-assembled with blood components during coagulation to engineer a living material that exhibits key compositional and structural properties of the RH. By exploiting non-selective and selective PA-blood interactions, the material can be immediately manipulated, mechanically-tuned, and 3D printed. The material preserves normal platelet behavior, generates and provides a continuous source of growth factors, and promotes in vitro growth of mesenchymal stromal cells, endothelial cells, and fibroblasts. Furthermore, using a personalized autologous approach to convert whole blood into PA-blood gel implants, bone regeneration is shown in a critical-sized rat calvarial defect. This study provides proof-of-concept for a biocooperative approach that goes beyond biomimicry by using mechanisms that Nature has evolved to heal as tools to engineer accessible, personalized, and regenerative biomaterials that can be readily formed at point of use.</p> +<p>Thrombosis is a significant threat to human health. However, the existing clinical treatment methods have limitations. Magnetic soft matter is used in the biomedical field for years, and ferromagnetic liquids exhibit tunable stiffness and on-demand movement advantages under magnetic fields. In this study, a ferromagnetic liquid robot (FMLR) is developed and applied it to thrombus removal in complex blood vessels. The FMLR consisted of Fe<sub>3</sub>O<sub>4</sub> magnetic nanoparticles and dimethyl silicone oil. The FMLR can pass through a narrow complex maze through shape deformation by tailoring the intensity and direction of the external magnetic field. Finite element simulation analysis is used to validate the mechanism of controllable FMLR movements. Importantly, the storage modulus of FMLR can be tuned from 0.1 to 2018 Pa by varying the external magnetic intensity, ensuring its effectiveness in removing rigid and stubborn thrombi present on the vascular walls. Toward medical robotic applications, FMLR can be used in telerobotic neurointerventional. Experiments demonstrating the capability of FMLR to remove thrombi in the ear veins of rabbits are conducted. This study introduces an efficient approach for thrombus elimination, broadening the utilization of FMLRs within the realm of clinical medicine.</p> -Soraya Padilla‐Lopategui, -Cosimo Ligorio, -Wenhuan Bu, -Chengcheng Yin, -Domenico Laurenza, -Carlos Redondo, -Robert Owen, -Hongchen Sun, -Felicity R.A.J. Rose, -Thomas Iskratsch, -Alvaro Mata +Zhuofan Li, +Shanfei Zhang, +Qi Wang, +Yizhuo Xu, +Yike Li, +Xiaojun Chen, +Peng Chen, +Dezhi Chen, +Yunsong Shi, +Bin Su Research Article - Biocooperative Regenerative Materials by Harnessing Blood‐Clotting and Peptide Self‐Assembly - 10.1002/adma.202407156 + Untethered & Stiffness‐Tunable Ferromagnetic Liquid Robots for Cleaning Thrombus in Complex Blood Vessels + 10.1002/adma.202409142 Advanced Materials - 10.1002/adma.202407156 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202407156 + 10.1002/adma.202409142 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409142 Research Article + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413268 - Thu, 14 Nov 2024 20:39:59 -0800 - 2024-11-14T08:39:59-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409175 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202413268 - An Ultrahigh‐Modulus Hydrogel Electrolyte for Dendrite‐Free Zinc Ion Batteries - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202409175 + Universal Ensemble‐Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Ultra‐tough hydrogel electrolytes with hydrophobic domains (established through dipole‐dipole interactions) and crystalline domains (formed via hydrogen bonds) are obtained by a strategy combining wet‐annealing, solvent‐exchange, and salting‐out processes. The synergy between nanoscale phase separation and high crystallinity results in the hydrogel electrolytes with excellent mechanical properties while maintaining high water contents. +This paper introduces GNNOpt, an equivariant graph‐neural‐network architecture incorporating universal embedding with automatic optimization. GNNOpt allows for precise prediction of optical spectra based exclusively on crystal structures and can be up to a million times faster than traditional first‐principles calculations. Consequently, GNNOpt can significantly speed up the development of photovoltaic and quantum materials. @@ -5824,45 +5753,44 @@ Ultra‐tough hydrogel electrolytes with hydrophobic domains (established th Abstract -Quasi‐solid‐state aqueous zinc ion batteries suffer from anodic zinc dendrite growth during plating/stripping processes, impeding their commercial application. The inhibition of zinc dendrites by high‐modulus electrolytes has been proven to be effective. However, hydrogel electrolytes are difficult to achieve high modulus owing to their inherent high water contents. This work reports a hydrogel electrolyte with ultrahigh modulus that can overcome the growth stress of zinc dendrites through mechanical suppression effect. By combining wet‐annealing, solvent‐exchange, and salting‐out processes and tuning the hydrophobic and crystalline domains, a hydrogel electrolyte is obtained with substantial water content (≈70%), high modulus (198.5 MPa), high toughness (274.3 MJ m−3), and high zinc‐ion conductivity (28.9 mS cm−1), which significantly outperforms the previously reported poly(vinyl alcohol)‐based hydrogels. As a result, the hydrogel electrolyte exhibits excellent dendrite‐suppression effect and achieves stable performance in Zn||Zn symmetric batteries (1800 h of cycle life at 1 mA cm−2). Moreover, the Zn||V2O5 pouch batteries display excellent cycling life and operate stably even under extreme conditions, such as large bending angle (180°) and automotive crushing. This work provides a promising approach for designing mechanically reliable hydrogel electrolytes for advanced aqueous zinc ion batteries. +Optical properties in solids, such as refractive index and absorption, hold vast applications ranging from solar panels to sensors, photodetectors, and transparent displays. However, first‐principles computation of optical properties from crystal structures is a complex task due to the high convergence criteria and computational cost. Recent progress in machine learning shows promise in predicting material properties, yet predicting optical properties from crystal structures remains challenging due to the lack of efficient atomic embeddings. Here, Graph Neural Network for Optical spectra prediction (GNNOpt) is introduced, an equivariant graph‐neural‐network architecture featuring universal embedding with automatic optimization. This enables high‐quality optical predictions with a dataset of only 944 materials. GNNOpt predicts all optical properties based on the Kramers‐Krönig relations, including absorption coefficient, complex dielectric function, complex refractive index, and reflectance. The trained model is applied to screen photovoltaic materials based on spectroscopic limited maximum efficiency and search for quantum materials based on quantum weight. First‐principles calculations validate the efficacy of the GNNOpt model, demonstrating excellent agreement in predicting the optical spectra of unseen materials. The discovery of new quantum materials with high predicted quantum weight, such as SiOs, which host exotic quasiparticles with multifold nontrivial topology, demonstrates the potential of GNNOpt in predicting optical properties across a broad range of materials and applications. - <img src="https://onlinelibrary.wiley.com/cms/asset/f7703d3a-e319-45df-982e-4d22de7475ba/adma202413268-gra-0001-m.png" - alt="An Ultrahigh-Modulus Hydrogel Electrolyte for Dendrite-Free Zinc Ion Batteries"/> -<p>Ultra-tough hydrogel electrolytes with hydrophobic domains (established through dipole-dipole interactions) and crystalline domains (formed via hydrogen bonds) are obtained by a strategy combining wet-annealing, solvent-exchange, and salting-out processes. The synergy between nanoscale phase separation and high crystallinity results in the hydrogel electrolytes with excellent mechanical properties while maintaining high water contents. + <img src="https://onlinelibrary.wiley.com/cms/asset/66e3de52-7fa6-4fed-b932-5a91397248bf/adma202409175-gra-0001-m.png" + alt="Universal Ensemble-Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures"/> +<p>This paper introduces GNNOpt, an equivariant graph-neural-network architecture incorporating universal embedding with automatic optimization. GNNOpt allows for precise prediction of optical spectra based exclusively on crystal structures and can be up to a million times faster than traditional first-principles calculations. Consequently, GNNOpt can significantly speed up the development of photovoltaic and quantum materials. </p> <br/> <h2>Abstract</h2> -<p>Quasi-solid-state aqueous zinc ion batteries suffer from anodic zinc dendrite growth during plating/stripping processes, impeding their commercial application. The inhibition of zinc dendrites by high-modulus electrolytes has been proven to be effective. However, hydrogel electrolytes are difficult to achieve high modulus owing to their inherent high water contents. This work reports a hydrogel electrolyte with ultrahigh modulus that can overcome the growth stress of zinc dendrites through mechanical suppression effect. By combining wet-annealing, solvent-exchange, and salting-out processes and tuning the hydrophobic and crystalline domains, a hydrogel electrolyte is obtained with substantial water content (≈70%), high modulus (198.5 MPa), high toughness (274.3 MJ m<sup>−3</sup>), and high zinc-ion conductivity (28.9 mS cm<sup>−1</sup>), which significantly outperforms the previously reported poly(vinyl alcohol)-based hydrogels. As a result, the hydrogel electrolyte exhibits excellent dendrite-suppression effect and achieves stable performance in Zn||Zn symmetric batteries (1800 h of cycle life at 1 mA cm<sup>−2</sup>). Moreover, the Zn||V<sub>2</sub>O<sub>5</sub> pouch batteries display excellent cycling life and operate stably even under extreme conditions, such as large bending angle (180°) and automotive crushing. This work provides a promising approach for designing mechanically reliable hydrogel electrolytes for advanced aqueous zinc ion batteries.</p> +<p>Optical properties in solids, such as refractive index and absorption, hold vast applications ranging from solar panels to sensors, photodetectors, and transparent displays. However, first-principles computation of optical properties from crystal structures is a complex task due to the high convergence criteria and computational cost. Recent progress in machine learning shows promise in predicting material properties, yet predicting optical properties from crystal structures remains challenging due to the lack of efficient atomic embeddings. Here, Graph Neural Network for Optical spectra prediction (GNNOpt) is introduced, an equivariant graph-neural-network architecture featuring universal embedding with automatic optimization. This enables high-quality optical predictions with a dataset of only 944 materials. GNNOpt predicts all optical properties based on the Kramers-Krönig relations, including absorption coefficient, complex dielectric function, complex refractive index, and reflectance. The trained model is applied to screen photovoltaic materials based on spectroscopic limited maximum efficiency and search for quantum materials based on quantum weight. First-principles calculations validate the efficacy of the GNNOpt model, demonstrating excellent agreement in predicting the optical spectra of unseen materials. The discovery of new quantum materials with high predicted quantum weight, such as SiOs, which host exotic quasiparticles with multifold nontrivial topology, demonstrates the potential of GNNOpt in predicting optical properties across a broad range of materials and applications.</p> -Zong‐Ju Chen, -Tian‐Yu Shen, -Xiong Xiao, -Xiu‐Chong He, -Yan‐Long Luo, -Zhong Jin, -Cheng‐Hui Li +Nguyen Tuan Hung, +Ryotaro Okabe, +Abhijatmedhi Chotrattanapituk, +Mingda Li Research Article - An Ultrahigh‐Modulus Hydrogel Electrolyte for Dendrite‐Free Zinc Ion Batteries - 10.1002/adma.202413268 + Universal Ensemble‐Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures + 10.1002/adma.202409175 Advanced Materials - 10.1002/adma.202413268 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413268 + 10.1002/adma.202409175 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409175 Research Article + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406118 - Thu, 14 Nov 2024 20:29:09 -0800 - 2024-11-14T08:29:09-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410669 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202406118 - Framework Nucleic Acid‐Based Selective Cell Catcher for Endogenous Stem Cell Recruitment - Advanced Materials, EarlyView. - -The “stem cell catcher” system, inspired by gold prospectors in the game “Gold Miner,” is a tFNA‐based structure embedded in a hyaluronic acid hydrogel for in vivo recruitment of stem cells in bone injuries. It mimics the process of mining for gold, targeting and capturing cellular gold necessary for craniofacial bone regeneration in challenging microenvironments. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202410669 + Innovative In Situ Passivation Strategy for High‐Efficiency Sb2(S,Se)3 Solar Cells + Advanced Materials, Volume 36, Issue 46, November 14, 2024. + +10.81%‐efficiency Sb2(S,Se)3 solar cell is achieved using an in situ passivation technique, which involves incorporating sodium selenosulfate to the precursor solution, effectively passivates deep‐level intrinsic defects, enhances film quality, and reduces non‐radiative recombination. @@ -5872,52 +5800,51 @@ The “stem cell catcher” system, inspired by gold prospectors in the Abstract -Cell‐surface engineering holds great promise in boosting endogenous stem cell attraction for tissue regeneration. However, challenges such as cellular internalization of ligand and the dynamic nature of cell membranes often complicate ligand–receptor interactions. The aim of this study is to harness the innovative potential of programmable tetrahedral framework nucleic acid (tFNA) to enable precise, tunable ligand–receptor interactions, thereby improving stem cell recruitment efficiency. This approach involves experimental screening and theoretical analysis using dissipative particle dynamics. The results demonstrate that altering the flexibility and topology of ligands on tFNA changes their cellular internalization and membrane binding efficiency. Furthermore, optimizing the distribution of the mesenchymal stem cell (MSC)‐binding aptamer 19S (Apt19S) on the tFNA enhances the stem cell capture efficiency. Following successful in vitro MSC capture, Apt19S‐modified tFNA is chemically linked to a hyaluronic acid hydrogel, forming an efficient “stem cell catcher” system. Subsequent in vivo experiments demonstrate that this system effectively promotes early stem cell recruitment and accelerates bone regeneration in different bone healing scenarios, including cranial and maxillary defects. +An effective defect passivation strategy is crucial for enhancing the performance of antimony selenosulfide (Sb2(S,Se)3) solar cells, as it significantly influences charge transport and extraction efficiency. Herein, a convenient and novel in situ passivation (ISP) technique is successfully introduced to enhance the performance of Sb2(S,Se)3 solar cells, achieving a champion efficiency of 10.81%, which is among the highest recorded for Sb2(S,Se)3 solar cells to date. The first principles calculations and the experimental data reveal that incorporating sodium selenosulfate in the ISP strategy effectively functions as an in situ selenization, effectively passivating deep‐level cation antisite SbSe defect within the Sb2(S,Se)3 films and significantly suppressing non‐radiative recombination in the devices. Space‐charge‐limited current (SCLC), photoluminescence (PL), and transient absorption spectroscopy (TAS) measurements verify the high quality of the passivated films, showing fewer traps and defects. Moreover, the ISP strategy improved the overall quality of the Sb2(S,Se)3 films, and fine‐tuned the energy levels, thereby facilitating enhanced carrier transport. This study thus provides a straightforward and effective method for passivating deep‐level defects in Sb2(S,Se)3 solar cells. - <img src="https://onlinelibrary.wiley.com/cms/asset/93dc5b4a-ec18-4120-a36d-6e9f87b3eac6/adma202406118-gra-0001-m.png" - alt="Framework Nucleic Acid-Based Selective Cell Catcher for Endogenous Stem Cell Recruitment"/> -<p>The “stem cell catcher” system, inspired by gold prospectors in the game “Gold Miner,” is a tFNA-based structure embedded in a hyaluronic acid hydrogel for in vivo recruitment of stem cells in bone injuries. It mimics the process of mining for gold, targeting and capturing cellular gold necessary for craniofacial bone regeneration in challenging microenvironments. + <img src="https://onlinelibrary.wiley.com/cms/asset/a159347a-126b-4446-89bd-159795f0ef3e/adma202410669-gra-0001-m.png" + alt="Innovative In Situ Passivation Strategy for High-Efficiency Sb2(S,Se)3 Solar Cells"/> +<p>10.81%-efficiency Sb<sub>2</sub>(S,Se)<sub>3</sub> solar cell is achieved using an in situ passivation technique, which involves incorporating sodium selenosulfate to the precursor solution, effectively passivates deep-level intrinsic defects, enhances film quality, and reduces non-radiative recombination. </p> <br/> <h2>Abstract</h2> -<p>Cell-surface engineering holds great promise in boosting endogenous stem cell attraction for tissue regeneration. However, challenges such as cellular internalization of ligand and the dynamic nature of cell membranes often complicate ligand–receptor interactions. The aim of this study is to harness the innovative potential of programmable tetrahedral framework nucleic acid (tFNA) to enable precise, tunable ligand–receptor interactions, thereby improving stem cell recruitment efficiency. This approach involves experimental screening and theoretical analysis using dissipative particle dynamics. The results demonstrate that altering the flexibility and topology of ligands on tFNA changes their cellular internalization and membrane binding efficiency. Furthermore, optimizing the distribution of the mesenchymal stem cell (MSC)-binding aptamer 19S (Apt19S) on the tFNA enhances the stem cell capture efficiency. Following successful in vitro MSC capture, Apt19S-modified tFNA is chemically linked to a hyaluronic acid hydrogel, forming an efficient “stem cell catcher” system. Subsequent in vivo experiments demonstrate that this system effectively promotes early stem cell recruitment and accelerates bone regeneration in different bone healing scenarios, including cranial and maxillary defects.</p> +<p>An effective defect passivation strategy is crucial for enhancing the performance of antimony selenosulfide (Sb<sub>2</sub>(S,Se)<sub>3</sub>) solar cells, as it significantly influences charge transport and extraction efficiency. Herein, a convenient and novel in situ passivation (ISP) technique is successfully introduced to enhance the performance of Sb<sub>2</sub>(S,Se)<sub>3</sub> solar cells, achieving a champion efficiency of 10.81%, which is among the highest recorded for Sb<sub>2</sub>(S,Se)<sub>3</sub> solar cells to date. The first principles calculations and the experimental data reveal that incorporating sodium selenosulfate in the ISP strategy effectively functions as an in situ selenization, effectively passivating deep-level cation antisite Sb<sub>Se</sub> defect within the Sb<sub>2</sub>(S,Se)<sub>3</sub> films and significantly suppressing non-radiative recombination in the devices. Space-charge-limited current (SCLC), photoluminescence (PL), and transient absorption spectroscopy (TAS) measurements verify the high quality of the passivated films, showing fewer traps and defects. Moreover, the ISP strategy improved the overall quality of the Sb<sub>2</sub>(S,Se)<sub>3</sub> films, and fine-tuned the energy levels, thereby facilitating enhanced carrier transport. This study thus provides a straightforward and effective method for passivating deep-level defects in Sb<sub>2</sub>(S,Se)<sub>3</sub> solar cells.</p> -Xingyu Chen, -Ziang Xu, -Yang Gao, -Ye Chen, -Wumeng Yin, -Zhiqiang Liu, -Weitong Cui, -Yong Li, -Jiafei Sun, -Yuting Yang, -Wenjuan Ma, -Tao Zhang, -Taoran Tian, -Yunfeng Lin +Yuqi Zhao, +Wentao Xu, +Jing Wen, +Xiaomin Wang, +Xueling Chen, +Bo Che, +Haolin Wang, +Junbo Gong, +Tao Chen, +Xudong Xiao, +Jianmin Li Research Article - Framework Nucleic Acid‐Based Selective Cell Catcher for Endogenous Stem Cell Recruitment - 10.1002/adma.202406118 + Innovative In Situ Passivation Strategy for High‐Efficiency Sb2(S,Se)3 Solar Cells + 10.1002/adma.202410669 Advanced Materials - 10.1002/adma.202406118 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202406118 + 10.1002/adma.202410669 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410669 Research Article + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414388 - Thu, 14 Nov 2024 20:28:24 -0800 - 2024-11-14T08:28:24-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410947 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202414388 - Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc‐Based Flow Batteries with High Capacity - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202410947 + De‐Passivation and Surface Crystal Plane Reconstruction via Chemical Polishing for Highly Reversible Zinc Anodes + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Designing current collector with gravity‐induced gradient copper nanoparticles (CF‐G‐Cu NPs), which can integrate gradient conductivity and zincophilicity to regulate zinc deposition and suppress side reactions. +The chemically polished Zn metal anode (CP‐Zn), achieved through a facile immersion method, effectively removes passivation layers and selectively exposes (002) crystal planes. This process ensures uniform zinc deposition and improved cell stability, demonstrated by over 4600 hours of stable cycling in symmetric cells and high capacity retention in full cells. @@ -5927,51 +5854,74 @@ Designing current collector with gravity‐induced gradient copper nanoparti Abstract -Current collectors, as reaction sites, play a crucial role in influencing various electrochemical performances in emerging cost‐effective zinc‐based flow batteries (Zn‐based FBs). 3D carbon felts (CF) are commonly used but lack effectiveness in improving Zn metal plating/stripping. Here, a current collector with gravity‐induced gradient copper nanoparticles (CF‐G‐Cu NPs) is developed, integrating gradient conductivity and zincophilicity to regulate Zn deposition and suppress side reactions. The CF‐G‐Cu NPs electrode modulates Zn nucleation and growth via the zincophilic Cu/CuZn5 alloy has been confirmed by density functional theory (DFT) calculations. Finite element simulation demonstrates the gradient internal structure effectively optimizes the local electric/current field distribution to regulate the Zn2+ flux, improving bottom‐up plating behavior for Zn metal and mitigating top‐surface dendrite growth. As a result, Zn‐based asymmetrical FBs with CF‐G‐Cu NPs electrodes achieve an areal capacity of 30 mAh cm−2 over 640 h with Coulombic efficiency of 99.5% at 40 mA cm−2. The integrated Zn‐Iodide FBs exhibit a competitive long‐term lifespan of 2910 h (5800 cycles) with low energy efficiency decay of 0.062% per cycle and high cumulative capacity of 112800 mAh cm−2 at a high current density of 100 mA cm−2. This gradient distribution strategy offers a simple mode for developing Zn‐based FB systems. +Despite the widespread adoption of Zn anodes for aqueous energy storage, the presence of an inherent passivation layer and the polycrystalline interface of commercial Zn foil consistently lead to non‐uniform electrodeposition, undermining stability and practicality. Herein, the study introduces a chemically polished Zn metal anode (CP‐Zn) fabricated via a simple immersion method. This “chemically polishing” process can effectively remove the interfacial passivation layer (de‐passivation), providing ample active sites for plating/stripping and ensuring the uniformly distributed electric field and Zn2+ ion flux. Additionally, selective etching during chemical polishing exposes more (002) crystal planes, promoting homogeneous and smooth zinc deposition while suppressing related side reactions. Demonstrated by CP‐Zn anode, the symmetric cell exhibits stable cycling over 4600 h at 1 mA cm−2 and 240 h at 50% depth of discharge (DOD), with a CP‐Zn||VO2 full cell maintaining ≈75.3% capacity retention over 1000 cycles at 3 A g−1. This chemically polishing strategy presents a promising avenue for advancing the commercialization of aqueous zinc‐ion batteries. - <img src="https://onlinelibrary.wiley.com/cms/asset/bfc3fb5a-d30a-4516-8e98-ccc6bf2d7678/adma202414388-gra-0001-m.png" - alt="Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc-Based Flow Batteries with High Capacity"/> -<p>Designing current collector with gravity-induced gradient copper nanoparticles (CF-G-Cu NPs), which can integrate gradient conductivity and zincophilicity to regulate zinc deposition and suppress side reactions. + <img src="https://onlinelibrary.wiley.com/cms/asset/63ba616d-bf3e-4006-890e-bee9204e7129/adma202410947-gra-0001-m.png" + alt="De-Passivation and Surface Crystal Plane Reconstruction via Chemical Polishing for Highly Reversible Zinc Anodes"/> +<p>The chemically polished Zn metal anode (CP-Zn), achieved through a facile immersion method, effectively removes passivation layers and selectively exposes (002) crystal planes. This process ensures uniform zinc deposition and improved cell stability, demonstrated by over 4600 hours of stable cycling in symmetric cells and high capacity retention in full cells. </p> <br/> <h2>Abstract</h2> -<p>Current collectors, as reaction sites, play a crucial role in influencing various electrochemical performances in emerging cost-effective zinc-based flow batteries (Zn-based FBs). 3D carbon felts (CF) are commonly used but lack effectiveness in improving Zn metal plating/stripping. Here, a current collector with gravity-induced gradient copper nanoparticles (CF-G-Cu NPs) is developed, integrating gradient conductivity and zincophilicity to regulate Zn deposition and suppress side reactions. The CF-G-Cu NPs electrode modulates Zn nucleation and growth via the zincophilic Cu/CuZn<sub>5</sub> alloy has been confirmed by density functional theory (DFT) calculations. Finite element simulation demonstrates the gradient internal structure effectively optimizes the local electric/current field distribution to regulate the Zn<sup>2+</sup> flux, improving bottom-up plating behavior for Zn metal and mitigating top-surface dendrite growth. As a result, Zn-based asymmetrical FBs with CF-G-Cu NPs electrodes achieve an areal capacity of 30 mAh cm<sup>−2</sup> over 640 h with Coulombic efficiency of 99.5% at 40 mA cm<sup>−2</sup>. The integrated Zn-Iodide FBs exhibit a competitive long-term lifespan of 2910 h (5800 cycles) with low energy efficiency decay of 0.062% per cycle and high cumulative capacity of 112800 mAh cm<sup>−2</sup> at a high current density of 100 mA cm<sup>−2</sup>. This gradient distribution strategy offers a simple mode for developing Zn-based FB systems.</p> +<p>Despite the widespread adoption of Zn anodes for aqueous energy storage, the presence of an inherent passivation layer and the polycrystalline interface of commercial Zn foil consistently lead to non-uniform electrodeposition, undermining stability and practicality. Herein, the study introduces a chemically polished Zn metal anode (CP-Zn) fabricated via a simple immersion method. This “chemically polishing” process can effectively remove the interfacial passivation layer (de-passivation), providing ample active sites for plating/stripping and ensuring the uniformly distributed electric field and Zn<sup>2+</sup> ion flux. Additionally, selective etching during chemical polishing exposes more (002) crystal planes, promoting homogeneous and smooth zinc deposition while suppressing related side reactions. Demonstrated by CP-Zn anode, the symmetric cell exhibits stable cycling over 4600 h at 1 mA cm<sup>−2</sup> and 240 h at 50% depth of discharge (DOD), with a CP-Zn||VO<sub>2</sub> full cell maintaining ≈75.3% capacity retention over 1000 cycles at 3 A g<sup>−1</sup>. This chemically polishing strategy presents a promising avenue for advancing the commercialization of aqueous zinc-ion batteries.</p> -Zhiquan Wei, -Guangmeng Qu, -Zhaodong Huang, -Yiqiao Wang, -Dedi Li, -Xinru Yang, -Shaoce Zhang, -Ao Chen, -Yanbo Wang, -Hu Hong, -Qing Li, -Chunyi Zhi +Jin Cao, +Xu Wang, +Shangshu Qian, +Dongdong Zhang, +Ding Luo, +Lulu Zhang, +Jiaqian Qin, +Xinyu Zhang, +Xuelin Yang, +Jun Lu Research Article - Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc‐Based Flow Batteries with High Capacity - 10.1002/adma.202414388 + De‐Passivation and Surface Crystal Plane Reconstruction via Chemical Polishing for Highly Reversible Zinc Anodes + 10.1002/adma.202410947 Advanced Materials - 10.1002/adma.202414388 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414388 + 10.1002/adma.202410947 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410947 Research Article + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408307 - Thu, 14 Nov 2024 20:27:42 -0800 - 2024-11-14T08:27:42-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470366 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202408307 - Charge‐Stabilized Nanodiscs as a New Class of Lipid Nanoparticles - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470366 + Masthead: (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. + + + + Masthead + Masthead: (Adv. Mater. 46/2024) + 10.1002/adma.202470366 + Advanced Materials + 10.1002/adma.202470366 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470366 + Masthead + 36 + 46 + + + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470364 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 + Wiley: Advanced Materials: Table of Contents + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470364 + Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Bottom‐up assembly of lipid‐based nanoparticles from mixed micelles containing di‐anionic lipids yield charge‐stabilized nanodiscs (CNDs). CNDs exhibit enhanced tumor accumulation compared to spherical liposomes. Surface chemistry modification via the layer‐by‐layer (LbL) technique improves tumor‐targeting properties compared to LbL‐liposomes. The insights presented can improve the assembly of delivery vehicles and expand the use of lipid‐based discoidal assemblies. - +Upcycling of Plastics +In the article number 2403728, Weipu Zhu and co‐workers report an optimal approach without additional catalysts and solvents for the upcycling of poly(ethylene terephthalate) (PET) waste. Specifically, bio‐based hydrogenated dimer acids are found to directly convert PET bottles into biodegradable copolyesters suitable for agricultural mulch films. This work provides an environmentally friendly and cost‐effective strategy for the large‐scale upcycling of PET waste. @@ -5979,50 +5929,45 @@ Bottom‐up assembly of lipid‐based nanoparticles from mixed micelles -Abstract -Nanoparticles have the potential to improve disease treatment and diagnosis due to their ability to incorporate drugs, alter pharmacokinetics, and enable tissue targeting. While considerable effort is placed on developing spherical lipid‐based nanocarriers, recent evidence suggests that high aspect ratio lipid nanocarriers can exhibit enhanced disease site targeting and altered cellular interactions. However, the assembly of lipid‐based nanoparticles into non‐spherical morphologies has typically required incorporating additional agents such as synthetic polymers, proteins, lipid‐polymer conjugates, or detergents. Here, charged lipid headgroups are used to generate stable discoidal lipid nanoparticles from mixed micelles, which are termed charge‐stabilized nanodiscs (CNDs). The ability to generate CNDs in buffers with physiological ionic strength is restricted to lipids with more than one anionic group, whereas monovalent lipids only generate small nanoliposomal assemblies. In mice, the smaller size and anisotropic shape of CNDs promote higher accumulation in subcutaneous tumors than spherical liposomes. Further, the surface chemistry of CNDs can be modified via layer‐by‐layer (LbL) assembly to improve their tumor‐targeting properties over state‐of‐the‐art LbL‐liposomes when tested using a metastatic model of ovarian cancer. The application of charge‐mediated anisotropy in lipid‐based assemblies can aid in the future design of biomaterials and cell‐membrane mimetic structures. - <img src="https://onlinelibrary.wiley.com/cms/asset/cdc6d096-0c86-4c41-a016-2226b5e15bbd/adma202408307-gra-0001-m.png" - alt="Charge-Stabilized Nanodiscs as a New Class of Lipid Nanoparticles"/> -<p>Bottom-up assembly of lipid-based nanoparticles from mixed micelles containing di-anionic lipids yield charge-stabilized nanodiscs (CNDs). CNDs exhibit enhanced tumor accumulation compared to spherical liposomes. Surface chemistry modification via the layer-by-layer (LbL) technique improves tumor-targeting properties compared to LbL-liposomes. The insights presented can improve the assembly of delivery vehicles and expand the use of lipid-based discoidal assemblies. + <img src="https://onlinelibrary.wiley.com/cms/asset/31a80b18-ba8a-4093-bab6-fc13532c217a/adma202470364-gra-0001-m.png" + alt="Catalyst- and Solvent-Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics (Adv. Mater. 46/2024)"/> +<p><b>Upcycling of Plastics</b></p> +<p>In the article number <a href="https://doi.org/10.1002/adma.202403728">2403728</a>, Weipu Zhu and co-workers report an optimal approach without additional catalysts and solvents for the upcycling of poly(ethylene terephthalate) (PET) waste. Specifically, bio-based hydrogenated dimer acids are found to directly convert PET bottles into biodegradable copolyesters suitable for agricultural mulch films. This work provides an environmentally friendly and cost-effective strategy for the large-scale upcycling of PET waste. </p> <br/> -<h2>Abstract</h2> -<p>Nanoparticles have the potential to improve disease treatment and diagnosis due to their ability to incorporate drugs, alter pharmacokinetics, and enable tissue targeting. While considerable effort is placed on developing spherical lipid-based nanocarriers, recent evidence suggests that high aspect ratio lipid nanocarriers can exhibit enhanced disease site targeting and altered cellular interactions. However, the assembly of lipid-based nanoparticles into non-spherical morphologies has typically required incorporating additional agents such as synthetic polymers, proteins, lipid-polymer conjugates, or detergents. Here, charged lipid headgroups are used to generate stable discoidal lipid nanoparticles from mixed micelles, which are termed charge-stabilized nanodiscs (CNDs). The ability to generate CNDs in buffers with physiological ionic strength is restricted to lipids with more than one anionic group, whereas monovalent lipids only generate small nanoliposomal assemblies. In mice, the smaller size and anisotropic shape of CNDs promote higher accumulation in subcutaneous tumors than spherical liposomes. Further, the surface chemistry of CNDs can be modified via layer-by-layer (LbL) assembly to improve their tumor-targeting properties over state-of-the-art LbL-liposomes when tested using a metastatic model of ovarian cancer. The application of charge-mediated anisotropy in lipid-based assemblies can aid in the future design of biomaterials and cell-membrane mimetic structures.</p> + -Ivan S. Pires, -Alexander Hostetler, -Gil Covarrubias, -Isabella S. Carlo, -Jack R. Suggs, -B.J. Kim, -Andrew J. Pickering, -Ezra Gordon, -Darrell J. Irvine, -Paula T. Hammond +Tianxiang Fang, +Weipo Jiang, +Tengfei Zheng, +Xuxia Yao, +Weipu Zhu - Research Article - Charge‐Stabilized Nanodiscs as a New Class of Lipid Nanoparticles - 10.1002/adma.202408307 + Cover Picture + Catalyst‐ and Solvent‐Free Upcycling of Poly(Ethylene Terephthalate) Waste to Biodegradable Plastics (Adv. Mater. 46/2024) + 10.1002/adma.202470364 Advanced Materials - 10.1002/adma.202408307 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408307 - Research Article + 10.1002/adma.202470364 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470364 + Cover Picture + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412059 - Thu, 14 Nov 2024 20:27:02 -0800 - 2024-11-14T08:27:02-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470365 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202412059 - A Polymeric Hole Transporter with Dual‐Interfacial Interactions Enables 25%‐Efficiency Blade‐Coated Perovskite Solar Cells - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470365 + Multi‐Functional Biomaterial for the Treatment and Prevention of Central Line‐Associated Bloodstream Infections (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A novel polymeric hole transporter named Poly‐DBPP with centrosymmetric biphosphonic acid groups is developed that can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously. Poly‐DBPP improves the efficiencies of blade‐coated perovskite solar cells and large‐area modules to 25.1% and 22.0%, respectively. - +Injectable Multi‐Functional Biomaterial +Catheter infections represent a major worldwide public health problem with no viable solution. In article number 2405805, Rahmi Oklu and co‐workers show that an injectable biomaterial can both prevent and treat catheter infections and promote healing of the catheter entry site. Image credit to Mike Austin, internalart.com @@ -6030,59 +5975,47 @@ A novel polymeric hole transporter named Poly‐DBPP with centrosymmetric bi -Abstract -Self‐assembly monolayer (SAM) hole transporters, consisting of anchoring, spacer, and terminal groups, have played a significant role in the development of inverted perovskite solar cells (PSCs). However, the weak interaction between perovskite and hydrophobic terminal group of SAMs limits surface wettability and interface stability. To address this issue, two novel hole transporters (named DBPP and Poly‐DBPP) with centrosymmetric biphosphonic acid groups are developed. Unlike conventional SAM hole transporters, the biphosphonic acid groups in DBPP and Poly‐DBPP can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously, improving surface wettability and suppressing interface recombination. Furthermore, compared to the small‐molecular DBPP, Poly‐DBPP exhibits higher conductance and excellent uniformity. This translates to a remarkable power conversion efficiency of 25.1% for blade‐coated PSCs and 22.0% for large‐area modules, respectively. Additionally, the PSCs based on Poly‐DBPP demonstrate impressive operational stability, retaining 92% of their initial PCE after 1,600 h of light soaking. This work presents a promising strategy for designing multifunctional hole transporters, paving the way for highly efficient and stable PSCs. - <img src="https://onlinelibrary.wiley.com/cms/asset/4a155cac-a899-44f5-9837-0f467d466924/adma202412059-gra-0001-m.png" - alt="A Polymeric Hole Transporter with Dual-Interfacial Interactions Enables 25%-Efficiency Blade-Coated Perovskite Solar Cells"/> -<p>A novel polymeric hole transporter named Poly-DBPP with centrosymmetric biphosphonic acid groups is developed that can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously. Poly-DBPP improves the efficiencies of blade-coated perovskite solar cells and large-area modules to 25.1% and 22.0%, respectively. + <img src="https://onlinelibrary.wiley.com/cms/asset/0be385eb-2773-43ca-867f-0be1416f92f8/adma202470365-gra-0001-m.png" + alt="Multi-Functional Biomaterial for the Treatment and Prevention of Central Line-Associated Bloodstream Infections (Adv. Mater. 46/2024)"/> +<p><b>Injectable Multi-Functional Biomaterial</b></p> +<p>Catheter infections represent a major worldwide public health problem with no viable solution. In article number <a href="https://doi.org/10.1002/adma.202405805">2405805</a>, Rahmi Oklu and co-workers show that an injectable biomaterial can both prevent and treat catheter infections and promote healing of the catheter entry site. Image credit to Mike Austin, internalart.com </p> <br/> -<h2>Abstract</h2> -<p>Self-assembly monolayer (SAM) hole transporters, consisting of anchoring, spacer, and terminal groups, have played a significant role in the development of inverted perovskite solar cells (PSCs). However, the weak interaction between perovskite and hydrophobic terminal group of SAMs limits surface wettability and interface stability. To address this issue, two novel hole transporters (named DBPP and Poly-DBPP) with centrosymmetric biphosphonic acid groups are developed. Unlike conventional SAM hole transporters, the biphosphonic acid groups in DBPP and Poly-DBPP can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously, improving surface wettability and suppressing interface recombination. Furthermore, compared to the small-molecular DBPP, Poly-DBPP exhibits higher conductance and excellent uniformity. This translates to a remarkable power conversion efficiency of 25.1% for blade-coated PSCs and 22.0% for large-area modules, respectively. Additionally, the PSCs based on Poly-DBPP demonstrate impressive operational stability, retaining 92% of their initial PCE after 1,600 h of light soaking. This work presents a promising strategy for designing multifunctional hole transporters, paving the way for highly efficient and stable PSCs.</p> + -Feifei Wang, -Tianxiao Liu, -Yangyang Liu, -Yuhan Zhou, -Xiaorui Dong, -Yaoyao Zhang, -Xiaoyu Shi, -Yunjie Dou, -Zhijun Ren, -Lingyuan Wang, -Yu Zhao, -Siwei Luo, -Xiaodong Hu, -Xiaoxiao Peng, -Chunxiong Bao, -Wei Wang, -Jingyang Wang, -Wenbing Hu, -Shangshang Chen +Jinjoo Kim, +Hyeongseop Keum, +Hassan Albadawi, +Zefu Zhang, +Erin H. Graf, +Enes Cevik, +Rahmi Oklu - Research Article - A Polymeric Hole Transporter with Dual‐Interfacial Interactions Enables 25%‐Efficiency Blade‐Coated Perovskite Solar Cells - 10.1002/adma.202412059 + Inside Front Cover + Multi‐Functional Biomaterial for the Treatment and Prevention of Central Line‐Associated Bloodstream Infections (Adv. Mater. 46/2024) + 10.1002/adma.202470365 Advanced Materials - 10.1002/adma.202412059 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412059 - Research Article + 10.1002/adma.202470365 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470365 + Inside Front Cover + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412598 - Thu, 14 Nov 2024 20:26:25 -0800 - 2024-11-14T08:26:25-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470367 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202412598 - Low‐Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470367 + Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye‐Incorporated Photonic Crystal‐Based Sensor Array (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Introducing multiple vacancy defects combined with V doping into NiFe‐LDH can boost the formation of low‐spin Fe3+, thereby modifying the interactions between 3d orbitals of Fe3+ and O 2p orbitals, which reduces the excessive adsorption of O* intermediates on Fe3+ sites, consequently altering the rate‐determining step of OER and lowering the reaction energy barrier, resulting in accelerating OER kinetics. - +Volatile Organic Compounds +In article number 2409297, Shu Yang and co‐workers present an innovative approach to enhance volatile organic compound (VOC) sensing by integrating dyes with colloidal photonic crystals. The broadened reflection peak allows for augmented dye absorption originating from the overlap between the photonic bandgap edge and the dye absorption peak, leading to a more noticeable color change discernible to the naked eye, eliminating the need for signal amplification. @@ -6090,62 +6023,45 @@ Introducing multiple vacancy defects combined with V doping into NiFe‐LDH -Abstract -Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin‐state manipulation holds great promise to break through this bottleneck. Low‐spin Fe3+ (LS, t2g5eg0) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe3+ in NiFe‐layered double hydroxide (NiFe‐LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their d orbital splitting energy. The as‐obtained catalyst exhibits extraordinary OER performance with an ultra‐low overpotential of 244 mV at the industrially required current density of 500 mA cm−2, which is 110 mV lower than that of the conventional NiFe‐LDH with high‐spin Fe3+ (HS, t2g3eg2) and superior to most previously reported NiFe‐based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe3+ configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate‐determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin‐dependent electrocatalysts for OER and beyond. - <img src="https://onlinelibrary.wiley.com/cms/asset/b7a3318e-0450-475f-8925-59c9b326a79b/adma202412598-gra-0001-m.png" - alt="Low-Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation"/> -<p>Introducing multiple vacancy defects combined with V doping into NiFe-LDH can boost the formation of low-spin Fe<sup>3+</sup>, thereby modifying the interactions between 3<i>d</i> orbitals of Fe<sup>3+</sup> and O 2<i>p</i> orbitals, which reduces the excessive adsorption of O* intermediates on Fe<sup>3+</sup> sites, consequently altering the rate-determining step of OER and lowering the reaction energy barrier, resulting in accelerating OER kinetics. + <img src="https://onlinelibrary.wiley.com/cms/asset/16e10b02-a66c-4abc-ac7e-5f0434b3e15a/adma202470367-gra-0001-m.png" + alt="Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye-Incorporated Photonic Crystal-Based Sensor Array (Adv. Mater. 46/2024)"/> +<p><b>Volatile Organic Compounds</b></p> +<p>In article number <a href="https://doi.org/10.1002/adma.202409297">2409297</a>, Shu Yang and co-workers present an innovative approach to enhance volatile organic compound (VOC) sensing by integrating dyes with colloidal photonic crystals. The broadened reflection peak allows for augmented dye absorption originating from the overlap between the photonic bandgap edge and the dye absorption peak, leading to a more noticeable color change discernible to the naked eye, eliminating the need for signal amplification. </p> <br/> -<h2>Abstract</h2> -<p>Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin-state manipulation holds great promise to break through this bottleneck. Low-spin Fe<sup>3+</sup> (LS, <i>t</i> -<sub>2g</sub> -<sup>5</sup> -<i>e</i> -<sub>g</sub> -<sup>0</sup>) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe<sup>3+</sup> in NiFe-layered double hydroxide (NiFe-LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their <i>d</i> orbital splitting energy. The as-obtained catalyst exhibits extraordinary OER performance with an ultra-low overpotential of 244 mV at the industrially required current density of 500 mA cm<sup>−2</sup>, which is 110 mV lower than that of the conventional NiFe-LDH with high-spin Fe<sup>3+</sup> (HS, <i>t</i> -<sub>2g</sub> -<sup>3</sup> -<i>e</i> -<sub>g</sub> -<sup>2</sup>) and superior to most previously reported NiFe-based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe<sup>3+</sup> configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate-determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin-dependent electrocatalysts for OER and beyond.</p> + -Yihao Wang, -Shanqing Li, -Xu Hou, -Tingting Cui, -Zechao Zhuang, -Yunhe Zhao, -Haozhi Wang, -Wei Wei, -Ming Xu, -Qiang Fu, -Chunxia Chen, -Dingsheng Wang +So Hee Nah, +Jong Bin Kim, +Hiu Ning Tiffany Chui, +Yeonjoon Suh, +Shu Yang - Research Article - Low‐Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation - 10.1002/adma.202412598 + Frontispiece + Enhanced Colorimetric Detection of Volatile Organic Compounds Using a Dye‐Incorporated Photonic Crystal‐Based Sensor Array (Adv. Mater. 46/2024) + 10.1002/adma.202470367 Advanced Materials - 10.1002/adma.202412598 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412598 - Research Article + 10.1002/adma.202470367 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470367 + Frontispiece + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411652 - Thu, 14 Nov 2024 20:25:52 -0800 - 2024-11-14T08:25:52-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470368 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202411652 - Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li‐CO2 Batteries - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470368 + Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This study regulates the local spin states by incorporating Ni into Co3O4 and explores their impact on activity in Li‐CO2 batteries. High spin Ni ions facilitate electron transfer from the catalyst to the unoccupied orbitals of CO2, providing sufficient active sites for the nucleation and growth of small Li2CO3 crystals, thereby improving reversibility. - +Programmable Instabilities +The article number 2406611 by David Melancon, Katia Bertoldi, and co‐workers focuses on the highly nonlinear response of elastomeric cylindrical shells during depressurization. Instability‐driven deformations are harnessed to build soft machines capable of a programmable sequence of movements with a single actuation input. @@ -6153,100 +6069,149 @@ This study regulates the local spin states by incorporating Ni into Co3O4 and ex -Abstract -Due to the high energy barrier, slow reaction kinetics, and complex reaction environments of Li‐CO2 batteries, the development of durable and efficient catalysts is essential. Transition metal oxides are promising for their availability, stability, and 3d electronic features, with spin states playing an important role in CO2 activation. In this study, the local spin states are regulated by incorporating Ni into Co3O4 and its impact on activity in Li‐CO2 batteries is explored. The results show that Ni atoms with high spin states in Ni0.1Co2.9O4 facilitate electron transfer from the catalyst to the unoccupied orbitals of CO2, providing sufficient active sites for the nucleation and growth of small Li2CO3 crystals. These small crystals have a low decomposition barrier, leading to improved battery efficiency. Therefore, Ni0.1Co2.9O4 shows superior catalytic performance with an overpotential of 0.72 V and an energy efficiency of ≈70% after 500 h. This work provides insights into the relationship between spin states and CO2 reactions, highlighting a promising avenue for developing high‐performance metal‐CO2 batteries. - <img src="https://onlinelibrary.wiley.com/cms/asset/810f9b20-24e9-4e36-928c-6791984c4c55/adma202411652-gra-0001-m.png" - alt="Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li-CO2 Batteries"/> -<p>This study regulates the local spin states by incorporating Ni into Co<sub>3</sub>O<sub>4</sub> and explores their impact on activity in Li-CO<sub>2</sub> batteries. High spin Ni ions facilitate electron transfer from the catalyst to the unoccupied orbitals of CO<sub>2</sub>, providing sufficient active sites for the nucleation and growth of small Li<sub>2</sub>CO<sub>3</sub> crystals, thereby improving reversibility. + <img src="https://onlinelibrary.wiley.com/cms/asset/cf027c89-642d-45e0-b277-d039c3af3130/adma202470368-gra-0001-m.png" + alt="Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities (Adv. Mater. 46/2024)"/> +<p><b>Programmable Instabilities</b></p> +<p>The article number <a href="https://doi.org/10.1002/adma.202406611">2406611</a> by David Melancon, Katia Bertoldi, and co-workers focuses on the highly nonlinear response of elastomeric cylindrical shells during depressurization. Instability-driven deformations are harnessed to build soft machines capable of a programmable sequence of movements with a single actuation input. </p> <br/> -<h2>Abstract</h2> -<p>Due to the high energy barrier, slow reaction kinetics, and complex reaction environments of Li-CO<sub>2</sub> batteries, the development of durable and efficient catalysts is essential. Transition metal oxides are promising for their availability, stability, and 3d electronic features, with spin states playing an important role in CO<sub>2</sub> activation. In this study, the local spin states are regulated by incorporating Ni into Co<sub>3</sub>O<sub>4</sub> and its impact on activity in Li-CO<sub>2</sub> batteries is explored. The results show that Ni atoms with high spin states in Ni<sub>0.1</sub>Co<sub>2.9</sub>O<sub>4</sub> facilitate electron transfer from the catalyst to the unoccupied orbitals of CO<sub>2</sub>, providing sufficient active sites for the nucleation and growth of small Li<sub>2</sub>CO<sub>3</sub> crystals. These small crystals have a low decomposition barrier, leading to improved battery efficiency. Therefore, Ni<sub>0.1</sub>Co<sub>2.9</sub>O<sub>4</sub> shows superior catalytic performance with an overpotential of 0.72 V and an energy efficiency of ≈70% after 500 h. This work provides insights into the relationship between spin states and CO<sub>2</sub> reactions, highlighting a promising avenue for developing high-performance metal-CO<sub>2</sub> batteries.</p> + -Yingqi Liu, -Xinru Wu, -Haotian Qu, -Gongxun Lu, -Yanli Chen, -Bingyi Lu, -Yanze Song, -Guangmin Zhou, -Hui‐Ming Cheng +Yi Yang, +Helen Read, +Mohammed Sbai, +Ahmad Zareei, +Antonio Elia Forte, +David Melancon, +Katia Bertoldi - Research Article - Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li‐CO2 Batteries - 10.1002/adma.202411652 + Frontispiece + Complex Deformation in Soft Cylindrical Structures via Programmable Sequential Instabilities (Adv. Mater. 46/2024) + 10.1002/adma.202470368 Advanced Materials - 10.1002/adma.202411652 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411652 - Research Article + 10.1002/adma.202470368 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470368 + Frontispiece + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408114 - Thu, 14 Nov 2024 20:24:10 -0800 - 2024-11-14T08:24:10-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470369 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202408114 - Synergistic Catalytic Sites in High‐Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470369 + Universal Ensemble‐Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A high‐entropy metal hydroxide organic framework (HE‐MHOF) is synthesized, combining five transition metals in a single‐phase crystalline structure. The material exhibits superior electrocatalytic performance for the oxygen evolution reaction, rivaling precious metal‐based catalysts. Operando X‐ray absorption spectroscopy and ab initio calculations reveal synergistic catalytic sites and the underlying reaction mechanism, demonstrating the potential of high‐entropy materials for sustainable energy technologies. +Universal Ensemble‐Embedding Graph‐Neural Network +In article number 2409175, Nguyen Tuan Hung, Mingda Li, and co‐workers present a graph‐neural network architecture featuring universal embedding to predict the optical properties of materials from only crystal structures. The model performs a highly precise optical prediction at the quantum simulation level, making it suitable for various applications, from solar cells to quantum materials. + + <img src="https://onlinelibrary.wiley.com/cms/asset/694b422e-efd9-4b7d-9f7d-359e6ad094ea/adma202470369-gra-0001-m.png" + alt="Universal Ensemble-Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures (Adv. Mater. 46/2024)"/> +<p><b>Universal Ensemble-Embedding Graph-Neural Network</b></p> +<p>In article number <a href="https://doi.org/10.1002/adma.202409175">2409175</a>, Nguyen Tuan Hung, Mingda Li, and co-workers present a graph-neural network architecture featuring universal embedding to predict the optical properties of materials from only crystal structures. The model performs a highly precise optical prediction at the quantum simulation level, making it suitable for various applications, from solar cells to quantum materials. +</p> +<br/> + + +Nguyen Tuan Hung, +Ryotaro Okabe, +Abhijatmedhi Chotrattanapituk, +Mingda Li + + Frontispiece + Universal Ensemble‐Embedding Graph Neural Network for Direct Prediction of Optical Spectra from Crystal Structures (Adv. Mater. 46/2024) + 10.1002/adma.202470369 + Advanced Materials + 10.1002/adma.202470369 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470369 + Frontispiece + 36 + 46 + + + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470370 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 + Wiley: Advanced Materials: Table of Contents + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470370 + Customized Corneal Cross‐Linking with Microneedle‐Mediated Riboflavin Delivery for Keratoconus Treatment (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. + +Customized Corneal Cross‐Linking +ln article number 2408136, Zhongxing Chen, Xingtao Zhou, Jinhai Huang, and co‐workers introduce an innovative customized corneal cross‐linking (CXL) therapy employing microneedles (MNs) for precise riboflavin (RF) delivery achieves notable CXL effects comparable to conventional epi‐off CXL protocol and enhances visual function by flattening the corneal curvature in the treated zone. The frontispiece metaphorically represents the customized CXL process as being skillfully manipulated by magicians, highlighting the precision and efficacy of using MNs to deliver RF directly into the stroma and reinforce specific corneal zone. + + + + -Abstract -The integration of multiple elements in a high‐entropy state is crucial in the design of high‐performance, durable electrocatalysts. High‐entropy metal hydroxide organic frameworks (HE‐MHOFs) are synthesized under mild solvothermal conditions. This novel crystalline metal–organic framework (MOF) features a random, homogeneous distribution of cations within high‐entropy hydroxide layers. HE‐MHOF exhibits excellent electrocatalytic performance for the oxygen evolution reaction (OER), reaching a current density of 100 mA cm−2 at ≈1.64 VRHE, and demonstrates remarkable durability, maintaining a current density of 10 mA cm−2 for over 100 h. Notably, HE‐MHOF outperforms precious metal‐based electrocatalysts despite containing only ≈60% OER active metals. Ab initio calculations and operando X‐ray absorption spectroscopy (XAS) demonstrate that the high‐entropy catalyst contains active sites that facilitate a multifaceted OER mechanism. This study highlights the benefits of high‐entropy MOFs in developing noble metal‐free electrocatalysts, reducing reliance on precious metals, lowering metal loading (especially for Ni, Co, and Mn), and ultimately reducing costs for sustainable water electrolysis technologies. - <img src="https://onlinelibrary.wiley.com/cms/asset/6aaa3328-d9f9-4186-8665-fb681b01f540/adma202408114-gra-0001-m.png" - alt="Synergistic Catalytic Sites in High-Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction"/> -<p>A high-entropy metal hydroxide organic framework (HE-MHOF) is synthesized, combining five transition metals in a single-phase crystalline structure. The material exhibits superior electrocatalytic performance for the oxygen evolution reaction, rivaling precious metal-based catalysts. Operando X-ray absorption spectroscopy and ab initio calculations reveal synergistic catalytic sites and the underlying reaction mechanism, demonstrating the potential of high-entropy materials for sustainable energy technologies. + <img src="https://onlinelibrary.wiley.com/cms/asset/96666f2c-52e5-4e3f-ab67-6a65b79373b3/adma202470370-gra-0001-m.png" + alt="Customized Corneal Cross-Linking with Microneedle-Mediated Riboflavin Delivery for Keratoconus Treatment (Adv. Mater. 46/2024)"/> +<p><b>Customized Corneal Cross-Linking</b></p> +<p>ln article number <a href="https://doi.org/10.1002/adma.202408136">2408136</a>, Zhongxing Chen, Xingtao Zhou, Jinhai Huang, and co-workers introduce an innovative customized corneal cross-linking (CXL) therapy employing microneedles (MNs) for precise riboflavin (RF) delivery achieves notable CXL effects comparable to conventional epi-off CXL protocol and enhances visual function by flattening the corneal curvature in the treated zone. The frontispiece metaphorically represents the customized CXL process as being skillfully manipulated by magicians, highlighting the precision and efficacy of using MNs to deliver RF directly into the stroma and reinforce specific corneal zone. </p> <br/> -<h2>Abstract</h2> -<p>The integration of multiple elements in a high-entropy state is crucial in the design of high-performance, durable electrocatalysts. High-entropy metal hydroxide organic frameworks (HE-MHOFs) are synthesized under mild solvothermal conditions. This novel crystalline metal–organic framework (MOF) features a random, homogeneous distribution of cations within high-entropy hydroxide layers. HE-MHOF exhibits excellent electrocatalytic performance for the oxygen evolution reaction (OER), reaching a current density of 100 mA cm<sup>−2</sup> at ≈1.64 V<sub>RHE</sub>, and demonstrates remarkable durability, maintaining a current density of 10 mA cm<sup>−2</sup> for over 100 h. Notably, HE-MHOF outperforms precious metal-based electrocatalysts despite containing only ≈60% OER active metals. Ab initio calculations and operando X-ray absorption spectroscopy (XAS) demonstrate that the high-entropy catalyst contains active sites that facilitate a multifaceted OER mechanism. This study highlights the benefits of high-entropy MOFs in developing noble metal-free electrocatalysts, reducing reliance on precious metals, lowering metal loading (especially for Ni, Co, and Mn), and ultimately reducing costs for sustainable water electrolysis technologies.</p> + -Arkendu Roy, -Sourabh Kumar, -Ana Guilherme Buzanich, -Carsten Prinz, -Emilia Götz, -Anika Retzmann, -Tilmann Hickel, -Biswajit Bhattacharya, -Franziska Emmerling +Mei Yang, +Hongxian Pan, +Tingting Chen, +Xin Chen, +Rui Ning, +Qianfang Ye, +Aodong Chen, +Jiawei Li, +Siheng Li, +Nan Zhao, +Yue Wu, +Xueyu Fu, +Keith M. Meek, +Lingxin Chen, +Xiaoying Wang, +Zhongxing Chen, +Xingtao Zhou, +Jinhai Huang - Research Article - Synergistic Catalytic Sites in High‐Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction - 10.1002/adma.202408114 + Frontispiece + Customized Corneal Cross‐Linking with Microneedle‐Mediated Riboflavin Delivery for Keratoconus Treatment (Adv. Mater. 46/2024) + 10.1002/adma.202470370 Advanced Materials - 10.1002/adma.202408114 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408114 - Research Article + 10.1002/adma.202470370 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470370 + Frontispiece + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412378 - Thu, 14 Nov 2024 02:22:49 -0800 - 2024-11-14T02:22:49-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470371 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202412378 - Stabilizing Metal Coating on Flexible Devices by Ultrathin Protein Nanofilms - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470371 + Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -This work introduces a concept to use an ultrathin protein nanofilm (UPN) as an adhesive layer to enhance the adhesion between polymer substrates and metal coatings. This method enables various functionalities, including transparency control, encryption devices, optical detection, and wearable sensors, highlighting UPN's potential in flexible hybrid devices. - +Microscopic Structures in Living Tumor Characterized by Magnetic Nanoparticles +The article number 2404766 by Satoshi Ot and co‐workers delves into the magnetic relaxation response of magnetic nanoparticles within tumors, unraveling insights into cancer cell distribution, stromal components, and vascularization. The intricate world of tumor microstructures is described by the combination of the non‐biological samples. Measuring magnetic relaxation time and analyzing tumor structures paves the way for non‐invasive cancer diagnostics and therapeutics using magnetic nanoparticles. @@ -6254,53 +6219,48 @@ This work introduces a concept to use an ultrathin protein nanofilm (UPN) as an -Abstract -The significant modulus difference between a metal coating and a polymer substrate leads to interface mismatches, seriously affecting the stability of flexible devices. Therefore, enhancing the adhesion stability of a metal layer on an inert polymer substrate to prevent delamination becomes a key challenge. Herein, an ultrathin protein nanofilm (UPN), synthesized by disulfide‐bond‐reducing protein aggregation, is proposed as a strong adhesive layer to enhance adhesion between polymer substrate and metal coating. Unlike traditional biopolymer adhesives with micrometer‐scale thicknesses, the UPN layer is minimized to nanometer/single‐molecular scale. Such UPN thereby effectively enhances the interfacial adhesive strength and reduces the cohesion contribution in the entire adhesion system by directly connecting two interfaces with a nearly single‐molecular thickness. Using UPN as the adhesive layer, a multifunctional metal coating could be reliably adhered on flexible polymer substrates by ion sputtering, delivering unprecedented adhesion stability even under repetitive mechanical deformation. Applications of this design include reversible transparency control, tension‐responsive encryption, reusable optical sensing, and wearable capacitive touch sensors. This work highlights UPN's potential to create strong bonding strength between flexible polymers and metal coatings, offering a biocompatible solution with high surface activity and low cohesion, facilitating the development of hybrid devices with stable metal nano‐coating. - <img src="https://onlinelibrary.wiley.com/cms/asset/803576cd-7379-4dcf-a370-c6de20f13132/adma202412378-gra-0001-m.png" - alt="Stabilizing Metal Coating on Flexible Devices by Ultrathin Protein Nanofilms"/> -<p>This work introduces a concept to use an ultrathin protein nanofilm (UPN) as an adhesive layer to enhance the adhesion between polymer substrates and metal coatings. This method enables various functionalities, including transparency control, encryption devices, optical detection, and wearable sensors, highlighting UPN's potential in flexible hybrid devices. + <img src="https://onlinelibrary.wiley.com/cms/asset/dd3e8a01-9289-495c-bca2-4b9796d3df89/adma202470371-gra-0001-m.png" + alt="Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles (Adv. Mater. 46/2024)"/> +<p><b>Microscopic Structures in Living Tumor Characterized by Magnetic Nanoparticles</b></p> +<p>The article number <a href="https://doi.org/10.1002/adma.202404766">2404766</a> by Satoshi Ot and co-workers delves into the magnetic relaxation response of magnetic nanoparticles within tumors, unraveling insights into cancer cell distribution, stromal components, and vascularization. The intricate world of tumor microstructures is described by the combination of the non-biological samples. Measuring magnetic relaxation time and analyzing tumor structures paves the way for non-invasive cancer diagnostics and therapeutics using magnetic nanoparticles. </p> <br/> -<h2>Abstract</h2> -<p>The significant modulus difference between a metal coating and a polymer substrate leads to interface mismatches, seriously affecting the stability of flexible devices. Therefore, enhancing the adhesion stability of a metal layer on an inert polymer substrate to prevent delamination becomes a key challenge. Herein, an ultrathin protein nanofilm (UPN), synthesized by disulfide-bond-reducing protein aggregation, is proposed as a strong adhesive layer to enhance adhesion between polymer substrate and metal coating. Unlike traditional biopolymer adhesives with micrometer-scale thicknesses, the UPN layer is minimized to nanometer/single-molecular scale. Such UPN thereby effectively enhances the interfacial adhesive strength and reduces the cohesion contribution in the entire adhesion system by directly connecting two interfaces with a nearly single-molecular thickness. Using UPN as the adhesive layer, a multifunctional metal coating could be reliably adhered on flexible polymer substrates by ion sputtering, delivering unprecedented adhesion stability even under repetitive mechanical deformation. Applications of this design include reversible transparency control, tension-responsive encryption, reusable optical sensing, and wearable capacitive touch sensors. This work highlights UPN's potential to create strong bonding strength between flexible polymers and metal coatings, offering a biocompatible solution with high surface activity and low cohesion, facilitating the development of hybrid devices with stable metal nano-coating.</p> + -Yingying Zhang, -Hao Ren, -Changhong Linghu, -Jiqing Zhang, -Aiting Gao, -Hao Su, -Shuting Miao, -Rongrong Qin, -Bowen Hu, -Xiaojie Chen, -Miaoran Deng, -Yongchun Liu, -Peng Yang +Satoshi Ota, +Hiroki Kosaka, +Keita Honda, +Kota Hoshino, +Haruki Goto, +Masato Futagawa, +Yasushi Takemura, +Kosuke Shimizu - Research Article - Stabilizing Metal Coating on Flexible Devices by Ultrathin Protein Nanofilms - 10.1002/adma.202412378 + Inside Back Cover + Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles (Adv. Mater. 46/2024) + 10.1002/adma.202470371 Advanced Materials - 10.1002/adma.202412378 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412378 - Research Article + 10.1002/adma.202470371 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470371 + Inside Back Cover + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408098 - Thu, 14 Nov 2024 02:11:27 -0800 - 2024-11-14T02:11:27-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470372 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202408098 - Dual‐Phase Singularity at a Single Incident Angle with Spectral Tunability in Tamm Cavities - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202470372 + Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface (Adv. Mater. 46/2024) + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -Realizing multiple‐phase singularities is important for phase engineering in flat optics, and to improve the detection limit of refractive index sensors. The existence of a dual‐phase singularity at a single incident angle with spectral tunability and its application for ultra‐sensitive hydrogen sensing is presented using phase change material‐based tunable Tamm plasmon polariton cavities. - +Methane Electrooxidation +The cover illustration represents the electrochemical oxidation of methane on ceria‐based electrodes. The concept uses an ‘infinite staircase’ to depict the challenge of water molecule production relative to carbon dioxide production ‐ a key finding of the article number 2403626 by Hyun You Kim, WooChul Jung, and co‐workers. For example, water molecules are portrayed as struggling and slowly ascending the stairs, while carbon dioxide molecules are shown energetically and rapidly moving upward. @@ -6308,45 +6268,50 @@ Realizing multiple‐phase singularities is important for phase engineering -Abstract -The phase singularity, a sudden phase change occurring at the reflection zero is widely explored using various nanophotonic systems such as metamaterials and thin film cavities. Typically, these systems exhibit a single reflection zero with a phase singularity at a specific incident angle, particularly at larger angles of incidence (>50 degrees). However, achieving multiple phase singularities at a single incident angle remains a formidable challenge. Here, the existence of a dual‐phase singularity is experimentally demonstrated at a lower incident angle using a tunable Tamm plasmon polariton (TPP) cavity that consists of gold‐coated ultralow‐loss phase change material Sb2S3‐based distributed Bragg reflector. It can excite narrowband TPP resonances from normal incidence to a wide angle of incidence for both s‐ and p‐polarizations of light. Notably, this TPP cavity shows dual‐phase singularity at lower angles of incidence since the excited TPP for s‐ and p‐polarizations exhibits zero reflection at slightly different wavelengths for the same incident angle. A TPP cavity‐based scalable hydrogen sensor is proposed and shows that the dual‐phase singularity can further improve the sensitivity of singular phase‐based sensing approaches. Moreover, spectrally tunable dual‐phase singularity is experimentally demonstrated at a lower incident angle using a metal‐free Tamm cavity. - <img src="https://onlinelibrary.wiley.com/cms/asset/3b5bc2be-5206-43e3-bab8-5d6b8c950c72/adma202408098-gra-0001-m.png" - alt="Dual-Phase Singularity at a Single Incident Angle with Spectral Tunability in Tamm Cavities"/> -<p>Realizing multiple-phase singularities is important for phase engineering in flat optics, and to improve the detection limit of refractive index sensors. The existence of a dual-phase singularity at a single incident angle with spectral tunability and its application for ultra-sensitive hydrogen sensing is presented using phase change material-based tunable Tamm plasmon polariton cavities. + <img src="https://onlinelibrary.wiley.com/cms/asset/a75719bd-3208-4a25-a3f9-e215e6f81559/adma202470372-gra-0001-m.png" + alt="Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface (Adv. Mater. 46/2024)"/> +<p><b>Methane Electrooxidation</b></p> +<p>The cover illustration represents the electrochemical oxidation of methane on ceria-based electrodes. The concept uses an ‘infinite staircase’ to depict the challenge of water molecule production relative to carbon dioxide production - a key finding of the article number <a href="https://doi.org/10.1002/adma.202403626">2403626</a> by Hyun You Kim, WooChul Jung, and co-workers. For example, water molecules are portrayed as struggling and slowly ascending the stairs, while carbon dioxide molecules are shown energetically and rapidly moving upward. </p> <br/> -<h2>Abstract</h2> -<p>The phase singularity, a sudden phase change occurring at the reflection zero is widely explored using various nanophotonic systems such as metamaterials and thin film cavities. Typically, these systems exhibit a single reflection zero with a phase singularity at a specific incident angle, particularly at larger angles of incidence (&gt;50 degrees). However, achieving multiple phase singularities at a single incident angle remains a formidable challenge. Here, the existence of a dual-phase singularity is experimentally demonstrated at a lower incident angle using a tunable Tamm plasmon polariton (TPP) cavity that consists of gold-coated ultralow-loss phase change material Sb<sub>2</sub>S<sub>3</sub>-based distributed Bragg reflector. It can excite narrowband TPP resonances from normal incidence to a wide angle of incidence for both <i>s</i>- and <i>p</i>-polarizations of light. Notably, this TPP cavity shows dual-phase singularity at lower angles of incidence since the excited TPP for <i>s</i>- and <i>p</i>-polarizations exhibits zero reflection at slightly different wavelengths for the same incident angle. A TPP cavity-based scalable hydrogen sensor is proposed and shows that the dual-phase singularity can further improve the sensitivity of singular phase-based sensing approaches. Moreover, spectrally tunable dual-phase singularity is experimentally demonstrated at a lower incident angle using a metal-free Tamm cavity.</p> + -Kandammathe Valiyaveedu Sreekanth, -Sambhu Jana, -Qing Yang Steve Wu, -Meng Zhao, -Ranjan Singh, -Jinghua Teng +Yoonseok Choi, +Hyunwoo Ha, +Jinwook Kim, +Han Gil Seo, +Hyuk Choi, +Beomgyun Jeong, +JeongDo Yoo, +Ethan J. Crumlin, +Graeme Henkelman, +Hyun You Kim, +WooChul Jung - Research Article - Dual‐Phase Singularity at a Single Incident Angle with Spectral Tunability in Tamm Cavities - 10.1002/adma.202408098 + Back Cover + Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface (Adv. Mater. 46/2024) + 10.1002/adma.202470372 Advanced Materials - 10.1002/adma.202408098 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408098 - Research Article + 10.1002/adma.202470372 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202470372 + Back Cover + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410073 - Thu, 14 Nov 2024 02:10:18 -0800 - 2024-11-14T02:10:18-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409663 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202410073 - High‐Performance Circularly Polarized Phosphorescence by Confining Isolated Chromophores with Chiral Counterions - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202409663 + Nanosonosensitizer Optimization for Enhanced Sonodynamic Disease Treatment + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -The strategy of confining isolated chromophores is used to achieve circularly polarized phosphorescence with glum up to 0.13 and ΦP up to 43.2%. The isolated chromophore is confined by chiral counterions with asymmetric stacking through multiple ionic bonds, which not only suppress the non‐radiative transitions of the triplet excitons for phosphorescence enhancement, but also construct a rigid chiral molecular environment for efficient chirality transfer and amplification. Moreover, chiral light transformation and multiple information encryption are demonstrated in photoelectric devices. +The review summarizes, discusses, and highlights the latest optimization strategies for nanosonosensitizers in sonodynamic therapy, emphasizing their high potential for treating tumors, bacterial infections, atherosclerosis, and autoimmune disorders. This review also discusses the biosafety and biocompatibility of these nanosonosensitizers for guaranteeing the clinical translation, which further provides an overview of facing challenges and emerging opportunities in nanosonosensitizer‐enabled sonodynamic therapy, aiming to promote its clinical implementation. @@ -6356,55 +6321,48 @@ The strategy of confining isolated chromophores is used to achieve circularly po Abstract -Organic room‐temperature phosphorescence (RTP) featuring circularly polarized luminescence (CPL) is highly valuable in chiroptoelectronics, but the trade‐off issue between luminescence efficiency (Φ) and dissymmetry factor (glum) is still challenging to be solved. Here, chiroptical ionic crystals (R/S‐DNP) are constructed through ionization‐induced assembly, in which isolated chromophore of carboxylic anion is tightly confined by the surrounding chiral counterions. The long‐range ordered and chiral counterions with asymmetric stacking are closely connected with isolated chromophores for molecular assembly via high‐density electrostatic interactions, thus enabling the simultaneous realization of excellent single‐molecule RTP emission and efficient chirality transfer. The synchronous enhancement of ΦP and glum is further achieved as 43.2% and 0.13, respectively. In view of the excellent CPL performances, the ionic materials hold the promising chiroptical encryption via programmable control in an electric‐driven circularly polarized phosphorescent device. This result not only makes deeper insights into the relationship between the structure and chiral RTP property but also provides a guide to developing highly efficient chiroptical materials for potential applications. +Low‐intensity ultrasound‐mediated sonodynamic therapy (SDT), which, by design, integrates sonosensitizers and molecular oxygen to generate therapeutic substances (e.g., toxic hydroxyl radicals, superoxide anions, or singlet oxygen) at disease sites, has shown enormous potential for the effective treatment of a variety of diseases. Nanoscale sonosensitizers play a crucial role in the SDT process because their structural, compositional, physicochemical, and biological characteristics are key determinants of therapeutic efficacy. In particular, advances in materials science and nanotechnology have invigorated a series of optimization strategies for augmenting the therapeutic efficacy of nanosonosensitizers. This comprehensive review systematically summarizes, discusses, and highlights state‐of‐the‐art studies on the current achievements of nanosonosensitizer optimization in enhanced sonodynamic disease treatment, with an emphasis on the general design principles of nanosonosensitizers and their optimization strategies, mainly including organic and inorganic nanosonosensitizers. Additionally, recent advancements in optimized nanosonosensitizers for therapeutic applications aimed at treating various diseases, such as cancer, bacterial infections, atherosclerosis, and autoimmune diseases, are clarified in detail. Furthermore, the biological effects of the improved nanosonosensitizers for versatile SDT applications are thoroughly discussed. The review concludes by highlighting the current challenges and future opportunities in this rapidly evolving research field to expedite its practical clinical translation and application. - <img src="https://onlinelibrary.wiley.com/cms/asset/c801cfa0-b617-47a8-be34-82055515e908/adma202410073-gra-0001-m.png" - alt="High-Performance Circularly Polarized Phosphorescence by Confining Isolated Chromophores with Chiral Counterions"/> -<p>The strategy of confining isolated chromophores is used to achieve circularly polarized phosphorescence with <i>g</i> -<sub>lum</sub> up to 0.13 and <i>Φ</i> -<sub>P</sub> up to 43.2%. The isolated chromophore is confined by chiral counterions with asymmetric stacking through multiple ionic bonds, which not only suppress the non-radiative transitions of the triplet excitons for phosphorescence enhancement, but also construct a rigid chiral molecular environment for efficient chirality transfer and amplification. Moreover, chiral light transformation and multiple information encryption are demonstrated in photoelectric devices. + <img src="https://onlinelibrary.wiley.com/cms/asset/65f009b8-456e-44dd-b34e-8d5bd9e1b16d/adma202409663-gra-0001-m.png" + alt="Nanosonosensitizer Optimization for Enhanced Sonodynamic Disease Treatment"/> +<p>The review summarizes, discusses, and highlights the latest optimization strategies for nanosonosensitizers in sonodynamic therapy, emphasizing their high potential for treating tumors, bacterial infections, atherosclerosis, and autoimmune disorders. This review also discusses the biosafety and biocompatibility of these nanosonosensitizers for guaranteeing the clinical translation, which further provides an overview of facing challenges and emerging opportunities in nanosonosensitizer-enabled sonodynamic therapy, aiming to promote its clinical implementation. </p> <br/> <h2>Abstract</h2> -<p>Organic room-temperature phosphorescence (RTP) featuring circularly polarized luminescence (CPL) is highly valuable in chiroptoelectronics, but the trade-off issue between luminescence efficiency (<i>Φ</i>) and dissymmetry factor (<i>g</i> -<sub>lum</sub>) is still challenging to be solved. Here, chiroptical ionic crystals (<i>R/S</i>-DNP) are constructed through ionization-induced assembly, in which isolated chromophore of carboxylic anion is tightly confined by the surrounding chiral counterions. The long-range ordered and chiral counterions with asymmetric stacking are closely connected with isolated chromophores for molecular assembly via high-density electrostatic interactions, thus enabling the simultaneous realization of excellent single-molecule RTP emission and efficient chirality transfer. The synchronous enhancement of <i>Φ</i> -<sub>P</sub> and <i>g</i> -<sub>lum</sub> is further achieved as 43.2% and 0.13, respectively. In view of the excellent CPL performances, the ionic materials hold the promising chiroptical encryption via programmable control in an electric-driven circularly polarized phosphorescent device. This result not only makes deeper insights into the relationship between the structure and chiral RTP property but also provides a guide to developing highly efficient chiroptical materials for potential applications.</p> +<p>Low-intensity ultrasound-mediated sonodynamic therapy (SDT), which, by design, integrates sonosensitizers and molecular oxygen to generate therapeutic substances (e.g., toxic hydroxyl radicals, superoxide anions, or singlet oxygen) at disease sites, has shown enormous potential for the effective treatment of a variety of diseases. Nanoscale sonosensitizers play a crucial role in the SDT process because their structural, compositional, physicochemical, and biological characteristics are key determinants of therapeutic efficacy. In particular, advances in materials science and nanotechnology have invigorated a series of optimization strategies for augmenting the therapeutic efficacy of nanosonosensitizers. This comprehensive review systematically summarizes, discusses, and highlights state-of-the-art studies on the current achievements of nanosonosensitizer optimization in enhanced sonodynamic disease treatment, with an emphasis on the general design principles of nanosonosensitizers and their optimization strategies, mainly including organic and inorganic nanosonosensitizers. Additionally, recent advancements in optimized nanosonosensitizers for therapeutic applications aimed at treating various diseases, such as cancer, bacterial infections, atherosclerosis, and autoimmune diseases, are clarified in detail. Furthermore, the biological effects of the improved nanosonosensitizers for versatile SDT applications are thoroughly discussed. The review concludes by highlighting the current challenges and future opportunities in this rapidly evolving research field to expedite its practical clinical translation and application.</p> -Wenpeng Ye, -Zhengong Meng, -Guixiang Zhan, -Anqi Lv, -Yanhua Gao, -Kang Shen, -Huili Ma, -Huifang Shi, -Wei Yao, -Lin Wang, -Wei Huang, -Zhongfu An +Min Zhang, +Dandan Sun, +Hui Huang, +Dayan Yang, +Xinran Song, +Wei Feng, +Xiangxiang Jing, +Yu Chen - Research Article - High‐Performance Circularly Polarized Phosphorescence by Confining Isolated Chromophores with Chiral Counterions - 10.1002/adma.202410073 + Review + Nanosonosensitizer Optimization for Enhanced Sonodynamic Disease Treatment + 10.1002/adma.202409663 Advanced Materials - 10.1002/adma.202410073 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410073 - Research Article + 10.1002/adma.202409663 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202409663 + Review + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412187 - Wed, 13 Nov 2024 22:14:50 -0800 - 2024-11-13T10:14:50-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410704 + Thu, 14 Nov 2024 22:16:54 -0800 + 2024-11-14T10:16:54-08:00 Wiley: Advanced Materials: Table of Contents - - - 10.1002/adma.202412187 - Water‐Stable Magnetic Lipiodol Micro‐Droplets as a Miniaturized Robotic Tool for Drug Delivery - Advanced Materials, EarlyView. + Fri, 01 Nov 2024 00:00:00 -0700 + Fri, 01 Nov 2024 00:00:00 -0700 + 10.1002/adma.202410704 + Routes to Bidirectional Cathodes for Reversible Aprotic Alkali Metal–CO2 Batteries + Advanced Materials, Volume 36, Issue 46, November 14, 2024. -A novel formulation referred to water‐stable magnetic lipiodol micro‐droplets (MLMD) possesses properties such as flowability, shape adaptability, efficient drug loading, and compatibility with digital subtraction angiography (DSA) imaging is presented. On this basis, a close‐looped magnetic navigation system featuring artificial intelligence (AI)‐driven visual feedback for autonomous control has also been designed, to improve MLMD maneuverability in image‐guided therapy. +This review summarizes the CO2 conversion reaction mechanisms and the “engineering strategies from internal catalyst to the external environment–cathode properties–CO2 conversion reaction kinetics and mechanisms–batteries performance” relationship through calculation and experiment results, to provide routes to bidirectional cathodes for reversible aprotic alkali metal–CO2 batteries and other gas batteries. @@ -6414,59 +6372,49 @@ A novel formulation referred to water‐stable magnetic lipiodol micro‐ Abstract -Magnetic microrobots, designed to navigate the complex environments of the human body, show promise for minimally invasive diagnosis and treatment. However, their clinical adoption faces hurdles such as biocompatibility, precise control, and intelligent tracking. Here a novel formulation (referred to water‐stable magnetic lipiodol micro‐droplets, MLMD), integrating clinically approved lipiodol, gelatin, and superparamagnetic iron oxide nanoparticles (SPION) with a fundamental understanding of the structure‐property relationships is presented. This formulation demonstrates multiple improved properties including flowability, shape adaptability, efficient drug loading, and compatibility with digital subtraction angiography (DSA) imaging in both in vitro and in vivo experiments. This enables the MLMD as a versatile tool for image‐guided therapy, supported by a close‐looped magnetic navigation system featuring artificial intelligence (AI)‐driven visual feedback for autonomous control. The system effectively performs navigational tasks, including pinpointing specific locations of MLMD, recognizing and avoiding obstacles, mapping and following predetermined paths, and utilizing magnetic fields for precise motion planning to achieve visual drug delivery. The MLMD combines magnetic actuation with an AI‐directed close‐looped navigation, offering a transformative platform for targeted therapeutic delivery. +Aprotic alkali metal–CO2 batteries (AAMCBs) have garnered significant interest owing to fixing CO2 and providing large energy storage capacity. The practical implementation of AAMCBs is constrained by the sluggish kinetics of the CO2 reduction reaction (CO2RR) and the CO2 evolution reaction (CO2ER). Because the CO2ER and CO2RR take place on the cathode, which connects the internal catalyst with the external environment. Building a bidirectional cathode with excellent CO2ER and CO2RR kinetics by optimizing the cathode's internal catalyst and environment has attracted most of the attention to improving the electrochemical performance of AAMCBs. However, there remains a lack of comprehensive understanding. This review aims to give a route to bidirectional cathodes for reversible AAMCBs, by systematically discussing engineering strategies of both the internal catalyst (atomic, nanoscopic, and macroscopic levels) and the external environment (photo, photo‐thermal, and force field). The CO2ER and CO2RR mechanisms and the “engineering strategies from internal catalyst to the external environment–cathode properties–CO2RR and CO2ER kinetics and mechanisms–batteries performance” relationship are elucidated by combining computational and experimental approaches. This review establishes a fundamental understanding for designing bidirectional cathodes and gives a route for developing reversible AAMCBs and similar metal–gas battery systems. - <img src="https://onlinelibrary.wiley.com/cms/asset/d2212d83-78ce-418c-a857-8dbbb46a271d/adma202412187-gra-0001-m.png" - alt="Water-Stable Magnetic Lipiodol Micro-Droplets as a Miniaturized Robotic Tool for Drug Delivery"/> -<p>A novel formulation referred to water-stable magnetic lipiodol micro-droplets (MLMD) possesses properties such as flowability, shape adaptability, efficient drug loading, and compatibility with digital subtraction angiography (DSA) imaging is presented. On this basis, a close-looped magnetic navigation system featuring artificial intelligence (AI)-driven visual feedback for autonomous control has also been designed, to improve MLMD maneuverability in image-guided therapy. + <img src="https://onlinelibrary.wiley.com/cms/asset/a177e1a8-5c7d-408a-a3fe-b7064896370c/adma202410704-gra-0001-m.png" + alt="Routes to Bidirectional Cathodes for Reversible Aprotic Alkali Metal–CO2 Batteries"/> +<p>This review summarizes the CO<sub>2</sub> conversion reaction mechanisms and the “engineering strategies from internal catalyst to the external environment–cathode properties–CO<sub>2</sub> conversion reaction kinetics and mechanisms–batteries performance” relationship through calculation and experiment results, to provide routes to bidirectional cathodes for reversible aprotic alkali metal–CO<sub>2</sub> batteries and other gas batteries. </p> <br/> <h2>Abstract</h2> -<p>Magnetic microrobots, designed to navigate the complex environments of the human body, show promise for minimally invasive diagnosis and treatment. However, their clinical adoption faces hurdles such as biocompatibility, precise control, and intelligent tracking. Here a novel formulation (referred to water-stable magnetic lipiodol micro-droplets, MLMD), integrating clinically approved lipiodol, gelatin, and superparamagnetic iron oxide nanoparticles (SPION) with a fundamental understanding of the structure-property relationships is presented. This formulation demonstrates multiple improved properties including flowability, shape adaptability, efficient drug loading, and compatibility with digital subtraction angiography (DSA) imaging in both in vitro and in vivo experiments. This enables the MLMD as a versatile tool for image-guided therapy, supported by a close-looped magnetic navigation system featuring artificial intelligence (AI)-driven visual feedback for autonomous control. The system effectively performs navigational tasks, including pinpointing specific locations of MLMD, recognizing and avoiding obstacles, mapping and following predetermined paths, and utilizing magnetic fields for precise motion planning to achieve visual drug delivery. The MLMD combines magnetic actuation with an AI-directed close-looped navigation, offering a transformative platform for targeted therapeutic delivery.</p> +<p>Aprotic alkali metal–CO<sub>2</sub> batteries (AAMCBs) have garnered significant interest owing to fixing CO<sub>2</sub> and providing large energy storage capacity. The practical implementation of AAMCBs is constrained by the sluggish kinetics of the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) and the CO<sub>2</sub> evolution reaction (CO<sub>2</sub>ER). Because the CO<sub>2</sub>ER and CO<sub>2</sub>RR take place on the cathode, which connects the internal catalyst with the external environment. Building a bidirectional cathode with excellent CO<sub>2</sub>ER and CO<sub>2</sub>RR kinetics by optimizing the cathode's internal catalyst and environment has attracted most of the attention to improving the electrochemical performance of AAMCBs. However, there remains a lack of comprehensive understanding. This review aims to give a route to bidirectional cathodes for reversible AAMCBs, by systematically discussing engineering strategies of both the internal catalyst (atomic, nanoscopic, and macroscopic levels) and the external environment (photo, photo-thermal, and force field). The CO<sub>2</sub>ER and CO<sub>2</sub>RR mechanisms and the “engineering strategies from internal catalyst to the external environment–cathode properties–CO<sub>2</sub>RR and CO<sub>2</sub>ER kinetics and mechanisms–batteries performance” relationship are elucidated by combining computational and experimental approaches. This review establishes a fundamental understanding for designing bidirectional cathodes and gives a route for developing reversible AAMCBs and similar metal–gas battery systems.</p> -En Ren, -Jing Hu, -Ziyang Mei, -Lin Lin, -Qian Zhang, -Pan He, -Junqing Wang, -Tao Sheng, -Hu Chen, -Hongwei Cheng, -Tiantian Xu, -Shiyao Pang, -Yang Zhang, -Qixuan Dai, -Xing Gao, -Hui Liu, -Hongjun Li, -Yang Zhao, -Zhen Gu, -Xiaohui Yan, -Gang Liu +Yihao Cheng, +Yuxuan Wang, +Biao Chen, +Xiaopeng Han, +Fang He, +Chunnian He, +Wenbin Hu, +Guangmin Zhou, +Naiqin Zhao - Research Article - Water‐Stable Magnetic Lipiodol Micro‐Droplets as a Miniaturized Robotic Tool for Drug Delivery - 10.1002/adma.202412187 + Review + Routes to Bidirectional Cathodes for Reversible Aprotic Alkali Metal–CO2 Batteries + 10.1002/adma.202410704 Advanced Materials - 10.1002/adma.202412187 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412187 - Research Article + 10.1002/adma.202410704 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410704 + Review + 36 + 46 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412962 - Wed, 13 Nov 2024 22:14:02 -0800 - 2024-11-13T10:14:02-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411449 + Thu, 14 Nov 2024 21:20:48 -0800 + 2024-11-14T09:20:48-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412962 - Programmable Shape‐Morphing Enables Ceramic Meta‐Aerogel Highly Stretchable for Thermal Protection + 10.1002/adma.202411449 + Plasticizer Design Principle of “Like Dissolves Like”: Semiconductor Fluid Plasticized Stretchable Fully π‐Conjugated Polymers Films for Uniform Large‐Area and Flexible Deep‐Blue Polymer Light‐Emitting Diodes Advanced Materials, EarlyView. -Stretchable ceramic meta‐aerogel with a binary cellular structure, combining anisotropic lamellated aerogel (grid section) and isotropic random aerogel (mesh section), is fabricated using kirigami stacking and subsequent nanofiber freeze‐drying techniques. This specific topological structure design enables the meta‐aerogel robust structure, highly elastic tensile deformation, exceptional fatigue resistance for tensile, compressive, and buckling cycles, temperature‐invariant superelastic, superior thermal insulation; and these properties make it a potential application for exploring thermal protective materials. +“Like Dissolves Like” design principle is established to prepare semiconductor fluid plasticizers for the preparation of intrinsically stretchable FπCPs films in flexible electronics. Model matched nonpolar M1 plasticizer is achieved to obtain stretchable PFO blended films. Plasticized PFO film presents an efficient, narrowband and stable deep‐blue emission, uniform morphology, and excellent intrinsic stretchability for the fabrication of deep‐blue FPLEDs. @@ -6476,41 +6424,50 @@ Stretchable ceramic meta‐aerogel with a binary cellular structure, combini Abstract -Ceramic aerogels hold significant potential for thermal insulation, yet their mechanical stretchability and thermal stability fall short in extreme environments. Here, the study presents a programmable shape‐morphing strategy aimed at engineering a binary network topology structure within ceramic aerogels to effectively dissipate stress and block heat transfer. The special topology design, which includes kirigami lamellated aerogels for bearing loading stress and randomly assembled aerogels for mechanical energy pre‐storage to transfer tensile stress, effectively achieves unexpected mechanical tensile properties and thermal stability. The resulting robust meta‐aerogels demonstrate remarkable structural stability with topology‐derived mechanical tensile of up to 85% strain, excellent resilience to 500 cycles of 50% tensile strain, 1000 cycles of 60% buckling strain, and 500 cycles of 50% compressive strain, temperature‐invariant tensile recovery capability; simultaneously, low thermal conductivity of 33.01 mW m−1 K−1 and tensile‐invariant thermal insulation makes the ceramic meta‐aerogels an ideal substitute material for various applications. +Physical blending of fully π‐conjugated polymers (FπCPs) is an effective strategy to achieve intrinsically stretchable films for the fabrication of flexible optoelectronic devices, but easily causes phase separation, nonuniform morphology and uncontrollable photo‐electronic processing. This may cause low efficiency, unstable and nonuniform emission, and poor color purity, which are undesirable for deep‐blue flexible polymer light‐emitting diodes (FPLEDs). Herein, a “Like Dissolves Like” design principle to prepare semiconductor fluid plasticizers (SFPs) is established and intrinsically stretchable FπCPs films via external plasticization for high‐performance deep‐blue FPLEDs are developed. Three fundamental requirements are proposed, “similar conjugated skeleton, similar molecular polarity, and similar electronic structures,” to prepare model‐matched nonpolar M1 and polar M2 plasticizers for poly(9,9‐dioctylfluorene) (PFO). Large‐area plasticized PFO films exhibit an efficient, narrowband, and stable ultra‐deep‐blue electroluminescence (FWHM < 40 nm, CIE: 0.12, 0.04), uniform morphology, and excellent intrinsic stretchability (fracture strain >20% and crack‐onset strain >120%). Efficient and uniform deep‐blue FPLEDs based on stretchable PFO films are fabricated with a high brightness of ≈3000 cd cm−2. Finally, blended PFO films exhibit outstanding stretch‐deformation cycling stability of their deep‐blue electroluminescent behavior, confirming the effectiveness of the “Like Dissolves Like” principle to design matched SFPs for stretchable FπCP films in flexible electronics. - <img src="https://onlinelibrary.wiley.com/cms/asset/c57dcb1d-d016-4832-9579-0b1bda0cd31f/adma202412962-gra-0001-m.png" - alt="Programmable Shape-Morphing Enables Ceramic Meta-Aerogel Highly Stretchable for Thermal Protection"/> -<p>Stretchable ceramic meta-aerogel with a binary cellular structure, combining anisotropic lamellated aerogel (grid section) and isotropic random aerogel (mesh section), is fabricated using kirigami stacking and subsequent nanofiber freeze-drying techniques. This specific topological structure design enables the meta-aerogel robust structure, highly elastic tensile deformation, exceptional fatigue resistance for tensile, compressive, and buckling cycles, temperature-invariant superelastic, superior thermal insulation; and these properties make it a potential application for exploring thermal protective materials. + <img src="https://onlinelibrary.wiley.com/cms/asset/44e73300-920b-4add-b0fd-b1965db367c9/adma202411449-gra-0001-m.png" + alt="Plasticizer Design Principle of “Like Dissolves Like”: Semiconductor Fluid Plasticized Stretchable Fully π-Conjugated Polymers Films for Uniform Large-Area and Flexible Deep-Blue Polymer Light-Emitting Diodes"/> +<p>“Like Dissolves Like” design principle is established to prepare semiconductor fluid plasticizers for the preparation of intrinsically stretchable FπCPs films in flexible electronics. Model matched nonpolar M1 plasticizer is achieved to obtain stretchable PFO blended films. Plasticized PFO film presents an efficient, narrowband and stable deep-blue emission, uniform morphology, and excellent intrinsic stretchability for the fabrication of deep-blue FPLEDs. </p> <br/> <h2>Abstract</h2> -<p>Ceramic aerogels hold significant potential for thermal insulation, yet their mechanical stretchability and thermal stability fall short in extreme environments. Here, the study presents a programmable shape-morphing strategy aimed at engineering a binary network topology structure within ceramic aerogels to effectively dissipate stress and block heat transfer. The special topology design, which includes kirigami lamellated aerogels for bearing loading stress and randomly assembled aerogels for mechanical energy pre-storage to transfer tensile stress, effectively achieves unexpected mechanical tensile properties and thermal stability. The resulting robust meta-aerogels demonstrate remarkable structural stability with topology-derived mechanical tensile of up to 85% strain, excellent resilience to 500 cycles of 50% tensile strain, 1000 cycles of 60% buckling strain, and 500 cycles of 50% compressive strain, temperature-invariant tensile recovery capability; simultaneously, low thermal conductivity of 33.01 mW m<sup>−1</sup> K<sup>−1</sup> and tensile-invariant thermal insulation makes the ceramic meta-aerogels an ideal substitute material for various applications.</p> +<p>Physical blending of fully π-conjugated polymers (FπCPs) is an effective strategy to achieve intrinsically stretchable films for the fabrication of flexible optoelectronic devices, but easily causes phase separation, nonuniform morphology and uncontrollable photo-electronic processing. This may cause low efficiency, unstable and nonuniform emission, and poor color purity, which are undesirable for deep-blue flexible polymer light-emitting diodes (FPLEDs). Herein, a “Like Dissolves Like” design principle to prepare semiconductor fluid plasticizers (SFPs) is established and intrinsically stretchable FπCPs films via external plasticization for high-performance deep-blue FPLEDs are developed. Three fundamental requirements are proposed, “similar conjugated skeleton, similar molecular polarity, and similar electronic structures,” to prepare model-matched nonpolar M1 and polar M2 plasticizers for poly(9,9-dioctylfluorene) (PFO). Large-area plasticized PFO films exhibit an efficient, narrowband, and stable ultra-deep-blue electroluminescence (FWHM &lt; 40 nm, CIE: 0.12, 0.04), uniform morphology, and excellent intrinsic stretchability (fracture strain &gt;20% and crack-onset strain &gt;120%). Efficient and uniform deep-blue FPLEDs based on stretchable PFO films are fabricated with a high brightness of ≈3000 cd cm<sup>−2</sup>. Finally, blended PFO films exhibit outstanding stretch-deformation cycling stability of their deep-blue electroluminescent behavior, confirming the effectiveness of the “Like Dissolves Like” principle to design matched SFPs for stretchable FπCP films in flexible electronics.</p> -Xuan Zhang, -Jianyong Yu, -Yang Si +Jingyao Ma, +Man Xu, +Zhiqiang Zhuo, +Kuande Wang, +Qianyi Li, +Hao Li, +Quanyou Feng, +Wenyu Chen, +Ningning Yu, +Mengyuan Li, +Linghai Xie, +Jinyi Lin Research Article - Programmable Shape‐Morphing Enables Ceramic Meta‐Aerogel Highly Stretchable for Thermal Protection - 10.1002/adma.202412962 + Plasticizer Design Principle of “Like Dissolves Like”: Semiconductor Fluid Plasticized Stretchable Fully π‐Conjugated Polymers Films for Uniform Large‐Area and Flexible Deep‐Blue Polymer Light‐Emitting Diodes + 10.1002/adma.202411449 Advanced Materials - 10.1002/adma.202412962 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412962 + 10.1002/adma.202411449 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411449 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413862 - Wed, 13 Nov 2024 22:13:15 -0800 - 2024-11-13T10:13:15-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407156 + Thu, 14 Nov 2024 21:20:20 -0800 + 2024-11-14T09:20:20-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413862 - A Simple Route for Open Fluidic Devices with Particle Walls + 10.1002/adma.202407156 + Biocooperative Regenerative Materials by Harnessing Blood‐Clotting and Peptide Self‐Assembly Advanced Materials, EarlyView. -Open fluidic devices are produced by integrating substrate patterning and particle walls, where there is a broad range of particle choices including carbon nanotubes (CNTs) and monolayers of SiO2 nanoparticles. The strategy allows for arbitrary production and extraordinary manipulation of open fluidic devices with significant potential for applications. +Nature has evolved to repair small fractures by leveraging the cellular and molecular components of regenerative hematoma (RH). This study introduces a biocooperative material approach that enables the use of key endogenous molecules and processes to engineer living regenerative biomaterials with tuneable structural and biological properties. in vitro and in vivo validation is demonstrated. @@ -6520,44 +6477,49 @@ Open fluidic devices are produced by integrating substrate patterning and partic Abstract -Open fluidics, allowing liquid in a flow channel to interact with the external environment, is a revolutionary concept. However, fabricating a highly stable open fluidic device of arbitrary complexity, while maintaining reconfigurability, is still a challenge. This is achieved by the use of a patterned substrate and liquids that are covered with functional, readily available hydrophobic particles, providing great flexibility in the construction and use of open fluidic structures. Decorated with a coating of modified carbon nanotubes (CNTs) to encapsulate the fluids, the study capitalizes on the photothermal characteristics of CNTs to fabricate a device to probe the effects of temperature on tumor chemotherapy. The strategy substantially increases the availability and potential use of open fluidic devices. +The immune system has evolved to heal small ruptures and fractures with remarkable efficacy through regulation of the regenerative hematoma (RH); a rich and dynamic environment that coordinates numerous molecular and cellular processes to achieve complete repair. Here, a biocooperative approach that harnesses endogenous molecules and natural healing to engineer personalized regenerative materials is presented. Peptide amphiphiles (PAs) are co‐assembled with blood components during coagulation to engineer a living material that exhibits key compositional and structural properties of the RH. By exploiting non‐selective and selective PA‐blood interactions, the material can be immediately manipulated, mechanically‐tuned, and 3D printed. The material preserves normal platelet behavior, generates and provides a continuous source of growth factors, and promotes in vitro growth of mesenchymal stromal cells, endothelial cells, and fibroblasts. Furthermore, using a personalized autologous approach to convert whole blood into PA‐blood gel implants, bone regeneration is shown in a critical‐sized rat calvarial defect. This study provides proof‐of‐concept for a biocooperative approach that goes beyond biomimicry by using mechanisms that Nature has evolved to heal as tools to engineer accessible, personalized, and regenerative biomaterials that can be readily formed at point of use. - <img src="https://onlinelibrary.wiley.com/cms/asset/c4cb375b-dca2-4ce4-ae82-0b434ef727f0/adma202413862-gra-0001-m.png" - alt="A Simple Route for Open Fluidic Devices with Particle Walls"/> -<p>Open fluidic devices are produced by integrating substrate patterning and particle walls, where there is a broad range of particle choices including carbon nanotubes (CNTs) and monolayers of SiO<sub>2</sub> nanoparticles. The strategy allows for arbitrary production and extraordinary manipulation of open fluidic devices with significant potential for applications. + <img src="https://onlinelibrary.wiley.com/cms/asset/5d347ea1-7a79-419e-8cba-3d5a99599cfc/adma202407156-gra-0001-m.png" + alt="Biocooperative Regenerative Materials by Harnessing Blood-Clotting and Peptide Self-Assembly"/> +<p>Nature has evolved to repair small fractures by leveraging the cellular and molecular components of regenerative hematoma (RH). This study introduces a biocooperative material approach that enables the use of key endogenous molecules and processes to engineer living regenerative biomaterials with tuneable structural and biological properties. in vitro and in vivo validation is demonstrated. </p> <br/> <h2>Abstract</h2> -<p>Open fluidics, allowing liquid in a flow channel to interact with the external environment, is a revolutionary concept. However, fabricating a highly stable open fluidic device of arbitrary complexity, while maintaining reconfigurability, is still a challenge. This is achieved by the use of a patterned substrate and liquids that are covered with functional, readily available hydrophobic particles, providing great flexibility in the construction and use of open fluidic structures. Decorated with a coating of modified carbon nanotubes (CNTs) to encapsulate the fluids, the study capitalizes on the photothermal characteristics of CNTs to fabricate a device to probe the effects of temperature on tumor chemotherapy. The strategy substantially increases the availability and potential use of open fluidic devices.</p> +<p>The immune system has evolved to heal small ruptures and fractures with remarkable efficacy through regulation of the regenerative hematoma (RH); a rich and dynamic environment that coordinates numerous molecular and cellular processes to achieve complete repair. Here, a biocooperative approach that harnesses endogenous molecules and natural healing to engineer personalized regenerative materials is presented. Peptide amphiphiles (PAs) are co-assembled with blood components during coagulation to engineer a living material that exhibits key compositional and structural properties of the RH. By exploiting non-selective and selective PA-blood interactions, the material can be immediately manipulated, mechanically-tuned, and 3D printed. The material preserves normal platelet behavior, generates and provides a continuous source of growth factors, and promotes in vitro growth of mesenchymal stromal cells, endothelial cells, and fibroblasts. Furthermore, using a personalized autologous approach to convert whole blood into PA-blood gel implants, bone regeneration is shown in a critical-sized rat calvarial defect. This study provides proof-of-concept for a biocooperative approach that goes beyond biomimicry by using mechanisms that Nature has evolved to heal as tools to engineer accessible, personalized, and regenerative biomaterials that can be readily formed at point of use.</p> -Heng Liu, -Xianglong Pang, -Mei Duan, -Zhujun Yang, -Thomas P. Russell, -Xiaoguang Li +Soraya Padilla‐Lopategui, +Cosimo Ligorio, +Wenhuan Bu, +Chengcheng Yin, +Domenico Laurenza, +Carlos Redondo, +Robert Owen, +Hongchen Sun, +Felicity R.A.J. Rose, +Thomas Iskratsch, +Alvaro Mata Research Article - A Simple Route for Open Fluidic Devices with Particle Walls - 10.1002/adma.202413862 + Biocooperative Regenerative Materials by Harnessing Blood‐Clotting and Peptide Self‐Assembly + 10.1002/adma.202407156 Advanced Materials - 10.1002/adma.202413862 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413862 + 10.1002/adma.202407156 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202407156 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412637 - Wed, 13 Nov 2024 22:12:35 -0800 - 2024-11-13T10:12:35-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413268 + Thu, 14 Nov 2024 20:39:59 -0800 + 2024-11-14T08:39:59-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412637 - Differentiated Intra‐Ligand Charge Transfer Boosting Multicolor Responsive MOF Heterostructures as Robust Anti‐Counterfeiting Labels + 10.1002/adma.202413268 + An Ultrahigh‐Modulus Hydrogel Electrolyte for Dendrite‐Free Zinc Ion Batteries Advanced Materials, EarlyView. -The differentiated design on intra‐ligand charge transfer is first reported to realize multicolor responsive metal–organic framework (MOF) heterostructures, which display the distinct responsive MOF regions under the same mild stimuli and generate multiple tunable color patterns, further functioning as robust photonic barcodes with high‐security convert states. These results provide enlightenment on the development of a smart‐responsive MOF heterosystem for advanced anti‐counterfeiting applications. +Ultra‐tough hydrogel electrolytes with hydrophobic domains (established through dipole‐dipole interactions) and crystalline domains (formed via hydrogen bonds) are obtained by a strategy combining wet‐annealing, solvent‐exchange, and salting‐out processes. The synergy between nanoscale phase separation and high crystallinity results in the hydrogel electrolytes with excellent mechanical properties while maintaining high water contents. @@ -6567,47 +6529,45 @@ The differentiated design on intra‐ligand charge transfer is first reporte Abstract -Metal–organic framework (MOF) heterostructures with hybrid architectures and abundant functional sites possess great potential applications in advanced information security, yet still suffer from the harsh stimuli mechanisms with restrained emission control. Herein, the differentiated design strategy on intra‐ligand charge transfer is first reported to realize smart‐responsive multicolor MOF heterostructures as robust anticounterfeiting labels. Designed similar MOF blocks with the differentiated intra‐ligand charge transfer are integrated via time‐dependent epitaxial growth to form multicolor MOF heterostructures. Different numbers of electron‐donating groups in MOF blocks offer distinct space regulation on the torsion of charge transfer ligands, which trigger the diverse responsive emissions under the same mild stimuli, thus generating multiple tunable color patterns in heterostructures. These spatial‐resolved MOF heterostructures with stable multicolor responsive modes permit the encoding of fingerprint information, which further functions as robust anti‐counterfeiting labels with high‐security convert states. These results offer a promising route for the function‐oriented exploitation of smart‐responsive MOF heterosystems for advanced information anticounterfeiting. +Quasi‐solid‐state aqueous zinc ion batteries suffer from anodic zinc dendrite growth during plating/stripping processes, impeding their commercial application. The inhibition of zinc dendrites by high‐modulus electrolytes has been proven to be effective. However, hydrogel electrolytes are difficult to achieve high modulus owing to their inherent high water contents. This work reports a hydrogel electrolyte with ultrahigh modulus that can overcome the growth stress of zinc dendrites through mechanical suppression effect. By combining wet‐annealing, solvent‐exchange, and salting‐out processes and tuning the hydrophobic and crystalline domains, a hydrogel electrolyte is obtained with substantial water content (≈70%), high modulus (198.5 MPa), high toughness (274.3 MJ m−3), and high zinc‐ion conductivity (28.9 mS cm−1), which significantly outperforms the previously reported poly(vinyl alcohol)‐based hydrogels. As a result, the hydrogel electrolyte exhibits excellent dendrite‐suppression effect and achieves stable performance in Zn||Zn symmetric batteries (1800 h of cycle life at 1 mA cm−2). Moreover, the Zn||V2O5 pouch batteries display excellent cycling life and operate stably even under extreme conditions, such as large bending angle (180°) and automotive crushing. This work provides a promising approach for designing mechanically reliable hydrogel electrolytes for advanced aqueous zinc ion batteries. - <img src="https://onlinelibrary.wiley.com/cms/asset/e4fa1b2b-a1aa-4f20-ac9f-5fb8ae4b66a0/adma202412637-gra-0001-m.png" - alt="Differentiated Intra-Ligand Charge Transfer Boosting Multicolor Responsive MOF Heterostructures as Robust Anti-Counterfeiting Labels"/> -<p>The differentiated design on intra-ligand charge transfer is first reported to realize multicolor responsive metal–organic framework (MOF) heterostructures, which display the distinct responsive MOF regions under the same mild stimuli and generate multiple tunable color patterns, further functioning as robust photonic barcodes with high-security convert states. These results provide enlightenment on the development of a smart-responsive MOF heterosystem for advanced anti-counterfeiting applications. + <img src="https://onlinelibrary.wiley.com/cms/asset/f7703d3a-e319-45df-982e-4d22de7475ba/adma202413268-gra-0001-m.png" + alt="An Ultrahigh-Modulus Hydrogel Electrolyte for Dendrite-Free Zinc Ion Batteries"/> +<p>Ultra-tough hydrogel electrolytes with hydrophobic domains (established through dipole-dipole interactions) and crystalline domains (formed via hydrogen bonds) are obtained by a strategy combining wet-annealing, solvent-exchange, and salting-out processes. The synergy between nanoscale phase separation and high crystallinity results in the hydrogel electrolytes with excellent mechanical properties while maintaining high water contents. </p> <br/> <h2>Abstract</h2> -<p>Metal–organic framework (MOF) heterostructures with hybrid architectures and abundant functional sites possess great potential applications in advanced information security, yet still suffer from the harsh stimuli mechanisms with restrained emission control. Herein, the differentiated design strategy on intra-ligand charge transfer is first reported to realize smart-responsive multicolor MOF heterostructures as robust anticounterfeiting labels. Designed similar MOF blocks with the differentiated intra-ligand charge transfer are integrated via time-dependent epitaxial growth to form multicolor MOF heterostructures. Different numbers of electron-donating groups in MOF blocks offer distinct space regulation on the torsion of charge transfer ligands, which trigger the diverse responsive emissions under the same mild stimuli, thus generating multiple tunable color patterns in heterostructures. These spatial-resolved MOF heterostructures with stable multicolor responsive modes permit the encoding of fingerprint information, which further functions as robust anti-counterfeiting labels with high-security convert states. These results offer a promising route for the function-oriented exploitation of smart-responsive MOF heterosystems for advanced information anticounterfeiting.</p> +<p>Quasi-solid-state aqueous zinc ion batteries suffer from anodic zinc dendrite growth during plating/stripping processes, impeding their commercial application. The inhibition of zinc dendrites by high-modulus electrolytes has been proven to be effective. However, hydrogel electrolytes are difficult to achieve high modulus owing to their inherent high water contents. This work reports a hydrogel electrolyte with ultrahigh modulus that can overcome the growth stress of zinc dendrites through mechanical suppression effect. By combining wet-annealing, solvent-exchange, and salting-out processes and tuning the hydrophobic and crystalline domains, a hydrogel electrolyte is obtained with substantial water content (≈70%), high modulus (198.5 MPa), high toughness (274.3 MJ m<sup>−3</sup>), and high zinc-ion conductivity (28.9 mS cm<sup>−1</sup>), which significantly outperforms the previously reported poly(vinyl alcohol)-based hydrogels. As a result, the hydrogel electrolyte exhibits excellent dendrite-suppression effect and achieves stable performance in Zn||Zn symmetric batteries (1800 h of cycle life at 1 mA cm<sup>−2</sup>). Moreover, the Zn||V<sub>2</sub>O<sub>5</sub> pouch batteries display excellent cycling life and operate stably even under extreme conditions, such as large bending angle (180°) and automotive crushing. This work provides a promising approach for designing mechanically reliable hydrogel electrolytes for advanced aqueous zinc ion batteries.</p> -Yuanchao Lv, -Chenwei Lin, -Xinming Liu, -Jiashuai Liang, -Yunbin Li, -Zizhu Yao, -Shengchang Xiang, -Banglin Chen, -Zhangjing Zhang +Zong‐Ju Chen, +Tian‐Yu Shen, +Xiong Xiao, +Xiu‐Chong He, +Yan‐Long Luo, +Zhong Jin, +Cheng‐Hui Li Research Article - Differentiated Intra‐Ligand Charge Transfer Boosting Multicolor Responsive MOF Heterostructures as Robust Anti‐Counterfeiting Labels - 10.1002/adma.202412637 + An Ultrahigh‐Modulus Hydrogel Electrolyte for Dendrite‐Free Zinc Ion Batteries + 10.1002/adma.202413268 Advanced Materials - 10.1002/adma.202412637 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412637 + 10.1002/adma.202413268 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202413268 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412344 - Wed, 13 Nov 2024 22:11:02 -0800 - 2024-11-13T10:11:02-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406118 + Thu, 14 Nov 2024 20:29:09 -0800 + 2024-11-14T08:29:09-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412344 - Giant Piezoelectric Coefficient of Polyvinylidene Fluoride with Rationally Engineered Ultrafine Domains Achieved by Rapid Freezing Processing + 10.1002/adma.202406118 + Framework Nucleic Acid‐Based Selective Cell Catcher for Endogenous Stem Cell Recruitment Advanced Materials, EarlyView. -Polyvinylidene fluoride (PVDF)‐homopolymer with nanoscale TTTGTTTG’‐conformational domain is fabricated by a simple modeling method of cyclic compression and rapid freezing. The domain engineered PVDF is able to provide ultrahigh d33 of 191.4 pC N−1. Meanwhile, only physical processing method is applied, indicating a method for preparing piezoelectric polymer with low cost, good mechanical properties, and ultra‐high piezoelectric coefficient. +The “stem cell catcher” system, inspired by gold prospectors in the game “Gold Miner,” is a tFNA‐based structure embedded in a hyaluronic acid hydrogel for in vivo recruitment of stem cells in bone injuries. It mimics the process of mining for gold, targeting and capturing cellular gold necessary for craniofacial bone regeneration in challenging microenvironments. @@ -6617,48 +6577,52 @@ Polyvinylidene fluoride (PVDF)‐homopolymer with nanoscale TTTGTTTG’& Abstract -Domains play an essential role in determining the piezoelectric properties of polymers. The conventional method for achieving ultrafine piezoelectric domain structures for polymers is multiphase polymerization, which is not the primary choice for industrial‐scale applications because of its complex synthesis and weak mechanical properties. In this study, it is demonstrated for the first time that a nanoscale domain design can be achieved in a commercially available polyvinylidene fluoride (PVDF) homopolymer through a simple fabrication method involving cyclic compression and rapid freezing. The domain‐engineered PVDF exhibits largely enhanced piezoelectric output with a record‐breaking piezoelectric coefficient (d33) of 191.4 picocoulombs per Newton (8.9 times higher than that of PVDF without engineered domain structure) and electromechanical coupling factor (k33) of 77.1%. Moreover, nanoscale domain‐induced ferroelectric and dielectric evolutions are revealed. A smaller domain is found to be beneficial for domain switching. An in‐depth understanding of the interplay between the domain structure and piezoelectric properties reveals a simple, low‐cost method for fabricating high‐performance polymeric piezoelectric. +Cell‐surface engineering holds great promise in boosting endogenous stem cell attraction for tissue regeneration. However, challenges such as cellular internalization of ligand and the dynamic nature of cell membranes often complicate ligand–receptor interactions. The aim of this study is to harness the innovative potential of programmable tetrahedral framework nucleic acid (tFNA) to enable precise, tunable ligand–receptor interactions, thereby improving stem cell recruitment efficiency. This approach involves experimental screening and theoretical analysis using dissipative particle dynamics. The results demonstrate that altering the flexibility and topology of ligands on tFNA changes their cellular internalization and membrane binding efficiency. Furthermore, optimizing the distribution of the mesenchymal stem cell (MSC)‐binding aptamer 19S (Apt19S) on the tFNA enhances the stem cell capture efficiency. Following successful in vitro MSC capture, Apt19S‐modified tFNA is chemically linked to a hyaluronic acid hydrogel, forming an efficient “stem cell catcher” system. Subsequent in vivo experiments demonstrate that this system effectively promotes early stem cell recruitment and accelerates bone regeneration in different bone healing scenarios, including cranial and maxillary defects. - <img src="https://onlinelibrary.wiley.com/cms/asset/66c3213c-eac1-482b-b697-343e4ca222e1/adma202412344-gra-0001-m.png" - alt="Giant Piezoelectric Coefficient of Polyvinylidene Fluoride with Rationally Engineered Ultrafine Domains Achieved by Rapid Freezing Processing"/> -<p>Polyvinylidene fluoride (PVDF)-homopolymer with nanoscale TTTGTTTG’-conformational domain is fabricated by a simple modeling method of cyclic compression and rapid freezing. The domain engineered PVDF is able to provide ultrahigh <i>d</i>33 of 191.4 pC N<sup>−1</sup>. Meanwhile, only physical processing method is applied, indicating a method for preparing piezoelectric polymer with low cost, good mechanical properties, and ultra-high piezoelectric coefficient. + <img src="https://onlinelibrary.wiley.com/cms/asset/93dc5b4a-ec18-4120-a36d-6e9f87b3eac6/adma202406118-gra-0001-m.png" + alt="Framework Nucleic Acid-Based Selective Cell Catcher for Endogenous Stem Cell Recruitment"/> +<p>The “stem cell catcher” system, inspired by gold prospectors in the game “Gold Miner,” is a tFNA-based structure embedded in a hyaluronic acid hydrogel for in vivo recruitment of stem cells in bone injuries. It mimics the process of mining for gold, targeting and capturing cellular gold necessary for craniofacial bone regeneration in challenging microenvironments. </p> <br/> <h2>Abstract</h2> -<p>Domains play an essential role in determining the piezoelectric properties of polymers. The conventional method for achieving ultrafine piezoelectric domain structures for polymers is multiphase polymerization, which is not the primary choice for industrial-scale applications because of its complex synthesis and weak mechanical properties. In this study, it is demonstrated for the first time that a nanoscale domain design can be achieved in a commercially available polyvinylidene fluoride (PVDF) homopolymer through a simple fabrication method involving cyclic compression and rapid freezing. The domain-engineered PVDF exhibits largely enhanced piezoelectric output with a record-breaking piezoelectric coefficient (<i>d</i> -<sub>33</sub>) of 191.4 picocoulombs per Newton (8.9 times higher than that of PVDF without engineered domain structure) and electromechanical coupling factor (<i>k</i> -<sub>33</sub>) of 77.1%. Moreover, nanoscale domain-induced ferroelectric and dielectric evolutions are revealed. A smaller domain is found to be beneficial for domain switching. An in-depth understanding of the interplay between the domain structure and piezoelectric properties reveals a simple, low-cost method for fabricating high-performance polymeric piezoelectric.</p> +<p>Cell-surface engineering holds great promise in boosting endogenous stem cell attraction for tissue regeneration. However, challenges such as cellular internalization of ligand and the dynamic nature of cell membranes often complicate ligand–receptor interactions. The aim of this study is to harness the innovative potential of programmable tetrahedral framework nucleic acid (tFNA) to enable precise, tunable ligand–receptor interactions, thereby improving stem cell recruitment efficiency. This approach involves experimental screening and theoretical analysis using dissipative particle dynamics. The results demonstrate that altering the flexibility and topology of ligands on tFNA changes their cellular internalization and membrane binding efficiency. Furthermore, optimizing the distribution of the mesenchymal stem cell (MSC)-binding aptamer 19S (Apt19S) on the tFNA enhances the stem cell capture efficiency. Following successful in vitro MSC capture, Apt19S-modified tFNA is chemically linked to a hyaluronic acid hydrogel, forming an efficient “stem cell catcher” system. Subsequent in vivo experiments demonstrate that this system effectively promotes early stem cell recruitment and accelerates bone regeneration in different bone healing scenarios, including cranial and maxillary defects.</p> -Yun‐Zhi Huang, -Zhaoqi Liu, -Lan‐Wei Li, -He‐Zhi He, -Zhong Lin Wang, -Jin‐Ping Qu, -Xiangyu Chen, -Zhao‐Xia Huang +Xingyu Chen, +Ziang Xu, +Yang Gao, +Ye Chen, +Wumeng Yin, +Zhiqiang Liu, +Weitong Cui, +Yong Li, +Jiafei Sun, +Yuting Yang, +Wenjuan Ma, +Tao Zhang, +Taoran Tian, +Yunfeng Lin Research Article - Giant Piezoelectric Coefficient of Polyvinylidene Fluoride with Rationally Engineered Ultrafine Domains Achieved by Rapid Freezing Processing - 10.1002/adma.202412344 + Framework Nucleic Acid‐Based Selective Cell Catcher for Endogenous Stem Cell Recruitment + 10.1002/adma.202406118 Advanced Materials - 10.1002/adma.202412344 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412344 + 10.1002/adma.202406118 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202406118 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410146 - Wed, 13 Nov 2024 05:35:23 -0800 - 2024-11-13T05:35:23-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414388 + Thu, 14 Nov 2024 20:28:24 -0800 + 2024-11-14T08:28:24-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202410146 - Highly Responsive Polar Vortices in All‐Ferroelectric Heterostructures + 10.1002/adma.202414388 + Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc‐Based Flow Batteries with High Capacity Advanced Materials, EarlyView. -Polar vortex formation is shown in all‐ferroelectric (PbTiO3)n/(PbxSr1−xTiO3)n heterostructures wherein the in‐plane polarization of PbxSr1−xTiO3 provides the required boundary conditions. These superlattices show superior piezoelectric and ferroelectric responses as the polarization in all layers can freely rotate to the out‐of‐plane direction. In the plane, the layers exhibit strong coupling during switching and show multistate switching when heterostructured with ferroelectric‐dielectric blocks. +Designing current collector with gravity‐induced gradient copper nanoparticles (CF‐G‐Cu NPs), which can integrate gradient conductivity and zincophilicity to regulate zinc deposition and suppress side reactions. @@ -6668,89 +6632,50 @@ Polar vortex formation is shown in all‐ferroelectric (PbTiO3)n/(PbxSr1W Abstract -The discovery of polar vortices and skyrmions in ferroelectric‐dielectric superlattices [such as (PbTiO3)n/(SrTiO3)n] has ushered in an era of novel dipolar topologies and corresponding emergent phenomena. The key to creating such emergent features has generally been considered to be related to counterpoising strongly polar and non‐polar materials thus creating the appropriate boundary conditions. This limits the utility these materials can have, however, by rendering (effectively) half of the structure unresponsive to applied stimuli. Here, using advanced thin‐film deposition and an array of characterization and simulation approaches, polar vortices are realized in all‐ferroelectric trilayers, multilayers, and superlattices built from the fundamental building block of (PbTiO3)n/(PbxSr1−xTiO3)n wherein in‐plane ferroelectric polarization in the PbxSr1−xTiO3 provides the appropriate boundary conditions. These superlattices exhibit substantially enhanced electromechanical and ferroelectric responses in the out‐of‐plane direction that arise from the ability of the polarization in both layers to rotate to the out‐of‐plane direction under field. In the in‐plane direction, the layers are found to be strongly coupled during switching and when heterostructured with ferroelectric‐dielectric building blocks, it is possible to produce multistate switching. This approach expands the realm of systems supporting emergent dipolar texture formation and does so with entirely ferroelectric materials thus greatly improving their responses. +Current collectors, as reaction sites, play a crucial role in influencing various electrochemical performances in emerging cost‐effective zinc‐based flow batteries (Zn‐based FBs). 3D carbon felts (CF) are commonly used but lack effectiveness in improving Zn metal plating/stripping. Here, a current collector with gravity‐induced gradient copper nanoparticles (CF‐G‐Cu NPs) is developed, integrating gradient conductivity and zincophilicity to regulate Zn deposition and suppress side reactions. The CF‐G‐Cu NPs electrode modulates Zn nucleation and growth via the zincophilic Cu/CuZn5 alloy has been confirmed by density functional theory (DFT) calculations. Finite element simulation demonstrates the gradient internal structure effectively optimizes the local electric/current field distribution to regulate the Zn2+ flux, improving bottom‐up plating behavior for Zn metal and mitigating top‐surface dendrite growth. As a result, Zn‐based asymmetrical FBs with CF‐G‐Cu NPs electrodes achieve an areal capacity of 30 mAh cm−2 over 640 h with Coulombic efficiency of 99.5% at 40 mA cm−2. The integrated Zn‐Iodide FBs exhibit a competitive long‐term lifespan of 2910 h (5800 cycles) with low energy efficiency decay of 0.062% per cycle and high cumulative capacity of 112800 mAh cm−2 at a high current density of 100 mA cm−2. This gradient distribution strategy offers a simple mode for developing Zn‐based FB systems. - <img src="https://onlinelibrary.wiley.com/cms/asset/67bd9bd7-8f34-48fa-a478-e3deb45bc636/adma202410146-gra-0001-m.png" - alt="Highly Responsive Polar Vortices in All-Ferroelectric Heterostructures"/> -<p>Polar vortex formation is shown in all-ferroelectric (PbTiO<sub>3</sub>)<i> - <sub>n</sub> -</i>/(Pb<i> - <sub>x</sub> -</i>Sr<sub>1−</sub> -<i> - <sub>x</sub> -</i>TiO<sub>3</sub>)<i> - <sub>n</sub> -</i> heterostructures wherein the in-plane polarization of Pb<i> - <sub>x</sub> -</i>Sr<sub>1−</sub> -<i> - <sub>x</sub> -</i>TiO<sub>3</sub> provides the required boundary conditions. These superlattices show superior piezoelectric and ferroelectric responses as the polarization in all layers can freely rotate to the out-of-plane direction. In the plane, the layers exhibit strong coupling during switching and show multistate switching when heterostructured with ferroelectric-dielectric blocks. + <img src="https://onlinelibrary.wiley.com/cms/asset/bfc3fb5a-d30a-4516-8e98-ccc6bf2d7678/adma202414388-gra-0001-m.png" + alt="Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc-Based Flow Batteries with High Capacity"/> +<p>Designing current collector with gravity-induced gradient copper nanoparticles (CF-G-Cu NPs), which can integrate gradient conductivity and zincophilicity to regulate zinc deposition and suppress side reactions. </p> <br/> <h2>Abstract</h2> -<p>The discovery of polar vortices and skyrmions in ferroelectric-dielectric superlattices [such as (PbTiO<sub>3</sub>)<i> - <sub>n</sub> -</i>/(SrTiO<sub>3</sub>)<i> - <sub>n</sub> -</i>] has ushered in an era of novel dipolar topologies and corresponding emergent phenomena. The key to creating such emergent features has generally been considered to be related to counterpoising strongly polar and non-polar materials thus creating the appropriate boundary conditions. This limits the utility these materials can have, however, by rendering (effectively) half of the structure unresponsive to applied stimuli. Here, using advanced thin-film deposition and an array of characterization and simulation approaches, polar vortices are realized in all-ferroelectric trilayers, multilayers, and superlattices built from the fundamental building block of (PbTiO<sub>3</sub>)<i> - <sub>n</sub> -</i>/(Pb<i> - <sub>x</sub> -</i>Sr<sub>1−</sub> -<i> - <sub>x</sub> -</i>TiO<sub>3</sub>)<i> - <sub>n</sub> -</i> wherein in-plane ferroelectric polarization in the Pb<i> - <sub>x</sub> -</i>Sr<sub>1−</sub> -<i> - <sub>x</sub> -</i>TiO<sub>3</sub> provides the appropriate boundary conditions. These superlattices exhibit substantially enhanced electromechanical and ferroelectric responses in the out-of-plane direction that arise from the ability of the polarization in both layers to rotate to the out-of-plane direction under field. In the in-plane direction, the layers are found to be strongly coupled during switching and when heterostructured with ferroelectric-dielectric building blocks, it is possible to produce multistate switching. This approach expands the realm of systems supporting emergent dipolar texture formation and does so with entirely ferroelectric materials thus greatly improving their responses.</p> +<p>Current collectors, as reaction sites, play a crucial role in influencing various electrochemical performances in emerging cost-effective zinc-based flow batteries (Zn-based FBs). 3D carbon felts (CF) are commonly used but lack effectiveness in improving Zn metal plating/stripping. Here, a current collector with gravity-induced gradient copper nanoparticles (CF-G-Cu NPs) is developed, integrating gradient conductivity and zincophilicity to regulate Zn deposition and suppress side reactions. The CF-G-Cu NPs electrode modulates Zn nucleation and growth via the zincophilic Cu/CuZn<sub>5</sub> alloy has been confirmed by density functional theory (DFT) calculations. Finite element simulation demonstrates the gradient internal structure effectively optimizes the local electric/current field distribution to regulate the Zn<sup>2+</sup> flux, improving bottom-up plating behavior for Zn metal and mitigating top-surface dendrite growth. As a result, Zn-based asymmetrical FBs with CF-G-Cu NPs electrodes achieve an areal capacity of 30 mAh cm<sup>−2</sup> over 640 h with Coulombic efficiency of 99.5% at 40 mA cm<sup>−2</sup>. The integrated Zn-Iodide FBs exhibit a competitive long-term lifespan of 2910 h (5800 cycles) with low energy efficiency decay of 0.062% per cycle and high cumulative capacity of 112800 mAh cm<sup>−2</sup> at a high current density of 100 mA cm<sup>−2</sup>. This gradient distribution strategy offers a simple mode for developing Zn-based FB systems.</p> -Pravin Kavle, -Aiden M. Ross, -Harikrishnan KP, -Peter Meisenheimer, -Arvind Dasgupta, -Jiyuan Yang, -Ching‐Che Lin, -Hao Pan, -Piush Behera, -Eric Parsonnet, -Xiaoxi Huang, -Jacob A. Zorn, -Yu‐Tsun Shao, -Sujit Das, -Shi Liu, -David A. Muller, -Ramamoorthy Ramesh, -Long‐Qing Chen, -Lane W. Martin +Zhiquan Wei, +Guangmeng Qu, +Zhaodong Huang, +Yiqiao Wang, +Dedi Li, +Xinru Yang, +Shaoce Zhang, +Ao Chen, +Yanbo Wang, +Hu Hong, +Qing Li, +Chunyi Zhi Research Article - Highly Responsive Polar Vortices in All‐Ferroelectric Heterostructures - 10.1002/adma.202410146 + Gradient Distribution of Zincophilic Sites for Stable Aqueous Zinc‐Based Flow Batteries with High Capacity + 10.1002/adma.202414388 Advanced Materials - 10.1002/adma.202410146 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410146 + 10.1002/adma.202414388 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202414388 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410395 - Wed, 13 Nov 2024 05:30:32 -0800 - 2024-11-13T05:30:32-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408307 + Thu, 14 Nov 2024 20:27:42 -0800 + 2024-11-14T08:27:42-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202410395 - A Stepwise Melting‐Polymerizing Molecule for Hydrophobic Grain‐Scale Encapsulated Perovskite Solar Cell + 10.1002/adma.202408307 + Charge‐Stabilized Nanodiscs as a New Class of Lipid Nanoparticles Advanced Materials, EarlyView. -Stepwise melting‐polymerizing molecule (SMPM) additive enables grain‐scale encapsulated perovskite, achieving highly water‐resistant perovskite solar cells (PSCs) with 25.21% efficiency and over 2000h T95 stability under 85% relative humidity. Unencapsulated SMPM‐PSCs even operate underwater and show effectively suppressed Pb‐leakage, potentially solving stability and environmental concerns for PSC commercialization. +Bottom‐up assembly of lipid‐based nanoparticles from mixed micelles containing di‐anionic lipids yield charge‐stabilized nanodiscs (CNDs). CNDs exhibit enhanced tumor accumulation compared to spherical liposomes. Surface chemistry modification via the layer‐by‐layer (LbL) technique improves tumor‐targeting properties compared to LbL‐liposomes. The insights presented can improve the assembly of delivery vehicles and expand the use of lipid‐based discoidal assemblies. @@ -6760,55 +6685,48 @@ Stepwise melting‐polymerizing molecule (SMPM) additive enables grain‐ Abstract -Despite the ongoing increase in the efficiency of perovskite solar cells, the stability issues of perovskite have been a significant hindrance to its commercialization. In response to this challenge, a stepwise melting‐polymerizing molecule (SMPM) is designed as an additive into FAPbI3 perovskite. SMPM undergoes a three‐stage phase transition during the perovskite annealing process: initially melting from solid to liquid state, followed by overflowing grain boundaries, and finally self‐polymerizing to form a hydrophobic grain‐scale encapsulation in perovskite solar cells, providing protection against humidity‐induced degradation. With this unique property, coupled with the advantages of improved crystallization, diminished non‐radiative recombination, and energy level alignment, FAPbI3‐based perovskite solar cells with a 25.21% (small‐area) and 22.94% (1 cm2) power conversion efficiency and over 2000 h T95% stability under 85% relative humidity is achieved. Furthermore, the SMPM‐based perovskite solar cells without external encapsulations sustain impressive stability during underwater operation, in which the black FAPbI3 phase is maintained and Pb‐leakage is also effectively suppressed. Therefore, the SMPM strategy can offer a sustainable settlement in both stability and environmental issues for the commercialization of perovskite solar cells. +Nanoparticles have the potential to improve disease treatment and diagnosis due to their ability to incorporate drugs, alter pharmacokinetics, and enable tissue targeting. While considerable effort is placed on developing spherical lipid‐based nanocarriers, recent evidence suggests that high aspect ratio lipid nanocarriers can exhibit enhanced disease site targeting and altered cellular interactions. However, the assembly of lipid‐based nanoparticles into non‐spherical morphologies has typically required incorporating additional agents such as synthetic polymers, proteins, lipid‐polymer conjugates, or detergents. Here, charged lipid headgroups are used to generate stable discoidal lipid nanoparticles from mixed micelles, which are termed charge‐stabilized nanodiscs (CNDs). The ability to generate CNDs in buffers with physiological ionic strength is restricted to lipids with more than one anionic group, whereas monovalent lipids only generate small nanoliposomal assemblies. In mice, the smaller size and anisotropic shape of CNDs promote higher accumulation in subcutaneous tumors than spherical liposomes. Further, the surface chemistry of CNDs can be modified via layer‐by‐layer (LbL) assembly to improve their tumor‐targeting properties over state‐of‐the‐art LbL‐liposomes when tested using a metastatic model of ovarian cancer. The application of charge‐mediated anisotropy in lipid‐based assemblies can aid in the future design of biomaterials and cell‐membrane mimetic structures. - <img src="https://onlinelibrary.wiley.com/cms/asset/cf1de21d-7696-4fed-baac-555ae7d42295/adma202410395-gra-0001-m.png" - alt="A Stepwise Melting-Polymerizing Molecule for Hydrophobic Grain-Scale Encapsulated Perovskite Solar Cell"/> -<p>Stepwise melting-polymerizing molecule (SMPM) additive enables grain-scale encapsulated perovskite, achieving highly water-resistant perovskite solar cells (PSCs) with 25.21% efficiency and over 2000h T<sub>95</sub> stability under 85% relative humidity. Unencapsulated SMPM-PSCs even operate underwater and show effectively suppressed Pb-leakage, potentially solving stability and environmental concerns for PSC commercialization. + <img src="https://onlinelibrary.wiley.com/cms/asset/cdc6d096-0c86-4c41-a016-2226b5e15bbd/adma202408307-gra-0001-m.png" + alt="Charge-Stabilized Nanodiscs as a New Class of Lipid Nanoparticles"/> +<p>Bottom-up assembly of lipid-based nanoparticles from mixed micelles containing di-anionic lipids yield charge-stabilized nanodiscs (CNDs). CNDs exhibit enhanced tumor accumulation compared to spherical liposomes. Surface chemistry modification via the layer-by-layer (LbL) technique improves tumor-targeting properties compared to LbL-liposomes. The insights presented can improve the assembly of delivery vehicles and expand the use of lipid-based discoidal assemblies. </p> <br/> <h2>Abstract</h2> -<p>Despite the ongoing increase in the efficiency of perovskite solar cells, the stability issues of perovskite have been a significant hindrance to its commercialization. In response to this challenge, a stepwise melting-polymerizing molecule (SMPM) is designed as an additive into FAPbI<sub>3</sub> perovskite. SMPM undergoes a three-stage phase transition during the perovskite annealing process: initially melting from solid to liquid state, followed by overflowing grain boundaries, and finally self-polymerizing to form a hydrophobic grain-scale encapsulation in perovskite solar cells, providing protection against humidity-induced degradation. With this unique property, coupled with the advantages of improved crystallization, diminished non-radiative recombination, and energy level alignment, FAPbI<sub>3</sub>-based perovskite solar cells with a 25.21% (small-area) and 22.94% (1 cm<sup>2</sup>) power conversion efficiency and over 2000 h T95% stability under 85% relative humidity is achieved. Furthermore, the SMPM-based perovskite solar cells without external encapsulations sustain impressive stability during underwater operation, in which the black FAPbI<sub>3</sub> phase is maintained and Pb-leakage is also effectively suppressed. Therefore, the SMPM strategy can offer a sustainable settlement in both stability and environmental issues for the commercialization of perovskite solar cells.</p> +<p>Nanoparticles have the potential to improve disease treatment and diagnosis due to their ability to incorporate drugs, alter pharmacokinetics, and enable tissue targeting. While considerable effort is placed on developing spherical lipid-based nanocarriers, recent evidence suggests that high aspect ratio lipid nanocarriers can exhibit enhanced disease site targeting and altered cellular interactions. However, the assembly of lipid-based nanoparticles into non-spherical morphologies has typically required incorporating additional agents such as synthetic polymers, proteins, lipid-polymer conjugates, or detergents. Here, charged lipid headgroups are used to generate stable discoidal lipid nanoparticles from mixed micelles, which are termed charge-stabilized nanodiscs (CNDs). The ability to generate CNDs in buffers with physiological ionic strength is restricted to lipids with more than one anionic group, whereas monovalent lipids only generate small nanoliposomal assemblies. In mice, the smaller size and anisotropic shape of CNDs promote higher accumulation in subcutaneous tumors than spherical liposomes. Further, the surface chemistry of CNDs can be modified via layer-by-layer (LbL) assembly to improve their tumor-targeting properties over state-of-the-art LbL-liposomes when tested using a metastatic model of ovarian cancer. The application of charge-mediated anisotropy in lipid-based assemblies can aid in the future design of biomaterials and cell-membrane mimetic structures.</p> -Riming Sun, -Shaoyu Chen, -Qingyun He, -Pinghui Yang, -Xuan Gao, -Mengyang Wu, -Junbo Wang, -Chongyu Zhong, -Xiangru Zhao, -Mubai Li, -Qiushuang Tian, -Yingguo Yang, -Aifei Wang, -Wei Huang, -Renzhi Li, -Tianshi Qin, -Fangfang Wang +Ivan S. Pires, +Alexander Hostetler, +Gil Covarrubias, +Isabella S. Carlo, +Jack R. Suggs, +B.J. Kim, +Andrew J. Pickering, +Ezra Gordon, +Darrell J. Irvine, +Paula T. Hammond Research Article - A Stepwise Melting‐Polymerizing Molecule for Hydrophobic Grain‐Scale Encapsulated Perovskite Solar Cell - 10.1002/adma.202410395 + Charge‐Stabilized Nanodiscs as a New Class of Lipid Nanoparticles + 10.1002/adma.202408307 Advanced Materials - 10.1002/adma.202410395 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410395 + 10.1002/adma.202408307 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408307 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410671 - Wed, 13 Nov 2024 05:24:39 -0800 - 2024-11-13T05:24:39-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412059 + Thu, 14 Nov 2024 20:27:02 -0800 + 2024-11-14T08:27:02-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202410671 - Photon‐Induced Ultrafast Multitemporal Programming of Terahertz Metadevices + 10.1002/adma.202412059 + A Polymeric Hole Transporter with Dual‐Interfacial Interactions Enables 25%‐Efficiency Blade‐Coated Perovskite Solar Cells Advanced Materials, EarlyView. -Combining the pixelated design with multi‐materials of different photocarrier responses and triggering switches, the photon‐induced multitemporal ultrafast programming is achieved in a Terahertz metadevice with the broadband and multiple polarization states. With this, time‐ and frequency‐switchable logic devices are demonstrated at a picosecond scale, which facilitates miniaturized light‐driven devices and integrated wave elements for optical computing, high‐quality communication, quantum, nonlinear optics, and others. +A novel polymeric hole transporter named Poly‐DBPP with centrosymmetric biphosphonic acid groups is developed that can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously. Poly‐DBPP improves the efficiencies of blade‐coated perovskite solar cells and large‐area modules to 25.1% and 22.0%, respectively. @@ -6818,46 +6736,57 @@ Combining the pixelated design with multi‐materials of different photocarr Abstract -Dynamic terahertz (THz) metasurface can feature modulated and multiplexed electromagnetic functionalities, important for wave‐based computation, six‐generation communications, and other applications. The versatile dynamic switching typically relies on a series of complex or incompatible multifield activations, with excessive system complexity, additional loss, slow modulation speed, and inertial time‐varying properties, limiting more widespread applications. Here, a photon‐induced ultrafast programmable THz metadevice is reoprted in time‐frequency dimensions with polarization‐decoupled temporal responses. By the pixelated design with multi‐materials and triggering switches, the multimodal modulation transcends the constraints inherent in materials, enabling the ultrafast programmable temporal evolution. All the resonances can be independently programmed at the working band from 0.6 to 2 THz. The tri‐temporal (with switching time of 1.25, 1, and 4.75 ps) and bi‐temporal (with switching time of 2.25 and 4.75 ps) dynamic manipulations are performed by all‐optical driven molecularization process of hybrid metasurfaces loaded with silicon (Si) and germanium (Ge) under different polarizations. Combining these features, the temporally programmed THz logic gates are last experimentally demonstrated, possessing basic operation of XNOR, NOR, and OR, as a proof‐of‐concept application. This reported light‐driven programmable THz flat‐optics allows ultrafast hybrid molecularization processes and new possibilities for miniaturized, flexible, multifunctional, and temporally programmable integrated devices. +Self‐assembly monolayer (SAM) hole transporters, consisting of anchoring, spacer, and terminal groups, have played a significant role in the development of inverted perovskite solar cells (PSCs). However, the weak interaction between perovskite and hydrophobic terminal group of SAMs limits surface wettability and interface stability. To address this issue, two novel hole transporters (named DBPP and Poly‐DBPP) with centrosymmetric biphosphonic acid groups are developed. Unlike conventional SAM hole transporters, the biphosphonic acid groups in DBPP and Poly‐DBPP can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously, improving surface wettability and suppressing interface recombination. Furthermore, compared to the small‐molecular DBPP, Poly‐DBPP exhibits higher conductance and excellent uniformity. This translates to a remarkable power conversion efficiency of 25.1% for blade‐coated PSCs and 22.0% for large‐area modules, respectively. Additionally, the PSCs based on Poly‐DBPP demonstrate impressive operational stability, retaining 92% of their initial PCE after 1,600 h of light soaking. This work presents a promising strategy for designing multifunctional hole transporters, paving the way for highly efficient and stable PSCs. - <img src="https://onlinelibrary.wiley.com/cms/asset/5d51f1bb-bd4a-4f00-ab28-5d60660371b1/adma202410671-gra-0001-m.png" - alt="Photon-Induced Ultrafast Multitemporal Programming of Terahertz Metadevices"/> -<p>Combining the pixelated design with multi-materials of different photocarrier responses and triggering switches, the photon-induced multitemporal ultrafast programming is achieved in a Terahertz metadevice with the broadband and multiple polarization states. With this, time- and frequency-switchable logic devices are demonstrated at a picosecond scale, which facilitates miniaturized light-driven devices and integrated wave elements for optical computing, high-quality communication, quantum, nonlinear optics, and others. + <img src="https://onlinelibrary.wiley.com/cms/asset/4a155cac-a899-44f5-9837-0f467d466924/adma202412059-gra-0001-m.png" + alt="A Polymeric Hole Transporter with Dual-Interfacial Interactions Enables 25%-Efficiency Blade-Coated Perovskite Solar Cells"/> +<p>A novel polymeric hole transporter named Poly-DBPP with centrosymmetric biphosphonic acid groups is developed that can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously. Poly-DBPP improves the efficiencies of blade-coated perovskite solar cells and large-area modules to 25.1% and 22.0%, respectively. </p> <br/> <h2>Abstract</h2> -<p>Dynamic terahertz (THz) metasurface can feature modulated and multiplexed electromagnetic functionalities, important for wave-based computation, six-generation communications, and other applications. The versatile dynamic switching typically relies on a series of complex or incompatible multifield activations, with excessive system complexity, additional loss, slow modulation speed, and inertial time-varying properties, limiting more widespread applications. Here, a photon-induced ultrafast programmable THz metadevice is reoprted in time-frequency dimensions with polarization-decoupled temporal responses. By the pixelated design with multi-materials and triggering switches, the multimodal modulation transcends the constraints inherent in materials, enabling the ultrafast programmable temporal evolution. All the resonances can be independently programmed at the working band from 0.6 to 2 THz. The tri-temporal (with switching time of 1.25, 1, and 4.75 ps) and bi-temporal (with switching time of 2.25 and 4.75 ps) dynamic manipulations are performed by all-optical driven molecularization process of hybrid metasurfaces loaded with silicon (Si) and germanium (Ge) under different polarizations. Combining these features, the temporally programmed THz logic gates are last experimentally demonstrated, possessing basic operation of XNOR, NOR, and OR, as a proof-of-concept application. This reported light-driven programmable THz flat-optics allows ultrafast hybrid molecularization processes and new possibilities for miniaturized, flexible, multifunctional, and temporally programmable integrated devices.</p> +<p>Self-assembly monolayer (SAM) hole transporters, consisting of anchoring, spacer, and terminal groups, have played a significant role in the development of inverted perovskite solar cells (PSCs). However, the weak interaction between perovskite and hydrophobic terminal group of SAMs limits surface wettability and interface stability. To address this issue, two novel hole transporters (named DBPP and Poly-DBPP) with centrosymmetric biphosphonic acid groups are developed. Unlike conventional SAM hole transporters, the biphosphonic acid groups in DBPP and Poly-DBPP can anchor to the underlying conductive substrate and interact with the perovskite layer simultaneously, improving surface wettability and suppressing interface recombination. Furthermore, compared to the small-molecular DBPP, Poly-DBPP exhibits higher conductance and excellent uniformity. This translates to a remarkable power conversion efficiency of 25.1% for blade-coated PSCs and 22.0% for large-area modules, respectively. Additionally, the PSCs based on Poly-DBPP demonstrate impressive operational stability, retaining 92% of their initial PCE after 1,600 h of light soaking. This work presents a promising strategy for designing multifunctional hole transporters, paving the way for highly efficient and stable PSCs.</p> -Jing Zhang, -Jing Lou, -Zhuochao Wang, -Jiangang Liang, -Xilai Zhao, -Yindong Huang, -Chao Chang, -Guangwei Hu +Feifei Wang, +Tianxiao Liu, +Yangyang Liu, +Yuhan Zhou, +Xiaorui Dong, +Yaoyao Zhang, +Xiaoyu Shi, +Yunjie Dou, +Zhijun Ren, +Lingyuan Wang, +Yu Zhao, +Siwei Luo, +Xiaodong Hu, +Xiaoxiao Peng, +Chunxiong Bao, +Wei Wang, +Jingyang Wang, +Wenbing Hu, +Shangshang Chen Research Article - Photon‐Induced Ultrafast Multitemporal Programming of Terahertz Metadevices - 10.1002/adma.202410671 + A Polymeric Hole Transporter with Dual‐Interfacial Interactions Enables 25%‐Efficiency Blade‐Coated Perovskite Solar Cells + 10.1002/adma.202412059 Advanced Materials - 10.1002/adma.202410671 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410671 + 10.1002/adma.202412059 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412059 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413349 - Wed, 13 Nov 2024 05:15:39 -0800 - 2024-11-13T05:15:39-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412598 + Thu, 14 Nov 2024 20:26:25 -0800 + 2024-11-14T08:26:25-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413349 - Assembly of Silicate–Phenolic Network Coatings with Tunable Properties for Controlled Release of Small Molecules + 10.1002/adma.202412598 + Low‐Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation Advanced Materials, EarlyView. -A strategy is presented to exploit the dynamic covalent coordination of silicate–phenolic networks (SPNs) for coating diverse substrates, enabling the engineering of SPN coatings with different physiochemical properties. The pH responsiveness and tailorable hydrophobicity of the SPN materials allow the controlled release of small molecules, such as fertilizers and micronutrients, making them of interest in agricultural applications and beyond. +Introducing multiple vacancy defects combined with V doping into NiFe‐LDH can boost the formation of low‐spin Fe3+, thereby modifying the interactions between 3d orbitals of Fe3+ and O 2p orbitals, which reduces the excessive adsorption of O* intermediates on Fe3+ sites, consequently altering the rate‐determining step of OER and lowering the reaction energy barrier, resulting in accelerating OER kinetics. @@ -6867,49 +6796,60 @@ A strategy is presented to exploit the dynamic covalent coordination of silicate Abstract -Engineered coatings are pivotal for tailoring the surface properties and release profiles of materials for applications across diverse areas. However, developing robust coatings that can both encapsulate and controllably release cargo is challenging. Herein, a dynamic covalent coordination assembly strategy is used to engineer robust silicate‐based coatings, termed silicate–phenolic networks (SPNs), using sodium metasilicate and phenolic ligands (tannic acid, gallic acid, pyrogallol). The coatings are pH‐responsive (owing to the dynamic covalent bonding), and their hydrophobicity can be tuned upon their post‐functionalization with hydrophobic gallates (propyl, octyl, lauryl gallates). The potential of the SPN coatings for the controlled release of small molecules, such as urea (a widely used fertilizer), is demonstrated—controlled release of urea in soil is achieved in response to different pHs (up to 7 days) and different hydrophobicity (up to 14 days). Furthermore, leveraging the presence of silicon (within the coating) and post‐functionalization of the SPN coatings with metal ions (Fe3+, Cu2+, Zn2+) generates a multipurpose delivery system for the sustained release of micronutrient fertilizers, and silicon and metal ions, over 28 and 14 days, respectively. These SPN coatings have potential applications beyond agriculture, including nutrient delivery, separations, food packaging, and medical device fabrication. +Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin‐state manipulation holds great promise to break through this bottleneck. Low‐spin Fe3+ (LS, t2g5eg0) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe3+ in NiFe‐layered double hydroxide (NiFe‐LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their d orbital splitting energy. The as‐obtained catalyst exhibits extraordinary OER performance with an ultra‐low overpotential of 244 mV at the industrially required current density of 500 mA cm−2, which is 110 mV lower than that of the conventional NiFe‐LDH with high‐spin Fe3+ (HS, t2g3eg2) and superior to most previously reported NiFe‐based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe3+ configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate‐determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin‐dependent electrocatalysts for OER and beyond. - <img src="https://onlinelibrary.wiley.com/cms/asset/64fdb462-3b8b-4b84-8751-e361a08f760d/adma202413349-gra-0001-m.png" - alt="Assembly of Silicate–Phenolic Network Coatings with Tunable Properties for Controlled Release of Small Molecules"/> -<p>A strategy is presented to exploit the dynamic covalent coordination of silicate–phenolic networks (SPNs) for coating diverse substrates, enabling the engineering of SPN coatings with different physiochemical properties. The pH responsiveness and tailorable hydrophobicity of the SPN materials allow the controlled release of small molecules, such as fertilizers and micronutrients, making them of interest in agricultural applications and beyond. + <img src="https://onlinelibrary.wiley.com/cms/asset/b7a3318e-0450-475f-8925-59c9b326a79b/adma202412598-gra-0001-m.png" + alt="Low-Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation"/> +<p>Introducing multiple vacancy defects combined with V doping into NiFe-LDH can boost the formation of low-spin Fe<sup>3+</sup>, thereby modifying the interactions between 3<i>d</i> orbitals of Fe<sup>3+</sup> and O 2<i>p</i> orbitals, which reduces the excessive adsorption of O* intermediates on Fe<sup>3+</sup> sites, consequently altering the rate-determining step of OER and lowering the reaction energy barrier, resulting in accelerating OER kinetics. </p> <br/> <h2>Abstract</h2> -<p>Engineered coatings are pivotal for tailoring the surface properties and release profiles of materials for applications across diverse areas. However, developing robust coatings that can both encapsulate and controllably release cargo is challenging. Herein, a dynamic covalent coordination assembly strategy is used to engineer robust silicate-based coatings, termed silicate–phenolic networks (SPNs), using sodium metasilicate and phenolic ligands (tannic acid, gallic acid, pyrogallol). The coatings are pH-responsive (owing to the dynamic covalent bonding), and their hydrophobicity can be tuned upon their post-functionalization with hydrophobic gallates (propyl, octyl, lauryl gallates). The potential of the SPN coatings for the controlled release of small molecules, such as urea (a widely used fertilizer), is demonstrated—controlled release of urea in soil is achieved in response to different pHs (up to 7 days) and different hydrophobicity (up to 14 days). Furthermore, leveraging the presence of silicon (within the coating) and post-functionalization of the SPN coatings with metal ions (Fe<sup>3+</sup>, Cu<sup>2+</sup>, Zn<sup>2+</sup>) generates a multipurpose delivery system for the sustained release of micronutrient fertilizers, and silicon and metal ions, over 28 and 14 days, respectively. These SPN coatings have potential applications beyond agriculture, including nutrient delivery, separations, food packaging, and medical device fabrication.</p> +<p>Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin-state manipulation holds great promise to break through this bottleneck. Low-spin Fe<sup>3+</sup> (LS, <i>t</i> +<sub>2g</sub> +<sup>5</sup> +<i>e</i> +<sub>g</sub> +<sup>0</sup>) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe<sup>3+</sup> in NiFe-layered double hydroxide (NiFe-LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their <i>d</i> orbital splitting energy. The as-obtained catalyst exhibits extraordinary OER performance with an ultra-low overpotential of 244 mV at the industrially required current density of 500 mA cm<sup>−2</sup>, which is 110 mV lower than that of the conventional NiFe-LDH with high-spin Fe<sup>3+</sup> (HS, <i>t</i> +<sub>2g</sub> +<sup>3</sup> +<i>e</i> +<sub>g</sub> +<sup>2</sup>) and superior to most previously reported NiFe-based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe<sup>3+</sup> configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate-determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin-dependent electrocatalysts for OER and beyond.</p> -Omid Mazaheri, -Zhixing Lin, -Wanjun Xu, -Mirudula Mohankumar, -Tianzheng Wang, -Ali Zavabeti, -Rebecca V. McQuillan, -Jingqu Chen, -Joseph J. Richardson, -Kathryn A. Mumford, -Frank Caruso +Yihao Wang, +Shanqing Li, +Xu Hou, +Tingting Cui, +Zechao Zhuang, +Yunhe Zhao, +Haozhi Wang, +Wei Wei, +Ming Xu, +Qiang Fu, +Chunxia Chen, +Dingsheng Wang Research Article - Assembly of Silicate–Phenolic Network Coatings with Tunable Properties for Controlled Release of Small Molecules - 10.1002/adma.202413349 + Low‐Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation + 10.1002/adma.202412598 Advanced Materials - 10.1002/adma.202413349 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413349 + 10.1002/adma.202412598 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412598 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413295 - Wed, 13 Nov 2024 05:14:54 -0800 - 2024-11-13T05:14:54-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411652 + Thu, 14 Nov 2024 20:25:52 -0800 + 2024-11-14T08:25:52-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202413295 - Fabrication of Ultrathin Ferroelectric Al0.7Sc0.3N Films under Complementary‐Metal‐Oxide‐Semiconductor Compatible Conditions by using HfN0.4 Electrode + 10.1002/adma.202411652 + Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li‐CO2 Batteries Advanced Materials, EarlyView. -Aluminum scandium nitride (AlScN), an innovative material for ferroelectric memory applications, is scaled down to an ultra‐thin thickness of 3 nm while maintaining compatibility with complementary metal‐oxide‐semiconductor fabrication standards, marking a notable breakthrough in the field. Moreover, reducing the operating voltage to 4.35 V represents a significant milestone in advancing low‐voltage AlScN‐based devices. +This study regulates the local spin states by incorporating Ni into Co3O4 and explores their impact on activity in Li‐CO2 batteries. High spin Ni ions facilitate electron transfer from the catalyst to the unoccupied orbitals of CO2, providing sufficient active sites for the nucleation and growth of small Li2CO3 crystals, thereby improving reversibility. @@ -6919,51 +6859,48 @@ Aluminum scandium nitride (AlScN), an innovative material for ferroelectric memo Abstract -Aluminum scandium nitride (AlScN) has emerged as a promising candidate for next‐generation ferroelectric memories, offering a much higher remanent charge density than other materials with a stable ferroelectric phase. However, the inherently high coercive field requires a substantial decrease in film thickness to lower the operating voltage. Significant leakage currents present a severe challenge during the thickness scaling, especially when maintaining compatibility with complementary‐metal‐oxide‐semiconductor (CMOS) fabrication standards. This study adopts a HfN0.4 bottom electrode, which minimizes lattice mismatch with Al0.7Sc0.3N (ASN), forming a coherent bottom interface that effectively reduces leakage currents even at thickness < 5 nm. CMOS‐compatible HfN0.4/ASN/TiN stack, deposited without vacuum break between each layer, demonstrates exceptional scalability, confirming the ferroelectricity of ASN films at thicknesses down to 3 nm. The coercive voltage is decreased to 4.35 V, significantly advancing low‐voltage AlScN devices that align with CMOS standards. +Due to the high energy barrier, slow reaction kinetics, and complex reaction environments of Li‐CO2 batteries, the development of durable and efficient catalysts is essential. Transition metal oxides are promising for their availability, stability, and 3d electronic features, with spin states playing an important role in CO2 activation. In this study, the local spin states are regulated by incorporating Ni into Co3O4 and its impact on activity in Li‐CO2 batteries is explored. The results show that Ni atoms with high spin states in Ni0.1Co2.9O4 facilitate electron transfer from the catalyst to the unoccupied orbitals of CO2, providing sufficient active sites for the nucleation and growth of small Li2CO3 crystals. These small crystals have a low decomposition barrier, leading to improved battery efficiency. Therefore, Ni0.1Co2.9O4 shows superior catalytic performance with an overpotential of 0.72 V and an energy efficiency of ≈70% after 500 h. This work provides insights into the relationship between spin states and CO2 reactions, highlighting a promising avenue for developing high‐performance metal‐CO2 batteries. - <img src="https://onlinelibrary.wiley.com/cms/asset/f9793676-8afa-4040-93ee-8b122b0fb999/adma202413295-gra-0001-m.png" - alt="Fabrication of Ultrathin Ferroelectric Al0.7Sc0.3N Films under Complementary-Metal-Oxide-Semiconductor Compatible Conditions by using HfN0.4 Electrode"/> -<p>Aluminum scandium nitride (AlScN), an innovative material for ferroelectric memory applications, is scaled down to an ultra-thin thickness of 3 nm while maintaining compatibility with complementary metal-oxide-semiconductor fabrication standards, marking a notable breakthrough in the field. Moreover, reducing the operating voltage to 4.35 V represents a significant milestone in advancing low-voltage AlScN-based devices. + <img src="https://onlinelibrary.wiley.com/cms/asset/810f9b20-24e9-4e36-928c-6791984c4c55/adma202411652-gra-0001-m.png" + alt="Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li-CO2 Batteries"/> +<p>This study regulates the local spin states by incorporating Ni into Co<sub>3</sub>O<sub>4</sub> and explores their impact on activity in Li-CO<sub>2</sub> batteries. High spin Ni ions facilitate electron transfer from the catalyst to the unoccupied orbitals of CO<sub>2</sub>, providing sufficient active sites for the nucleation and growth of small Li<sub>2</sub>CO<sub>3</sub> crystals, thereby improving reversibility. </p> <br/> <h2>Abstract</h2> -<p>Aluminum scandium nitride (AlScN) has emerged as a promising candidate for next-generation ferroelectric memories, offering a much higher remanent charge density than other materials with a stable ferroelectric phase. However, the inherently high coercive field requires a substantial decrease in film thickness to lower the operating voltage. Significant leakage currents present a severe challenge during the thickness scaling, especially when maintaining compatibility with complementary-metal-oxide-semiconductor (CMOS) fabrication standards. This study adopts a HfN<sub>0.4</sub> bottom electrode, which minimizes lattice mismatch with Al<sub>0.7</sub>Sc<sub>0.3</sub>N (ASN), forming a coherent bottom interface that effectively reduces leakage currents even at thickness &lt; 5 nm. CMOS-compatible HfN<sub>0.4</sub>/ASN/TiN stack, deposited without vacuum break between each layer, demonstrates exceptional scalability, confirming the ferroelectricity of ASN films at thicknesses down to 3 nm. The coercive voltage is decreased to 4.35 V, significantly advancing low-voltage AlScN devices that align with CMOS standards.</p> +<p>Due to the high energy barrier, slow reaction kinetics, and complex reaction environments of Li-CO<sub>2</sub> batteries, the development of durable and efficient catalysts is essential. Transition metal oxides are promising for their availability, stability, and 3d electronic features, with spin states playing an important role in CO<sub>2</sub> activation. In this study, the local spin states are regulated by incorporating Ni into Co<sub>3</sub>O<sub>4</sub> and its impact on activity in Li-CO<sub>2</sub> batteries is explored. The results show that Ni atoms with high spin states in Ni<sub>0.1</sub>Co<sub>2.9</sub>O<sub>4</sub> facilitate electron transfer from the catalyst to the unoccupied orbitals of CO<sub>2</sub>, providing sufficient active sites for the nucleation and growth of small Li<sub>2</sub>CO<sub>3</sub> crystals. These small crystals have a low decomposition barrier, leading to improved battery efficiency. Therefore, Ni<sub>0.1</sub>Co<sub>2.9</sub>O<sub>4</sub> shows superior catalytic performance with an overpotential of 0.72 V and an energy efficiency of ≈70% after 500 h. This work provides insights into the relationship between spin states and CO<sub>2</sub> reactions, highlighting a promising avenue for developing high-performance metal-CO<sub>2</sub> batteries.</p> -Seung Kyu Ryoo, -Kyung Do Kim, -Wonho Choi, -Panithan Sriboriboon, -Seungjae Heo, -Haengha Seo, -Yoon Ho Jang, -Jeong Woo Jeon, -Min Kyu Yeom, -Suk Hyun Lee, -Han Sol Park, -Yunseok Kim, -Cheol Seong Hwang +Yingqi Liu, +Xinru Wu, +Haotian Qu, +Gongxun Lu, +Yanli Chen, +Bingyi Lu, +Yanze Song, +Guangmin Zhou, +Hui‐Ming Cheng Research Article - Fabrication of Ultrathin Ferroelectric Al0.7Sc0.3N Films under Complementary‐Metal‐Oxide‐Semiconductor Compatible Conditions by using HfN0.4 Electrode - 10.1002/adma.202413295 + Regulating the Local Spin States in Spinel Oxides to Promote the Activity of Li‐CO2 Batteries + 10.1002/adma.202411652 Advanced Materials - 10.1002/adma.202413295 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202413295 + 10.1002/adma.202411652 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202411652 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414283 - Wed, 13 Nov 2024 05:14:17 -0800 - 2024-11-13T05:14:17-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408114 + Thu, 14 Nov 2024 20:24:10 -0800 + 2024-11-14T08:24:10-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202414283 - Engineering Topological and Chemical Disorder in Pd Sites for Record‐Breaking Formic Acid Electrocatalytic Oxidation + 10.1002/adma.202408114 + Synergistic Catalytic Sites in High‐Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction Advanced Materials, EarlyView. -A novel catalyst is constructed to regulate the geometric and electronic structure of palladium sites by topological and chemical disorder engineering. The deliberate design of palladium‐based high‐entropy amorphous alloys with porous frameworks (Net‐Pd‐HEAA) is successfully synthesized through thoughtful composition selection and precision experimental control, showcasing its outstanding efficacy as a formic acid oxidation reaction electrocatalyst. +A high‐entropy metal hydroxide organic framework (HE‐MHOF) is synthesized, combining five transition metals in a single‐phase crystalline structure. The material exhibits superior electrocatalytic performance for the oxygen evolution reaction, rivaling precious metal‐based catalysts. Operando X‐ray absorption spectroscopy and ab initio calculations reveal synergistic catalytic sites and the underlying reaction mechanism, demonstrating the potential of high‐entropy materials for sustainable energy technologies. + @@ -6973,47 +6910,47 @@ A novel catalyst is constructed to regulate the geometric and electronic structu Abstract -Designing palladium‐based formic acid oxidation reaction (FAOR) catalysts to achieve significant breakthroughs in catalytic activity, pathway selectivity, and toxicity resistance is both urgent and challenging. Here, these challenges are addressed by pioneering a novel catalyst design that incorporates both topological and chemical disorder, developing a new class of PdCuLaYMnW high‐entropy amorphous alloys with a porous network (Net‐Pd‐HEAA) as a highly active, selective, and stable FAOR electrocatalyst. This novel Net‐Pd‐HEAA demonstrates record‐breaking FAOR performance, achieving the mass and specific activities of 5.94 A mgPd−1 and 8.94 mA cm−2, respectively, surpassing all previously reported Pd‐based catalysts and showing strong competitiveness against advanced Pt‐based catalysts. Simulataneously, Net‐Pd‐HEAA exhibits extraordinary stability in accelerated durability tests (ADT) and chronoamperometry (CA) tests. Advanced characterization and in situ, spectral analysis reveal that the extremely disordered atomic structure effectively regulates the geometric and electronic structure of the Pd sites, enhancing active intermediate coverage, facilitating dehydrogenation pathway, and inhibiting the production/adsorption of CO. Furthermore, when employed as the anode catalyst in proton exchange membrane water electrolysis (PEMWE), Net‐Pd‐HEAA only requires a potential of 1.28 V to obtain a current density of 1 A cm−2, and operates stably in a highly corrosive electrolyte for over 100 h. +The integration of multiple elements in a high‐entropy state is crucial in the design of high‐performance, durable electrocatalysts. High‐entropy metal hydroxide organic frameworks (HE‐MHOFs) are synthesized under mild solvothermal conditions. This novel crystalline metal–organic framework (MOF) features a random, homogeneous distribution of cations within high‐entropy hydroxide layers. HE‐MHOF exhibits excellent electrocatalytic performance for the oxygen evolution reaction (OER), reaching a current density of 100 mA cm−2 at ≈1.64 VRHE, and demonstrates remarkable durability, maintaining a current density of 10 mA cm−2 for over 100 h. Notably, HE‐MHOF outperforms precious metal‐based electrocatalysts despite containing only ≈60% OER active metals. Ab initio calculations and operando X‐ray absorption spectroscopy (XAS) demonstrate that the high‐entropy catalyst contains active sites that facilitate a multifaceted OER mechanism. This study highlights the benefits of high‐entropy MOFs in developing noble metal‐free electrocatalysts, reducing reliance on precious metals, lowering metal loading (especially for Ni, Co, and Mn), and ultimately reducing costs for sustainable water electrolysis technologies. - <img src="https://onlinelibrary.wiley.com/cms/asset/2b4e68b4-874d-4ba6-8b1c-834318b8642c/adma202414283-gra-0001-m.png" - alt="Engineering Topological and Chemical Disorder in Pd Sites for Record-Breaking Formic Acid Electrocatalytic Oxidation"/> -<p>A novel catalyst is constructed to regulate the geometric and electronic structure of palladium sites by topological and chemical disorder engineering. The deliberate design of palladium-based high-entropy amorphous alloys with porous frameworks (Net-Pd-HEAA) is successfully synthesized through thoughtful composition selection and precision experimental control, showcasing its outstanding efficacy as a formic acid oxidation reaction electrocatalyst. + <img src="https://onlinelibrary.wiley.com/cms/asset/6aaa3328-d9f9-4186-8665-fb681b01f540/adma202408114-gra-0001-m.png" + alt="Synergistic Catalytic Sites in High-Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction"/> +<p>A high-entropy metal hydroxide organic framework (HE-MHOF) is synthesized, combining five transition metals in a single-phase crystalline structure. The material exhibits superior electrocatalytic performance for the oxygen evolution reaction, rivaling precious metal-based catalysts. Operando X-ray absorption spectroscopy and ab initio calculations reveal synergistic catalytic sites and the underlying reaction mechanism, demonstrating the potential of high-entropy materials for sustainable energy technologies. </p> <br/> <h2>Abstract</h2> -<p>Designing palladium-based formic acid oxidation reaction (FAOR) catalysts to achieve significant breakthroughs in catalytic activity, pathway selectivity, and toxicity resistance is both urgent and challenging. Here, these challenges are addressed by pioneering a novel catalyst design that incorporates both topological and chemical disorder, developing a new class of PdCuLaYMnW high-entropy amorphous alloys with a porous network (Net-Pd-HEAA) as a highly active, selective, and stable FAOR electrocatalyst. This novel Net-Pd-HEAA demonstrates record-breaking FAOR performance, achieving the mass and specific activities of 5.94 A mg<sub>Pd</sub> -<sup>−1</sup> and 8.94 mA cm<sup>−2</sup>, respectively, surpassing all previously reported Pd-based catalysts and showing strong competitiveness against advanced Pt-based catalysts. Simulataneously, Net-Pd-HEAA exhibits extraordinary stability in accelerated durability tests (ADT) and chronoamperometry (CA) tests. Advanced characterization and in situ, spectral analysis reveal that the extremely disordered atomic structure effectively regulates the geometric and electronic structure of the Pd sites, enhancing active intermediate coverage, facilitating dehydrogenation pathway, and inhibiting the production/adsorption of CO. Furthermore, when employed as the anode catalyst in proton exchange membrane water electrolysis (PEMWE), Net-Pd-HEAA only requires a potential of 1.28 V to obtain a current density of 1 A cm<sup>−2</sup>, and operates stably in a highly corrosive electrolyte for over 100 h.</p> +<p>The integration of multiple elements in a high-entropy state is crucial in the design of high-performance, durable electrocatalysts. High-entropy metal hydroxide organic frameworks (HE-MHOFs) are synthesized under mild solvothermal conditions. This novel crystalline metal–organic framework (MOF) features a random, homogeneous distribution of cations within high-entropy hydroxide layers. HE-MHOF exhibits excellent electrocatalytic performance for the oxygen evolution reaction (OER), reaching a current density of 100 mA cm<sup>−2</sup> at ≈1.64 V<sub>RHE</sub>, and demonstrates remarkable durability, maintaining a current density of 10 mA cm<sup>−2</sup> for over 100 h. Notably, HE-MHOF outperforms precious metal-based electrocatalysts despite containing only ≈60% OER active metals. Ab initio calculations and operando X-ray absorption spectroscopy (XAS) demonstrate that the high-entropy catalyst contains active sites that facilitate a multifaceted OER mechanism. This study highlights the benefits of high-entropy MOFs in developing noble metal-free electrocatalysts, reducing reliance on precious metals, lowering metal loading (especially for Ni, Co, and Mn), and ultimately reducing costs for sustainable water electrolysis technologies.</p> -Xiaohong Tan, -Jiarui Wang, -Yuhang Xiao, -Yingying Guo, -Weidong He, -Binjie Du, -Hao Cui, -Chengxin Wang +Arkendu Roy, +Sourabh Kumar, +Ana Guilherme Buzanich, +Carsten Prinz, +Emilia Götz, +Anika Retzmann, +Tilmann Hickel, +Biswajit Bhattacharya, +Franziska Emmerling Research Article - Engineering Topological and Chemical Disorder in Pd Sites for Record‐Breaking Formic Acid Electrocatalytic Oxidation - 10.1002/adma.202414283 + Synergistic Catalytic Sites in High‐Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction + 10.1002/adma.202408114 Advanced Materials - 10.1002/adma.202414283 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202414283 + 10.1002/adma.202408114 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408114 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411599 - Wed, 13 Nov 2024 02:42:39 -0800 - 2024-11-13T02:42:39-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412378 + Thu, 14 Nov 2024 02:22:49 -0800 + 2024-11-14T02:22:49-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202411599 - Multiscale Manufacturing of Recyclable Polyimide Composite Aerogels + 10.1002/adma.202412378 + Stabilizing Metal Coating on Flexible Devices by Ultrathin Protein Nanofilms Advanced Materials, EarlyView. -Mitigating embodied emissions is becoming increasingly crucial as the energy supply shifts toward more sustainable sources. A recycling strategy is guided by molecular simulation to reach recycling of high‐performance polyimide‐based aerogels. The recyclable composites can be fabricated using various manufacturing techniques to produce fibers (1D), membranes (2D), and complex structures (3D). The unique combination facilitates the sustainable utilization of outstanding aerogel composites in protective clothing, electric mobility, consumer goods, and aeronautics. +This work introduces a concept to use an ultrathin protein nanofilm (UPN) as an adhesive layer to enhance the adhesion between polymer substrates and metal coatings. This method enables various functionalities, including transparency control, encryption devices, optical detection, and wearable sensors, highlighting UPN's potential in flexible hybrid devices. @@ -7023,51 +6960,51 @@ Mitigating embodied emissions is becoming increasingly crucial as the energy sup Abstract -Mitigating embodied emissions is becoming increasingly crucial as the energy supply shifts toward more sustainable sources. Bio‐based materials present a potentially more sustainable alternative to synthetic polymers; however, it often do not yet match the performance of synthetic materials. Given the ongoing reliance on high‐performance, high‐environmental‐impact materials, it is essential to ensure their complete recyclability. Aerogels, recognized by IUPAC as one of the top ten emerging technologies, are witnessing rapid market growth in thermal insulation and thermal protection applications. In certain applications, synthetic and composite aerogels exhibit superior performance, particularly under high temperatures. Here, molecular simulation tools are employed to elucidate the interaction forces between polymers and solvents, develop a recycling strategy for polyimide‐based aerogels, and demonstrate their application in thermal protection for firefighter textiles and thermal runaway protection for Li‐ion battery packs. These composites are engineered for disassembly, allowing for the complete recovery of starting materials without any degradation of components after multiple recycling cycles. The recyclable composites can be fabricated using various manufacturing techniques to produce fibers (1D), membranes (2D), and complex structures (3D). This unique combination of outstanding performance and excellent recyclability facilitates the sustainable utilization of aerogels in protective clothing, electric mobility, consumer goods, and aeronautics. +The significant modulus difference between a metal coating and a polymer substrate leads to interface mismatches, seriously affecting the stability of flexible devices. Therefore, enhancing the adhesion stability of a metal layer on an inert polymer substrate to prevent delamination becomes a key challenge. Herein, an ultrathin protein nanofilm (UPN), synthesized by disulfide‐bond‐reducing protein aggregation, is proposed as a strong adhesive layer to enhance adhesion between polymer substrate and metal coating. Unlike traditional biopolymer adhesives with micrometer‐scale thicknesses, the UPN layer is minimized to nanometer/single‐molecular scale. Such UPN thereby effectively enhances the interfacial adhesive strength and reduces the cohesion contribution in the entire adhesion system by directly connecting two interfaces with a nearly single‐molecular thickness. Using UPN as the adhesive layer, a multifunctional metal coating could be reliably adhered on flexible polymer substrates by ion sputtering, delivering unprecedented adhesion stability even under repetitive mechanical deformation. Applications of this design include reversible transparency control, tension‐responsive encryption, reusable optical sensing, and wearable capacitive touch sensors. This work highlights UPN's potential to create strong bonding strength between flexible polymers and metal coatings, offering a biocompatible solution with high surface activity and low cohesion, facilitating the development of hybrid devices with stable metal nano‐coating. - <img src="https://onlinelibrary.wiley.com/cms/asset/0d7df565-7eb3-4808-9416-96166e5aca04/adma202411599-gra-0001-m.png" - alt="Multiscale Manufacturing of Recyclable Polyimide Composite Aerogels"/> -<p>Mitigating embodied emissions is becoming increasingly crucial as the energy supply shifts toward more sustainable sources. A recycling strategy is guided by molecular simulation to reach recycling of high-performance polyimide-based aerogels. The recyclable composites can be fabricated using various manufacturing techniques to produce fibers (1D), membranes (2D), and complex structures (3D). The unique combination facilitates the sustainable utilization of outstanding aerogel composites in protective clothing, electric mobility, consumer goods, and aeronautics. + <img src="https://onlinelibrary.wiley.com/cms/asset/803576cd-7379-4dcf-a370-c6de20f13132/adma202412378-gra-0001-m.png" + alt="Stabilizing Metal Coating on Flexible Devices by Ultrathin Protein Nanofilms"/> +<p>This work introduces a concept to use an ultrathin protein nanofilm (UPN) as an adhesive layer to enhance the adhesion between polymer substrates and metal coatings. This method enables various functionalities, including transparency control, encryption devices, optical detection, and wearable sensors, highlighting UPN's potential in flexible hybrid devices. </p> <br/> <h2>Abstract</h2> -<p>Mitigating embodied emissions is becoming increasingly crucial as the energy supply shifts toward more sustainable sources. Bio-based materials present a potentially more sustainable alternative to synthetic polymers; however, it often do not yet match the performance of synthetic materials. Given the ongoing reliance on high-performance, high-environmental-impact materials, it is essential to ensure their complete recyclability. Aerogels, recognized by IUPAC as one of the top ten emerging technologies, are witnessing rapid market growth in thermal insulation and thermal protection applications. In certain applications, synthetic and composite aerogels exhibit superior performance, particularly under high temperatures. Here, molecular simulation tools are employed to elucidate the interaction forces between polymers and solvents, develop a recycling strategy for polyimide-based aerogels, and demonstrate their application in thermal protection for firefighter textiles and thermal runaway protection for Li-ion battery packs. These composites are engineered for disassembly, allowing for the complete recovery of starting materials without any degradation of components after multiple recycling cycles. The recyclable composites can be fabricated using various manufacturing techniques to produce fibers (1D), membranes (2D), and complex structures (3D). This unique combination of outstanding performance and excellent recyclability facilitates the sustainable utilization of aerogels in protective clothing, electric mobility, consumer goods, and aeronautics.</p> +<p>The significant modulus difference between a metal coating and a polymer substrate leads to interface mismatches, seriously affecting the stability of flexible devices. Therefore, enhancing the adhesion stability of a metal layer on an inert polymer substrate to prevent delamination becomes a key challenge. Herein, an ultrathin protein nanofilm (UPN), synthesized by disulfide-bond-reducing protein aggregation, is proposed as a strong adhesive layer to enhance adhesion between polymer substrate and metal coating. Unlike traditional biopolymer adhesives with micrometer-scale thicknesses, the UPN layer is minimized to nanometer/single-molecular scale. Such UPN thereby effectively enhances the interfacial adhesive strength and reduces the cohesion contribution in the entire adhesion system by directly connecting two interfaces with a nearly single-molecular thickness. Using UPN as the adhesive layer, a multifunctional metal coating could be reliably adhered on flexible polymer substrates by ion sputtering, delivering unprecedented adhesion stability even under repetitive mechanical deformation. Applications of this design include reversible transparency control, tension-responsive encryption, reusable optical sensing, and wearable capacitive touch sensors. This work highlights UPN's potential to create strong bonding strength between flexible polymers and metal coatings, offering a biocompatible solution with high surface activity and low cohesion, facilitating the development of hybrid devices with stable metal nano-coating.</p> -Mengmeng Li, -Tingting Wu, -Zhiyang Zhao, -Lei Li, -Tongxin Shan, -Hui Wu, -Robert Zboray, -Francesco Bernasconi, -Yongjie Cui, -Peiying Hu, -Wim J. Malfait, -Qinghua Zhang, -Shanyu Zhao +Yingying Zhang, +Hao Ren, +Changhong Linghu, +Jiqing Zhang, +Aiting Gao, +Hao Su, +Shuting Miao, +Rongrong Qin, +Bowen Hu, +Xiaojie Chen, +Miaoran Deng, +Yongchun Liu, +Peng Yang Research Article - Multiscale Manufacturing of Recyclable Polyimide Composite Aerogels - 10.1002/adma.202411599 + Stabilizing Metal Coating on Flexible Devices by Ultrathin Protein Nanofilms + 10.1002/adma.202412378 Advanced Materials - 10.1002/adma.202411599 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411599 + 10.1002/adma.202412378 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412378 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412327 - Wed, 13 Nov 2024 02:41:41 -0800 - 2024-11-13T02:41:41-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408098 + Thu, 14 Nov 2024 02:11:27 -0800 + 2024-11-14T02:11:27-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202412327 - Polymeric Charge‐Transporting Materials for Inverted Perovskite Solar Cells + 10.1002/adma.202408098 + Dual‐Phase Singularity at a Single Incident Angle with Spectral Tunability in Tamm Cavities Advanced Materials, EarlyView. -Polymeric charge transporters hold immense potential for inverted perovskite solar cells due to their tunable structures, high conductivity, and inherent flexibility. This review comprehensively explores recent advancements in these polymeric materials, while also delving into the remaining challenges and proposing practical design strategies for their future optimization. +Realizing multiple‐phase singularities is important for phase engineering in flat optics, and to improve the detection limit of refractive index sensors. The existence of a dual‐phase singularity at a single incident angle with spectral tunability and its application for ultra‐sensitive hydrogen sensing is presented using phase change material‐based tunable Tamm plasmon polariton cavities. @@ -7077,43 +7014,44 @@ Polymeric charge transporters hold immense potential for inverted perovskite sol Abstract -Inverted perovskite solar cells (PSCs) hold exceptional promise as next‐generation photovoltaic technology, where both perovskite absorbers and charge‐transporting materials (CTMs) play critical roles in cell performance. In recent years, polymeric CTMs have played an important role in developing efficient, stable, and large‐area inverted PSCs due to their unique properties of high conductivity, tunable structures, and mechanical flexibility. This review provides a comprehensive overview of polymeric CTMs used in inverted PSCs, encompassing polymeric hole transport materials (HTMs) and electron transport materials (ETMs). the relationship between their molecular structures, modification strategies are systematically summarized and analyzed for adjusting energy levels, and improving charge extraction, enabling a deep understanding of these widely used materials. The review also explores effective strategies for designing even more efficient polymeric CTMs. Finally, an outlook is proposed on the exciting research of novel polymeric CTMs, paving the way for their commercialized applications in PSCs. +The phase singularity, a sudden phase change occurring at the reflection zero is widely explored using various nanophotonic systems such as metamaterials and thin film cavities. Typically, these systems exhibit a single reflection zero with a phase singularity at a specific incident angle, particularly at larger angles of incidence (>50 degrees). However, achieving multiple phase singularities at a single incident angle remains a formidable challenge. Here, the existence of a dual‐phase singularity is experimentally demonstrated at a lower incident angle using a tunable Tamm plasmon polariton (TPP) cavity that consists of gold‐coated ultralow‐loss phase change material Sb2S3‐based distributed Bragg reflector. It can excite narrowband TPP resonances from normal incidence to a wide angle of incidence for both s‐ and p‐polarizations of light. Notably, this TPP cavity shows dual‐phase singularity at lower angles of incidence since the excited TPP for s‐ and p‐polarizations exhibits zero reflection at slightly different wavelengths for the same incident angle. A TPP cavity‐based scalable hydrogen sensor is proposed and shows that the dual‐phase singularity can further improve the sensitivity of singular phase‐based sensing approaches. Moreover, spectrally tunable dual‐phase singularity is experimentally demonstrated at a lower incident angle using a metal‐free Tamm cavity. - <img src="https://onlinelibrary.wiley.com/cms/asset/bd6e2d22-b635-48c2-8355-aeecffae0240/adma202412327-gra-0001-m.png" - alt="Polymeric Charge-Transporting Materials for Inverted Perovskite Solar Cells"/> -<p>Polymeric charge transporters hold immense potential for inverted perovskite solar cells due to their tunable structures, high conductivity, and inherent flexibility. This review comprehensively explores recent advancements in these polymeric materials, while also delving into the remaining challenges and proposing practical design strategies for their future optimization. + <img src="https://onlinelibrary.wiley.com/cms/asset/3b5bc2be-5206-43e3-bab8-5d6b8c950c72/adma202408098-gra-0001-m.png" + alt="Dual-Phase Singularity at a Single Incident Angle with Spectral Tunability in Tamm Cavities"/> +<p>Realizing multiple-phase singularities is important for phase engineering in flat optics, and to improve the detection limit of refractive index sensors. The existence of a dual-phase singularity at a single incident angle with spectral tunability and its application for ultra-sensitive hydrogen sensing is presented using phase change material-based tunable Tamm plasmon polariton cavities. </p> <br/> <h2>Abstract</h2> -<p>Inverted perovskite solar cells (PSCs) hold exceptional promise as next-generation photovoltaic technology, where both perovskite absorbers and charge-transporting materials (CTMs) play critical roles in cell performance. In recent years, polymeric CTMs have played an important role in developing efficient, stable, and large-area inverted PSCs due to their unique properties of high conductivity, tunable structures, and mechanical flexibility. This review provides a comprehensive overview of polymeric CTMs used in inverted PSCs, encompassing polymeric hole transport materials (HTMs) and electron transport materials (ETMs). the relationship between their molecular structures, modification strategies are systematically summarized and analyzed for adjusting energy levels, and improving charge extraction, enabling a deep understanding of these widely used materials. The review also explores effective strategies for designing even more efficient polymeric CTMs. Finally, an outlook is proposed on the exciting research of novel polymeric CTMs, paving the way for their commercialized applications in PSCs.</p> +<p>The phase singularity, a sudden phase change occurring at the reflection zero is widely explored using various nanophotonic systems such as metamaterials and thin film cavities. Typically, these systems exhibit a single reflection zero with a phase singularity at a specific incident angle, particularly at larger angles of incidence (&gt;50 degrees). However, achieving multiple phase singularities at a single incident angle remains a formidable challenge. Here, the existence of a dual-phase singularity is experimentally demonstrated at a lower incident angle using a tunable Tamm plasmon polariton (TPP) cavity that consists of gold-coated ultralow-loss phase change material Sb<sub>2</sub>S<sub>3</sub>-based distributed Bragg reflector. It can excite narrowband TPP resonances from normal incidence to a wide angle of incidence for both <i>s</i>- and <i>p</i>-polarizations of light. Notably, this TPP cavity shows dual-phase singularity at lower angles of incidence since the excited TPP for <i>s</i>- and <i>p</i>-polarizations exhibits zero reflection at slightly different wavelengths for the same incident angle. A TPP cavity-based scalable hydrogen sensor is proposed and shows that the dual-phase singularity can further improve the sensitivity of singular phase-based sensing approaches. Moreover, spectrally tunable dual-phase singularity is experimentally demonstrated at a lower incident angle using a metal-free Tamm cavity.</p> -Xiaodong Hu, -Lingyuan Wang, -Siwei Luo, -He Yan, -Shangshang Chen +Kandammathe Valiyaveedu Sreekanth, +Sambhu Jana, +Qing Yang Steve Wu, +Meng Zhao, +Ranjan Singh, +Jinghua Teng - Review - Polymeric Charge‐Transporting Materials for Inverted Perovskite Solar Cells - 10.1002/adma.202412327 + Research Article + Dual‐Phase Singularity at a Single Incident Angle with Spectral Tunability in Tamm Cavities + 10.1002/adma.202408098 Advanced Materials - 10.1002/adma.202412327 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202412327 - Review + 10.1002/adma.202408098 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202408098 + Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408664 - Tue, 12 Nov 2024 21:05:18 -0800 - 2024-11-12T09:05:18-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410073 + Thu, 14 Nov 2024 02:10:18 -0800 + 2024-11-14T02:10:18-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202408664 - Colossal Strain Tuning of Ferroelectric Transitions in KNbO3 Thin Films + 10.1002/adma.202410073 + High‐Performance Circularly Polarized Phosphorescence by Confining Isolated Chromophores with Chiral Counterions Advanced Materials, EarlyView. -Colossal strain tuning of ferroelectricity is demonstrated in biaxially compressive strained epitaxial KNbO3 thin films, demonstrating a dramatic strain enhancement of ferroelectric polarization and the Curie temperature, eliminating all bulk phase transitions and stabilizing a single tetragonal phase from 5 K to 975 K. +The strategy of confining isolated chromophores is used to achieve circularly polarized phosphorescence with glum up to 0.13 and ΦP up to 43.2%. The isolated chromophore is confined by chiral counterions with asymmetric stacking through multiple ionic bonds, which not only suppress the non‐radiative transitions of the triplet excitons for phosphorescence enhancement, but also construct a rigid chiral molecular environment for efficient chirality transfer and amplification. Moreover, chiral light transformation and multiple information encryption are demonstrated in photoelectric devices. @@ -7123,70 +7061,55 @@ Colossal strain tuning of ferroelectricity is demonstrated in biaxially compress Abstract -Strong coupling between polarization (P) and strain (ɛ) in ferroelectric complex oxides offers unique opportunities to dramatically tune their properties. Here colossal strain tuning of ferroelectricity in epitaxial KNbO3 thin films grown by sub‐oxide molecular beam epitaxy is demonstrated. While bulk KNbO3 exhibits three ferroelectric transitions and a Curie temperature (Tc) of ≈676 K, phase‐field modeling predicts that a biaxial strain of as little as −0.6% pushes its Tc > 975 K, its decomposition temperature in air, and for −1.4% strain, to Tc > 1325 K, its melting point. Furthermore, a strain of −1.5% can stabilize a single phase throughout the entire temperature range of its stability. A combination of temperature‐dependent second harmonic generation measurements, synchrotron‐based X‐ray reciprocal space mapping, ferroelectric measurements, and transmission electron microscopy reveal a single tetragonal phase from 10 K to 975 K, an enhancement of ≈46% in the tetragonal phase remanent polarization (Pr), and a ≈200% enhancement in its optical second harmonic generation coefficients over bulk values. These properties in a lead‐free system, but with properties comparable or superior to lead‐based systems, make it an attractive candidate for applications ranging from high‐temperature ferroelectric memory to cryogenic temperature quantum computing. +Organic room‐temperature phosphorescence (RTP) featuring circularly polarized luminescence (CPL) is highly valuable in chiroptoelectronics, but the trade‐off issue between luminescence efficiency (Φ) and dissymmetry factor (glum) is still challenging to be solved. Here, chiroptical ionic crystals (R/S‐DNP) are constructed through ionization‐induced assembly, in which isolated chromophore of carboxylic anion is tightly confined by the surrounding chiral counterions. The long‐range ordered and chiral counterions with asymmetric stacking are closely connected with isolated chromophores for molecular assembly via high‐density electrostatic interactions, thus enabling the simultaneous realization of excellent single‐molecule RTP emission and efficient chirality transfer. The synchronous enhancement of ΦP and glum is further achieved as 43.2% and 0.13, respectively. In view of the excellent CPL performances, the ionic materials hold the promising chiroptical encryption via programmable control in an electric‐driven circularly polarized phosphorescent device. This result not only makes deeper insights into the relationship between the structure and chiral RTP property but also provides a guide to developing highly efficient chiroptical materials for potential applications. - <img src="https://onlinelibrary.wiley.com/cms/asset/0fde4abc-f889-48e0-abba-3567240bc671/adma202408664-gra-0001-m.png" - alt="Colossal Strain Tuning of Ferroelectric Transitions in KNbO3 Thin Films"/> -<p>Colossal strain tuning of ferroelectricity is demonstrated in biaxially compressive strained epitaxial KNbO<sub>3</sub> thin films, demonstrating a dramatic strain enhancement of ferroelectric polarization and the Curie temperature, eliminating all bulk phase transitions and stabilizing a single tetragonal phase from 5 K to 975 K. + <img src="https://onlinelibrary.wiley.com/cms/asset/c801cfa0-b617-47a8-be34-82055515e908/adma202410073-gra-0001-m.png" + alt="High-Performance Circularly Polarized Phosphorescence by Confining Isolated Chromophores with Chiral Counterions"/> +<p>The strategy of confining isolated chromophores is used to achieve circularly polarized phosphorescence with <i>g</i> +<sub>lum</sub> up to 0.13 and <i>Φ</i> +<sub>P</sub> up to 43.2%. The isolated chromophore is confined by chiral counterions with asymmetric stacking through multiple ionic bonds, which not only suppress the non-radiative transitions of the triplet excitons for phosphorescence enhancement, but also construct a rigid chiral molecular environment for efficient chirality transfer and amplification. Moreover, chiral light transformation and multiple information encryption are demonstrated in photoelectric devices. </p> <br/> <h2>Abstract</h2> -<p>Strong coupling between polarization (<i>P</i>) and strain (ɛ) in ferroelectric complex oxides offers unique opportunities to dramatically tune their properties. Here colossal strain tuning of ferroelectricity in epitaxial KNbO<sub>3</sub> thin films grown by sub-oxide molecular beam epitaxy is demonstrated. While bulk KNbO<sub>3</sub> exhibits three ferroelectric transitions and a Curie temperature (<i>T<sub>c</sub> -</i>) of ≈676 K, phase-field modeling predicts that a biaxial strain of as little as −0.6% pushes its <i>T<sub>c</sub> -</i> &gt; 975 K, its decomposition temperature in air, and for −1.4% strain, to <i>T<sub>c</sub> -</i> &gt; 1325 K, its melting point. Furthermore, a strain of −1.5% can stabilize a single phase throughout the entire temperature range of its stability. A combination of temperature-dependent second harmonic generation measurements, synchrotron-based X-ray reciprocal space mapping, ferroelectric measurements, and transmission electron microscopy reveal a single tetragonal phase from 10 K to 975 K, an enhancement of ≈46% in the tetragonal phase remanent polarization (<i>P<sub>r</sub> -</i>), and a ≈200% enhancement in its optical second harmonic generation coefficients over bulk values. These properties in a lead-free system, but with properties comparable or superior to lead-based systems, make it an attractive candidate for applications ranging from high-temperature ferroelectric memory to cryogenic temperature quantum computing.</p> +<p>Organic room-temperature phosphorescence (RTP) featuring circularly polarized luminescence (CPL) is highly valuable in chiroptoelectronics, but the trade-off issue between luminescence efficiency (<i>Φ</i>) and dissymmetry factor (<i>g</i> +<sub>lum</sub>) is still challenging to be solved. Here, chiroptical ionic crystals (<i>R/S</i>-DNP) are constructed through ionization-induced assembly, in which isolated chromophore of carboxylic anion is tightly confined by the surrounding chiral counterions. The long-range ordered and chiral counterions with asymmetric stacking are closely connected with isolated chromophores for molecular assembly via high-density electrostatic interactions, thus enabling the simultaneous realization of excellent single-molecule RTP emission and efficient chirality transfer. The synchronous enhancement of <i>Φ</i> +<sub>P</sub> and <i>g</i> +<sub>lum</sub> is further achieved as 43.2% and 0.13, respectively. In view of the excellent CPL performances, the ionic materials hold the promising chiroptical encryption via programmable control in an electric-driven circularly polarized phosphorescent device. This result not only makes deeper insights into the relationship between the structure and chiral RTP property but also provides a guide to developing highly efficient chiroptical materials for potential applications.</p> -Sankalpa Hazra, -Tobias Schwaigert, -Aiden Ross, -Haidong Lu, -Utkarsh Saha, -Victor Trinquet, -Betul Akkopru‐Akgun, -Benjamin Z. Gregory, -Anudeep Mangu, -Suchismita Sarker, -Tatiana Kuznetsova, -Saugata Sarker, -Xin Li, -Matthew R. Barone, -Xiaoshan Xu, -John W. Freeland, -Roman Engel‐Herbert, -Aaron M. Lindenberg, -Andrej Singer, -Susan Trolier‐McKinstry, -David A. Muller, -Gian‐Marco Rignanese, -Salva Salmani‐Rezaie, -Vladimir A. Stoica, -Alexei Gruverman, -Long‐Qing Chen, -Darrell G. Schlom, -Venkatraman Gopalan +Wenpeng Ye, +Zhengong Meng, +Guixiang Zhan, +Anqi Lv, +Yanhua Gao, +Kang Shen, +Huili Ma, +Huifang Shi, +Wei Yao, +Lin Wang, +Wei Huang, +Zhongfu An Research Article - Colossal Strain Tuning of Ferroelectric Transitions in KNbO3 Thin Films - 10.1002/adma.202408664 + High‐Performance Circularly Polarized Phosphorescence by Confining Isolated Chromophores with Chiral Counterions + 10.1002/adma.202410073 Advanced Materials - 10.1002/adma.202408664 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202408664 + 10.1002/adma.202410073 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202410073 Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411067 - Tue, 12 Nov 2024 21:04:18 -0800 - 2024-11-12T09:04:18-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412187 + Wed, 13 Nov 2024 22:14:50 -0800 + 2024-11-13T10:14:50-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202411067 - High‐Throughput Approaches to Engineer Fluorescent Nanosensors + 10.1002/adma.202412187 + Water‐Stable Magnetic Lipiodol Micro‐Droplets as a Miniaturized Robotic Tool for Drug Delivery Advanced Materials, EarlyView. -Nanomaterial‐based optical sensors are powerful tools to identify and image (biological) molecules. Optimizing surface chemistry and photophysics of these sensors is essential, but current methods limit throughput. This article discusses bottlenecks and highlights opportunities and requirements for high throughput and the scalability of non‐classical recognition strategies. +A novel formulation referred to water‐stable magnetic lipiodol micro‐droplets (MLMD) possesses properties such as flowability, shape adaptability, efficient drug loading, and compatibility with digital subtraction angiography (DSA) imaging is presented. On this basis, a close‐looped magnetic navigation system featuring artificial intelligence (AI)‐driven visual feedback for autonomous control has also been designed, to improve MLMD maneuverability in image‐guided therapy. @@ -7196,42 +7119,59 @@ Nanomaterial‐based optical sensors are powerful tools to identify and imag Abstract -Optical sensors are powerful tools to identify and image (biological) molecules. Because of their optoelectronic properties, nanomaterials are often used as building blocks. To transduce the chemical interaction with the analyte into an optical signal, the interplay between surface chemistry and nanomaterial photophysics has to be optimized. Understanding these aspects promises major opportunities for tailored sensors with optimal performance. However, this requires methods to create and explore the many chemical permutations. Indeed, many current approaches are limited in throughput. This affects the chemical design space that can be studied, the application of machine learning approaches as well as fundamental mechanistic understanding. Here, an overview of selection‐limited and synthesis‐limited approaches is provided to create and identify molecular nanosensors. Bottlenecks are discussed and opportunities of non‐classical recognition strategies are highlighted such as corona phase molecular recognition as well as the requirements for high throughput and scalability. Fluorescent carbon nanotubes are powerful building blocks for sensors and their huge chemical design space makes them an ideal platform for high throughput approaches. Therefore, they are the focus of this article, but the insights are transferable to any nanosensor system. Overall, this perspective aims to provide a fresh perspective to overcome current challenges in the nanosensor field. +Magnetic microrobots, designed to navigate the complex environments of the human body, show promise for minimally invasive diagnosis and treatment. However, their clinical adoption faces hurdles such as biocompatibility, precise control, and intelligent tracking. Here a novel formulation (referred to water‐stable magnetic lipiodol micro‐droplets, MLMD), integrating clinically approved lipiodol, gelatin, and superparamagnetic iron oxide nanoparticles (SPION) with a fundamental understanding of the structure‐property relationships is presented. This formulation demonstrates multiple improved properties including flowability, shape adaptability, efficient drug loading, and compatibility with digital subtraction angiography (DSA) imaging in both in vitro and in vivo experiments. This enables the MLMD as a versatile tool for image‐guided therapy, supported by a close‐looped magnetic navigation system featuring artificial intelligence (AI)‐driven visual feedback for autonomous control. The system effectively performs navigational tasks, including pinpointing specific locations of MLMD, recognizing and avoiding obstacles, mapping and following predetermined paths, and utilizing magnetic fields for precise motion planning to achieve visual drug delivery. The MLMD combines magnetic actuation with an AI‐directed close‐looped navigation, offering a transformative platform for targeted therapeutic delivery. - <img src="https://onlinelibrary.wiley.com/cms/asset/4d36796a-22de-407c-94c3-de5d477b5d1f/adma202411067-gra-0001-m.png" - alt="High-Throughput Approaches to Engineer Fluorescent Nanosensors"/> -<p>Nanomaterial-based optical sensors are powerful tools to identify and image (biological) molecules. Optimizing surface chemistry and photophysics of these sensors is essential, but current methods limit throughput. This article discusses bottlenecks and highlights opportunities and requirements for high throughput and the scalability of non-classical recognition strategies. + <img src="https://onlinelibrary.wiley.com/cms/asset/d2212d83-78ce-418c-a857-8dbbb46a271d/adma202412187-gra-0001-m.png" + alt="Water-Stable Magnetic Lipiodol Micro-Droplets as a Miniaturized Robotic Tool for Drug Delivery"/> +<p>A novel formulation referred to water-stable magnetic lipiodol micro-droplets (MLMD) possesses properties such as flowability, shape adaptability, efficient drug loading, and compatibility with digital subtraction angiography (DSA) imaging is presented. On this basis, a close-looped magnetic navigation system featuring artificial intelligence (AI)-driven visual feedback for autonomous control has also been designed, to improve MLMD maneuverability in image-guided therapy. </p> <br/> <h2>Abstract</h2> -<p>Optical sensors are powerful tools to identify and image (biological) molecules. Because of their optoelectronic properties, nanomaterials are often used as building blocks. To transduce the chemical interaction with the analyte into an optical signal, the interplay between surface chemistry and nanomaterial photophysics has to be optimized. Understanding these aspects promises major opportunities for tailored sensors with optimal performance. However, this requires methods to create and explore the many chemical permutations. Indeed, many current approaches are limited in throughput. This affects the chemical design space that can be studied, the application of machine learning approaches as well as fundamental mechanistic understanding. Here, an overview of selection-limited and synthesis-limited approaches is provided to create and identify molecular nanosensors. Bottlenecks are discussed and opportunities of non-classical recognition strategies are highlighted such as corona phase molecular recognition as well as the requirements for high throughput and scalability. Fluorescent carbon nanotubes are powerful building blocks for sensors and their huge chemical design space makes them an ideal platform for high throughput approaches. Therefore, they are the focus of this article, but the insights are transferable to any nanosensor system. Overall, this perspective aims to provide a fresh perspective to overcome current challenges in the nanosensor field.</p> +<p>Magnetic microrobots, designed to navigate the complex environments of the human body, show promise for minimally invasive diagnosis and treatment. However, their clinical adoption faces hurdles such as biocompatibility, precise control, and intelligent tracking. Here a novel formulation (referred to water-stable magnetic lipiodol micro-droplets, MLMD), integrating clinically approved lipiodol, gelatin, and superparamagnetic iron oxide nanoparticles (SPION) with a fundamental understanding of the structure-property relationships is presented. This formulation demonstrates multiple improved properties including flowability, shape adaptability, efficient drug loading, and compatibility with digital subtraction angiography (DSA) imaging in both in vitro and in vivo experiments. This enables the MLMD as a versatile tool for image-guided therapy, supported by a close-looped magnetic navigation system featuring artificial intelligence (AI)-driven visual feedback for autonomous control. The system effectively performs navigational tasks, including pinpointing specific locations of MLMD, recognizing and avoiding obstacles, mapping and following predetermined paths, and utilizing magnetic fields for precise motion planning to achieve visual drug delivery. The MLMD combines magnetic actuation with an AI-directed close-looped navigation, offering a transformative platform for targeted therapeutic delivery.</p> -Justus T. Metternich, -Sujit K. Patjoshi, -Tanuja Kistwal, -Sebastian Kruss +En Ren, +Jing Hu, +Ziyang Mei, +Lin Lin, +Qian Zhang, +Pan He, +Junqing Wang, +Tao Sheng, +Hu Chen, +Hongwei Cheng, +Tiantian Xu, +Shiyao Pang, +Yang Zhang, +Qixuan Dai, +Xing Gao, +Hui Liu, +Hongjun Li, +Yang Zhao, +Zhen Gu, +Xiaohui Yan, +Gang Liu - Perspective - High‐Throughput Approaches to Engineer Fluorescent Nanosensors - 10.1002/adma.202411067 + Research Article + Water‐Stable Magnetic Lipiodol Micro‐Droplets as a Miniaturized Robotic Tool for Drug Delivery + 10.1002/adma.202412187 Advanced Materials - 10.1002/adma.202411067 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202411067 - Perspective + 10.1002/adma.202412187 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412187 + Research Article - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410845 - Tue, 12 Nov 2024 21:03:48 -0800 - 2024-11-12T09:03:48-08:00 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412962 + Wed, 13 Nov 2024 22:14:02 -0800 + 2024-11-13T10:14:02-08:00 Wiley: Advanced Materials: Table of Contents - 10.1002/adma.202410845 - Naturally Inspired Tree‐Ring Structured Dressing Provides Sustained Wound Tightening and Accelerates Closure + 10.1002/adma.202412962 + Programmable Shape‐Morphing Enables Ceramic Meta‐Aerogel Highly Stretchable for Thermal Protection Advanced Materials, EarlyView. -Inspired by the tree ring structure, a core ring structure hydrogel dressing with mechanical modulation has been designed. The ring portion adheres tightly to the wound edge, while the core portion spontaneously contracts with body temperature, continuously pulling and contracting the wound. This ingenious design provides excellent therapeutic benefits including epidermal regeneration, collagen deposition, extracellular matrix organization, and vascular maturation. +Stretchable ceramic meta‐aerogel with a binary cellular structure, combining anisotropic lamellated aerogel (grid section) and isotropic random aerogel (mesh section), is fabricated using kirigami stacking and subsequent nanofiber freeze‐drying techniques. This specific topological structure design enables the meta‐aerogel robust structure, highly elastic tensile deformation, exceptional fatigue resistance for tensile, compressive, and buckling cycles, temperature‐invariant superelastic, superior thermal insulation; and these properties make it a potential application for exploring thermal protective materials. @@ -7241,31 +7181,27 @@ Inspired by the tree ring structure, a core ring structure hydrogel dressing wit Abstract -Mechanically regulated wound dressings require a rational combination of contraction and adhesion functions as well as balancing exudate‐induced swelling issues. However, many of the reported dressings face the dilemma of impaired function and impeded wound self‐contraction due to fluid‐absorbing swelling. In this study, inspired by the tree ring, a core–ring structured hydrogel dressing capable of mechanical modulation is designed, and prepare it using a simple two‐step photopolymerization process. The core covers the center of the wound, contracts spontaneously at body temperature to generate a contractile force of 3.4 kPa, and resists swelling. Meanwhile, the ring adheres to the normal epidermis around the wound and transfers the contraction stress to the wound edge. The integration of a functionally independent core and ring ultimately achieves effective wound traction and avoids dressing swelling. In murine and porcine skin wound‐healing models, this hydrogel with a closely connected core and ring promotes healing by accelerating epidermal closure (50% closure in mouse skin on day 2, 85% closure in pig skin on day 8), collagen deposition, vascular maturation, and extracellular matrix remodeling. These results can guide further research on mechanical force modulation in wound healing, with the potential for clinical translation. +Ceramic aerogels hold significant potential for thermal insulation, yet their mechanical stretchability and thermal stability fall short in extreme environments. Here, the study presents a programmable shape‐morphing strategy aimed at engineering a binary network topology structure within ceramic aerogels to effectively dissipate stress and block heat transfer. The special topology design, which includes kirigami lamellated aerogels for bearing loading stress and randomly assembled aerogels for mechanical energy pre‐storage to transfer tensile stress, effectively achieves unexpected mechanical tensile properties and thermal stability. The resulting robust meta‐aerogels demonstrate remarkable structural stability with topology‐derived mechanical tensile of up to 85% strain, excellent resilience to 500 cycles of 50% tensile strain, 1000 cycles of 60% buckling strain, and 500 cycles of 50% compressive strain, temperature‐invariant tensile recovery capability; simultaneously, low thermal conductivity of 33.01 mW m−1 K−1 and tensile‐invariant thermal insulation makes the ceramic meta‐aerogels an ideal substitute material for various applications. - <img src="https://onlinelibrary.wiley.com/cms/asset/145c693a-2aae-43c6-abb1-d634317d076e/adma202410845-gra-0001-m.png" - alt="Naturally Inspired Tree-Ring Structured Dressing Provides Sustained Wound Tightening and Accelerates Closure"/> -<p>Inspired by the tree ring structure, a core ring structure hydrogel dressing with mechanical modulation has been designed. The ring portion adheres tightly to the wound edge, while the core portion spontaneously contracts with body temperature, continuously pulling and contracting the wound. This ingenious design provides excellent therapeutic benefits including epidermal regeneration, collagen deposition, extracellular matrix organization, and vascular maturation. + <img src="https://onlinelibrary.wiley.com/cms/asset/c57dcb1d-d016-4832-9579-0b1bda0cd31f/adma202412962-gra-0001-m.png" + alt="Programmable Shape-Morphing Enables Ceramic Meta-Aerogel Highly Stretchable for Thermal Protection"/> +<p>Stretchable ceramic meta-aerogel with a binary cellular structure, combining anisotropic lamellated aerogel (grid section) and isotropic random aerogel (mesh section), is fabricated using kirigami stacking and subsequent nanofiber freeze-drying techniques. This specific topological structure design enables the meta-aerogel robust structure, highly elastic tensile deformation, exceptional fatigue resistance for tensile, compressive, and buckling cycles, temperature-invariant superelastic, superior thermal insulation; and these properties make it a potential application for exploring thermal protective materials. </p> <br/> <h2>Abstract</h2> -<p>Mechanically regulated wound dressings require a rational combination of contraction and adhesion functions as well as balancing exudate-induced swelling issues. However, many of the reported dressings face the dilemma of impaired function and impeded wound self-contraction due to fluid-absorbing swelling. In this study, inspired by the tree ring, a core–ring structured hydrogel dressing capable of mechanical modulation is designed, and prepare it using a simple two-step photopolymerization process. The core covers the center of the wound, contracts spontaneously at body temperature to generate a contractile force of 3.4 kPa, and resists swelling. Meanwhile, the ring adheres to the normal epidermis around the wound and transfers the contraction stress to the wound edge. The integration of a functionally independent core and ring ultimately achieves effective wound traction and avoids dressing swelling. In murine and porcine skin wound-healing models, this hydrogel with a closely connected core and ring promotes healing by accelerating epidermal closure (50% closure in mouse skin on day 2, 85% closure in pig skin on day 8), collagen deposition, vascular maturation, and extracellular matrix remodeling. These results can guide further research on mechanical force modulation in wound healing, with the potential for clinical translation.</p> +<p>Ceramic aerogels hold significant potential for thermal insulation, yet their mechanical stretchability and thermal stability fall short in extreme environments. Here, the study presents a programmable shape-morphing strategy aimed at engineering a binary network topology structure within ceramic aerogels to effectively dissipate stress and block heat transfer. The special topology design, which includes kirigami lamellated aerogels for bearing loading stress and randomly assembled aerogels for mechanical energy pre-storage to transfer tensile stress, effectively achieves unexpected mechanical tensile properties and thermal stability. The resulting robust meta-aerogels demonstrate remarkable structural stability with topology-derived mechanical tensile of up to 85% strain, excellent resilience to 500 cycles of 50% tensile strain, 1000 cycles of 60% buckling strain, and 500 cycles of 50% compressive strain, temperature-invariant tensile recovery capability; simultaneously, low thermal conductivity of 33.01 mW m<sup>−1</sup> K<sup>−1</sup> and tensile-invariant thermal insulation makes the ceramic meta-aerogels an ideal substitute material for various applications.</p> -Honggui Chen, -Rui Zhang, -Guo Zhang, -Xiaoyang Liang, -Chen Xu, -Yang Li, -Fu‐Jian Xu +Xuan Zhang, +Jianyong Yu, +Yang Si Research Article - Naturally Inspired Tree‐Ring Structured Dressing Provides Sustained Wound Tightening and Accelerates Closure - 10.1002/adma.202410845 + Programmable Shape‐Morphing Enables Ceramic Meta‐Aerogel Highly Stretchable for Thermal Protection + 10.1002/adma.202412962 Advanced Materials - 10.1002/adma.202410845 - https://onlinelibrary.wiley.com/doi/10.1002/adma.202410845 + 10.1002/adma.202412962 + https://onlinelibrary.wiley.com/doi/10.1002/adma.202412962 Research Article diff --git a/advmater_old.csv b/advmater_old.csv index 5255d33c..c761dfa7 100644 --- a/advmater_old.csv +++ b/advmater_old.csv @@ -12300,3 +12300,17 @@ "10.1002/adma.202412276","2024-11-17" "10.1002/adma.202412185","2024-11-17" "10.1002/adma.202409971","2024-11-17" +"10.1002/adma.202410779","2024-11-18" +"10.1002/adma.202410604","2024-11-18" +"10.1002/adma.202416210","2024-11-18" +"10.1002/adma.202415138","2024-11-19" +"10.1002/adma.202414450","2024-11-19" +"10.1002/adma.202414790","2024-11-19" +"10.1002/adma.202414628","2024-11-19" +"10.1002/adma.202412950","2024-11-19" +"10.1002/adma.202411856","2024-11-19" +"10.1002/adma.202412414","2024-11-19" +"10.1002/adma.202411558","2024-11-19" +"10.1002/adma.202413618","2024-11-19" +"10.1002/adma.202413270","2024-11-19" +"10.1002/adma.202401504","2024-11-19" diff --git a/ejoc.xml b/ejoc.xml index 159c764d..c48f3849 100644 --- a/ejoc.xml +++ b/ejoc.xml @@ -6,8 +6,8 @@ en-US © Wiley-VCH GmbH, Weinheim wileyonlinelibrary@wiley.com (Chemistry Europe) - Mon, 18 Nov 2024 08:14:17 +0000 - Mon, 18 Nov 2024 08:14:17 +0000 + Tue, 19 Nov 2024 08:06:25 +0000 + Tue, 19 Nov 2024 08:06:25 +0000 Atypon® Literatum™ https://validator.w3.org/feed/docs/rss2.html 10080 @@ -20,6 +20,58 @@ https://chemistry-europe.onlinelibrary.wiley.com/pb-assets/journal-banners/10990690.jpg https://chemistry-europe.onlinelibrary.wiley.com/journal/10990690 + + https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202400805 + Mon, 18 Nov 2024 19:29:46 -0800 + 2024-11-18T07:29:46-08:00 + Wiley: European Journal of Organic Chemistry: Table of Contents + + + 10.1002/ejoc.202400805 + Exploring the reactivity of (hetero)aryl amides in the Chan‐Evans‐Lam reaction with arylalkenyl boron reagents + European Journal of Organic Chemistry, Accepted Article. + The unique reactivity and stability of enamides make them attractive reagents in organic synthesis. Herein, we investigated the reactivity of acetanilides and pyridyl acetamides in the formation of a C–N bond through a Chan‐Evans‐Lam reaction using arylalkenyl boron‐based reagents yielding a wide scope of N‐aryl enamides with an E configuration. The products obtained have been applied in the synthesis of N‐heterocycles, an important scaffold in several biologically active compounds, via sequential Heck reaction to prove the practical utility of the prepared N‐aryl enamides. + <p>The unique reactivity and stability of enamides make them attractive reagents in organic synthesis. Herein, we investigated the reactivity of acetanilides and pyridyl acetamides in the formation of a C–N bond through a Chan-Evans-Lam reaction using arylalkenyl boron-based reagents yielding a wide scope of N-aryl enamides with an E configuration. The products obtained have been applied in the synthesis of N-heterocycles, an important scaffold in several biologically active compounds, via sequential Heck reaction to prove the practical utility of the prepared N-aryl enamides.</p> + +M. Manuel B. Marques, +Joana R. M. Ferreira, +Bruna F. L. Guerreiro, +Fábio M. F. Santos, +Samuel Guieu + + Research Article + Exploring the reactivity of (hetero)aryl amides in the Chan‐Evans‐Lam reaction with arylalkenyl boron reagents + 10.1002/ejoc.202400805 + European Journal of Organic Chemistry + 10.1002/ejoc.202400805 + https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202400805 + Research Article + + + https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202401153 + Mon, 18 Nov 2024 19:29:31 -0800 + 2024-11-18T07:29:31-08:00 + Wiley: European Journal of Organic Chemistry: Table of Contents + + + 10.1002/ejoc.202401153 + On the Halogenation of Tyrosine N‐Oxime Methyl Ester + European Journal of Organic Chemistry, Accepted Article. + Efficient syntheses of mono‐, di‐, and heterodihalogenated derivatives of tyrosine N‐oxime methyl ester are reported. Monohalogenation with N‐bromosuccinimide (NBS), N‐chlorosuccinimide (NCS) or N‐iodosuccinimide (NIS) was optimized by addition of acid to suppress dihalogenation, affording bromo, chloro, and iodo derivatives in 71%, 50‐53%, and 78‐80% yields, respectively. Homodihalogenation utilized a two‐step, one‐flask process via a spirocyclic intermediate, yielding dibromo, dichloro, and diiodo analogues, respectively (75‐76%, 54‐56%, 79‐80%). This strategy was extended to synthesize heterodihalogenated bromochloro, bromoiodo, and chloroiodo derivatives from monohalogenated analogues (50‐77%). Key to this approach was the formation of an oxidized spirocyclic intermediate using excess N‐halosuccinimide, followed by Na₂S₂O₄ reduction. This method ensures complete conversion and simplifies purification. Nine halogenated building blocks were prepared. These methods provide practical access to versatile precursors for natural product synthesis and derivatization, offering potential for diverse synthetic applications including regioselective palladium‐catalyzed couplings. + <p>Efficient syntheses of mono-, di-, and heterodihalogenated derivatives of tyrosine N-oxime methyl ester are reported. Monohalogenation with N-bromosuccinimide (NBS), N-chlorosuccinimide (NCS) or N-iodosuccinimide (NIS) was optimized by addition of acid to suppress dihalogenation, affording bromo, chloro, and iodo derivatives in 71%, 50-53%, and 78-80% yields, respectively. Homodihalogenation utilized a two-step, one-flask process via a spirocyclic intermediate, yielding dibromo, dichloro, and diiodo analogues, respectively (75-76%, 54-56%, 79-80%). This strategy was extended to synthesize heterodihalogenated bromochloro, bromoiodo, and chloroiodo derivatives from monohalogenated analogues (50-77%). Key to this approach was the formation of an oxidized spirocyclic intermediate using excess N-halosuccinimide, followed by Na₂S₂O₄ reduction. This method ensures complete conversion and simplifies purification. Nine halogenated building blocks were prepared. These methods provide practical access to versatile precursors for natural product synthesis and derivatization, offering potential for diverse synthetic applications including regioselective palladium-catalyzed couplings.</p> + +Morgan Payne, +Luke Fossatti, +Stephen Chamberland + + Research Article + On the Halogenation of Tyrosine N‐Oxime Methyl Ester + 10.1002/ejoc.202401153 + European Journal of Organic Chemistry + 10.1002/ejoc.202401153 + https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202401153 + Research Article + https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejoc.202400969 Sun, 17 Nov 2024 23:58:47 -0800 diff --git a/ejoc_old.csv b/ejoc_old.csv index 7d8af755..3ce8a942 100644 --- a/ejoc_old.csv +++ b/ejoc_old.csv @@ -3347,3 +3347,5 @@ "10.1002/ejoc.202401239","2024-11-12" "10.1002/ejoc.202401027","2024-11-14" "10.1002/ejoc.202484201","2024-11-14" +"10.1002/ejoc.202401153","2024-11-18" +"10.1002/ejoc.202400805","2024-11-18"