Jie Sun, Ping Li, Zhongling Cheng, Cheng Tang, Aijun Du, Haijiao Zhang
Bacteria‐derived carbon anode materials have shown appealing potential for advanced energy storage applications due to their low cost and good sustainability. However, the few intrinsic defects, sluggish transmission dynamics, and low capacity become the main bottleneck for their further development. Herein, the study designs a highly B, N co‐doped mesoporous carbon (BNMC)/staphylococcus aureus‐derived carbon (SAC) composite via a facile assembly route, followed by boron‐doping. Enabled by heteroatom doping and pore construction, the resulting BNMC/SAC anode for lithium‐ion batteries demonstrates a high reversible capacity of 621.77 mAh g−1 at 200 mA g−1 even after 500 cycles, and an excellent rate performance of 405.14 mAh g−1 at 2 A g−1. Importantly, in situ/ex situ characterizations and theoretical simulation results further unveil that high B, N co‐doping along with a small amount of P doping can significantly increase the intrinsic defects of BNMC/SAC, thus providing more active sites for lithium‐ion storage. Furthermore, these structural features are conducive to improving the interfacial stability of the whole electrode, achieving a thin and uniform SEI film. The multi‐component co‐doping strategy along with pore engineering presents a scalable approach for enhancing the interfacial stability and transfer dynamics of carbon‐based electrode materials for low‐cost energy storage.
{"title":"Bacteria‐Derived Carbon Composite Anode for Highly Durable Lithium‐Ion Storage Enabled by Heteroatom Doping and Pore Construction","authors":"Jie Sun, Ping Li, Zhongling Cheng, Cheng Tang, Aijun Du, Haijiao Zhang","doi":"10.1002/adfm.202500154","DOIUrl":"https://doi.org/10.1002/adfm.202500154","url":null,"abstract":"Bacteria‐derived carbon anode materials have shown appealing potential for advanced energy storage applications due to their low cost and good sustainability. However, the few intrinsic defects, sluggish transmission dynamics, and low capacity become the main bottleneck for their further development. Herein, the study designs a highly B, N co‐doped mesoporous carbon (BNMC)/staphylococcus aureus‐derived carbon (SAC) composite via a facile assembly route, followed by boron‐doping. Enabled by heteroatom doping and pore construction, the resulting BNMC/SAC anode for lithium‐ion batteries demonstrates a high reversible capacity of 621.77 mAh g<jats:sup>−1</jats:sup> at 200 mA g<jats:sup>−1</jats:sup> even after 500 cycles, and an excellent rate performance of 405.14 mAh g<jats:sup>−1</jats:sup> at 2 A g<jats:sup>−1</jats:sup>. Importantly, in situ/ex situ characterizations and theoretical simulation results further unveil that high B, N co‐doping along with a small amount of P doping can significantly increase the intrinsic defects of BNMC/SAC, thus providing more active sites for lithium‐ion storage. Furthermore, these structural features are conducive to improving the interfacial stability of the whole electrode, achieving a thin and uniform SEI film. The multi‐component co‐doping strategy along with pore engineering presents a scalable approach for enhancing the interfacial stability and transfer dynamics of carbon‐based electrode materials for low‐cost energy storage.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"15 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Na Li, Jin‐Biao Zhang, Christof Wöll, Zhi‐Gang Gu, Jian Zhang
Chiral sensing is essential in pharmaceuticals, food safety, and environmental monitoring, but effectively and accurately detecting various enantiomers continues to be a substantial challenge. Inspired by the dynamic conformational change of olfactory receptor proteins, natural L‐carnosine (Car) is used as a ligand to assemble the first highly crystalline and oriented chiral peptide‐based metal‐organic framework (MOF) thin films with liquid‐phase epitaxial layer‐by‐layer approach (named surfac‐coordinated MOF thin films, SURMOFs). By adjusting the solvent environment, these chiral and at the same time porous SURMOFs mimic the conformational flexibility of receptor proteins, exhibiting dynamic structural changes. This “breathing effect” enables ZnCar SURMOFs to selectively sense six fragrance enantiomers, including (+)/(−)‐carvone, (+)/(−)‐menthol, and (+)/(−)‐limonene. By incorporating these films into a quartz crystal microbalance (QCM) and analyzing the frequency shifts using convolutional neural networks (CNN), a highly sensitive gravimetric biomimetic chiral sensor capable of detecting multiple enantiomers has been developed. With a sensitivity range of 10 to 200 ppm, the sensor reached a recognition accuracy of 98.58% for these six enantiomers, showcasing outstanding selectivity and flexibility.
{"title":"Breathable Biomimetic Chiral Porous MOF Thin Films for Multiple Enantiomers Sensing","authors":"Na Li, Jin‐Biao Zhang, Christof Wöll, Zhi‐Gang Gu, Jian Zhang","doi":"10.1002/adfm.202422860","DOIUrl":"https://doi.org/10.1002/adfm.202422860","url":null,"abstract":"Chiral sensing is essential in pharmaceuticals, food safety, and environmental monitoring, but effectively and accurately detecting various enantiomers continues to be a substantial challenge. Inspired by the dynamic conformational change of olfactory receptor proteins, natural L‐carnosine (Car) is used as a ligand to assemble the first highly crystalline and oriented chiral peptide‐based metal‐organic framework (MOF) thin films with liquid‐phase epitaxial layer‐by‐layer approach (named surfac‐coordinated MOF thin films, SURMOFs). By adjusting the solvent environment, these chiral and at the same time porous SURMOFs mimic the conformational flexibility of receptor proteins, exhibiting dynamic structural changes. This “breathing effect” enables ZnCar SURMOFs to selectively sense six fragrance enantiomers, including (+)/(−)‐carvone, (+)/(−)‐menthol, and (+)/(−)‐limonene. By incorporating these films into a quartz crystal microbalance (QCM) and analyzing the frequency shifts using convolutional neural networks (CNN), a highly sensitive gravimetric biomimetic chiral sensor capable of detecting multiple enantiomers has been developed. With a sensitivity range of 10 to 200 ppm, the sensor reached a recognition accuracy of 98.58% for these six enantiomers, showcasing outstanding selectivity and flexibility.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"14 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tianqi Yang, Jiatao Lou, Liuyi Hu, Qi Liu, Zhouyu Huang, Qingru Zhou, Haiyuan Zhang, Wenlong Song, Hui Huang, Yao Wang, Xinyong Tao, Yang Xia, Wenkui Zhang, Jun Zhang
Succinonitrile (SN)-based in situ polymerized solid-state electrolytes (SIPSSEs) for lithium batteries have attracted considerable attention due to their high ionic conductivity, wide electrochemical stability window (ESW), and potential for large-scale applications. Despite these advantages, the polar cyano groups in SN molecules lead to significant interfacial problems upon direct contact with metallic lithium (Li), including unstable solid electrolyte interface (SEI) and the growth of Li dendrites, which impede the further application of SIPSSEs to solid-state lithium metal batteries (SSLMBs). To address these challenges, here a GaF3-modified SIPSSE (GSNE) is developed by incorporating GaF3 and fluoroethylene carbonate to passivate metallic Li and employing ethoxylated trimethylolpropane triacrylate to anchor SN molecules. As a result of this strategic electrolyte component design, GSNE achieves an ionic conductivity of 1.3 × 10−3 S cm−1 at 30 °C as well as wide ESW up to 4.6 V. Additionally, a LiF/Li3N/LixGa hybrid SEI is formed on the metallic Li surface through an in situ alloying reaction. This hybrid SEI demonstrates superior interfacial stability and fast Li⁺ transport kinetics, as confirmed by various advanced characterization techniques and theoretical calculations. Consequently, LiFePO4/GSNE/Li cells exhibit excellent rate performance and cycling stability. This work provides new insights into the designing of long-lifespan SIPSSEs-based SSLMBs.
{"title":"In Situ Construction of LiF/Li3N/LixGa Hybrid SEI to Boost Long-Lifespan Succinonitrile-Based Solid-State Lithium Metal Batteries","authors":"Tianqi Yang, Jiatao Lou, Liuyi Hu, Qi Liu, Zhouyu Huang, Qingru Zhou, Haiyuan Zhang, Wenlong Song, Hui Huang, Yao Wang, Xinyong Tao, Yang Xia, Wenkui Zhang, Jun Zhang","doi":"10.1002/adfm.202423719","DOIUrl":"https://doi.org/10.1002/adfm.202423719","url":null,"abstract":"Succinonitrile (SN)-based in situ polymerized solid-state electrolytes (SIPSSEs) for lithium batteries have attracted considerable attention due to their high ionic conductivity, wide electrochemical stability window (ESW), and potential for large-scale applications. Despite these advantages, the polar cyano groups in SN molecules lead to significant interfacial problems upon direct contact with metallic lithium (Li), including unstable solid electrolyte interface (SEI) and the growth of Li dendrites, which impede the further application of SIPSSEs to solid-state lithium metal batteries (SSLMBs). To address these challenges, here a GaF<sub>3</sub>-modified SIPSSE (GSNE) is developed by incorporating GaF<sub>3</sub> and fluoroethylene carbonate to passivate metallic Li and employing ethoxylated trimethylolpropane triacrylate to anchor SN molecules. As a result of this strategic electrolyte component design, GSNE achieves an ionic conductivity of 1.3 × 10<sup>−3</sup> S cm<sup>−1</sup> at 30 °C as well as wide ESW up to 4.6 V. Additionally, a LiF/Li<sub>3</sub>N/Li<sub>x</sub>Ga hybrid SEI is formed on the metallic Li surface through an in situ alloying reaction. This hybrid SEI demonstrates superior interfacial stability and fast Li⁺ transport kinetics, as confirmed by various advanced characterization techniques and theoretical calculations. Consequently, LiFePO<sub>4</sub>/GSNE/Li cells exhibit excellent rate performance and cycling stability. This work provides new insights into the designing of long-lifespan SIPSSEs-based SSLMBs.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"19 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shinsuke Maekawa, Lander Verstraete, Hyo Seon Suh, Takehiro Seshimo, Takahiro Dazai, Kazufumi Sato, Kan Hatakeyama-Sato, Yuta Nabae, Teruaki Hayakawa
Extreme ultraviolet (EUV) lithography currently enables the creation of ultrafine patterns. However, as miniaturization progresses, stochastic defects become a significant challenge. Directed self-assembly (DSA) of block copolymers (BCPs) has gained attention for pattern rectification to improve the quality of EUV patterns or for density multiplication to obtain sub-10 nm features. DSA is one of the most promising miniaturization processes because it does not cause stochastic defects. However, dislocation defects are an important issue in density multiplication using strongly segregating BCP. This study demonstrates the use of DSA on 300 mm silicon wafers with higher-Flory-Huggins interaction parameter (χ) polystyrene-block-poly(methyl methacrylate) derivatives for sub-10 nm features. These higher-χ polymers, synthesized from polystyrene-block-[poly(glycidyl methacrylate)-random-poly(methyl methacrylate)] (PS-b-PGM) and 2,2,2-trifluoroethanethiol (PS-b-PGFM), show excellent reproducibility of perpendicular lamellae. Line patterns with a sub-10 nm half-pitch are successfully formed by DSA on 300 mm wafers. Line patterns without parallel-oriented structures or dislocations can be achieved by optimizing the chemical guides and annealing conditions. A polymer with a higher χN value exhibits improved roughness in the resulting line patterns.
{"title":"High-Fidelity Directed Self-Assembly Using Higher-χ Polystyrene-Block-Poly(Methyl Methacrylate) Derivatives for Dislocation-Free Sub-10 nm Features","authors":"Shinsuke Maekawa, Lander Verstraete, Hyo Seon Suh, Takehiro Seshimo, Takahiro Dazai, Kazufumi Sato, Kan Hatakeyama-Sato, Yuta Nabae, Teruaki Hayakawa","doi":"10.1002/adfm.202421066","DOIUrl":"https://doi.org/10.1002/adfm.202421066","url":null,"abstract":"Extreme ultraviolet (EUV) lithography currently enables the creation of ultrafine patterns. However, as miniaturization progresses, stochastic defects become a significant challenge. Directed self-assembly (DSA) of block copolymers (BCPs) has gained attention for pattern rectification to improve the quality of EUV patterns or for density multiplication to obtain sub-10 nm features. DSA is one of the most promising miniaturization processes because it does not cause stochastic defects. However, dislocation defects are an important issue in density multiplication using strongly segregating BCP. This study demonstrates the use of DSA on 300 mm silicon wafers with higher-Flory-Huggins interaction parameter (<i>χ</i>) polystyrene-<i>block</i>-poly(methyl methacrylate) derivatives for sub-10 nm features. These higher-<i>χ</i> polymers, synthesized from polystyrene-<i>block</i>-[poly(glycidyl methacrylate)-<i>random</i>-poly(methyl methacrylate)] (PS-<i>b</i>-PGM) and 2,2,2-trifluoroethanethiol (PS-<i>b</i>-PG<sub>F</sub>M), show excellent reproducibility of perpendicular lamellae. Line patterns with a sub-10 nm half-pitch are successfully formed by DSA on 300 mm wafers. Line patterns without parallel-oriented structures or dislocations can be achieved by optimizing the chemical guides and annealing conditions. A polymer with a higher <i>χN</i> value exhibits improved roughness in the resulting line patterns.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"23 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Miniature swimmers hold considerable potential for precision tasks in the confined environments, yet challenges persist with a simple, sustained, and controllable actuation for their large-scale applications in real-world scenarios. Marangoni-propelled miniature swimmers (MPMSs), leveraging surface-tension-gradient-driven interfacial flows, emerg as a promising solution due to simple implementation and scalable operation. The Marangoni effect, characterized by interfacial flow caused by surface tension gradients, offers a promising propulsion mechanism for the object movement at the liquid surfaces. Leveraging this effect, MPMSs have attracted great interest all over the world. In this regard, this review provides an overview of the latest advancement in the design and application of MPMSs, highlighting the synergy of various responsive materials and structural engineering to enable on-demand surface tension gradients for sustained Marangoni propulsion of the MPMSs. First, it systematically introduces different mechanisms for the generation of surface tension gradient to actuate these swimmers. Subsequently, it elaborately discusses the preparation materials and specialized structural designs employed in MPMSs while elucidating the correlation between propulsion mechanisms and swimmer design strategies. Furthermore, potential practical applications of MPMSs across various scenarios are presented briefly. Finally, remaining challenges along with possible solutions are presented.
{"title":"Marangoni Effect Enabling Autonomously Miniatured Swimmers: Mechanisms, Design Strategy, and Applications","authors":"Haidong Yu, Yiming Wang, Zhiqiang Hou, Xiaohu Xia, Haotian Chen, Bingsuo Zou, Yabin Zhang","doi":"10.1002/adfm.202424235","DOIUrl":"https://doi.org/10.1002/adfm.202424235","url":null,"abstract":"Miniature swimmers hold considerable potential for precision tasks in the confined environments, yet challenges persist with a simple, sustained, and controllable actuation for their large-scale applications in real-world scenarios. Marangoni-propelled miniature swimmers (MPMSs), leveraging surface-tension-gradient-driven interfacial flows, emerg as a promising solution due to simple implementation and scalable operation. The Marangoni effect, characterized by interfacial flow caused by surface tension gradients, offers a promising propulsion mechanism for the object movement at the liquid surfaces. Leveraging this effect, MPMSs have attracted great interest all over the world. In this regard, this review provides an overview of the latest advancement in the design and application of MPMSs, highlighting the synergy of various responsive materials and structural engineering to enable on-demand surface tension gradients for sustained Marangoni propulsion of the MPMSs. First, it systematically introduces different mechanisms for the generation of surface tension gradient to actuate these swimmers. Subsequently, it elaborately discusses the preparation materials and specialized structural designs employed in MPMSs while elucidating the correlation between propulsion mechanisms and swimmer design strategies. Furthermore, potential practical applications of MPMSs across various scenarios are presented briefly. Finally, remaining challenges along with possible solutions are presented.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"4 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yue Jiang, Jiajun Zhang, Hongyang Ma, Shujie Zhou, Hsun-Yen Lin, Sajjad S. Mofarah, Mark Lockrey, Teng Lu, Hangjuan Ren, Xiaoran Zheng, Michael Guanwan, Suchen Huang, Yu-Chun Huang, Fenglin Zhuo, Dali Ji, Judy N. Hart, Yun Liu, Jyh Ming Wu, Muthupandian Ashokkumar, Danyang Wang, Pramod Koshy, Charles C. Sorrell
The catalytic conversion of bioethanol to ethylene (C2H4) and acetylene (C2H2) offers a transformative approach to sustainable production of two industrial cornerstones for organic compound and polymer syntheses, thereby offering significant economic and environmental advantages. In contrast, current methods for the synthesis of these C2 hydrocarbons rely on energy- and carbon-intensive processes that require high temperatures and pressures. The present work addresses these limitations with a novel, low-energy, bioethanol-conversion strategy operating at room temperature and ambient pressure using sono-piezo-photocatalysts. A novel heterostructure of graphene oxide fragments (GO) and sodium bismuth titanate (NBT) within a core-shell microstructure achieved outstanding C2H4 and C2H2 production rates of 134.1 and 55.5 µmol/g/h, respectively. The conversion mechanism is driven by (1) bubble collapse during ultrasound irradiation, generating localized high temperatures (≈4000 K) and pressures (≈100 MPa), and (2) piezo-photocatalytic tuning of GO/NBT by enhanced charge separation and transfer. DFT simulations revealed detailed sono-piezo-photocatalytic conversion pathways, showing significant reductions in energy barriers for C2H4 (22.0 kcal mol−1) and C2H2 (48.0 kcal mol−1) formation. These findings emphasize the critical role of the catalyst in cleaving both C─H and C─O bonds effectively, leading to the desired product formation.
{"title":"Sono-Piezo-Photosynthesis of Ethylene and Acetylene from Bioethanol under Ambient Conditions","authors":"Yue Jiang, Jiajun Zhang, Hongyang Ma, Shujie Zhou, Hsun-Yen Lin, Sajjad S. Mofarah, Mark Lockrey, Teng Lu, Hangjuan Ren, Xiaoran Zheng, Michael Guanwan, Suchen Huang, Yu-Chun Huang, Fenglin Zhuo, Dali Ji, Judy N. Hart, Yun Liu, Jyh Ming Wu, Muthupandian Ashokkumar, Danyang Wang, Pramod Koshy, Charles C. Sorrell","doi":"10.1002/adfm.202425784","DOIUrl":"https://doi.org/10.1002/adfm.202425784","url":null,"abstract":"The catalytic conversion of bioethanol to ethylene (C<sub>2</sub>H<sub>4</sub>) and acetylene (C<sub>2</sub>H<sub>2</sub>) offers a transformative approach to sustainable production of two industrial cornerstones for organic compound and polymer syntheses, thereby offering significant economic and environmental advantages. In contrast, current methods for the synthesis of these C<sub>2</sub> hydrocarbons rely on energy- and carbon-intensive processes that require high temperatures and pressures. The present work addresses these limitations with a novel, low-energy, bioethanol-conversion strategy operating at room temperature and ambient pressure using sono-piezo-photocatalysts. A novel heterostructure of graphene oxide fragments (GO) and sodium bismuth titanate (NBT) within a core-shell microstructure achieved outstanding C<sub>2</sub>H<sub>4</sub> and C<sub>2</sub>H<sub>2</sub> production rates of 134.1 and 55.5 µmol/g/h, respectively. The conversion mechanism is driven by (1) bubble collapse during ultrasound irradiation, generating localized high temperatures (≈4000 K) and pressures (≈100 MPa), and (2) piezo-photocatalytic tuning of GO/NBT by enhanced charge separation and transfer. DFT simulations revealed detailed sono-piezo-photocatalytic conversion pathways, showing significant reductions in energy barriers for C<sub>2</sub>H<sub>4</sub> (22.0 kcal mol<sup>−1</sup>) and C<sub>2</sub>H<sub>2</sub> (48.0 kcal mol<sup>−1</sup>) formation. These findings emphasize the critical role of the catalyst in cleaving both C─H and C─O bonds effectively, leading to the desired product formation.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"19 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393822","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The skin microenvironment is a highly intricate and dynamic system, characterized by an acidic pH, a diverse microbiota, various metabolites, and numerous enzymes, creating both challenges and opportunities for the development of innovative drug delivery systems. Dissolving Microneedles (MNs) have emerged as a promising, pain‐free alternative to conventional invasive injections, offering the ability to deliver therapeutics through gradual degradation within the skin's interstitial fluids. Building upon the unique properties of both the skin microenvironment and dissolving MNs, a novel concept is introduced wherein dissolving MNs serve as in situ chemical reaction chambers. In this framework, MNs can deliver chemical reactants or catalysts to the skin, enabling the initiation of specific chemical reactions, such as prodrug activation for targeted therapy, the degradation of harmful metabolites, or the enhanced synthesis of beneficial molecules. Moreover, this review systematically explores the potential of dissolving MNs as chemical reaction chambers, discussing key aspects such as their sustained release mechanisms, design strategies, and a range of therapeutic applications. Finally, a forward‐looking perspective is provided on the future development of dissolving MNs, addressing the challenges and opportunities for their broader clinical translation and application in personalized medicine.
{"title":"Dissolving Microneedles as In Situ Chemical Reaction Chambers: from Design Strategies to Versatile Biomedical Applications","authors":"Yu Tian, Lili Xia, Xinran Song, Yu Chen","doi":"10.1002/adfm.202422274","DOIUrl":"https://doi.org/10.1002/adfm.202422274","url":null,"abstract":"The skin microenvironment is a highly intricate and dynamic system, characterized by an acidic pH, a diverse microbiota, various metabolites, and numerous enzymes, creating both challenges and opportunities for the development of innovative drug delivery systems. Dissolving Microneedles (MNs) have emerged as a promising, pain‐free alternative to conventional invasive injections, offering the ability to deliver therapeutics through gradual degradation within the skin's interstitial fluids. Building upon the unique properties of both the skin microenvironment and dissolving MNs, a novel concept is introduced wherein dissolving MNs serve as in situ chemical reaction chambers. In this framework, MNs can deliver chemical reactants or catalysts to the skin, enabling the initiation of specific chemical reactions, such as prodrug activation for targeted therapy, the degradation of harmful metabolites, or the enhanced synthesis of beneficial molecules. Moreover, this review systematically explores the potential of dissolving MNs as chemical reaction chambers, discussing key aspects such as their sustained release mechanisms, design strategies, and a range of therapeutic applications. Finally, a forward‐looking perspective is provided on the future development of dissolving MNs, addressing the challenges and opportunities for their broader clinical translation and application in personalized medicine.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"15 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385227","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qi Zhao, Siyi Lin, Penghao Sun, Ya Lu, Qian Li, Zhennan Tian, Xuguan Bai, Jike Wang, Lu Wang, Shigui Chen
Advancing anhydrous proton‐conducting materials is essential for the fabrication of high‐temperature (>373 K) polymer electrolyte membrane fuel cells (HT‐PEMFCs) and remains a significant challenge. Herein, halogen‐bonded organic frameworks linked by [N···I··N]+ interactions are reported as outstanding high‐temperature conductive materials. By incorporating carbazole groups into the monomers, two highly crystalline halogen‐bonded organic frameworks (XOF‐CSP/CTP) are constructed. These XOFs exhibit a high intrinsic conductivity (σ = 1.22 × 10−3 S cm−1) under high‐temperature anhydrous conditions. Doping the XOFs with H3PO4 allows the nitrogen sites and I+ sites on the pore walls to stabilize and tightly confine the H3PO4 network within the porous framework through hydrogen bonding, thereby enhancing proton conductivity under anhydrous conditions (σ = 1.02 × 10−2 S cm−1). Temperature‐dependent curves and theoretical calculations indicate that proton transport is governed by a low‐energy barrier hopping mechanism. These materials exhibit excellent stability and maintain high proton conductivity across a broad temperature range. This work provides a new platform for designing anhydrous proton‐conducting materials with significant potential as high‐temperature proton exchange membranes.
{"title":"Efficient Proton Conduction through [N···X···N]+ Halogen Bond Coordination in Halogen‐Bonded Organic Frameworks","authors":"Qi Zhao, Siyi Lin, Penghao Sun, Ya Lu, Qian Li, Zhennan Tian, Xuguan Bai, Jike Wang, Lu Wang, Shigui Chen","doi":"10.1002/adfm.202421755","DOIUrl":"https://doi.org/10.1002/adfm.202421755","url":null,"abstract":"Advancing anhydrous proton‐conducting materials is essential for the fabrication of high‐temperature (>373 K) polymer electrolyte membrane fuel cells (HT‐PEMFCs) and remains a significant challenge. Herein, halogen‐bonded organic frameworks linked by [N···I··N]<jats:sup>+</jats:sup> interactions are reported as outstanding high‐temperature conductive materials. By incorporating carbazole groups into the monomers, two highly crystalline halogen‐bonded organic frameworks (XOF‐CSP/CTP) are constructed. These XOFs exhibit a high intrinsic conductivity (σ = 1.22 × 10<jats:sup>−3</jats:sup> S cm<jats:sup>−1</jats:sup>) under high‐temperature anhydrous conditions. Doping the XOFs with H<jats:sub>3</jats:sub>PO<jats:sub>4</jats:sub> allows the nitrogen sites and I<jats:sup>+</jats:sup> sites on the pore walls to stabilize and tightly confine the H<jats:sub>3</jats:sub>PO<jats:sub>4</jats:sub> network within the porous framework through hydrogen bonding, thereby enhancing proton conductivity under anhydrous conditions (σ = 1.02 × 10<jats:sup>−2</jats:sup> S cm<jats:sup>−1</jats:sup>). Temperature‐dependent curves and theoretical calculations indicate that proton transport is governed by a low‐energy barrier hopping mechanism. These materials exhibit excellent stability and maintain high proton conductivity across a broad temperature range. This work provides a new platform for designing anhydrous proton‐conducting materials with significant potential as high‐temperature proton exchange membranes.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"55 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ruanye Zhang, Hai Xu, Zhemin Li, Hui Dou, Xiaogang Zhang
Recently, the development of Zn‐host materials in metal‐free aqueous Zinc ion batteries (AZIBs) has emerged as an effective strategy to address the challenges of uncontrollable dendrite growth and severe corrosion in Zn anodes. Herein, the layer‐by‐layer assembly conjugated polyimide nanocomposite (PTN‐MXene) through in situ polymerization is proposed to realize high energy density and stability metal‐free AZIBs. Specifically, the unique layered structure and abundant redox centers of conjugated diketone‐based polyimide (PTN), combined with its high structural compatibility with MXene, enable the formation of a layer‐by‐layer assembled 2D/2D heterostructure. This design ensures sufficient contact and expands the interlayer spacing of MXene, facilitating faster electron/ion transport kinetics and providing better access to redox centers. Importantly, the regulation of ion transport behavior from H+ or Zn2+ to H+/Zn2+ coinsertion in PTN‐MXene is achieved and verified by different characterization techniques. Thus, PTN‐MXene anode exhibits high specific capacity (283.4 mAh g−1 at 0.1 A g−1), excellent rate performance and outstanding cycling performance. As a proof‐of‐concept, the full batteries fabricated by Prussian blue analogs cathode and PTN‐MXene anode deliver a high energy density of 72.4 Wh kg−1 and exceptional cycling stability over 2000 cycles.
{"title":"Regulation of Ion Transport Behavior in Layer‐by‐Layer Assembled Polymer/MXene Heterostructure Anodes for Metal‐Free Aqueous Zinc Ion Batteries","authors":"Ruanye Zhang, Hai Xu, Zhemin Li, Hui Dou, Xiaogang Zhang","doi":"10.1002/adfm.202424649","DOIUrl":"https://doi.org/10.1002/adfm.202424649","url":null,"abstract":"Recently, the development of Zn‐host materials in metal‐free aqueous Zinc ion batteries (AZIBs) has emerged as an effective strategy to address the challenges of uncontrollable dendrite growth and severe corrosion in Zn anodes. Herein, the layer‐by‐layer assembly conjugated polyimide nanocomposite (PTN‐MXene) through in situ polymerization is proposed to realize high energy density and stability metal‐free AZIBs. Specifically, the unique layered structure and abundant redox centers of conjugated diketone‐based polyimide (PTN), combined with its high structural compatibility with MXene, enable the formation of a layer‐by‐layer assembled 2D/2D heterostructure. This design ensures sufficient contact and expands the interlayer spacing of MXene, facilitating faster electron/ion transport kinetics and providing better access to redox centers. Importantly, the regulation of ion transport behavior from H<jats:sup>+</jats:sup> or Zn<jats:sup>2+</jats:sup> to H<jats:sup>+</jats:sup>/Zn<jats:sup>2+</jats:sup> coinsertion in PTN‐MXene is achieved and verified by different characterization techniques. Thus, PTN‐MXene anode exhibits high specific capacity (283.4 mAh g<jats:sup>−1</jats:sup> at 0.1 A g<jats:sup>−1</jats:sup>), excellent rate performance and outstanding cycling performance. As a proof‐of‐concept, the full batteries fabricated by Prussian blue analogs cathode and PTN‐MXene anode deliver a high energy density of 72.4 Wh kg<jats:sup>−1</jats:sup> and exceptional cycling stability over 2000 cycles.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"21 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385234","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chiral metamaterials have attracted pronounced attention due to their great potential in detecting vortex-structured light and enantiomeric chiral molecules. However, most previously-explored rigid chiral structures are constrained by poor tunability, resulting from their inability to achieve bidirectionally symmetric fabrication. Though the integration of smart materials with femtosecond laser printing has advanced the development of 3D tunable microstructures, unfortunately, the asymmetric deformation of those smart materials breaks the chiral symmetry of fabricated structures. Herein, a feasible strategy namely angle compensation coupling with laser-induced self-assembly of pH-sensitive microstructures to restore the symmetry of chiral self-assemblies, is proposed. Relying on the laser-printing guided capillary force self-assembly, the targeted chiral microstructures featuring bidirectional symmetry and shape-morphing reversibility are successfully harvested, witnessing its unparalleled fabricating flexibility and accurate controllability. Significantly, once the vortex light serves as a probe, the assembled chiral enantiomers yield symmetrically distributed dichroism spectra, evidencing the feasibility of current approaches. This work grants a paradigm for the rapid and steerable manufacture of chiral metasurfaces and further enhances the potential in the fields of optical communication, chemical sensing, and chiral photonics.
{"title":"Bidirectionally Symmetric Self-Assembly of Switchable Chiral Microstructures Based on Angle Compensation and pH Regulation Strategy for Chiroptical Metamaterials","authors":"Zhaoxin Lao, Xin Liu, Qiaoqiao Qi, Haijian Hu, Meiqi Liu, Haojie Zhu, Rui Dong, Yachao Zhang, Sizhu Wu, Chenchu Zhang, Chao Chen, Li Zhang","doi":"10.1002/adfm.202423425","DOIUrl":"https://doi.org/10.1002/adfm.202423425","url":null,"abstract":"Chiral metamaterials have attracted pronounced attention due to their great potential in detecting vortex-structured light and enantiomeric chiral molecules. However, most previously-explored rigid chiral structures are constrained by poor tunability, resulting from their inability to achieve bidirectionally symmetric fabrication. Though the integration of smart materials with femtosecond laser printing has advanced the development of 3D tunable microstructures, unfortunately, the asymmetric deformation of those smart materials breaks the chiral symmetry of fabricated structures. Herein, a feasible strategy namely angle compensation coupling with laser-induced self-assembly of pH-sensitive microstructures to restore the symmetry of chiral self-assemblies, is proposed. Relying on the laser-printing guided capillary force self-assembly, the targeted chiral microstructures featuring bidirectional symmetry and shape-morphing reversibility are successfully harvested, witnessing its unparalleled fabricating flexibility and accurate controllability. Significantly, once the vortex light serves as a probe, the assembled chiral enantiomers yield symmetrically distributed dichroism spectra, evidencing the feasibility of current approaches. This work grants a paradigm for the rapid and steerable manufacture of chiral metasurfaces and further enhances the potential in the fields of optical communication, chemical sensing, and chiral photonics.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"10 1","pages":""},"PeriodicalIF":19.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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