Insufficient reactive oxygen species originating from hypoxia and high glutathione (GSH) in the tumor microenvironment (TME) is an important reason for radiotherapy (RT) resistance. Currently, radiosensitizers that remodel TME are widely investigated to enhance RT. However, developing an effective nano-radiosensitization system that removes radiotherapy-resistant factors from TME to boost RT effect while visualizing tumor imaging to aid therapy remains a challenge. Herein, MnO2 nanosheets are grown on the surface of ultrasmall Eu-doped NaGdF4 (NaGdF4:Eu3+) nanoparticles and modified by biocompatible DSPE-PEG2000 to prepare NaGdF4:Eu3+@MnO2@PEG nanoparticles (denoted as GMP NPs) as a radiosensitizer, which not only can reverse the TME by degrading H2O2 to produce oxygen and consuming high GSH but also achieve computed tomography (CT)and magnetic resonance (MR) imaging. When GMP NPs synergize with X-ray, a better antitumor effect is achieved in both HeLa cells and tumor-bearing mice, compared with X-ray alone. In addition, both paramagnetic Mn2+ ionsproduced by decomposing MnO2 in TME and NaGdF4:Eu3+ nanoparticles enhance T1-weighted MR imaging. NaGdF4:Eu3+ nanoparticles containing high atomic number of Gd/Eu effectively attenuate X-ray to enhance CT imaging. The work provides new insights for developing an efficient RT sensitization platform integrating antitumor therapeutic effect as well as CT/MR dual-modal imaging.
肿瘤微环境（TME）中缺氧和高谷胱甘肽（GSH）导致的活性氧不足是放疗（RT）耐药的重要原因。目前，重塑肿瘤微环境的放射增敏剂被广泛用于增强放疗。然而，开发一种有效的纳米放射增敏系统，既能清除肿瘤微环境中的放疗耐药因子，提高放疗效果，又能通过可视化肿瘤成像辅助治疗，仍然是一项挑战。在此，MnO2 纳米片生长在超小 Eu 掺杂 NaGdF4（NaGdF4:Eu3+）纳米颗粒表面，并用生物相容性 DSPE-PEG2000 修饰，制备出 NaGdF4：Eu3+@MnO2@PEG 纳米粒子（简称 GMP NPs）作为放射增敏剂，不仅能通过降解 H2O2 产生氧气和消耗大量 GSH 来逆转 TME，还能实现计算机断层扫描（CT）和磁共振（MR）成像。当 GMP NPs 与 X 射线协同作用时，对 HeLa 细胞和肿瘤小鼠的抗肿瘤效果比单独使用 X 射线更好。此外，TME 中 MnO2 分解产生的顺磁 Mn2+ 离子和 NaGdF4:Eu3+ 纳米粒子都能增强 T1 加权磁共振成像。含有高原子序数 Gd/Eu 的 NaGdF4:Eu3+ 纳米粒子能有效衰减 X 射线，从而增强 CT 成像。这项工作为开发集抗肿瘤治疗效果和 CT/MR 双模态成像于一体的高效 RT 增敏平台提供了新的思路。
{"title":"Gadolinium-Manganese-Based Nanoplatform Reverses Radiotherapy Resistant Factors for Radiotherapy Sensitization and Computed Tomography/Magnetic Resonance Dual-Modal Imaging","authors":"Yingwen Li, Panhong Niu, Zhenzhong Han, Xueqian Wang, Duanmin Gao, Yunjian Xu, Qingbin He, Jianfeng Qiu, Yinglun Sun","doi":"10.1002/sstr.202400033","DOIUrl":"https://doi.org/10.1002/sstr.202400033","url":null,"abstract":"Insufficient reactive oxygen species originating from hypoxia and high glutathione (GSH) in the tumor microenvironment (TME) is an important reason for radiotherapy (RT) resistance. Currently, radiosensitizers that remodel TME are widely investigated to enhance RT. However, developing an effective nano-radiosensitization system that removes radiotherapy-resistant factors from TME to boost RT effect while visualizing tumor imaging to aid therapy remains a challenge. Herein, MnO<sub>2</sub> nanosheets are grown on the surface of ultrasmall Eu-doped NaGdF<sub>4</sub> (NaGdF<sub>4</sub>:Eu<sup>3+</sup>) nanoparticles and modified by biocompatible DSPE-PEG<sub>2000</sub> to prepare NaGdF<sub>4</sub>:Eu<sup>3+</sup>@MnO<sub>2</sub>@PEG nanoparticles (denoted as GMP NPs) as a radiosensitizer, which not only can reverse the TME by degrading H<sub>2</sub>O<sub>2</sub> to produce oxygen and consuming high GSH but also achieve computed tomography (CT)and magnetic resonance (MR) imaging. When GMP NPs synergize with X-ray, a better antitumor effect is achieved in both HeLa cells and tumor-bearing mice, compared with X-ray alone. In addition, both paramagnetic Mn<sup>2+</sup> ionsproduced by decomposing MnO<sub>2</sub> in TME and NaGdF<sub>4</sub>:Eu<sup>3+</sup> nanoparticles enhance T<sub>1</sub>-weighted MR imaging. NaGdF<sub>4</sub>:Eu<sup>3+</sup> nanoparticles containing high atomic number of Gd/Eu effectively attenuate X-ray to enhance CT imaging. The work provides new insights for developing an efficient RT sensitization platform integrating antitumor therapeutic effect as well as CT/MR dual-modal imaging.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"125 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141585442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiacheng Liu, Song-Zhu Kure-Chu, Shuji Katsuta, Mengmeng Zhang, Shaoli Fang, Takashi Matsubara, Yoko Sakurai, Takehiko Hihara, Ray H. Baughman, Hitoshi Yashiro, Long Pan, Wei Zhang, Zheng Ming Sun
Enhancing tribological performance through nanostructure control is crucial for saving energy and improving wear resistance for diverse applications. We introduce a new electrochemical approach that integrates aluminum (Al) anodization, tin alternating current (AC) electrodeposition, and anodic MoS2 electrosynthesis for fabricating nanostructured Al2O3/Sn(S)MoS2 composite films on AlSiCu casting alloys. Our unique process uses Sn-modified MoS2 deposition to form robust solid lubricant MoS2–SnS electrodeposits within the nanochannels and microsized voids/defects of anodic alumina matrix films on the base materials, resulting in a bilayered Al2O3/SnSMoS2 and MoS2–SnS–Sn composite film. The AC-deposited Sn enhances conductivity in the anodic alumina matrix film, acts as catalytic nuclei for Sn@SnS@MoS2 core-shell nanoparticles and a dense top layer, and serves as a reductant for the direct synthesis of hybrid solid lubricant MoS2–SnS from MoS3 by anodic electrolysis of MoS42− ions. The resulting nanocomposite film provides a two-fold increase in lubricity (friction coefficient (COF) μ = 0.14 ⇒ 0.07) and a ten-fold improvement in wear resistance (COF μ < 0.2) compared to conventional Al2O3/MoS2 film formed by anodizing and reanodizing. The effectiveness of the Al2O3/Sn(S)MoS2 composite is further validated through real automotive engine piston tests.
{"title":"Tenfold Enhancement of Wear Resistance by Electrosynthesis of a Nanostructured Self-Lubricating Al2O3/Sn(S)?MoS2 Composite Film on Al?Si?Cu Casting Alloys","authors":"Jiacheng Liu, Song-Zhu Kure-Chu, Shuji Katsuta, Mengmeng Zhang, Shaoli Fang, Takashi Matsubara, Yoko Sakurai, Takehiko Hihara, Ray H. Baughman, Hitoshi Yashiro, Long Pan, Wei Zhang, Zheng Ming Sun","doi":"10.1002/sstr.202400172","DOIUrl":"https://doi.org/10.1002/sstr.202400172","url":null,"abstract":"Enhancing tribological performance through nanostructure control is crucial for saving energy and improving wear resistance for diverse applications. We introduce a new electrochemical approach that integrates aluminum (Al) anodization, tin alternating current (AC) electrodeposition, and anodic MoS<sub>2</sub> electrosynthesis for fabricating nanostructured Al<sub>2</sub>O<sub>3</sub>/Sn(S)<span></span>MoS<sub>2</sub> composite films on Al<span></span>Si<span></span>Cu casting alloys. Our unique process uses Sn-modified MoS<sub>2</sub> deposition to form robust solid lubricant MoS<sub>2</sub>–SnS electrodeposits within the nanochannels and microsized voids/defects of anodic alumina matrix films on the base materials, resulting in a bilayered Al<sub>2</sub>O<sub>3</sub>/SnS<span></span>MoS<sub>2</sub> and MoS<sub>2</sub>–SnS–Sn composite film. The AC-deposited Sn enhances conductivity in the anodic alumina matrix film, acts as catalytic nuclei for Sn@SnS@MoS<sub>2</sub> core-shell nanoparticles and a dense top layer, and serves as a reductant for the direct synthesis of hybrid solid lubricant MoS<sub>2</sub>–SnS from MoS<sub>3</sub> by anodic electrolysis of MoS<sub>4</sub><sup>2−</sup> ions. The resulting nanocomposite film provides a two-fold increase in lubricity (friction coefficient (COF) μ = 0.14 ⇒ 0.07) and a ten-fold improvement in wear resistance (COF μ < 0.2) compared to conventional Al<sub>2</sub>O<sub>3</sub>/MoS<sub>2</sub> film formed by anodizing and reanodizing. The effectiveness of the Al<sub>2</sub>O<sub>3</sub>/Sn(S)<span></span>MoS<sub>2</sub> composite is further validated through real automotive engine piston tests.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"29 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141585447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Torben Hüsing, Daniel Van Opdenbosch, Broder Rühmann, Cordt Zollfrank, Ellen Reuter, Volker Sieber
Biohybrid Materials
生物杂交材料
{"title":"Characterization of Functional Biohybrid Materials Based on Saccharomyces Cerevisiae Biomass","authors":"Torben Hüsing, Daniel Van Opdenbosch, Broder Rühmann, Cordt Zollfrank, Ellen Reuter, Volker Sieber","doi":"10.1002/sstr.202470033","DOIUrl":"https://doi.org/10.1002/sstr.202470033","url":null,"abstract":"<b>Biohybrid Materials</b>","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"41 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Diogo V. Saraiva, Steven N. Remiëns, Ethan I. L. Jull, Ivo R. Vermaire, Lisa Tran
Cellulose Nanocrystals
纤维素纳米晶体
{"title":"Flexible, Photonic Films of Surfactant-Functionalized Cellulose Nanocrystals for Pressure and Humidity Sensing","authors":"Diogo V. Saraiva, Steven N. Remiëns, Ethan I. L. Jull, Ivo R. Vermaire, Lisa Tran","doi":"10.1002/sstr.202470032","DOIUrl":"https://doi.org/10.1002/sstr.202470032","url":null,"abstract":"<b>Cellulose Nanocrystals</b>","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"18 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis of Red, Green, and Blue Carbon Quantum Dots and Construction of Multicolor Cellulose-Based Light-Emitting Diodes","authors":"Xinrui Chen, Xing Han, Caixia Zhang, Xue Ou, Xiaoli Liu, Junhua Zhang, Wei Liu, Arthur J. Ragauskas, Xueping Song, Zhanying Zhang","doi":"10.1002/sstr.202470034","DOIUrl":"https://doi.org/10.1002/sstr.202470034","url":null,"abstract":"<b>Light-Emitting Diodes</b>","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"54 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tianxin Bai, Qiujie Wang, Yunfei Bai, Qichao Meng, Hongyuan Zhao, Ziying Wen, Haibo Sun, Li Huang, Junke Jiang, Dan Huang, Feng Liu, William W. Yu
Lanthanide-Based Metal Halides
镧系金属卤化物
{"title":"From Dopant to Host: Solution Synthesis and Light-Emitting Applications of Organic-Inorganic Lanthanide-Based Metal Halides","authors":"Tianxin Bai, Qiujie Wang, Yunfei Bai, Qichao Meng, Hongyuan Zhao, Ziying Wen, Haibo Sun, Li Huang, Junke Jiang, Dan Huang, Feng Liu, William W. Yu","doi":"10.1002/sstr.202470030","DOIUrl":"https://doi.org/10.1002/sstr.202470030","url":null,"abstract":"<b>Lanthanide-Based Metal Halides</b>","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"78 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141571184","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Frank Sailer, Hipassia M. Moura, Taniya Purkait, Lars Vogelsang, Markus Sauer, Annette Foelske, Rainer F. Winter, Alexandre Ponrouch, Miriam M. Unterlass
Hybrid materials (HMs) combine the high diversity of functionalities of organic compounds with properties typical for inorganic materials, such as high mechanical strength or high thermal stability. Herein, HMs combining organic pigment molecules and TiO2 as inorganic component, with covalently linked components, i.e., so-called class II HMs, are reported. The synthesis of such HMs is intrinsically challenging, as the apolar organic pigment component and the inorganic polar TiO2 component require different conditions for their respective formation. Herein, we circumvent this issue by employing solvothermal synthesis in superheated isopropanol, which through temperature tunability of the solvent properties allows for both generating and linking both components in one-pot. First, it is shown that an organic benzimidazole-based pigment molecule designed for readily binding to Ti can be synthesized solvothermally. Second, new class II titanium-based HMs are generated from Ti(OiPr)4 and pigment precursors in a solvothermal reaction. The pigment@TiO2 HMs feature significant porosity and are structurally identified as layered structures of lepidocrocite-like TiO2 linked via pigment molecules. These layered HMs assemble into hierarchical nanoflowers, and depending on the pigment segments, different interlayer spacings in between inorganic layers are observed. Third, the pigment@TiO2 materials are shown to be usable as electrode materials in lithium-ion batteries.
混合材料（HMs）结合了有机化合物的高功能多样性和无机材料的典型特性，如高机械强度或高热稳定性。本文报告了有机颜料分子与作为无机成分的二氧化钛（TiO2）共价结合的混合材料，即所谓的第二类混合材料。由于极性有机颜料成分和无机极性二氧化钛成分的形成需要不同的条件，因此合成此类 HMs 本身就具有挑战性。在本文中，我们通过在过热异丙醇中采用溶解热合成法来规避这一问题，该方法通过对溶剂特性的温度调节，可在一锅内同时生成和连接两种成分。首先，我们证明了一种基于苯并咪唑的有机颜料分子可以通过溶解热合成的方式与钛结合。其次，在溶热反应中由 Ti(OiPr)4 和颜料前体生成新的第二类钛基 HM。颜料@TiO2 HMs 具有显著的多孔性，在结构上被确定为通过颜料分子连接的鳞片状二氧化钛的层状结构。这些分层的 HMs 组装成分层的纳米花束，根据颜料段的不同，无机层之间的层间距也不同。第三，颜料@TiO2 材料可用作锂离子电池的电极材料。
{"title":"Covalently Linked Pigment@TiO2 Hybrid Materials by One-Pot Solvothermal Synthesis","authors":"Frank Sailer, Hipassia M. Moura, Taniya Purkait, Lars Vogelsang, Markus Sauer, Annette Foelske, Rainer F. Winter, Alexandre Ponrouch, Miriam M. Unterlass","doi":"10.1002/sstr.202400074","DOIUrl":"https://doi.org/10.1002/sstr.202400074","url":null,"abstract":"Hybrid materials (HMs) combine the high diversity of functionalities of organic compounds with properties typical for inorganic materials, such as high mechanical strength or high thermal stability. Herein, HMs combining organic pigment molecules and TiO<sub>2</sub> as inorganic component, with covalently linked components, i.e., so-called class II HMs, are reported. The synthesis of such HMs is intrinsically challenging, as the apolar organic pigment component and the inorganic polar TiO<sub>2</sub> component require different conditions for their respective formation. Herein, we circumvent this issue by employing solvothermal synthesis in superheated isopropanol, which through temperature tunability of the solvent properties allows for both generating and linking both components in one-pot. First, it is shown that an organic benzimidazole-based pigment molecule designed for readily binding to Ti can be synthesized solvothermally. Second, new class II titanium-based HMs are generated from Ti(O<sup><i>i</i></sup>Pr)<sub>4</sub> and pigment precursors in a solvothermal reaction. The pigment@TiO<sub>2</sub> HMs feature significant porosity and are structurally identified as layered structures of lepidocrocite-like TiO<sub>2</sub> linked via pigment molecules. These layered HMs assemble into hierarchical nanoflowers, and depending on the pigment segments, different interlayer spacings in between inorganic layers are observed. Third, the pigment@TiO<sub>2</sub> materials are shown to be usable as electrode materials in lithium-ion batteries.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141552071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ayelet Tashakory, Sanjit Mondal, Venugopala Rao Battula, Gabriel Mark, Tirza Shmila, Michael Volokh, Menny Shalom
Polymeric carbon nitride (CN) has emerged as a promising photoanodic material in water-splitting photoelectrochemical cells (PEC). However, the current deposition methods of CN layers on substrates usually include a long heating process at 500−550 °C, which might cause sublimation or decomposition of the CN monomers and destruction of the substrate, leading to a nonuniform CN film. Herein, a simple, fast, and scalable energy-economic procedure to synthesize homogenous CN films is introduced. The predesigned CN monomers film is subjected for several minutes to higher temperatures than the standard calcination procedure. The short heating process allows the formation of a uniform CN layer, with excellent contact with the substrate and good activity as a photoanode in PEC. The optimal CN photoanode reaches photocurrent densities of ≈200 μA cm−2 at 1.23 versus reversible hydrogen electrode in neutral and acidic solutions and 120 μA cm−2 in a basic solution.
{"title":"Minute-Scale High-Temperature Synthesis of Polymeric Carbon Nitride Photoanodes","authors":"Ayelet Tashakory, Sanjit Mondal, Venugopala Rao Battula, Gabriel Mark, Tirza Shmila, Michael Volokh, Menny Shalom","doi":"10.1002/sstr.202400123","DOIUrl":"https://doi.org/10.1002/sstr.202400123","url":null,"abstract":"Polymeric carbon nitride (CN) has emerged as a promising photoanodic material in water-splitting photoelectrochemical cells (PEC). However, the current deposition methods of CN layers on substrates usually include a long heating process at 500−550 °C, which might cause sublimation or decomposition of the CN monomers and destruction of the substrate, leading to a nonuniform CN film. Herein, a simple, fast, and scalable energy-economic procedure to synthesize homogenous CN films is introduced. The predesigned CN monomers film is subjected for several minutes to higher temperatures than the standard calcination procedure. The short heating process allows the formation of a uniform CN layer, with excellent contact with the substrate and good activity as a photoanode in PEC. The optimal CN photoanode reaches photocurrent densities of ≈200 μA cm<sup>−2</sup> at 1.23 versus reversible hydrogen electrode in neutral and acidic solutions and 120 μA cm<sup>−2</sup> in a basic solution.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"187 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The evolution of flexible Zn-ion batteries (FZIBs) significantly hinges on the development of gel electrolytes, characterized by their mechanical properties, ionic conductivity, and environmentally friendly production processes. The prevailing challenge in this domain has been devising a gel electrolyte that encapsulates all these critical attributes effectively for practical application. This study presents a novel zinc ion gel (Zn-gel) electrolyte developed for FZIBs, synthesized via ethanol vapor-induced assembly of cellulose molecules. This innovative process fosters significant hydrogen bonding and ion-complexation with Zn2+ ions, resulting in a gel with exceptional mechanical strength (0.88 MPa), high ion transference (over 0.7), and impressive ionic conductivity (8.39 mS cm−1). The Zn-gel enables a FZIB to achieve a reversible capacity of 207.3 mAh g−1 and over 93% Coulombic efficiency after 500 cycles, devoid of liquid electrolyte. Highlighting a promising route for high-performance, eco-friendly gel electrolytes, this research advances flexible electronics and portable device applications, demonstrating the profound potential of bio-based polymers in enhancing energy storage technology.
柔性锌离子电池（FZIB）的发展在很大程度上取决于凝胶电解质的开发，凝胶电解质具有机械性能、离子导电性和环保生产工艺等特点。这一领域面临的主要挑战是设计出一种凝胶电解质，它能有效封装所有这些关键属性，以实现实际应用。本研究介绍了一种为 FZIB 开发的新型锌离子凝胶（Zn-gel）电解质，它是通过乙醇蒸汽诱导纤维素分子组装合成的。这种创新工艺促进了与 Zn2+ 离子的氢键和离子络合，从而使凝胶具有超强的机械强度（0.88 兆帕）、高离子转移率（超过 0.7）和惊人的离子电导率（8.39 mS cm-1）。在不使用液态电解质的情况下，锌凝胶使 FZIB 在 500 次循环后达到 207.3 mAh g-1 的可逆容量和 93% 以上的库仑效率。这项研究为高性能、环保型凝胶电解质开辟了一条前景广阔的途径，推动了柔性电子器件和便携式设备的应用，展示了生物基聚合物在提高储能技术方面的巨大潜力。
{"title":"Ethanol Vapor-Induced Synthesis of Robust, High-Efficiency Zinc Ion Gel Electrolytes for Flexible Zn-Ion Batteries","authors":"Zihao Zheng, Wanke Cheng, Geyuan Jiang, Xiaona Li, Jinsong Sun, Ying Zhu, Dawei Zhao, Haipeng Yu","doi":"10.1002/sstr.202400180","DOIUrl":"https://doi.org/10.1002/sstr.202400180","url":null,"abstract":"The evolution of flexible Zn-ion batteries (FZIBs) significantly hinges on the development of gel electrolytes, characterized by their mechanical properties, ionic conductivity, and environmentally friendly production processes. The prevailing challenge in this domain has been devising a gel electrolyte that encapsulates all these critical attributes effectively for practical application. This study presents a novel zinc ion gel (Zn-gel) electrolyte developed for FZIBs, synthesized via ethanol vapor-induced assembly of cellulose molecules. This innovative process fosters significant hydrogen bonding and ion-complexation with Zn<sup>2+</sup> ions, resulting in a gel with exceptional mechanical strength (0.88 MPa), high ion transference (over 0.7), and impressive ionic conductivity (8.39 mS cm<sup>−1</sup>). The Zn-gel enables a FZIB to achieve a reversible capacity of 207.3 mAh g<sup>−1</sup> and over 93% Coulombic efficiency after 500 cycles, devoid of liquid electrolyte. Highlighting a promising route for high-performance, eco-friendly gel electrolytes, this research advances flexible electronics and portable device applications, demonstrating the profound potential of bio-based polymers in enhancing energy storage technology.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"23 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Current advances in synthesizing and characterizing atomically precise monodisperse metal clusters (AMCs) at the subnanometer scale have opened up new possibilities in quantum materials research. Their quantizied “molecule-like” electronic structure showcases unique stability, and physical and chemical properties differentiate them from larger nanoparticles. When integrated into inorganic materials that interact with the environment and sunlight, AMCs serve to enhance their (photo)catalytic activity and optoelectronic properties. Their tiny size makes AMCs isolated in the gas phase amenable to atom-scale modeling using either density functional theory (DFT) or methods at a high level of ab initio theory, even addressing nonadiabatic (e.g., Jahn–Teller) effects. Surface-supported AMCs can be routinely modeled using DFT, enabling long real-time molecular dynamics simulations. Their optical properties can also be addressed using time-dependent DFT or reduced density matrix (RDM) theory. These theoretical–computational efforts aim to achieve predictability and molecular-level understanding of the stability and properties of AMCs as function of their composition, size, and structural fluxionality in different thermodynamical conditions (temperature and pressure). In this perspective, the potential of ab initio and DFT-based modeling is illustrated through recent studies of unsupported and surface-supported AMCs. Future directions of research are also discussed, including applications and methodological enhancements beyond the state-of-the-art.
目前在亚纳米尺度合成和表征原子精确单分散金属团簇（AMC）方面取得的进展为量子材料研究开辟了新的可能性。它们量子化的 "分子状 "电子结构显示出独特的稳定性，其物理和化学特性也有别于较大的纳米颗粒。当将 AMC 集成到与环境和阳光相互作用的无机材料中时，AMC 可增强其（光）催化活性和光电特性。由于 AMC 的尺寸极小，因此可以使用密度泛函理论（DFT）或高水平的 ab initio 理论方法，甚至是非绝热（如 Jahn-Teller）效应，对分离在气相中的 AMC 进行原子尺度建模。表面支持的 AMC 可以使用 DFT 进行常规建模，从而实现长时间的实时分子动力学模拟。它们的光学特性也可以使用随时间变化的 DFT 或还原密度矩阵 (RDM) 理论来解决。这些理论计算工作旨在实现对 AMC 在不同热力学条件（温度和压力）下的稳定性和特性的可预测性和分子级理解，这些特性是其组成、尺寸和结构通性的函数。从这个角度出发，通过对无支撑和表面支撑 AMC 的最新研究，说明了基于 ab initio 和 DFT 的建模潜力。此外，还讨论了未来的研究方向，包括最新技术之外的应用和方法改进。
{"title":"An Ab Initio Journey toward the Molecular-Level Understanding and Predictability of Subnanometric Metal Clusters","authors":"María Pilar de Lara-Castells","doi":"10.1002/sstr.202400147","DOIUrl":"https://doi.org/10.1002/sstr.202400147","url":null,"abstract":"Current advances in synthesizing and characterizing atomically precise monodisperse metal clusters (AMCs) at the subnanometer scale have opened up new possibilities in quantum materials research. Their quantizied “molecule-like” electronic structure showcases unique stability, and physical and chemical properties differentiate them from larger nanoparticles. When integrated into inorganic materials that interact with the environment and sunlight, AMCs serve to enhance their (photo)catalytic activity and optoelectronic properties. Their tiny size makes AMCs isolated in the gas phase amenable to atom-scale modeling using either density functional theory (DFT) or methods at a high level of <i>ab initio</i> theory, even addressing nonadiabatic (e.g., Jahn–Teller) effects. Surface-supported AMCs can be routinely modeled using DFT, enabling long real-time molecular dynamics simulations. Their optical properties can also be addressed using time-dependent DFT or reduced density matrix (RDM) theory. These theoretical–computational efforts aim to achieve predictability and molecular-level understanding of the stability and properties of AMCs as function of their composition, size, and structural fluxionality in different thermodynamical conditions (temperature and pressure). In this perspective, the potential of <i>ab initio</i> and DFT-based modeling is illustrated through recent studies of unsupported and surface-supported AMCs. Future directions of research are also discussed, including applications and methodological enhancements beyond the state-of-the-art.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"19 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514426","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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