Aqueous organic redox flow batteries (AORFBs) have attracted growing interest for grid-scale energy storage by reducing reliance on scarce mineral resources used in transition metal-based systems. Natural naphthoquinone derivatives, while environmentally friendly and abundant, suffer from poor solubility and electrochemical instability, hindering their practical use in AORFBs. To address these challenges, we report the functionalization of a naturally abundant dye, lawsone (i.e., 2-HNQ), through non-planar π-conjugation extension and asymmetric intramolecular charge distribution, yielding a non-planar π-conjugated polar naphthoquinone derivative (namely BANQ) with enhanced water solubility and redox reversibility. Computational simulations and spectroscopic analysis confirmed that the introduction of benzoic acid group imparts a polar π-conjugation extended structure with asymmetric charge distribution. This structural modification efficiently enhances aqueous solubility and suppresses degradation pathways, such as Michael addition and irreversible keto-enol tautomerism. Compared with 2-HNQ precursor, BANQ exhibits lower sensitivity to nucleophilic and electrophilic attacks. The BANQ anolyte exhibited a very low-capacity decay rate of merely 0.00018% per cycle (or 0.045% per day), representing a two-order-of-magnitude reduction compared to that of 2-HNQ (0.032% per cycle or 8.22% per day). This study highlights the potential of modifying natural-derived products with rationally designed conjugated electron structure for green and sustainable energy storage solutions.
{"title":"Structurally Asymmetric Nonplanar π-Conjugated Naphthoquinone Derivatives Modified from Natural Lawsone for High-Stability Aqueous Redox Flow Batteries.","authors":"Pengbo Zhang,Sheng Wen,Yongkang Chen,Yuzhu Liu,Jie Wei,Zuoao Wu,Guochun Ding,Xinmei Song,Tengfei Dai,Zhihu You,Qingbo Guo,Peng Liu,Jianwen Guo,Zuoxiu Tie,Zhong Jin","doi":"10.1002/anie.202519793","DOIUrl":"https://doi.org/10.1002/anie.202519793","url":null,"abstract":"Aqueous organic redox flow batteries (AORFBs) have attracted growing interest for grid-scale energy storage by reducing reliance on scarce mineral resources used in transition metal-based systems. Natural naphthoquinone derivatives, while environmentally friendly and abundant, suffer from poor solubility and electrochemical instability, hindering their practical use in AORFBs. To address these challenges, we report the functionalization of a naturally abundant dye, lawsone (i.e., 2-HNQ), through non-planar π-conjugation extension and asymmetric intramolecular charge distribution, yielding a non-planar π-conjugated polar naphthoquinone derivative (namely BANQ) with enhanced water solubility and redox reversibility. Computational simulations and spectroscopic analysis confirmed that the introduction of benzoic acid group imparts a polar π-conjugation extended structure with asymmetric charge distribution. This structural modification efficiently enhances aqueous solubility and suppresses degradation pathways, such as Michael addition and irreversible keto-enol tautomerism. Compared with 2-HNQ precursor, BANQ exhibits lower sensitivity to nucleophilic and electrophilic attacks. The BANQ anolyte exhibited a very low-capacity decay rate of merely 0.00018% per cycle (or 0.045% per day), representing a two-order-of-magnitude reduction compared to that of 2-HNQ (0.032% per cycle or 8.22% per day). This study highlights the potential of modifying natural-derived products with rationally designed conjugated electron structure for green and sustainable energy storage solutions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"39 1","pages":"e19793"},"PeriodicalIF":16.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Christian Gutheil,Alessia Petti,Julius Gemen,Nils H Rendel,Saeed Amirjalayer,Herbert Feld,Björn Braunschweig,Frank Glorius
N-Heterocyclic carbenes (NHCs) have recently emerged as the next-generation surface ligands with improved stability and molecular flexibility. Despite these premises, research on NHC-enriched flat surfaces is mainly limited to noble metals, while formation of free NHCs often requires the use of vacuum, bases, or strictly air- and moisture-free conditions. We hereby report an unprecedented radical-to-carbene-based approach for fabricating NHC monolayers on earth-abundant and naturally oxidized metal surfaces of nickel, iron, and stainless steel. Following an open-cell electrografting approach, 2-azolyl radicals are firstly formed and immobilized on the metal to then rearrange into NHC monolayers apparently composed of flat-lying NHCs, as corroborated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), sum-frequency generation (SFG), and cyclic voltammetry (CV) measurements. Density functional theory (DFT) calculations highlighted the role of metal adatoms in facilitating the radical-to-carbene transition. A surface stability test was conducted to assess the tolerance of the NHC-enriched surfaces toward physical, chemical, and electrochemical stress. Ultimately, this work expands the application field of carbenes-on-surfaces to cost-effective and widely used materials, while offering an agile and, until now, mechanistically unknown approach to their generation.
n -杂环碳烯（NHCs）是近年来出现的新一代表面配体，具有更好的稳定性和分子柔韧性。尽管有这些前提，但对富含nhc的平面的研究主要局限于贵金属，而游离nhc的形成通常需要使用真空、碱基或严格的无空气和无湿条件。我们在此报告了一种前所未有的基于自由基到碳烯的方法，用于在地球上丰富的自然氧化金属表面（镍、铁和不锈钢）上制造NHC单层。在开孔电接枝方法下，2-偶氮基自由基首先形成并固定在金属上，然后重新排列成NHC单层，显然由平坦的NHC组成，x射线光电子能谱（XPS）、飞行时间二次离子质谱（ToF-SIMS）、和频生成（SFG）和循环伏安法（CV）测量证实了这一点。密度泛函理论（DFT）计算强调了金属配原子在促进自由基到碳过渡中的作用。进行了表面稳定性测试，以评估富含nhc的表面对物理、化学和电化学应力的耐受性。最终，这项工作将表面碳化合物的应用领域扩展到具有成本效益和广泛使用的材料上，同时为它们的生成提供了一种灵活的、迄今为止尚不为人知的机械方法。
{"title":"N-Heterocyclic Carbene Monolayers on Nickel, Iron, and Steel by a Radical-to-Carbene Strategy.","authors":"Christian Gutheil,Alessia Petti,Julius Gemen,Nils H Rendel,Saeed Amirjalayer,Herbert Feld,Björn Braunschweig,Frank Glorius","doi":"10.1002/anie.202518099","DOIUrl":"https://doi.org/10.1002/anie.202518099","url":null,"abstract":"N-Heterocyclic carbenes (NHCs) have recently emerged as the next-generation surface ligands with improved stability and molecular flexibility. Despite these premises, research on NHC-enriched flat surfaces is mainly limited to noble metals, while formation of free NHCs often requires the use of vacuum, bases, or strictly air- and moisture-free conditions. We hereby report an unprecedented radical-to-carbene-based approach for fabricating NHC monolayers on earth-abundant and naturally oxidized metal surfaces of nickel, iron, and stainless steel. Following an open-cell electrografting approach, 2-azolyl radicals are firstly formed and immobilized on the metal to then rearrange into NHC monolayers apparently composed of flat-lying NHCs, as corroborated by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), sum-frequency generation (SFG), and cyclic voltammetry (CV) measurements. Density functional theory (DFT) calculations highlighted the role of metal adatoms in facilitating the radical-to-carbene transition. A surface stability test was conducted to assess the tolerance of the NHC-enriched surfaces toward physical, chemical, and electrochemical stress. Ultimately, this work expands the application field of carbenes-on-surfaces to cost-effective and widely used materials, while offering an agile and, until now, mechanistically unknown approach to their generation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":"e18099"},"PeriodicalIF":16.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949697","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ao Feng,Nan Fang,Xiao-Tian Yuan,Kun-Lin Li,Xuantao Deng,Jia-Feng Du,Zhi-Ming Zhang,Si-Ying Li,De-Yin Wu,Jin-Yu Ye,Qi-Zheng Zheng,Zhi-You Zhou,Shi-Gang Sun
Efficient electrochemical conversion of CO2 to multi-carbon (C2+) products remains significant challenges, particularly under broad pH ranges and high-current-density conditions. Herein, we report ampere-level CO2-to-C2+ electroreduction with exceptional efficiency across a wide pH range using ytterbium-doped CuOx catalysts. The catalyst achieves Faradaic efficiency of 87 ± 2%, 77 ± 1%, and 78 ± 1% under alkaline, neutral, and acidic conditions, respectively. Electrochemical in situ infrared spectroscopy and Raman spectroscopy reveal that Yb-stabilizing Cu+ species and enriching *CO on Cu terrace sites are two critical factors for enhancing C─C coupling. This work not only develops a highly efficient electrocatalysts for sustainable C2+ production, but also establishes a doping strategy for stabilizing active sites and optimizing *CO adsorption configurations.
{"title":"Yb-Doped Cu-Based Catalyst Boosting Electrochemical CO2-to-C2+ Reduction Across pH Range at Ampere-Level Current Density.","authors":"Ao Feng,Nan Fang,Xiao-Tian Yuan,Kun-Lin Li,Xuantao Deng,Jia-Feng Du,Zhi-Ming Zhang,Si-Ying Li,De-Yin Wu,Jin-Yu Ye,Qi-Zheng Zheng,Zhi-You Zhou,Shi-Gang Sun","doi":"10.1002/anie.202510755","DOIUrl":"https://doi.org/10.1002/anie.202510755","url":null,"abstract":"Efficient electrochemical conversion of CO2 to multi-carbon (C2+) products remains significant challenges, particularly under broad pH ranges and high-current-density conditions. Herein, we report ampere-level CO2-to-C2+ electroreduction with exceptional efficiency across a wide pH range using ytterbium-doped CuOx catalysts. The catalyst achieves Faradaic efficiency of 87 ± 2%, 77 ± 1%, and 78 ± 1% under alkaline, neutral, and acidic conditions, respectively. Electrochemical in situ infrared spectroscopy and Raman spectroscopy reveal that Yb-stabilizing Cu+ species and enriching *CO on Cu terrace sites are two critical factors for enhancing C─C coupling. This work not only develops a highly efficient electrocatalysts for sustainable C2+ production, but also establishes a doping strategy for stabilizing active sites and optimizing *CO adsorption configurations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"265 1","pages":"e10755"},"PeriodicalIF":16.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949701","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Interfacial instability remains a key barrier for sulfide electrolyte-based all-solid-state lithium-organic batteries (ASSLOBs). While prior efforts have mainly focused on improving chemical compatibility between active materials and electrolytes, the role of mechanical stress in interfacial degradation has been largely overlooked. Here, we report dibenzo[b,i]thianthrene-5,7,12,14-tetraone (DTT) as a conductive organic cathode integrated with a Li6PS5Cl (LPSC)-Li10GeP2S12 (LGPS)-Li6PS5Cl trilayer electrolyte and a lithium metal anode. Linear sweep voltammetry (LSV), operando pressure monitoring, and in situ electrochemical impedance spectroscopy coupled with distribution of relaxation times (EIS-DRT) reveal that the trilayer design effectively mitigates stress accumulation and suppresses interfacial degradation, while cross-sectional backscattered scanning electron microscopy (BSEM) and energy-dispersive X-ray spectroscopy (EDS) confirm superior structural integrity. Benefiting from this architecture, the ASSLOB delivers 296 mAh g-1 (0.1C) with remarkable long-term stability (90.2% retention after 4800 cycles at 2 C, 60 °C), together with excellent low-temperature and high-loading performance, representing the best results reported for ASSOLBs using lithium anode. Our work establishes electrolyte architecture engineering as a versatile strategy to achieve high-rate, durable, and temperature-resilient solid-state batteries.
界面不稳定性仍然是硫化物电解质基全固态有机锂电池（asslob）的关键障碍。虽然先前的努力主要集中在改善活性材料和电解质之间的化学相容性，但机械应力在界面降解中的作用在很大程度上被忽视了。在这里，我们报道了二苯并[b，i]噻吩-5,7,12,14-四酮（DTT）作为导电有机阴极与Li6PS5Cl (LPSC)-Li10GeP2S12 (LGPS)-Li6PS5Cl三层电解质和锂金属阳极集成。线性扫描伏安法（LSV）、操作压力监测、结合弛豫时间分布的原位电化学阻抗谱（EIS-DRT）显示，三层设计有效地减轻了应力积累，抑制了界面退化，而截面背散射扫描电子显微镜（BSEM）和能量色散x射线光谱（EDS）证实了优越的结构完整性。得益于这种结构，ASSLOB提供296 mAh g-1 (0.1C)，具有卓越的长期稳定性（在2℃，60℃下4800次循环后保持90.2%），以及出色的低温和高负载性能，代表了使用锂阳极的ASSLOB的最佳结果。我们的工作建立了电解质结构工程作为实现高速率，耐用和温度弹性固态电池的通用策略。
{"title":"Multilayer Sulfide-Electrolyte Engineering Stabilizes Interfaces for Long-Cycling, Wide-Temperature Lithium-Organic Solid-State Batteries.","authors":"Wenwen Deng,Ying Zhou,Xuyong Feng,Qingqing Ma,Longfei Li,Yuhang Guo,Weiwei Huang,Lingyun Zhu,Linghao Deng,Yonggang Wang","doi":"10.1002/anie.202524363","DOIUrl":"https://doi.org/10.1002/anie.202524363","url":null,"abstract":"Interfacial instability remains a key barrier for sulfide electrolyte-based all-solid-state lithium-organic batteries (ASSLOBs). While prior efforts have mainly focused on improving chemical compatibility between active materials and electrolytes, the role of mechanical stress in interfacial degradation has been largely overlooked. Here, we report dibenzo[b,i]thianthrene-5,7,12,14-tetraone (DTT) as a conductive organic cathode integrated with a Li6PS5Cl (LPSC)-Li10GeP2S12 (LGPS)-Li6PS5Cl trilayer electrolyte and a lithium metal anode. Linear sweep voltammetry (LSV), operando pressure monitoring, and in situ electrochemical impedance spectroscopy coupled with distribution of relaxation times (EIS-DRT) reveal that the trilayer design effectively mitigates stress accumulation and suppresses interfacial degradation, while cross-sectional backscattered scanning electron microscopy (BSEM) and energy-dispersive X-ray spectroscopy (EDS) confirm superior structural integrity. Benefiting from this architecture, the ASSLOB delivers 296 mAh g-1 (0.1C) with remarkable long-term stability (90.2% retention after 4800 cycles at 2 C, 60 °C), together with excellent low-temperature and high-loading performance, representing the best results reported for ASSOLBs using lithium anode. Our work establishes electrolyte architecture engineering as a versatile strategy to achieve high-rate, durable, and temperature-resilient solid-state batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":"e24363"},"PeriodicalIF":16.6,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chen Zhao, Na Li, Sijia Shi, Jue Hou, Li Gao, Benny D. Freeman, Huanting Wang, Huacheng Zhang
Biological NaK channels integrate exquisite ion selectivity with dynamic gating to regulate life processes, yet achieving such multifunctionality in synthetic channels has remained a formidable challenge. Here, we present a metal–organic framework (MOF) channel membrane that combines two complementary ion‐conduction motifs: carboxyl groups from UiO‐66‐COOH and carboxybenzo‐15‐crown‐5 (15C5‐COOH), assembled in a one‐step coordination strategy. This hybrid architecture recapitulates essential NaK channel functions, offering both ultrahigh ion selectivity and controllable gating. The membrane enables highly selective conduction of monovalent cations while effectively excluding Mg 2+ , yielding M + /Mg 2+ selectivity above 10 2 . Under mixed‐ion conditions, it achieves unprecedented Na⁺/K⁺ selectivity exceeding 10 3 , far surpassing reported artificial ion channels. Remarkably, Mg 2+ ions dynamically gate Na⁺ and K⁺ transport with sustainable on–off ratios around 30. These outstanding performances arise from the synergistic interplay of crown ether and carboxyl groups confined within subnanometer MOF pores. This work establishes a versatile strategy for designing multifunctional artificial ion channels, opening avenues toward advanced ionic devices for artificial cells and biomedical technologies.
{"title":"Biomimetic NaK Channel Membrane Enabled by a Crown Ether‐Coordinated Metal–Organic Framework","authors":"Chen Zhao, Na Li, Sijia Shi, Jue Hou, Li Gao, Benny D. Freeman, Huanting Wang, Huacheng Zhang","doi":"10.1002/anie.202521527","DOIUrl":"https://doi.org/10.1002/anie.202521527","url":null,"abstract":"Biological NaK channels integrate exquisite ion selectivity with dynamic gating to regulate life processes, yet achieving such multifunctionality in synthetic channels has remained a formidable challenge. Here, we present a metal–organic framework (MOF) channel membrane that combines two complementary ion‐conduction motifs: carboxyl groups from UiO‐66‐COOH and carboxybenzo‐15‐crown‐5 (15C5‐COOH), assembled in a one‐step coordination strategy. This hybrid architecture recapitulates essential NaK channel functions, offering both ultrahigh ion selectivity and controllable gating. The membrane enables highly selective conduction of monovalent cations while effectively excluding Mg <jats:sup>2+</jats:sup> , yielding M <jats:sup>+</jats:sup> /Mg <jats:sup>2+</jats:sup> selectivity above 10 <jats:sup>2</jats:sup> . Under mixed‐ion conditions, it achieves unprecedented Na⁺/K⁺ selectivity exceeding 10 <jats:sup>3</jats:sup> , far surpassing reported artificial ion channels. Remarkably, Mg <jats:sup>2+</jats:sup> ions dynamically gate Na⁺ and K⁺ transport with sustainable on–off ratios around 30. These outstanding performances arise from the synergistic interplay of crown ether and carboxyl groups confined within subnanometer MOF pores. This work establishes a versatile strategy for designing multifunctional artificial ion channels, opening avenues toward advanced ionic devices for artificial cells and biomedical technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuning Lou, Wen‐Xiong Shi, Yuejiang Han, Qiu‐Ping Zhao, Tianshuo Li, Lin Liu, Zhi‐Ming Zhang, Zhengbo Han
Ultrafine metal oxide nanoclusters (UMONs) exhibit remarkable catalytic potential due to their high specific surface area; however, achieving precise control over both the size and crystal phase of UMONs remains a significant challenge. Herein, we developed a dual‐induced confined synthesis strategy that couples hydrophobic gating with thermally triggered phase transformation to precisely confine UMONs within the pores of a metal–organic framework (MOF). 13 UMONs@MOF composites were successfully synthesized with the metal cations in UMONs spanning different regions of the periodic table. Notably, sub‐3 nm metastable γ‐MnO 2 was stabilized and confined within MIL‐101(Fe) for the first time. The optimized 15% γ‐MnO 2 @MIL‐101(Fe) showed a durable 100% O 3 removal efficiency for over 100 h. This performance was maintained in a continuous air flow containing 40 ppm O 3 at a high gas hourly space velocity of 1.7 × 10 5 h −1 over a wide humidity range of 10%–90%. Mechanistic studies reveal that its superior catalytic activity originates from the synergistic effect between the confined γ‐MnO 2 active sites and the Fe 3 O clusters in the MIL‐101(Fe). This work provides a universal approach for the precise control of the size and crystal phase of UMONs, paving the way for designing high‐performance catalysts.
{"title":"Dual‐Induced Confined Synthesis of Metastable γ‐MnO 2 Nanoclusters in Metal–Organic Frameworks for Highly Efficient Ozone Decomposition","authors":"Yuning Lou, Wen‐Xiong Shi, Yuejiang Han, Qiu‐Ping Zhao, Tianshuo Li, Lin Liu, Zhi‐Ming Zhang, Zhengbo Han","doi":"10.1002/anie.5562966","DOIUrl":"https://doi.org/10.1002/anie.5562966","url":null,"abstract":"Ultrafine metal oxide nanoclusters (UMONs) exhibit remarkable catalytic potential due to their high specific surface area; however, achieving precise control over both the size and crystal phase of UMONs remains a significant challenge. Herein, we developed a dual‐induced confined synthesis strategy that couples hydrophobic gating with thermally triggered phase transformation to precisely confine UMONs within the pores of a metal–organic framework (MOF). 13 UMONs@MOF composites were successfully synthesized with the metal cations in UMONs spanning different regions of the periodic table. Notably, sub‐3 nm metastable γ‐MnO <jats:sub>2</jats:sub> was stabilized and confined within MIL‐101(Fe) for the first time. The optimized 15% γ‐MnO <jats:sub>2</jats:sub> @MIL‐101(Fe) showed a durable 100% O <jats:sub>3</jats:sub> removal efficiency for over 100 h. This performance was maintained in a continuous air flow containing 40 ppm O <jats:sub>3</jats:sub> at a high gas hourly space velocity of 1.7 × 10 <jats:sup>5</jats:sup> h <jats:sup>−1</jats:sup> over a wide humidity range of 10%–90%. Mechanistic studies reveal that its superior catalytic activity originates from the synergistic effect between the confined γ‐MnO <jats:sub>2</jats:sub> active sites and the Fe <jats:sub>3</jats:sub> O clusters in the MIL‐101(Fe). This work provides a universal approach for the precise control of the size and crystal phase of UMONs, paving the way for designing high‐performance catalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wanying Zhu, Yufan Zhang, Hanwen Yu, Da Wang, Xinyue Zhang, Xiaowen Du, Shanshan Wu, Bingzhi Li, Yizhou Zhang, Hongliang Xin, Xing Guo, Yan Liu
Acetylcholine (ACh) is a critical neurotransmitter that regulates diverse physiological functions, such as cognition and muscle contraction, through synaptic transmission. However, in situ quantitative chemical analysis of single‐vesicle storage and release dynamics at single‐cell level remains a major technical challenge, hindering mechanistic understanding of cholinergic synaptic plasticity across physiological and pathological states. To address this, we developed an Ti 3 C 2 T x MXene/enzyme‐functionalized (M@E@CF) nanosensor, enabling real‐time monitoring of vesicular ACh storage and exocytotic release in primary cholinergic neurons and human spinal cord organoids. Our findings reveal a sub‐quantal release mode in both mouse and human‐derived neurons. To further elucidate the regulatory principles of exocytosis kinetics, we classified single‐vesicle exocytosis patterns based on signal peak shapes using a 1D convolutional neural network (1D‐CNN) deep learning model, uncovering significant differences in the number of released molecules and kinetic parameters across modes. Critically, in Down syndrome models, we observed significantly reduced single vesicle ACh storage and release alongside an elevated release fraction, concurrent with shortened fusion pore durations during exocytosis. Thus, the M@E@CF nanosensor platform establishes a versatile tool for spatiotemporal investigation of neurotransmitter storage and release dynamics, providing a critical technical foundation for exploring physiological functions and pathological mechanisms of the cholinergic system.
{"title":"A Novel Acetylcholine Nanosensor for Single Vesicle Storage and Sub‐Quantal Exocytosis in Living Neurons and Organoids","authors":"Wanying Zhu, Yufan Zhang, Hanwen Yu, Da Wang, Xinyue Zhang, Xiaowen Du, Shanshan Wu, Bingzhi Li, Yizhou Zhang, Hongliang Xin, Xing Guo, Yan Liu","doi":"10.1002/anie.202520854","DOIUrl":"https://doi.org/10.1002/anie.202520854","url":null,"abstract":"Acetylcholine (ACh) is a critical neurotransmitter that regulates diverse physiological functions, such as cognition and muscle contraction, through synaptic transmission. However, in situ quantitative chemical analysis of single‐vesicle storage and release dynamics at single‐cell level remains a major technical challenge, hindering mechanistic understanding of cholinergic synaptic plasticity across physiological and pathological states. To address this, we developed an Ti <jats:sub>3</jats:sub> C <jats:sub>2</jats:sub> T <jats:sub>x</jats:sub> MXene/enzyme‐functionalized (M@E@CF) nanosensor, enabling real‐time monitoring of vesicular ACh storage and exocytotic release in primary cholinergic neurons and human spinal cord organoids. Our findings reveal a sub‐quantal release mode in both mouse and human‐derived neurons. To further elucidate the regulatory principles of exocytosis kinetics, we classified single‐vesicle exocytosis patterns based on signal peak shapes using a 1D convolutional neural network (1D‐CNN) deep learning model, uncovering significant differences in the number of released molecules and kinetic parameters across modes. Critically, in Down syndrome models, we observed significantly reduced single vesicle ACh storage and release alongside an elevated release fraction, concurrent with shortened fusion pore durations during exocytosis. Thus, the M@E@CF nanosensor platform establishes a versatile tool for spatiotemporal investigation of neurotransmitter storage and release dynamics, providing a critical technical foundation for exploring physiological functions and pathological mechanisms of the cholinergic system.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"83 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Decoupling key intermediates’ adsorption via asymmetric 3d-5d-orbital hybridization overcomes the intrinsic scaling relation bottleneck, enabling rational design of high-performance, durable multifunctional electrocatalysts for anion exchange membrane water electrolyzers (AEMWEs) and Zn–air batteries (ZABs). Here, we reveal that asymmetric 3d-5d-orbital hybridization, engineered through the synergy of lattice strain and defect structures in a nitrogen-doped carbon-supported PtCo alloy (PtCo@NPC), effectively decouples these adsorption energies of key intermediates. PtCo@NPC demonstrates exceptional multifunctional electrocatalytic performance for the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction in alkaline media. Density functional theory calculations suggest that electronic structure modulation tunes the adsorption characteristics of intermediates, while X-ray absorption fine structure spectroscopy confirms the corresponding changes in the electronic states of surface Pt and Co atoms. When deployed in devices, PtCo@NPC enables AEMWEs to operate stably for 522 h at 1000 mA cm−2 with a voltage decay rate of only 0.103 mV h−1 and empowers ZABs to achieve a long cycle life of over 2520 cycles at 5.0 mA cm−2. This study highlights electronic-structure modulation as a powerful strategy for advanced energy technologies.
通过不对称3d-5d轨道杂化实现关键中间体的解耦吸附，克服了固有的结垢关系瓶颈，实现了阴离子交换膜水电解槽（AEMWEs）和锌空气电池（ZABs）高性能、耐用多功能电催化剂的合理设计。在这里，我们揭示了不对称的3d-5d轨道杂化，通过氮掺杂碳负载PtCo合金（PtCo@NPC）的晶格应变和缺陷结构的协同作用，有效地解耦了这些关键中间体的吸附能。PtCo@NPC在碱性介质中对析氢反应、析氧反应和氧还原反应表现出优异的多功能电催化性能。密度泛函理论计算表明，电子结构调制调节了中间体的吸附特性，而x射线吸收精细结构光谱证实了表面Pt和Co原子电子态的相应变化。当部署在器件中时，PtCo@NPC使AEMWEs能够在1000 mA cm - 2下稳定运行522小时，电压衰减率仅为0.103 mV h - 1，并使ZABs能够在5.0 mA cm - 2下实现超过2520个周期的长循环寿命。这项研究强调了电子结构调制作为先进能源技术的有力策略。
{"title":"Decoupling Adsorption of Key Intermediates Enabled by Asymmetric 3d-5d-Orbital Hybridization: Durable High-Performance AEM Water Electrolysis and Zn–Air Batteries","authors":"Xin-Yi Zhang, Hang Yin, Han-Hao Liu, Ying-Di Ge, Cong-Cong Dang, Shuo-Hang Zheng, Zhen-Yi Gu, Jun-Ming Cao, Jin-Zhi Guo, Xing-Long Wu","doi":"10.1002/anie.202524805","DOIUrl":"https://doi.org/10.1002/anie.202524805","url":null,"abstract":"Decoupling key intermediates’ adsorption via asymmetric 3d-5d-orbital hybridization overcomes the intrinsic scaling relation bottleneck, enabling rational design of high-performance, durable multifunctional electrocatalysts for anion exchange membrane water electrolyzers (AEMWEs) and Zn–air batteries (ZABs). Here, we reveal that asymmetric 3d-5d-orbital hybridization, engineered through the synergy of lattice strain and defect structures in a nitrogen-doped carbon-supported PtCo alloy (PtCo@NPC), effectively decouples these adsorption energies of key intermediates. PtCo@NPC demonstrates exceptional multifunctional electrocatalytic performance for the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction in alkaline media. Density functional theory calculations suggest that electronic structure modulation tunes the adsorption characteristics of intermediates, while X-ray absorption fine structure spectroscopy confirms the corresponding changes in the electronic states of surface Pt and Co atoms. When deployed in devices, PtCo@NPC enables AEMWEs to operate stably for 522 h at 1000 mA cm<sup>−2</sup> with a voltage decay rate of only 0.103 mV h<sup>−1</sup> and empowers ZABs to achieve a long cycle life of over 2520 cycles at 5.0 mA cm<sup>−2</sup>. This study highlights electronic-structure modulation as a powerful strategy for advanced energy technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"185 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cyclopropane‐fused medium rings (CFMR) are attractive structural motifs that combine high strain with unique three dimensionality, however their efficient and modular synthesis remains a formidable challenge. Herein, we present a general photocatalytic skeletal editing strategy that enables a direct topological leap—a single‐step reorganization that simultaneously alters both ring size and fusion topology—from readily available five‐ to eight‐membered cyclic ketones into diverse seven‐ to ten‐membered cyclopropane‐fused medium rings. This transformation proceeds through a novel energy‐transfer‐induced, diradical‐mediated 1,4‐carbonyl migration, orchestrating a “ring expansion–collapse” cascade to forge the strained bicyclic frameworks straightforward, which is supported by DFT calculations. This strategy features broad substrate scope, excellent functional‐group compatibility, and high efficiency, enabling the late‐stage diversification of complex molecules and exploration of CFMR chemical space that was previously inaccessible. Moreover, integration of this strategy with further skeletal modification enables rapid construction of versatile [n.3.0] bicycles.
{"title":"Energy‐Transfer‐Enabled Skeletal Rearrangement of Cyclic Ketones into Strained Cyclopropane‐Fused Medium Rings","authors":"Yingru Xu, Zehui Wang, Jianjian Huang, Tengfei Pang, Miao Jiang, Fangrui Zhong, Guojiao Wu","doi":"10.1002/anie.202522620","DOIUrl":"https://doi.org/10.1002/anie.202522620","url":null,"abstract":"Cyclopropane‐fused medium rings (CFMR) are attractive structural motifs that combine high strain with unique three dimensionality, however their efficient and modular synthesis remains a formidable challenge. Herein, we present a general photocatalytic skeletal editing strategy that enables a direct topological leap—a single‐step reorganization that simultaneously alters both ring size and fusion topology—from readily available five‐ to eight‐membered cyclic ketones into diverse seven‐ to ten‐membered cyclopropane‐fused medium rings. This transformation proceeds through a novel energy‐transfer‐induced, diradical‐mediated 1,4‐carbonyl migration, orchestrating a “ring expansion–collapse” cascade to forge the strained bicyclic frameworks straightforward, which is supported by DFT calculations. This strategy features broad substrate scope, excellent functional‐group compatibility, and high efficiency, enabling the late‐stage diversification of complex molecules and exploration of CFMR chemical space that was previously inaccessible. Moreover, integration of this strategy with further skeletal modification enables rapid construction of versatile [n.3.0] bicycles.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"48 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Margaux Roux, Amandine Roux, Thomas Boukéké-Lespulier, François Riobé, Christian Chapelle, Nicolas Foos, Elise Dumont, Eric Girard, Natacha Gillet, Olivier Maury
The synthesis and photophysical characterization of a new family of terbium(III) complexes called Imaging-crystallophore, substituted by π-conjugated antennas, is reported. Previous crystallophore variants (such as Tb-Xo4) have shown very interesting nucleating properties to obtain high-quality protein crystals. In addition, the Imaging-crystallophore emits in the green and accumulates in the protein crystals, enabling very easy crystal detection using fluorescence microscopy under one-photon but also under two-photon excitations. X-ray diffraction crystallography and molecular dynamics simulations demonstrate that the binding site of the Imaging-crystallophore in hen-egg white lysozyme (HEWL) is similar to that of the Tb-Xo4 but present additional hydrophobic interactions with the conjugated antennas. However, its nucleating properties are not as effective as those of Tb-Xo4. Finally, we emphasize the synergy between the two generations of crystallophore by preparing and analyzing the properties of the mix (10/0.2) corresponding to a mixture of Tb-Xo4 and Imaging-crystallophore. By combining the best of nucleating and imaging properties, we can easily obtain and detect high-quality protein crystals
{"title":"Synergistic Action of Crystallophore and Imaging-Crystallophore Enhances the Production and Imaging of Protein Crystals","authors":"Margaux Roux, Amandine Roux, Thomas Boukéké-Lespulier, François Riobé, Christian Chapelle, Nicolas Foos, Elise Dumont, Eric Girard, Natacha Gillet, Olivier Maury","doi":"10.1002/anie.202525011","DOIUrl":"https://doi.org/10.1002/anie.202525011","url":null,"abstract":"The synthesis and photophysical characterization of a new family of terbium(III) complexes called <i>Imaging</i>-crystallophore, substituted by π-conjugated antennas, is reported. Previous crystallophore variants (such as Tb-Xo4) have shown very interesting nucleating properties to obtain high-quality protein crystals. In addition, the <i>Imaging</i>-crystallophore emits in the green and accumulates in the protein crystals, enabling very easy crystal detection using fluorescence microscopy under one-photon but also under two-photon excitations. X-ray diffraction crystallography and molecular dynamics simulations demonstrate that the binding site of the <i>Imaging</i>-crystallophore in hen-egg white lysozyme (HEWL) is similar to that of the Tb-Xo4 but present additional hydrophobic interactions with the conjugated antennas. However, its nucleating properties are not as effective as those of Tb-Xo4. Finally, we emphasize the synergy between the two generations of crystallophore by preparing and analyzing the properties of the <b><i>mix</i></b> (10/0.2) corresponding to a mixture of Tb-Xo4 and <i>Imaging</i>-crystallophore. By combining the best of nucleating and imaging properties, we can easily obtain and detect high-quality protein crystals","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"47 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：