Angewandte Chemie (International ed. in English)最新文献

Decoding Perovskite Interfaces: Machine Learning Uncovers Geometry-Matched Dual-Site Hydrogen Bonding. 解码钙钛矿界面：机器学习揭示几何匹配的双点氢键。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-20 DOI: 10.1002/anie.9718249

Can Cheng, Xinyu Gu, Kai Sun, Renjie Wang, Zefeng Yang, Yuehao Xu, Pihuang Yang, Zhen Wang, Jionghua Wu, Hao Chen, Ling Wu

{"title":"Decoding Perovskite Interfaces: Machine Learning Uncovers Geometry-Matched Dual-Site Hydrogen Bonding.","authors":"Can Cheng, Xinyu Gu, Kai Sun, Renjie Wang, Zefeng Yang, Yuehao Xu, Pihuang Yang, Zhen Wang, Jionghua Wu, Hao Chen, Ling Wu","doi":"10.1002/anie.9718249","DOIUrl":"https://doi.org/10.1002/anie.9718249","url":null,"abstract":"Molecular passivation is central to efficient and stable perovskite photovoltaics, yet interfacial molecules are still largely selected through chemical intuition and iterative experimentation. Here, an interpretable machine-learning framework is developed that extracts chemically meaningful structure-performance relationships from literature data and uses them to guide molecular screening. Using approximately 100 data points, the model quantitatively relates six molecular and material features to photovoltaic performance, while SHapley Additive exPlanations (SHAP) analysis ranks their relative contributions and identifies hydrogen-bonding capacity and adsorption strength as the two most influential factors. Guided by these data-derived relationships, nine previously unexplored molecules were screened, with 2-amino-thiazole-4-carboxamide (ATC) and 1-(2-aminoethyl)-1H-pyrrole-2,5-dione (MPD) emerging as leading candidates. Theoretical and experimental investigations show that MPD exhibits stronger Pb2 + coordination, whereas ATC forms stronger geometry-matched multisite N─H···I interactions, increasing the calculated iodide-migration barrier from 0.39 to 0.67 eV and suppressing interfacial iodide redistribution. ATC-modified cells achieve a PCE of 27.13% and a certified stabilized efficiency of 26.59%, while retaining 90% of their initial efficiency after 1460 h of unencapsulated operation. The strategy further delivers efficiencies of 24.01% and 21.14% in 20.98 cm2 rigid and 21.0 cm2 flexible modules, respectively, providing a data-to-mechanism route for rational and scalable perovskite interface engineering.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e9718249"},"PeriodicalIF":16.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149229784","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}

引用次数: 0

Unidirectional Hydrogen Migration Through Interfacial Engineering for Promoted Brønsted Acid Catalysis. 界面工程促进Brønsted酸催化的单向氢迁移。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-20 DOI: 10.1002/anie.3609898

Shuangfeng Xing, Shudong Liang, Shaocheng Zhang, Qian Jiang, Jingrui Ti, Jingyuan Ma, Yong Qin, Jianlin Shi, Zhe Gao

{"title":"Unidirectional Hydrogen Migration Through Interfacial Engineering for Promoted Brønsted Acid Catalysis.","authors":"Shuangfeng Xing, Shudong Liang, Shaocheng Zhang, Qian Jiang, Jingrui Ti, Jingyuan Ma, Yong Qin, Jianlin Shi, Zhe Gao","doi":"10.1002/anie.3609898","DOIUrl":"https://doi.org/10.1002/anie.3609898","url":null,"abstract":"Though playing a critical role, the controllable and directional migration of reactive species in chemical reactions is still hard to achieve. Here, we propose an interfacial engineering strategy for constructing a hydrogen spillover nanodiode that channels hydrogen unidirectionally. Such a nanodiode design is materialized in a composite WOx/TiO2/Pt catalyst with spatially separated structure, where WOx and Pt particles are dispersed on the outer and inner surfaces of porous TiO2 nanotubes, respectively. This nanodevice permits forward H migration (Pt→TiO2→WOx) while suppresses the reverse path (WOx→TiO2), as directly evidenced by in situ x-ray absorption fine structure characterization under hydrogenation and H2 generation reactions. This rectification behavior originates from the diode characteristics of the TiO2-WOx heterojunction, which hinders both proton and electron transfer from WOx to TiO2. Consequently, WOx/TiO2/Pt accumulates highly concentrated Brønsted acid sites in H2 atmosphere and thus exhibits superior catalytic performance compared to the closely contacted WOx-Pt/TiO2 catalyst. Up to 5.3 times higher liquid alkane yield has been achieved over WOx/TiO2/Pt relative to WOx-Pt/TiO2 in the polyethylene hydrocracking reaction. This nanodiode design strategy is general and can be extended to other catalysts/species, offering mechanistic insight and boosting catalytic performance in diverse reactions.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e3609898"},"PeriodicalIF":16.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149229792","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}

引用次数: 0

Helical Multi-Resonance Thermally Activated Delayed Fluorescence Emitters for High-Performance Anti-Quenching Narrowband Blue OLEDs. 用于高性能抗猝灭窄带蓝色oled的螺旋多共振热激活延迟荧光发射器。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-20 DOI: 10.1002/anie.9731976

Shuai Tang, Wei Ping, Jinyang Zhao, Lei Hua, Junjie Wang, Shian Ying, Yuchao Liu, Zhongjie Ren

{"title":"Helical Multi-Resonance Thermally Activated Delayed Fluorescence Emitters for High-Performance Anti-Quenching Narrowband Blue OLEDs.","authors":"Shuai Tang, Wei Ping, Jinyang Zhao, Lei Hua, Junjie Wang, Shian Ying, Yuchao Liu, Zhongjie Ren","doi":"10.1002/anie.9731976","DOIUrl":"https://doi.org/10.1002/anie.9731976","url":null,"abstract":"Multi-resonance thermally activated delayed fluorescence (MR-TADF) has established a new approach for narrowband blue organic light emitting diodes (OLEDs), yet effectively suppressing intermolecular interactions especially at high doping concentrations while preserving the intrinsic narrowband emission remains a formidable challenge. Herein, a novel designing paradigm is proposed for achieving anti-quenching narrowband emission in MR-TADF molecules by embedding the indeno[2,1-b]carbazole unit into the polycyclic aromatic hydrocarbon skeleton. The proof-of-concept emitter DT-BON1 reveals a favorable twist angle of 31.8°, manifesting formation of helical architecture within MR core. As a result, the emission peaks and full width at half maximum show virtually no variation with changing doping concentration from 1 wt% to 20 wt%. Moreover, the photoluminance quantum yields exceed 90% even at 20 wt% doping concentration endowed by the outstanding anti-quenching characteristics. The DT-BON1 based OLEDs can achieve maximum external quantum efficiency (EQEmax) of exceeding 30%. Especially, the alleviated exciton quenching effects can be firmly demonstrated by marginally decreased EQEmax values, attaining 29.2% in 10 wt%-based OLEDs and 27.3% even in heavily doped devices (20 wt%), which is at a record high for MR-TADF with blue emission at such high doping concentration.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e9731976"},"PeriodicalIF":16.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149229816","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}

引用次数: 0

Anion-Cation Targeted Regulation Enables Ultrafast and Stable Sodium Metal Batteries at Low Temperatures. 阴离子-阳离子定向调节使低温下的超快和稳定的钠金属电池成为可能。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-20 DOI: 10.1002/anie.6809424

Tonghui Zhang, Ying Xiao, Yu Han, Xinyu Wang, Yu Yang, Heyu Wang, Zhengkun Xie, Shimou Chen

{"title":"Anion-Cation Targeted Regulation Enables Ultrafast and Stable Sodium Metal Batteries at Low Temperatures.","authors":"Tonghui Zhang, Ying Xiao, Yu Han, Xinyu Wang, Yu Yang, Heyu Wang, Zhengkun Xie, Shimou Chen","doi":"10.1002/anie.6809424","DOIUrl":"https://doi.org/10.1002/anie.6809424","url":null,"abstract":"Anion-dominated solvation and artificial interfacial engineering have been intensively pursued for low-temperature sodium-metal batteries (SMBs), yet they face constraints from temperature-sensitive solvation dynamics and interfacial control. Here we propose anion-cation-targeted regulation via Sn(OTf)2 that simultaneously constructs a solvent-reinforced solvation structure and electrochemically induces an alloy-based solid electrolyte interphase (SEI) (Na15Sn4), which goes beyond the prevailing anion-centric strategy to address the critical challenges of SMBs at subzero temperatures. Competitive Sn2+-Na+ coordination excludes PF6 - from the primary solvation sheath, while OTf- and the ether groups of diethylene glycol dimethyl ether (DEGDME) coupling foster a solvent-dominated configuration, substantially reducing the Na+ desolvation energy barrier at low temperatures. This design enables Na||Na3V2(PO4)3 cells to deliver a recorded 1050 cycles at -20°C and 20 C, and nearly 700 cycles at -50°C. Ah-scale pouch cells sustain durable 450 cycles at -20°C, with a 6 Ah cell reaching 215 Wh kg-1 at 25°C (total cell mass). Our findings resolve the longstanding trade-off between low-temperature kinetics and stability in SMBs, offering a new design rationale beyond conventional interfacial engineering.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e6809424"},"PeriodicalIF":16.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149229805","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}

引用次数: 0

Supramolecular Enforcement of Planar Tetracoordinate Halides. 平面四坐标卤化物的超分子强化。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-20 DOI: 10.1002/anie.1850882

Jie Zhang, Avijit Maiti, Lutz Greb

{"title":"Supramolecular Enforcement of Planar Tetracoordinate Halides.","authors":"Jie Zhang, Avijit Maiti, Lutz Greb","doi":"10.1002/anie.1850882","DOIUrl":"https://doi.org/10.1002/anie.1850882","url":null,"abstract":"Planar tetracoordinate halides have been widely explored by quantum computational approaches but remain rare as deliberately targeted experimental motifs. Here we show that these geometries can be accessed by supramolecular enforcement, and challenge its connection to the VSEPR model. Bowl-shaped calix[4]pyrrolato indium units preorganize four lithium ions into a confined Li4 pocket that traps Cl-, Br-, and I- in strongly flattened to ideal planar tetracoordinate environments. Computational analysis of the parent tetrahedral [Li4X]3 + units reveals small planarization energies that can be overcome by a charge-attenuating host of appropriate shape. The experimental series shows that halide planarity is highly sensitive to subtle supramolecular effects, such as calix[4]pyrrolato doming and crystal packing, experimentally confirming the generally low angular deformation energies. The results establish supramolecular enforcement as a rational design principle for planar tetracoordinate heavier halides and show that such motifs are accessible outcomes of engineered electrostatic cavities.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e1850882"},"PeriodicalIF":16.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149229776","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}

引用次数: 0

Achieving Near-Unity Glyoxylate Selectivity in Ethylene Glycol Oxidation by Spatiotemporal Coupling of Pulsed Electrolysis and Interface Engineering. 通过脉冲电解和界面工程的时空耦合实现乙二醇氧化中近统一的乙醛酸选择性。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-08-28 DOI: 10.1002/anie.3451661

Weipeng Zhao, Pengwei Zhao, Bin Chen, Zhuo Chen, Huanyu Fu, Wenchao Peng, Yang Li, Danyun Xu, Qicheng Zhang, Xiaobin Fan

{"title":"Achieving Near-Unity Glyoxylate Selectivity in Ethylene Glycol Oxidation by Spatiotemporal Coupling of Pulsed Electrolysis and Interface Engineering.","authors":"Weipeng Zhao, Pengwei Zhao, Bin Chen, Zhuo Chen, Huanyu Fu, Wenchao Peng, Yang Li, Danyun Xu, Qicheng Zhang, Xiaobin Fan","doi":"10.1002/anie.3451661","DOIUrl":"10.1002/anie.3451661","url":null,"abstract":"Electrochemical cascade reactions suffer from suboptimal selectivity toward high-value intermediates due to the uncontrollable sequential conversion inherent in conventional steady-state electrolysis. To transcend the intrinsic limitations of one-dimensional control, we propose a spatiotemporal synergy strategy for precision electrocatalysis. In this framework, the temporal dimension is governed by pulsed electrolysis, facilitating the rhythmic generation and rapid liberation of target intermediates. Simultaneously, the spatial dimension is engineered via molecular steric modifiers (p-toluidine) to create a persistent hydrophobic interface that effectively suppresses deleterious hydration-driven overoxidation pathways. Synergistically, this dual-dimensional orchestration achieves unprecedented precision, as evidenced by a dramatic leap in glyoxylate selectivity from 25.5% to >99.0%. This work demonstrates a promising and transferable design principle for precision electrocatalysis in complex reaction networks. The spatiotemporal decoupling strategy, integrating temporal pulsed electrolysis for intermediate release and spatial interface engineering for overconsumption suppression, is demonstrated here for ethylene glycol oxidation and provides a rational basis for addressing similar selectivity challenges in other electrocatalytic systems.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e3451661"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852059","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}

引用次数: 0

Odd-Even Alkyl Chain Effect of Aromatic Monoammoniums on the Interlayer Architecture and Stability of Ruddlesden-Popper 2D Perovskites. 芳香单铵奇偶烷基链效应对Ruddlesden-Popper二维钙钛矿层间结构和稳定性的影响。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-08-28 DOI: 10.1002/anie.6772439

Yang Liu, Jianfei Fu, Qingyong Tian, Huaiqing Luo, Jiaxing Song, Zaifang Li, Jifeng Wu, Bin Fan, Wei Chen, Qiuju Liu

{"title":"Odd-Even Alkyl Chain Effect of Aromatic Monoammoniums on the Interlayer Architecture and Stability of Ruddlesden-Popper 2D Perovskites.","authors":"Yang Liu, Jianfei Fu, Qingyong Tian, Huaiqing Luo, Jiaxing Song, Zaifang Li, Jifeng Wu, Bin Fan, Wei Chen, Qiuju Liu","doi":"10.1002/anie.6772439","DOIUrl":"10.1002/anie.6772439","url":null,"abstract":"Ruddlesden-Popper (RP) 2D perovskites with organic bilayers attract great interest for optoelectronics owing to their high stability and tunable functionality. However, the relationship between the interlayer architecture, molecular configuration of aromatic cations, and resulting stability remains poorly understood. Herein, we systematically investigate phenyl alkylammonium-based RP 2D perovskites with varying alkyl chain lengths (─(CH2)mNH3 + with m = 1-4) of organic cations. We find that odd-carbon cations (m = 1, 3) preferentially form type-I 2D perovskites featuring interdigitated organic cations, which induces substantial inorganic distortion and lower octahedral symmetry to the C1 point group. Even-carbon cations (m = 2, 4) favor type-II 2D perovskites with well-defined interlayer gaps, wherein the alkylammonium groups rotate to optimize registry with the inorganic sublattice, minimizing distortion and yielding higher-symmetry D2 h octahedra. Furthermore, we demonstrate that intrinsic structural stability of RP 2D perovskites is primarily governed by π-π packing within the organic layer, whereas air stability of the thin films is determined by surface hydrophobicity. The type-II films exhibit higher hydrophobicity, conferring enhanced stability under ambient conditions compared to type-I films. These findings establish odd-even alkyl chain parity as a design principle for tailoring structurally diverse yet stable RP 2D perovskites.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e6772439"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852275","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}

引用次数: 0

Raising the Mayan Pyramids: Construction of Polyoxothiomolybdates via In Situ Sulfurization for Enhanced Antitumor Therapy. 提高玛雅金字塔：通过原位硫化构建多氧硫钼酸盐以增强抗肿瘤治疗。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-09-02 DOI: 10.1002/anie.1190782

Zi-Yu Xu, Dao-Jing Yuan, Lin-Jie Lan, Yue Zhao, Ke-Wei Tong, Chao-Qin Chen, Pan-Chao Yin, Jing Du, Teng Gong, Peng Yang

{"title":"Raising the Mayan Pyramids: Construction of Polyoxothiomolybdates via In Situ Sulfurization for Enhanced Antitumor Therapy.","authors":"Zi-Yu Xu, Dao-Jing Yuan, Lin-Jie Lan, Yue Zhao, Ke-Wei Tong, Chao-Qin Chen, Pan-Chao Yin, Jing Du, Teng Gong, Peng Yang","doi":"10.1002/anie.1190782","DOIUrl":"10.1002/anie.1190782","url":null,"abstract":"The advancement of atomic-level sulfurization technology is ushering materials engineering from coarse regulation toward precise editing. As represented by polyoxothiometalates (POTMs), the available sulfurization methods remain limited and nongreen, imposing severe constraints on their structural diversity and functional applications. In this study, an in situ sulfurization approach was developed to construct the Mo-based POTMs (POTMos) in a distinct and eco-friendly manner. The emergence of unprecedented building blocks gave birth to two POTMos featuring single or fused Mayan-pyramidal frameworks. Enabled by the structural modulation and enhanced biocompatibility via sulfur incorporation, the Mo-57-oxothio polyanion (Mo57) demonstrated potent antitumor efficacy. Combined experimental and theoretical analyses revealed that Mo57 could disrupt the cell respiratory chain via two synergistic routes: catalytic oxidation of NADH and electrostatic adsorption of NAD+. Such dual interference triggered mitochondrial dysfunction and a consequent inhibition of tumor proliferation.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e1190782"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877175","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}

引用次数: 0

Light- and pH-Gated Reversible Modulation of Peptide Coacervates via Noncovalent Integration of Spiropyran Photoswitches. 通过螺吡喃光开关非共价整合的光和ph门控多肽凝聚的可逆调制。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-09-04 DOI: 10.1002/anie.9579523

Yifan Zheng, Yingjie Liu, Hanbo Xu, Guodong Wang, Shuang Zhang, Yi Sun, Yue Yuan, Kohei Sato, Chuang Li

{"title":"Light- and pH-Gated Reversible Modulation of Peptide Coacervates via Noncovalent Integration of Spiropyran Photoswitches.","authors":"Yifan Zheng, Yingjie Liu, Hanbo Xu, Guodong Wang, Shuang Zhang, Yi Sun, Yue Yuan, Kohei Sato, Chuang Li","doi":"10.1002/anie.9579523","DOIUrl":"10.1002/anie.9579523","url":null,"abstract":"Peptide coacervates formed via liquid-liquid phase separation (LLPS) have emerged as versatile cell-like compartments for protocell studies and spatially confined catalysis. However, achieving remote, noninvasive modulation of their assembly‒disassembly lifecycle remains a key challenge. Here, we report a supramolecular design that enables light- and pH-gated reversible coacervation of peptides through non-covalent integration of spiropyran photoswitches. The mechanism relies on photoisomerization-induced charge shift in spiropyran, which consequently modulates interpeptide electrostatic interactions to drive coacervate formation. Dissociation occurs reversibly via thermal relaxation upon the cessation of light, a process further regulated by pH, thereby enabling distinct on-demand on- and off-coacervation regimes. We validate this principle through systematic structural variations of both components, establishing a direct link between molecular design and phase behavior. Exploiting their reversible sequestration capability, we demonstrate that these coacervates serve as efficient light‑ and pH-activated microreactors with OR logic gate functions that are capable of accelerating cascade reactions under dilute conditions and as dynamic reusable templates with cascaded OR-AND logic gate functions for recyclable synthesis of nanogels with tunable dimensions. This work establishes a versatile approach for dual-mode regulation of peptide coacervates, opening avenues for the development of photo- and pH-responsive microreactors and adaptive templates for material synthesis.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e9579523"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893305","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}

引用次数: 0

ALDH Inhibition-Primed Photocatalysis Disrupts Cancer Stemness Plasticity. ALDH抑制引发的光催化破坏癌茎可塑性。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-08-28 DOI: 10.1002/anie.5856873

Yujin Kim, Shankun Yao, Ji Hyeon Kim, Rongrong Huang, Hyeonji Rha, Shumeng Li, Kippeum Lee, Yunjie Xu, Xiaogang Liu, Yuncong Chen, Jong Seung Kim

{"title":"ALDH Inhibition-Primed Photocatalysis Disrupts Cancer Stemness Plasticity.","authors":"Yujin Kim, Shankun Yao, Ji Hyeon Kim, Rongrong Huang, Hyeonji Rha, Shumeng Li, Kippeum Lee, Yunjie Xu, Xiaogang Liu, Yuncong Chen, Jong Seung Kim","doi":"10.1002/anie.5856873","DOIUrl":"10.1002/anie.5856873","url":null,"abstract":"Light-driven photoredox catalysis can shift intracellular NADH/NAD+ balance by oxidizing NADH, but intracellular NADH pools are dynamically replenished through enzyme-coupled redox metabolism. We show that ALDH-mediated restoration of NADH/NAD+ balance can buffer photoredox-induced NADH depletion, providing a design rationale for coupling enzyme inhibition with photoredox catalysis. To counteract this redox-buffering process, we introduce an enzymatic-photocatalytic strategy, termed E-PC, that integrates ALDH inhibition with NIR-driven photocatalytic NADH oxidation within a single molecular construct. A small-molecule conjugate, DE-Et, was constructed by covalently linking DEAB, which can inhibit ALDH, to a near-infrared (NIR)-active Nile Blue Sulfide-derived photocatalyst (NBS) through a ROS-cleavable thioacetal linker. Upon NIR irradiation, DE-Et releases DEAB while catalytically oxidizing intracellular NADH through single-electron transfer, thereby attenuating ALDH-mediated redox restoration and sustaining NADH/NAD+ imbalance. This dual action compromises mitochondrial ATP production and activates caspase-3/GSDME-dependent pyroptosis. In stemness-enriched tumor models, DE-Et suppresses ALDH activity, clonogenic growth, spheroid integrity, and tumor growth in vivo. Local photoactivation further promotes systemic antitumor immune responses, consistent with immunogenic pyroptotic cell death. E-PC thus establishes a chemical strategy for light-activated co-delivery of photoredox catalysis and inhibition of a tumor-overexpressed enzyme, converting an adaptive enzymatic buffer into a therapeutic vulnerability.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5856873"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13676394/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0