Equilibrium-limited endothermic reactions play a crucial role in the transition toward a more sustainable chemical industry, but are typically plagued by the need for high operation temperatures (>500°C). Here, we show that the temperature gradients generated by the selective and localized heating of catalyst materials in a colder reactor environment shift the equilibrium of thermodynamically-limited endothermic reactions and improve their performance. In particular, the reverse water gas shift reaction and magnetic induction are selected as the model reaction and selective catalyst heating method, respectively. Magnetically induced catalysis using standard Cu-Al spinel-derived catalyst functionalized with carbon-coated iron nanoparticles enables high CO yield (up to 62%) at mild catalyst and reactor temperatures (estimated at 300°C and determined as 25-123°C, respectively). We demonstrate that the catalyst temperature and not the reactor temperature governs the equilibrium product composition of the rWGS, and that the temperature gradient promotes the in situ removal of water to shift the gas phase thermodynamic equilibrium. These two points synergistically result in a CO yield that would require a reactor temperature of 650°C in a conventionally heated gas phase reaction.
{"title":"Low-Temperature Reverse Water-Gas Shift Enabled by Magnetically Induced Catalysis.","authors":"Junhui Hu,Lise Marie Lacroix,Jacob Johny,Sourav Ghosh,Elisabeth Hannah Wolf,Jeongmin Ji,Sheng-Hsiang Lin,Manisha Durai,Alin Benice Schöne,Walid Hetaba,Holger Ruland,Walter Leitner,Alexis Bordet","doi":"10.1002/anie.202523576","DOIUrl":"https://doi.org/10.1002/anie.202523576","url":null,"abstract":"Equilibrium-limited endothermic reactions play a crucial role in the transition toward a more sustainable chemical industry, but are typically plagued by the need for high operation temperatures (>500°C). Here, we show that the temperature gradients generated by the selective and localized heating of catalyst materials in a colder reactor environment shift the equilibrium of thermodynamically-limited endothermic reactions and improve their performance. In particular, the reverse water gas shift reaction and magnetic induction are selected as the model reaction and selective catalyst heating method, respectively. Magnetically induced catalysis using standard Cu-Al spinel-derived catalyst functionalized with carbon-coated iron nanoparticles enables high CO yield (up to 62%) at mild catalyst and reactor temperatures (estimated at 300°C and determined as 25-123°C, respectively). We demonstrate that the catalyst temperature and not the reactor temperature governs the equilibrium product composition of the rWGS, and that the temperature gradient promotes the in situ removal of water to shift the gas phase thermodynamic equilibrium. These two points synergistically result in a CO yield that would require a reactor temperature of 650°C in a conventionally heated gas phase reaction.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":"e23576"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056885","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}
Zhen Wang,Fengrui Xiang,Xingyu Liao,Qingsong Wu,Jinbiao Jiao,Angzhi Bi,Siyang Liu,Dan Wang,Minyan Wang,Zijian Guo,Jie P Li
Reactions that excel in small-molecule settings typically require metal loadings far exceeding the number of protein reaction sites (often ≥10-fold) once transplanted into proteinaceous media-conditions that are not truly "catalytic." Here, we show that biologically inert metal-ligand complexes based on bathocuproine disulfonic acid disodium salt (BCS) overcome this barrier and enable ligand-accelerated catalysis (LAC) on proteins under substoichiometric conditions. For example, Ni-BCS effects complete deprotection of green fluorescent protein bearing Nε-propargyloxycarbonyl-L-lysine (GFP-ProcLys) at 5 mol% catalyst with an observed turnover number (TON) ≈ 20, surpassing all previously reported metal-catalyzed depropargylation reactions. Mechanistic studies indicate that an in situ Ni-H intermediate mediates multiple transformations on proteins, including reductive deuteration of terminal alkenes/alkynes and efficient decaging across diverse amino acid side chains. Likewise, Cu-BCS enables copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) on proteins at 10 mol% with low residual copper and no protein oxidation, in sharp contrast to the benchmark Cu-BTTAA (tris((1-tert-butyl-1H-1,2,3-triazol-4-yl)methyl)amine) system. These outcomes stem from a screening strategy that prioritized metal-ligand stability, eliminating metal complexes susceptible to protein sequestration and selecting strongly coordinating, physiologically inert pairs. The resulting rational ligand-design framework for protein-level transition-metal catalysis expands the frontier of protein chemistry and paves the way to translate advanced small-molecule LAC strategies onto protein substrates for posttranslational mutagenesis.
{"title":"Inert Complexes Unlock Ligand-Accelerated Transition-Metal Catalysis on Proteins.","authors":"Zhen Wang,Fengrui Xiang,Xingyu Liao,Qingsong Wu,Jinbiao Jiao,Angzhi Bi,Siyang Liu,Dan Wang,Minyan Wang,Zijian Guo,Jie P Li","doi":"10.1002/anie.202522057","DOIUrl":"https://doi.org/10.1002/anie.202522057","url":null,"abstract":"Reactions that excel in small-molecule settings typically require metal loadings far exceeding the number of protein reaction sites (often ≥10-fold) once transplanted into proteinaceous media-conditions that are not truly \"catalytic.\" Here, we show that biologically inert metal-ligand complexes based on bathocuproine disulfonic acid disodium salt (BCS) overcome this barrier and enable ligand-accelerated catalysis (LAC) on proteins under substoichiometric conditions. For example, Ni-BCS effects complete deprotection of green fluorescent protein bearing Nε-propargyloxycarbonyl-L-lysine (GFP-ProcLys) at 5 mol% catalyst with an observed turnover number (TON) ≈ 20, surpassing all previously reported metal-catalyzed depropargylation reactions. Mechanistic studies indicate that an in situ Ni-H intermediate mediates multiple transformations on proteins, including reductive deuteration of terminal alkenes/alkynes and efficient decaging across diverse amino acid side chains. Likewise, Cu-BCS enables copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) on proteins at 10 mol% with low residual copper and no protein oxidation, in sharp contrast to the benchmark Cu-BTTAA (tris((1-tert-butyl-1H-1,2,3-triazol-4-yl)methyl)amine) system. These outcomes stem from a screening strategy that prioritized metal-ligand stability, eliminating metal complexes susceptible to protein sequestration and selecting strongly coordinating, physiologically inert pairs. The resulting rational ligand-design framework for protein-level transition-metal catalysis expands the frontier of protein chemistry and paves the way to translate advanced small-molecule LAC strategies onto protein substrates for posttranslational mutagenesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"272 1","pages":"e22057"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070041","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}
Conventional small-molecule hole-transporting materials (SM-HTMs), although morphologically robust, typically suffer from limited hole mobility, interfacial energy misalignment, and inefficient charge extraction, which collectively hinder power conversion efficiencies (PCEs) above 25% in inverted perovskite solar cells (PSCs). Herein, breaking from conventional design paradigm, novel spatial molecular engineering was targeted proposed for SM-HTMs to overcome inherent limitations while reinforcing advantages. By spatially exposing the functional heterocyclic core to release its full potential, the tailored WH13 dramatically enhances the perovskite/HTM interfacial interactions, promotes crystallization, and facilitates hole extraction. More importantly, the resultant planar-steric architecture enables long-range π-stacking order while supporting nanocrystal-level film-formation, thereby achieving an optimal balance between charge transport dynamics and morphological features. Consequently, WH13-based inverted PSCs achieve a champion PCE of 26.6% (certified 26.24%) with exceptional operational stability (>99%, ISOS-L-1 500 h), representing the highest efficiency reported to date for SM-HTM-based PSCs. This spatial molecular engineering strategy establishes a generalizable design paradigm for next-generation HTMs, opening a promising pathway toward high-performance, operationally stable, and commercially viable PSCs.
传统的小分子空穴传输材料（SM-HTMs）虽然形态稳定，但通常存在空穴迁移率有限、界面能错位和电荷提取效率低下等问题，这些问题共同阻碍了倒置钙钛矿太阳能电池（PSCs）的功率转换效率（pce）达到25%以上。本文突破传统设计范式，针对sm - htm提出了一种新的空间分子工程设计方法，以克服其固有的局限性，增强其优势。通过在空间上暴露功能杂环核心以释放其全部潜力，定制的WH13显着增强了钙钛矿/HTM界面相互作用，促进了结晶，并有利于孔提取。更重要的是，由此产生的平面立体结构在支持纳米级成膜的同时，实现了远距离π堆积顺序，从而实现了电荷输运动力学和形态特征之间的最佳平衡。因此，基于wh13的倒置PSCs实现了26.6%（认证26.24%）的冠军PCE，具有出色的运行稳定性（bbb99 %， iso - l -1 500小时），代表了迄今为止基于sm - html的PSCs的最高效率。这种空间分子工程策略为下一代HTMs建立了一种通用的设计范式，为高性能、操作稳定和商业可行的psc开辟了一条有希望的途径。
{"title":"Spatial Molecular Engineering of Hole Semiconductors Enables Record Efficiency and Durability in Inverted Perovskite Solar Cells.","authors":"Zongyuan Yang,Chenzhe Xu,Zhe Wang,Zhihui Wang,Zhaolong Ma,Mengyuan Li,Rui Kong,Hui Cheng,Xin Xiong,Suhao Yan,Xueping Zong,Lixin Xiao,Mao Liang","doi":"10.1002/anie.202523665","DOIUrl":"https://doi.org/10.1002/anie.202523665","url":null,"abstract":"Conventional small-molecule hole-transporting materials (SM-HTMs), although morphologically robust, typically suffer from limited hole mobility, interfacial energy misalignment, and inefficient charge extraction, which collectively hinder power conversion efficiencies (PCEs) above 25% in inverted perovskite solar cells (PSCs). Herein, breaking from conventional design paradigm, novel spatial molecular engineering was targeted proposed for SM-HTMs to overcome inherent limitations while reinforcing advantages. By spatially exposing the functional heterocyclic core to release its full potential, the tailored WH13 dramatically enhances the perovskite/HTM interfacial interactions, promotes crystallization, and facilitates hole extraction. More importantly, the resultant planar-steric architecture enables long-range π-stacking order while supporting nanocrystal-level film-formation, thereby achieving an optimal balance between charge transport dynamics and morphological features. Consequently, WH13-based inverted PSCs achieve a champion PCE of 26.6% (certified 26.24%) with exceptional operational stability (>99%, ISOS-L-1 500 h), representing the highest efficiency reported to date for SM-HTM-based PSCs. This spatial molecular engineering strategy establishes a generalizable design paradigm for next-generation HTMs, opening a promising pathway toward high-performance, operationally stable, and commercially viable PSCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":"e23665"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056855","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}
Achieving spatially coupled and functionally complementary active sites in synthetic catalysts remains a significant challenge. Inspired by the enzymatic cascade involving nitrate reductase and nitrite reductase, we report a nanozyme comprising iron clusters and iron-doped nickel phosphide nanoparticles on CeO2 nanorods (Fe-FexNi2-xP/CeO2) in proximity for efficient electrocatalytic nitrate-to-ammonia conversion and Zn-NO3 - battery. The Fe clusters serve as nitrate reductase mimics, promoting the deoxygenation step of NO3 - to NO2 -, while the adjacent FexNi2-xP nanoparticles serve as nitrite reductase mimics, accelerating the subsequent hydrogenation steps to NH3. The CeO2 nanorods stabilize the dual active sites and function as proton reservoirs to suppress the hydrogen evolution reaction. Thus, the nanozyme delivers exceptional performance in NH3 electrosynthesis, achieving a high yield rate of 43.5 mg h-1 cm-2 with a Faradaic efficiency (FE) of 91.2% at -0.7 V versus RHE in an H-type cell and an industrial-level current density of 800 mA cm-2 for over 100 h under flow-cell conditions (FENH3 > 90%) at the same potential. When employed Fe-FexNi2-xP/CeO2 as a cathode in a rechargeable Zn-NO3 - battery, it enables simultaneous NH3 production and power generation, delivering a peak power density of 21.1 mW cm-2 and an NH3 yield rate of 1.9 mg h-1 cm-2.
{"title":"Enzyme-Mimicking Metal-Phosphide Tandem Catalytic Centers for Efficient Electrochemical Nitrate-to-Ammonia Conversion and Zinc-Nitrate Battery.","authors":"Xinnan Xie,Yi Zhong,Pandi Muthukumar,Boyu Zhang,Jianxiao Yang,Jian-Ke Sun,Xinchun Yang,Hui-Ming Cheng","doi":"10.1002/anie.202525416","DOIUrl":"https://doi.org/10.1002/anie.202525416","url":null,"abstract":"Achieving spatially coupled and functionally complementary active sites in synthetic catalysts remains a significant challenge. Inspired by the enzymatic cascade involving nitrate reductase and nitrite reductase, we report a nanozyme comprising iron clusters and iron-doped nickel phosphide nanoparticles on CeO2 nanorods (Fe-FexNi2-xP/CeO2) in proximity for efficient electrocatalytic nitrate-to-ammonia conversion and Zn-NO3 - battery. The Fe clusters serve as nitrate reductase mimics, promoting the deoxygenation step of NO3 - to NO2 -, while the adjacent FexNi2-xP nanoparticles serve as nitrite reductase mimics, accelerating the subsequent hydrogenation steps to NH3. The CeO2 nanorods stabilize the dual active sites and function as proton reservoirs to suppress the hydrogen evolution reaction. Thus, the nanozyme delivers exceptional performance in NH3 electrosynthesis, achieving a high yield rate of 43.5 mg h-1 cm-2 with a Faradaic efficiency (FE) of 91.2% at -0.7 V versus RHE in an H-type cell and an industrial-level current density of 800 mA cm-2 for over 100 h under flow-cell conditions (FENH3 > 90%) at the same potential. When employed Fe-FexNi2-xP/CeO2 as a cathode in a rechargeable Zn-NO3 - battery, it enables simultaneous NH3 production and power generation, delivering a peak power density of 21.1 mW cm-2 and an NH3 yield rate of 1.9 mg h-1 cm-2.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"22 1","pages":"e25416"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056744","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}
Birefringent crystals underpin polarization control and angular phase matching in nonlinear optics and therefore, attract sustained interest. However, achieving large birefringence (Δn) has largely depended on inorganic frameworks composed of metals with limited natural abundance or sustainability concerns. By contrast, organic cocrystals offer simple preparation and readily tunable packing. Here we design a series of diazapyrene derivatives and obtain 13 crystals, including three single-component crystals and ten two-component cocrystals formed separately with three distinct benzene derivatives, whose crystal-packing anisotropy can be programmed to yield Δn = 0.152-1.269. Two compositions, D27N and D13N, combine suitable optical band gaps with exceptional birefringence (Δn = 1.223 and 1.269 at 546 nm, respectively), ranking among the highest reported for purely organic crystals, and under identical conditions, surpassing all reported inorganic birefringent crystals. Across the series, we uncover a Boltzmann-type relationship between Δn and a geometric descriptor ΔS (minimal/maximal projected area of the conjugated core on crystallographic planes), thereby quantitatively linking molecular-level packing anisotropy to macroscopic Δn. Cocrystal engineering also modulates second-order nonlinear optical responses, including symmetry control and second-harmonic generation tuning. This work establishes a metal-free, designable route to high-Δn optical crystals and provides a predictive metric for anisotropy-driven materials discovery.
{"title":"Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.2.","authors":"Lingyan Sun,Gangji Yi,Guohong Zou,Cheng Zhang","doi":"10.1002/anie.202524207","DOIUrl":"https://doi.org/10.1002/anie.202524207","url":null,"abstract":"Birefringent crystals underpin polarization control and angular phase matching in nonlinear optics and therefore, attract sustained interest. However, achieving large birefringence (Δn) has largely depended on inorganic frameworks composed of metals with limited natural abundance or sustainability concerns. By contrast, organic cocrystals offer simple preparation and readily tunable packing. Here we design a series of diazapyrene derivatives and obtain 13 crystals, including three single-component crystals and ten two-component cocrystals formed separately with three distinct benzene derivatives, whose crystal-packing anisotropy can be programmed to yield Δn = 0.152-1.269. Two compositions, D27N and D13N, combine suitable optical band gaps with exceptional birefringence (Δn = 1.223 and 1.269 at 546 nm, respectively), ranking among the highest reported for purely organic crystals, and under identical conditions, surpassing all reported inorganic birefringent crystals. Across the series, we uncover a Boltzmann-type relationship between Δn and a geometric descriptor ΔS (minimal/maximal projected area of the conjugated core on crystallographic planes), thereby quantitatively linking molecular-level packing anisotropy to macroscopic Δn. Cocrystal engineering also modulates second-order nonlinear optical responses, including symmetry control and second-harmonic generation tuning. This work establishes a metal-free, designable route to high-Δn optical crystals and provides a predictive metric for anisotropy-driven materials discovery.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 1","pages":"e24207"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056840","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}
Cyclic peptides have attracted significant attentiondue to their persistent structures and particular biological effects, which are also key building blocks for creating functional chiral materials. Here, we report a double-cyclized dipeptide structure-a macrocycle embedded with a cyclic dipeptide-and its use in constructing superhelical structures. By further cyclizing modified cyclic diphenylalanine, a macrocyclic arene embedded with a cyclodipeptide was synthesized. Its unique, rigid structure allows to give hierarchical helical structures by bottom-up assembly process in solution. These superhelical structures are macroscopic, reaching lengths of at centimeter scale. This demonstrates a bottom-up, multiscale transfer of chirality from the molecular to the macroscopic scale. Moreover, assembly patterns can be precisely controlled by adjusting kinetic conditions such as temperature, concentration, enantiomeric ratio, and solvent, allowing for both rigid and flexible arrangement modalities. The presence of the macrocycle in these superhelices enables the encapsulation of cationic dyes, leading to both ground-state and excited-state chirality transfer. This provides a valuable template for designing macroscopic chiroptical materials.
{"title":"Double-Cyclized Dipeptides for Hierarchical Self-Assembly Into Crystalline Macroscopic Superhelices.","authors":"Yitong Gai,Zhuoer Wang,Aiyou Hao,Pengyao Xing","doi":"10.1002/anie.2476901","DOIUrl":"https://doi.org/10.1002/anie.2476901","url":null,"abstract":"Cyclic peptides have attracted significant attentiondue to their persistent structures and particular biological effects, which are also key building blocks for creating functional chiral materials. Here, we report a double-cyclized dipeptide structure-a macrocycle embedded with a cyclic dipeptide-and its use in constructing superhelical structures. By further cyclizing modified cyclic diphenylalanine, a macrocyclic arene embedded with a cyclodipeptide was synthesized. Its unique, rigid structure allows to give hierarchical helical structures by bottom-up assembly process in solution. These superhelical structures are macroscopic, reaching lengths of at centimeter scale. This demonstrates a bottom-up, multiscale transfer of chirality from the molecular to the macroscopic scale. Moreover, assembly patterns can be precisely controlled by adjusting kinetic conditions such as temperature, concentration, enantiomeric ratio, and solvent, allowing for both rigid and flexible arrangement modalities. The presence of the macrocycle in these superhelices enables the encapsulation of cationic dyes, leading to both ground-state and excited-state chirality transfer. This provides a valuable template for designing macroscopic chiroptical materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":"e2476901"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056853","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}
Proton-activated ion channels mediate ion transport in response to extracellular acidification, enabling cellular adaptation to acidic microenvironments. Despite their biological importance, mimicking proton-activated functionality in artificial ion channels remains a significant challenge. Here, we present a novel class of proton-activated artificial ion channels built from self-assembled peptide chains integrated into a pH-responsive 2,2'-bipyridine scaffold. Protonation induces a conformational switch in the channel-forming units, promoting one-dimensional self-assembly and subsequent hydrophobic packing into functional channels capable of transporting small molecules. As extracellular pH decreases from 7.4 to 6.5, C-FF exhibits a 10.3-fold enhancement in cytotoxicity against human colorectal carcinoma cells, boosting an IC50 of 2.8 µM, mediated through apoptosis induction and cell cycle arrest resulting from disruption of the autophagic process. Significantly, C-FF demonstrates exceptional selectivity for cancer cells, achieving a selectivity index of 8.5, surpassing that of doxorubicin by one order of magnitude while maintaining comparable potency, highlighting its potential as a pH-responsive platform for selective anticancer therapy in acidic tumor microenvironments.
{"title":"Proton-Activated Artificial Channels for pH-Selective Cancer Therapy.","authors":"Daoxin Luo,Chunyan Jia,Yuchao Lin,Jin Zhou,Congrui Ren,Xiaopan Xie,Tong Chen,Zhiping Zeng,Weifeng Li,Yuguang Mu,Changliang Ren","doi":"10.1002/anie.202525440","DOIUrl":"https://doi.org/10.1002/anie.202525440","url":null,"abstract":"Proton-activated ion channels mediate ion transport in response to extracellular acidification, enabling cellular adaptation to acidic microenvironments. Despite their biological importance, mimicking proton-activated functionality in artificial ion channels remains a significant challenge. Here, we present a novel class of proton-activated artificial ion channels built from self-assembled peptide chains integrated into a pH-responsive 2,2'-bipyridine scaffold. Protonation induces a conformational switch in the channel-forming units, promoting one-dimensional self-assembly and subsequent hydrophobic packing into functional channels capable of transporting small molecules. As extracellular pH decreases from 7.4 to 6.5, C-FF exhibits a 10.3-fold enhancement in cytotoxicity against human colorectal carcinoma cells, boosting an IC50 of 2.8 µM, mediated through apoptosis induction and cell cycle arrest resulting from disruption of the autophagic process. Significantly, C-FF demonstrates exceptional selectivity for cancer cells, achieving a selectivity index of 8.5, surpassing that of doxorubicin by one order of magnitude while maintaining comparable potency, highlighting its potential as a pH-responsive platform for selective anticancer therapy in acidic tumor microenvironments.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"44 1","pages":"e25440"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070045","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}
Molecular iodine release under working conditions remains a major obstacle to the long-term stability of perovskite solar cells (PSCs). Despite significant progress, developing a simple yet effective strategy to suppress this degradation pathway-while reconciling high photothermal stability and high efficiency without sacrificing charge transport-remains challenging. Here, through integrated molecular design, theoretical modeling, and experimental validation, we develop a new class of piperazine (PA)-tailored fullerene derivative, PCBM-PA, that uniquely exhibits dual functionality in iodine capture and dissociation. Density functional theory (DFT) calculations reveal that PCBM-PA promotes I2 adsorption and I─I bond cleavage at the perovskite surface, facilitating dynamic iodide regeneration. Comprehensive experiments further confirm that PCBM-PA effectively suppresses I2 release through robust N···I halogen-bonding (XB) interactions, while simultaneously promoting I─I bond cleavage and restoration of iodide ions, consistent with theoretical insights. This coupled "iodine adsorption-dissociation" behavior, unprecedented among previously reported XB acceptors, enables dynamic self-repair of iodine vacancy defects. Consequently, inverted PSCs incorporating PCBM-PA exhibit outstanding photothermal stability, retaining over 93% of their initial efficiency after 1000 h under maximum power point tracking (MPPT) at 65 °C, together with a champion efficiency of 26.26%. This work offers a new molecular-engineering pathway toward iodine-resilient, high-performance perovskite photovoltaics.
{"title":"Dynamic Iodide Regeneration Enabled by Piperazine-Tailored PCBM Interfaces for Photothermally Stable and Efficient Inverted Perovskite Photovoltaics.","authors":"Yulong Chen,Zijin Wu,Liangyu Zhao,Huaiman Cao,Xufan Zheng,Runze Liu,Geert Brocks,Shuxia Tao,Ze Yu","doi":"10.1002/anie.6909224","DOIUrl":"https://doi.org/10.1002/anie.6909224","url":null,"abstract":"Molecular iodine release under working conditions remains a major obstacle to the long-term stability of perovskite solar cells (PSCs). Despite significant progress, developing a simple yet effective strategy to suppress this degradation pathway-while reconciling high photothermal stability and high efficiency without sacrificing charge transport-remains challenging. Here, through integrated molecular design, theoretical modeling, and experimental validation, we develop a new class of piperazine (PA)-tailored fullerene derivative, PCBM-PA, that uniquely exhibits dual functionality in iodine capture and dissociation. Density functional theory (DFT) calculations reveal that PCBM-PA promotes I2 adsorption and I─I bond cleavage at the perovskite surface, facilitating dynamic iodide regeneration. Comprehensive experiments further confirm that PCBM-PA effectively suppresses I2 release through robust N···I halogen-bonding (XB) interactions, while simultaneously promoting I─I bond cleavage and restoration of iodide ions, consistent with theoretical insights. This coupled \"iodine adsorption-dissociation\" behavior, unprecedented among previously reported XB acceptors, enables dynamic self-repair of iodine vacancy defects. Consequently, inverted PSCs incorporating PCBM-PA exhibit outstanding photothermal stability, retaining over 93% of their initial efficiency after 1000 h under maximum power point tracking (MPPT) at 65 °C, together with a champion efficiency of 26.26%. This work offers a new molecular-engineering pathway toward iodine-resilient, high-performance perovskite photovoltaics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"40 1","pages":"e6909224"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070039","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}
Xiang-Yu Li,Yan-Long Zhao,Xin Zhang,Xuefeng Bai,Muzi Li,Jian-Rong Li
The capture of sulfur hexafluoride (SF6), the most potent greenhouse gas, is of critical importance. Enhancement of dynamic SF6 capture capacity presents significant challenges due to its chemical inertness and low concentration in industrial effluent streams. Herein, we demonstrate that the isoreticular functionalization of zinc-pyrazolate metal-organic frameworks (MOFs) enables simultaneous enhancement of both SF6 adsorption capacity and uptake kinetics. Through replacement of benzene with pyridine in the ligand, BUT-125 (BUT: Beijing University of Technology) achieves a record-high SF6 adsorption capacity of 3.57 mmol cm-3 at 0.1 bar and 298 K, representing a 27% improvement over its structural analogue Zn-DPB (DPB: 1,3-di(pyrazolate-4-yl)benzene). Density functional theory (DFT) calculations reveal that pyridine functionalization increases the positive charge density on hydrogen atoms within molecular trap sites, strengthening C─H···F interactions with SF6 molecules. Remarkably, BUT-125 also exhibits outstanding adsorption kinetics, that combined with high equilibrium uptake, leads to an exceptional dynamic SF6 capture capacity of 3.42 mmol cm-3 from the SF6/N2 (10/90) mixture, surpassing reported porous sorbents.
{"title":"Simultaneous Boost of SF6 Adsorption Capacity and Kinetics Through Isoreticular Functionalization of Zinc(II)-Pyrazolate Frameworks.","authors":"Xiang-Yu Li,Yan-Long Zhao,Xin Zhang,Xuefeng Bai,Muzi Li,Jian-Rong Li","doi":"10.1002/anie.5036296","DOIUrl":"https://doi.org/10.1002/anie.5036296","url":null,"abstract":"The capture of sulfur hexafluoride (SF6), the most potent greenhouse gas, is of critical importance. Enhancement of dynamic SF6 capture capacity presents significant challenges due to its chemical inertness and low concentration in industrial effluent streams. Herein, we demonstrate that the isoreticular functionalization of zinc-pyrazolate metal-organic frameworks (MOFs) enables simultaneous enhancement of both SF6 adsorption capacity and uptake kinetics. Through replacement of benzene with pyridine in the ligand, BUT-125 (BUT: Beijing University of Technology) achieves a record-high SF6 adsorption capacity of 3.57 mmol cm-3 at 0.1 bar and 298 K, representing a 27% improvement over its structural analogue Zn-DPB (DPB: 1,3-di(pyrazolate-4-yl)benzene). Density functional theory (DFT) calculations reveal that pyridine functionalization increases the positive charge density on hydrogen atoms within molecular trap sites, strengthening C─H···F interactions with SF6 molecules. Remarkably, BUT-125 also exhibits outstanding adsorption kinetics, that combined with high equilibrium uptake, leads to an exceptional dynamic SF6 capture capacity of 3.42 mmol cm-3 from the SF6/N2 (10/90) mixture, surpassing reported porous sorbents.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"71 1","pages":"e5036296"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070040","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}
Yang Xi,Chenchen Wang,Linlin Fan,Yetong Zhang,Wei-Hong Zhu,Jingping Qu,Yifeng Chen
Transition metal-catalyzed carbonylation employing CO as a C1 feedstock is fundamental for synthesizing carbonyl compounds in industrial/fine chemical synthesis. Despite the ubiquity of chiral carbonyl motifs in bioactive molecules, general methods for catalytic asymmetric carbonylation under mild conditions remain scarce, hindered by stereocontrol challenges and competing pathways. Current approaches often rely on multistep sequences or restrictive intramolecular strategies. Herein, we report palladium-catalyzed intermolecular four-component carbonylative dicarbofunctionalization of internal alkenes, aryl diazonium salts, and nucleophiles under 1 atm CO. This method enables simultaneous control over regio-, diastereo-, and enantioselectivity, efficiently constructing congested vicinal stereocenters in acyclic chiral carbonyl scaffolds. Nucleophile modularity affords diverse enantioenriched esters or ketones in high yields and stereoselectivity. The mild conditions prevent racemization of chiral carbonyls, and derivatizations highlight broad synthetic utility.
{"title":"Palladium-Catalyzed Enantioselective Four-Component Carbonylative Dicarbofunctionalization of Internal Alkenes With 1 Atm CO.","authors":"Yang Xi,Chenchen Wang,Linlin Fan,Yetong Zhang,Wei-Hong Zhu,Jingping Qu,Yifeng Chen","doi":"10.1002/anie.6399534","DOIUrl":"https://doi.org/10.1002/anie.6399534","url":null,"abstract":"Transition metal-catalyzed carbonylation employing CO as a C1 feedstock is fundamental for synthesizing carbonyl compounds in industrial/fine chemical synthesis. Despite the ubiquity of chiral carbonyl motifs in bioactive molecules, general methods for catalytic asymmetric carbonylation under mild conditions remain scarce, hindered by stereocontrol challenges and competing pathways. Current approaches often rely on multistep sequences or restrictive intramolecular strategies. Herein, we report palladium-catalyzed intermolecular four-component carbonylative dicarbofunctionalization of internal alkenes, aryl diazonium salts, and nucleophiles under 1 atm CO. This method enables simultaneous control over regio-, diastereo-, and enantioselectivity, efficiently constructing congested vicinal stereocenters in acyclic chiral carbonyl scaffolds. Nucleophile modularity affords diverse enantioenriched esters or ketones in high yields and stereoselectivity. The mild conditions prevent racemization of chiral carbonyls, and derivatizations highlight broad synthetic utility.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"41 1","pages":"e6399534"},"PeriodicalIF":16.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056792","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}
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