Homologation is of high value in organic synthesis, yet the two‐carbon extension of electron‐deficient alkenes remains challenging. Here we report a photoinduced cobalt‐catalyzed homologation of electron‐withdrawing‐group (EWG)‐substituted alkenes using acetylene as a C2 building block and water as a hydrogen source. Complementing existing methods that are largely limited to non‐electron‐deficient alkenes, this protocol enables both the direct homologation of electron‐deficient alkenes and a slow‐release approach that employs readily accessible β ‐chloro compounds as alkene precursors. The method demonstrates broad functional group compatibility and enables efficient synthesis of valuable compounds, including bioactive pheromones and fragrance molecules. Mechanistic studies reveal that the catalytically active Co(III)─H species forms via oxidative addition of Co(I) to a proton source. This work provides a practical and complementary platform for alkene homologation.
{"title":"Photoinduced Cobalt Catalysis for Direct and Slow‐Release Homologation of Electron‐Deficient Alkenes Using Acetylene","authors":"Haijing Xiao, Yang Chen, Shifa Zhu","doi":"10.1002/anie.1679175","DOIUrl":"https://doi.org/10.1002/anie.1679175","url":null,"abstract":"Homologation is of high value in organic synthesis, yet the two‐carbon extension of electron‐deficient alkenes remains challenging. Here we report a photoinduced cobalt‐catalyzed homologation of electron‐withdrawing‐group (EWG)‐substituted alkenes using acetylene as a C2 building block and water as a hydrogen source. Complementing existing methods that are largely limited to non‐electron‐deficient alkenes, this protocol enables both the direct homologation of electron‐deficient alkenes and a slow‐release approach that employs readily accessible <jats:italic>β</jats:italic> ‐chloro compounds as alkene precursors. The method demonstrates broad functional group compatibility and enables efficient synthesis of valuable compounds, including bioactive pheromones and fragrance molecules. Mechanistic studies reveal that the catalytically active Co(III)─H species forms via oxidative addition of Co(I) to a proton source. This work provides a practical and complementary platform for alkene homologation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"101 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478643","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}
Ionic thermoelectric materials combine large thermopower, quasi-solid-state behavior, mechanical flexibility, and intrinsic stability, offering a low-cost route for harvesting low-grade heat energy. While p-type ionogels based on ionic liquids have achieved excellent performance, efficient n-type analogues remain challenging. Here, we design a poly(vinyl alcohol) (PVA)-based n-type ionogel by incorporating poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), ionic liquid, and zinc bromide. Upon annealing, strong coordination between Zn2+ ions and hydroxyl/sulfonic groups, together with the formation of anion-rich clusters via preferential ion association, promotes rapid anion transport and enhances the Eastman entropy change. Simultaneously, the hierarchically layered ionic architecture suppresses phonon propagation and enhances carrier selectivity, resulting in a desirable balance between high ionic conductivity and low thermal conductivity. Consequently, the hydrogel achieves a remarkable thermopower of -128 mV K-1, an ultrahigh power factor of 16.7 µW cm-1 K-2, and an excellent thermoelectric figure of merit of 1.1 at room temperature. This work establishes a universal strategy for designing high-performance n-type ionic thermoelectric materials and opens avenues for flexible and sustainable heat-to-electricity conversion.
{"title":"Ionic Coordination and Hierarchical Architecture Enable Record n-Type Thermoelectric Efficiency in Soft Hydrogels.","authors":"Chenyang Zhang,Xiao-Lei Shi,Xujiang Chao,Mingxu Wang,Wenyi Chen,Qian Liu,Tianyi Cao,Boxuan Hu,Shuai Sun,Zhi-Gang Chen","doi":"10.1002/anie.4172130","DOIUrl":"https://doi.org/10.1002/anie.4172130","url":null,"abstract":"Ionic thermoelectric materials combine large thermopower, quasi-solid-state behavior, mechanical flexibility, and intrinsic stability, offering a low-cost route for harvesting low-grade heat energy. While p-type ionogels based on ionic liquids have achieved excellent performance, efficient n-type analogues remain challenging. Here, we design a poly(vinyl alcohol) (PVA)-based n-type ionogel by incorporating poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), ionic liquid, and zinc bromide. Upon annealing, strong coordination between Zn2+ ions and hydroxyl/sulfonic groups, together with the formation of anion-rich clusters via preferential ion association, promotes rapid anion transport and enhances the Eastman entropy change. Simultaneously, the hierarchically layered ionic architecture suppresses phonon propagation and enhances carrier selectivity, resulting in a desirable balance between high ionic conductivity and low thermal conductivity. Consequently, the hydrogel achieves a remarkable thermopower of -128 mV K-1, an ultrahigh power factor of 16.7 µW cm-1 K-2, and an excellent thermoelectric figure of merit of 1.1 at room temperature. This work establishes a universal strategy for designing high-performance n-type ionic thermoelectric materials and opens avenues for flexible and sustainable heat-to-electricity conversion.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":"e4172130"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471503","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}
Hwangho Lee,Anvitha Puritipati,Youngkyu Park,Oleg Mironov,Son-Jong Hwang,Stacey I Zones,Alexander Katz
We demonstrate the synthesis of Cu(AlOx)a(SiOy)b clusters under the confines of MER zeolite, which hydrogenate CO2 to methanol and dimethyl ether with 96% selectivity and a space time yield of 15.0 mmolC gCu -1 h-1 at 250 °C (4:1 H2:CO2 and 5 MPa). A crucial aspect of the synthesis involves MER zeolite calcination, leading to framework dealumination and loss of long-range order. These Cu(AlOx)a(SiOy)b clusters consist of a high density of coordinatively unsaturated aluminum sites, which are lacking in conventional copper catalysts with similar stoichiometry, and stabilize copper in a more oxidic form that is characterized by higher reduction temperatures. Other copper-containing zeolites consisting of stable frameworks that do not dealuminate upon calcination (Cu-Li-FAU and Cu-Li-RHO zeolites) exhibit 99% selectivity to CO under the same reaction conditions. When compared with these catalysts and an industrial CuZnAl catalyst, kinetic analysis shows the Cu(AlOx)a(SiOy)b clusters are more intrinsically selective for methanol over the reverse water gas shift reaction at low CO2 converions.
{"title":"Coordinatively Unsaturated Aluminum Enables Methanol-Selective CO2 Hydrogenation With Zeolite-Supported Copper Catalysts.","authors":"Hwangho Lee,Anvitha Puritipati,Youngkyu Park,Oleg Mironov,Son-Jong Hwang,Stacey I Zones,Alexander Katz","doi":"10.1002/anie.202525717","DOIUrl":"https://doi.org/10.1002/anie.202525717","url":null,"abstract":"We demonstrate the synthesis of Cu(AlOx)a(SiOy)b clusters under the confines of MER zeolite, which hydrogenate CO2 to methanol and dimethyl ether with 96% selectivity and a space time yield of 15.0 mmolC gCu -1 h-1 at 250 °C (4:1 H2:CO2 and 5 MPa). A crucial aspect of the synthesis involves MER zeolite calcination, leading to framework dealumination and loss of long-range order. These Cu(AlOx)a(SiOy)b clusters consist of a high density of coordinatively unsaturated aluminum sites, which are lacking in conventional copper catalysts with similar stoichiometry, and stabilize copper in a more oxidic form that is characterized by higher reduction temperatures. Other copper-containing zeolites consisting of stable frameworks that do not dealuminate upon calcination (Cu-Li-FAU and Cu-Li-RHO zeolites) exhibit 99% selectivity to CO under the same reaction conditions. When compared with these catalysts and an industrial CuZnAl catalyst, kinetic analysis shows the Cu(AlOx)a(SiOy)b clusters are more intrinsically selective for methanol over the reverse water gas shift reaction at low CO2 converions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"12 1","pages":"e25717"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471506","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}
Impurities in organic phosphorescent materials have caused extensive discussions in recent years. In this work, we demonstrate the impressive afterglow of commercial benzene-carboxylic acid (BCA) derivatives are attributed to trace impurities identified as biphenyl carboxylic acid derivatives. One of the impurities even induces detectable phosphorescence when the doping ratio is as low as 0.1 ppm (molar ratio). Inspired by the structural similarity between impurities and the main component, we propose a pseudo-homologues strategy for constructing afterglow materials. Based on this model, several groups of compounds are used to prepare 275 doped samples. Surprisingly, pseudo-homologues exhibit a markedly higher success rate for afterglow (73.3%) compared to that of other samples (6.5%). This structural model offers new perspectives for the construction of dual-component afterglow materials.
{"title":"Pseudo-Homologue Doping Strategy for Afterglow Materials.","authors":"Jiayu Wang,Liangwei Ma,Bingbing Ding,Lei Zhou,Siyu Sun,Zhenyi He,Jinming Song,Zhiqin Wu,He Tian,Xiang Ma","doi":"10.1002/anie.5554671","DOIUrl":"https://doi.org/10.1002/anie.5554671","url":null,"abstract":"Impurities in organic phosphorescent materials have caused extensive discussions in recent years. In this work, we demonstrate the impressive afterglow of commercial benzene-carboxylic acid (BCA) derivatives are attributed to trace impurities identified as biphenyl carboxylic acid derivatives. One of the impurities even induces detectable phosphorescence when the doping ratio is as low as 0.1 ppm (molar ratio). Inspired by the structural similarity between impurities and the main component, we propose a pseudo-homologues strategy for constructing afterglow materials. Based on this model, several groups of compounds are used to prepare 275 doped samples. Surprisingly, pseudo-homologues exhibit a markedly higher success rate for afterglow (73.3%) compared to that of other samples (6.5%). This structural model offers new perspectives for the construction of dual-component afterglow materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":"e5554671"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471510","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}
Developing high photochromic contrast photoswitches in the solid state remains a significant challenge in organic smart materials. We here provide an oxygen-acceptor strategy for constructing an excited-state intramolecular proton transfer (ESIPT)-inspired organic photoswitch, namely tpmSA. By introducing a bulky triphenylmethane into the salicylaldehyde skeleton, tpmSA can achieve photochromic behavior in the solid state. Upon exposure to ultraviolet (UV) light, tpmSA displays distinct color variation from white to yellow, yielding a high photochromic contrast (ΔE*Lab>74). Kinetic studies suggest that tpmSA can undergo rapid photoisomerization and is capable of reversible switching for over 20 cycles, demonstrating superior fatigue resistance. Mechanistic studies reveal that the weakly alkaline oxygen-acceptor in tpmSA significantly enhances photochromic contrast by suppressing the ground-state intramolecular proton transfer (GSIPT) pathway. The photopatterning and high-level information encryption were successfully developed by tpmSA. This study proposes an oxygen-acceptor strategy for developing solid-state photoswitches with high photochromic contrast, demonstrating great potential for advanced information encryption materials.
{"title":"Oxygen-Acceptor-Driven High Photochromic Contrast Solid-State Excited-State Intramolecular Proton Transfer Photoswitches.","authors":"Yahui Chen,Wenjing Wang,Hao Gu,Qinlin Yuan,Yeju Lee,Xin He,Chao Wang,Yaqian Huang,Juyoung Yoon,Xiaoqiang Chen,Xiaojun Peng","doi":"10.1002/anie.5193191","DOIUrl":"https://doi.org/10.1002/anie.5193191","url":null,"abstract":"Developing high photochromic contrast photoswitches in the solid state remains a significant challenge in organic smart materials. We here provide an oxygen-acceptor strategy for constructing an excited-state intramolecular proton transfer (ESIPT)-inspired organic photoswitch, namely tpmSA. By introducing a bulky triphenylmethane into the salicylaldehyde skeleton, tpmSA can achieve photochromic behavior in the solid state. Upon exposure to ultraviolet (UV) light, tpmSA displays distinct color variation from white to yellow, yielding a high photochromic contrast (ΔE*Lab>74). Kinetic studies suggest that tpmSA can undergo rapid photoisomerization and is capable of reversible switching for over 20 cycles, demonstrating superior fatigue resistance. Mechanistic studies reveal that the weakly alkaline oxygen-acceptor in tpmSA significantly enhances photochromic contrast by suppressing the ground-state intramolecular proton transfer (GSIPT) pathway. The photopatterning and high-level information encryption were successfully developed by tpmSA. This study proposes an oxygen-acceptor strategy for developing solid-state photoswitches with high photochromic contrast, demonstrating great potential for advanced information encryption materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"119 1","pages":"e5193191"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471511","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}
Jianke Su,Chu Wang,Zhongping Cai,Jiale Wu,Xu Yan Chen,Jie Wu
Carbyne equivalents represent ideal trivalent carbon synthons, capable of forming C─C and C─X bonds through their three nonbonded electrons. This unique reactivity profile offers high modularity for rapid assemble complicate molecular scaffolds. However, the selective introduction of three σ-bonds at a single carbon center remains a formidable challenge, owing to the multifaceted reactivity of the carbyne center. Herein, we report a cascade reaction, which sequentially regulates the radical, nucleophilic, and electrophilic reactivity of carbyne equivalents under light irradiation. This cascade enables precise spatial and temporal activation, facilitating the selective and efficient construction of densely functionalized spirocyclic ethers from allylic and homoallylic acetates, with three σ-bonds introduced at the carbyne center. A wide range of spirocyclic ethers bearing diverse functional groups and structural motifs was obtained with excellent diastereoselectivity, underscoring the capability of carbyne equivalents for rapid construction of drug-like molecules. The reaction was readily scalable up to 50 mmol, either in batch mode or using a high-speed circulation-flow reactor. Mechanistic studies, including UV-vis spectroscopy, cyclic voltammetry, radical trapping, structure-reactivity relationship experiments, isotope labeling, as well as theoretical calculations, provide insights into the dynamic evolution of reactive intermediates, shedding light on the diverse reactivity of carbyne equivalents in organic synthesis.
{"title":"Photoinduced Selective Construction of Densely Functionalized Spirocyclic Ethers With Carbyne Equivalents.","authors":"Jianke Su,Chu Wang,Zhongping Cai,Jiale Wu,Xu Yan Chen,Jie Wu","doi":"10.1002/anie.1489528","DOIUrl":"https://doi.org/10.1002/anie.1489528","url":null,"abstract":"Carbyne equivalents represent ideal trivalent carbon synthons, capable of forming C─C and C─X bonds through their three nonbonded electrons. This unique reactivity profile offers high modularity for rapid assemble complicate molecular scaffolds. However, the selective introduction of three σ-bonds at a single carbon center remains a formidable challenge, owing to the multifaceted reactivity of the carbyne center. Herein, we report a cascade reaction, which sequentially regulates the radical, nucleophilic, and electrophilic reactivity of carbyne equivalents under light irradiation. This cascade enables precise spatial and temporal activation, facilitating the selective and efficient construction of densely functionalized spirocyclic ethers from allylic and homoallylic acetates, with three σ-bonds introduced at the carbyne center. A wide range of spirocyclic ethers bearing diverse functional groups and structural motifs was obtained with excellent diastereoselectivity, underscoring the capability of carbyne equivalents for rapid construction of drug-like molecules. The reaction was readily scalable up to 50 mmol, either in batch mode or using a high-speed circulation-flow reactor. Mechanistic studies, including UV-vis spectroscopy, cyclic voltammetry, radical trapping, structure-reactivity relationship experiments, isotope labeling, as well as theoretical calculations, provide insights into the dynamic evolution of reactive intermediates, shedding light on the diverse reactivity of carbyne equivalents in organic synthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"88 1","pages":"e1489528"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471512","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}
The operation of low-earth orbit satellites, Antarctic research stations, and certain extreme cold environments demands energy storage devices (ESDs) capable of functioning at -100°C or lower. Conventional electrolytes are limited by sluggish ion transport and unstable electrode-electrolyte interphases at low temperatures, severely degrading the performance of electrochemical ESDs under extreme cold. Herein, we report a weak-aggregation (AGG-w) electrolyte reconciling bulk-phase ion transport with interfacial kinetics at ultra-low temperatures (ULT). This is achieved through the strategic incorporation of unilaterally fluorinated motif as strong electron-withdrawing group, which enhances steric hindrance and reconfigure molecular dipole to reinforce dipole-dipole interaction with the solvents anchored in the primary solvation shell. Such restructuring enables unprecedented solvent-anion cooperativity by weakening Li+-dipole interaction and promoting greater anion participation, thereby accelerating desolvation kinetics, reducing interfacial resistance, and simultaneously preserving low viscosity and high ionic conductivity at ULT. Notably, 1100 F real pouch cells with AGG-w electrolyte maintain 97.9% capacity retention after 7 months of continuous operation at -40°C and demonstrate emerging discharge capability at -100°C, a milestone never previously reported. This work underscores weak-interaction engineering as a critical paradigm for electrolyte design and establishes a generalizable strategy for high-performance electrochemistry in extreme conditions.
{"title":"A Weak-Aggregation Electrolyte Enables Lithium-Ion Capacitors at Ultra-Low Temperature.","authors":"Chunlei Zhang,Qifan Peng,Kai Wang,Xudong Zhang,Yinghua Chen,Yabin An,Yanan Xu,Xianzhong Sun,Xiong Zhang,Qian Li,Pushpendra Kumar,Zhao Li,Jun Ming,Guangmin Zhou,Yanwei Ma","doi":"10.1002/anie.6979216","DOIUrl":"https://doi.org/10.1002/anie.6979216","url":null,"abstract":"The operation of low-earth orbit satellites, Antarctic research stations, and certain extreme cold environments demands energy storage devices (ESDs) capable of functioning at -100°C or lower. Conventional electrolytes are limited by sluggish ion transport and unstable electrode-electrolyte interphases at low temperatures, severely degrading the performance of electrochemical ESDs under extreme cold. Herein, we report a weak-aggregation (AGG-w) electrolyte reconciling bulk-phase ion transport with interfacial kinetics at ultra-low temperatures (ULT). This is achieved through the strategic incorporation of unilaterally fluorinated motif as strong electron-withdrawing group, which enhances steric hindrance and reconfigure molecular dipole to reinforce dipole-dipole interaction with the solvents anchored in the primary solvation shell. Such restructuring enables unprecedented solvent-anion cooperativity by weakening Li+-dipole interaction and promoting greater anion participation, thereby accelerating desolvation kinetics, reducing interfacial resistance, and simultaneously preserving low viscosity and high ionic conductivity at ULT. Notably, 1100 F real pouch cells with AGG-w electrolyte maintain 97.9% capacity retention after 7 months of continuous operation at -40°C and demonstrate emerging discharge capability at -100°C, a milestone never previously reported. This work underscores weak-interaction engineering as a critical paradigm for electrolyte design and establishes a generalizable strategy for high-performance electrochemistry in extreme conditions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"12 1","pages":"e6979216"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471508","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}
Single-atom catalysts (SACs) are a promising class of electrochemical oxygen reduction reaction (ORR) catalysts, enabling either a four-electron (4e-) pathway for energy conversion or a two-electron (2e-) pathway for H2O2 production. However, the precise control and optimization of the ORR pathway remain challenging due to the lack of strategies for fine-tuning the SACs coordination structures. Herein, we developed a curvature engineering strategy that enables, for the first time, continuous steering of the ORR pathway from 2e- to 4e- over Cu-based SACs. Through theoretical calculations and in-situ spectroscopy, we revealed the essential mechanism by which active-site tensile strain and interfacial water restructuring, induced by carbon nanotubes with varying curvature, jointly govern ORR activity and selectivity. The Cu single-atom sites on high-curvature CNTs exhibit 4e- ORR performance comparable to that of Pt/C, while those on low-curvature CNTs achieve up to 99.5% 2e- ORR selectivity. Proof-of-concept solid-electrolyte electrolyzer equipped with Cu SACs demonstrates exceptional performance for H2O2 electrosynthesis, achieving H2O2 Faradaic efficiencies of 96.4% and 92.5% at 200 and 300 mA cm-2, respectively, and sustaining >90% efficiency for over 100 h at a total current of 3 A. This work establishes curvature engineering as an ORR descriptor for precisely regulating SACs and designing advanced electrocatalysts.
单原子催化剂（SACs）是一类很有前途的电化学氧还原反应（ORR）催化剂，它既可以通过四电子（4e-）途径进行能量转换，也可以通过两电子（2e-）途径产生H2O2。然而，由于缺乏对SACs协调结构进行微调的策略，ORR通路的精确控制和优化仍然具有挑战性。在此，我们开发了一种曲率工程策略，首次实现了在基于cu的sac上从2e到4e的ORR路径的连续转向。通过理论计算和原位光谱分析，揭示了变曲率碳纳米管诱导的活性位点拉伸应变和界面水重构共同影响ORR活性和选择性的基本机制。高曲率碳纳米管上的Cu单原子位点表现出与Pt/C相当的4e- ORR性能，而低曲率碳纳米管上的Cu单原子位点可达到99.5%的2e- ORR选择性。配备Cu SACs的概念验证型固体电解质电解槽在H2O2电合成方面表现出色，在200和300 mA cm-2下，H2O2的法拉第效率分别为96.4%和92.5%，在总电流为3a的情况下，效率保持在90%以上100小时。这项工作建立了曲率工程作为精确调节sac和设计先进电催化剂的ORR描述符。
{"title":"Curvature-Engineered Steering of Oxygen Electroreduction Pathways on Single-Atom Catalysts.","authors":"Hongyin Xia,Hounan Sun,Dongyue Yang,Jiwu Zhao,Ge Gao,Lie Wu,Liang Huang,Xiue Jiang","doi":"10.1002/anie.3924995","DOIUrl":"https://doi.org/10.1002/anie.3924995","url":null,"abstract":"Single-atom catalysts (SACs) are a promising class of electrochemical oxygen reduction reaction (ORR) catalysts, enabling either a four-electron (4e-) pathway for energy conversion or a two-electron (2e-) pathway for H2O2 production. However, the precise control and optimization of the ORR pathway remain challenging due to the lack of strategies for fine-tuning the SACs coordination structures. Herein, we developed a curvature engineering strategy that enables, for the first time, continuous steering of the ORR pathway from 2e- to 4e- over Cu-based SACs. Through theoretical calculations and in-situ spectroscopy, we revealed the essential mechanism by which active-site tensile strain and interfacial water restructuring, induced by carbon nanotubes with varying curvature, jointly govern ORR activity and selectivity. The Cu single-atom sites on high-curvature CNTs exhibit 4e- ORR performance comparable to that of Pt/C, while those on low-curvature CNTs achieve up to 99.5% 2e- ORR selectivity. Proof-of-concept solid-electrolyte electrolyzer equipped with Cu SACs demonstrates exceptional performance for H2O2 electrosynthesis, achieving H2O2 Faradaic efficiencies of 96.4% and 92.5% at 200 and 300 mA cm-2, respectively, and sustaining >90% efficiency for over 100 h at a total current of 3 A. This work establishes curvature engineering as an ORR descriptor for precisely regulating SACs and designing advanced electrocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"213 1","pages":"e3924995"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471504","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}
4-Amino-2,4-pentadienoate-containing cyclolipodepsipeptides (APD-CLDs) represent a structurally distinctive family of natural products known for their selective activity against hypoxic cancer cells. To explore the structural diversity of APD-CLDs, we have identified and prioritized cryptic APD-CLD biosynthetic gene clusters (BGCs) for compound discovery. Using a combination of genetic and chemical methods, we successfully activated three dormant BGCs, leading to the discovery of 12 new APD-CLDs. These newly discovered metabolites significantly expanded the diversity of the APD-CLD family, with chloromalamides and arabimalamides representing the first halogenated and glycosylated members, respectively. Unexpectedly, chloromalamides and arabimalamides exhibited potent antiplasmodial activity, with IC50 values in the 25-161 nM range against drug-sensitive and multidrug-resistant Plasmodium falciparum strains. Phenotypic studies revealed arabimalamide B halted parasite development during the asexual blood stage life cycle, resulting in enlarged digestive vacuoles, dispersed hemozoin, and ultimately reduced reinvasion efficiency. These phenotypes are reminiscent of the effect of chloroquine and other 4-aminoquinoline drugs, suggesting that arabimalamides may disrupt the parasite's heme detoxification mechanism. Biosynthetic studies identified key scaffold-forming and modifying enzymes, including a rare membrane glycosyltransferase in arabimalamide biosynthesis. Together, these findings unveil APD-CLDs as new antimalarial lead scaffolds and set the stage for structural diversification and optimization.
{"title":"Genome-Guided Discovery of Antimalarial 4-Amino-2,4-Pentadienoate-Containing Cyclolipodepsipeptides.","authors":"Hartono Candra,Xue-Jiao Wang,Ka Diam Go,Li Feng,Miaomiao Cai,Guang-Lei Ma,Clarissa Widyantoro,Lik Tong Tan,Zbynek Bozdech,Zhe Wang,Zhao-Xun Liang","doi":"10.1002/anie.202523372","DOIUrl":"https://doi.org/10.1002/anie.202523372","url":null,"abstract":"4-Amino-2,4-pentadienoate-containing cyclolipodepsipeptides (APD-CLDs) represent a structurally distinctive family of natural products known for their selective activity against hypoxic cancer cells. To explore the structural diversity of APD-CLDs, we have identified and prioritized cryptic APD-CLD biosynthetic gene clusters (BGCs) for compound discovery. Using a combination of genetic and chemical methods, we successfully activated three dormant BGCs, leading to the discovery of 12 new APD-CLDs. These newly discovered metabolites significantly expanded the diversity of the APD-CLD family, with chloromalamides and arabimalamides representing the first halogenated and glycosylated members, respectively. Unexpectedly, chloromalamides and arabimalamides exhibited potent antiplasmodial activity, with IC50 values in the 25-161 nM range against drug-sensitive and multidrug-resistant Plasmodium falciparum strains. Phenotypic studies revealed arabimalamide B halted parasite development during the asexual blood stage life cycle, resulting in enlarged digestive vacuoles, dispersed hemozoin, and ultimately reduced reinvasion efficiency. These phenotypes are reminiscent of the effect of chloroquine and other 4-aminoquinoline drugs, suggesting that arabimalamides may disrupt the parasite's heme detoxification mechanism. Biosynthetic studies identified key scaffold-forming and modifying enzymes, including a rare membrane glycosyltransferase in arabimalamide biosynthesis. Together, these findings unveil APD-CLDs as new antimalarial lead scaffolds and set the stage for structural diversification and optimization.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":"e23372"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471509","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}
Guoliang Wei,Guangyuan He,Jinying Yu,Kuizhi Chen,Xuebing Li,Yu Gu,Donghai Mei,Hui Shi
Modern catalytic approaches to manipulating reactivities predominantly rely on (post-)synthetic methods that engineer active sites and their local environments from a materials perspective, while the dynamic creation and disruption of reactive and spectator species through co-adsorbate interactions is much less explored and understood. Herein, C3─C6 aliphatic alkanones have been identified as potent promotors for Brønsted acid-catalyzed alkanol dehydration within the subnanometric zeolite pores, with the MFI topology being the most efficacious (up to two orders of magnitude rate enhancement and > 99.8% olefin) and featuring a remarkable stability (> 140 h on stream) at both kinetically limited and practically relevant conversions. Rigorous kinetic descriptions are combined with density functional theory methods to assess the structures, stabilities and reactivities of all plausible intermediates derived from the reactant and cofeed during 2-propanol (IPA) dehydration in MFI pores. Stoichiometric clustering of alkanones with IPA-derived monomers and dimers, driven by strong H-bonds and stabilized by pore confinement, induces the formation of protonated bi- and termolecular species with distinct reactivities for intra- and intermolecular dehydration, which depends on the alkanone identity. These mechanistic underpinnings reward us with an ability to predict reactivity and selectivity trends and rationally design optimal solvent systems or cofeeding schemes for alkanol dehydration.
{"title":"Stabilization of Alkanol-Alkanone Heteroclusters in Medium-Pore Zeolites Drives Orders-of-Magnitude Rate Enhancements in Proton-Catalyzed Dehydration Reactions.","authors":"Guoliang Wei,Guangyuan He,Jinying Yu,Kuizhi Chen,Xuebing Li,Yu Gu,Donghai Mei,Hui Shi","doi":"10.1002/anie.202519476","DOIUrl":"https://doi.org/10.1002/anie.202519476","url":null,"abstract":"Modern catalytic approaches to manipulating reactivities predominantly rely on (post-)synthetic methods that engineer active sites and their local environments from a materials perspective, while the dynamic creation and disruption of reactive and spectator species through co-adsorbate interactions is much less explored and understood. Herein, C3─C6 aliphatic alkanones have been identified as potent promotors for Brønsted acid-catalyzed alkanol dehydration within the subnanometric zeolite pores, with the MFI topology being the most efficacious (up to two orders of magnitude rate enhancement and > 99.8% olefin) and featuring a remarkable stability (> 140 h on stream) at both kinetically limited and practically relevant conversions. Rigorous kinetic descriptions are combined with density functional theory methods to assess the structures, stabilities and reactivities of all plausible intermediates derived from the reactant and cofeed during 2-propanol (IPA) dehydration in MFI pores. Stoichiometric clustering of alkanones with IPA-derived monomers and dimers, driven by strong H-bonds and stabilized by pore confinement, induces the formation of protonated bi- and termolecular species with distinct reactivities for intra- and intermolecular dehydration, which depends on the alkanone identity. These mechanistic underpinnings reward us with an ability to predict reactivity and selectivity trends and rationally design optimal solvent systems or cofeeding schemes for alkanol dehydration.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"8 1","pages":"e19476"},"PeriodicalIF":16.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471579","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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