Angewandte Chemie International Edition最新文献

Deconstructive Functionalization of Cyclic Ketones via Electrochemical Interrupted Dowd-Beckwith Reaction. 电化学中断Dowd-Beckwith反应中环酮的解构功能化。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202505155

Tushar Singha,Jyothirlatha V N Kasu,Durga Prasad Hari

{"title":"Deconstructive Functionalization of Cyclic Ketones via Electrochemical Interrupted Dowd-Beckwith Reaction.","authors":"Tushar Singha,Jyothirlatha V N Kasu,Durga Prasad Hari","doi":"10.1002/anie.202505155","DOIUrl":"https://doi.org/10.1002/anie.202505155","url":null,"abstract":"Deconstructive functionalization of cyclic molecules has recently emerged as a prominent strategy to access unique architectures that are challenging to prepare through traditional methods. While significant progress has been made in the deconstructive functionalization of cyclic alcohols and amines, the strategies for deconstructing cyclic ketones remain largely unexplored. The Dowd-Beckwith reaction, a ring-expansion of cyclic ketones, is a powerful method for synthesizing medium- and large-ring compounds. Herein, we developed the first interrupted Dowd-Beckwith (IDB) reaction for highly regioselective deconstructive functionalization of cyclic ketones using electricity as the sole oxidant. This protocol is widely applicable for the deconstruction of small, medium-sized, and macrocyclic ketones bearing a diverse range of functional groups. Remarkably, various naturally occurring complex cyclic ketones were successfully deconstructed into acyclic molecules, which are difficult to access by known strategies. The method was applied to the asymmetric synthesis of planococcol, citrilol acetate, maconelliol, and its derivatives. Furthermore, the functional groups incorporated during the transformation provided versatile handles for subsequent synthetic modifications. Mechanistic experiments and computational studies support an oxidative radical-polar crossover followed by deconstructive functionalization.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"41 1","pages":"e202505155"},"PeriodicalIF":16.6,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087612","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}

引用次数: 0

π-Bridge Linked Ionic Covalent Organic Framework with Fast Reaction Kinetics for High-Rate-Capacity Lithium Ion Batteries. 高倍率容量锂离子电池的快速反应动力学π-桥联离子共价有机骨架。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202505207

Ju Duan,Feng Chen,Huajie Yu,Shenbo Zhu,Likuan Teng,Kexiang Wang,Tiejun Chen,Wei Lyu,Huawei Hu,Yaozu Liao

{"title":"π-Bridge Linked Ionic Covalent Organic Framework with Fast Reaction Kinetics for High-Rate-Capacity Lithium Ion Batteries.","authors":"Ju Duan,Feng Chen,Huajie Yu,Shenbo Zhu,Likuan Teng,Kexiang Wang,Tiejun Chen,Wei Lyu,Huawei Hu,Yaozu Liao","doi":"10.1002/anie.202505207","DOIUrl":"https://doi.org/10.1002/anie.202505207","url":null,"abstract":"Covalent organic frameworks (COFs) have emerged as promising cathode materials for high-performance lithium-ion batteries (LIBs) due to their well-defined topologies and tunable pore architectures. However, their practical application is often limited by intrinsically sluggish charge transfer and inferior reaction kinetics. To address these challenges, we develop an ionic quinoline-linked COF (iQCOF) cathode via a one-pot Povarov reaction with triazole ionic liquid. The iQCOF architecture achieves a synergistic enhancement by integrating π-bridge-induced charge delocalization to facilitate charge transport, the specific adsorption effect to gain fast ionic atmosphere dissociation rate, and polar triazine units to enable uniform ion flux for stable interfaces. As a result, iQCOF delivers a high specific capacity of 407 mAh g-1 with 701 Wh kg-1, and exceptional rate capability (121 mAh g-1 at 10 A g-1) with 0.0027% per cycle over 10000 cycles, further highlighting its potential as a high-performance organic cathode. This work provides a convenient strategy for advanced COF-based cathodes with fast reaction kinetics for high-rate performance, paving the way for next-generation energy storage technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":"e202505207"},"PeriodicalIF":16.6,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087615","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}

引用次数: 0

Breaking Symmetry of Active Sites in Metal-Organic Frameworks for Efficient Photocatalytic Valorization of Polyester Plastics. 金属-有机骨架中活性位点的破缺对称性对聚酯塑料高效光催化增值的影响。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202505786

Jibo Qin,Jianchi Zhou,Jin Ma,Shuang Li,Awu Zhou,Linhua Xie,Yibo Dou,Yuanjian Zhang

{"title":"Breaking Symmetry of Active Sites in Metal-Organic Frameworks for Efficient Photocatalytic Valorization of Polyester Plastics.","authors":"Jibo Qin,Jianchi Zhou,Jin Ma,Shuang Li,Awu Zhou,Linhua Xie,Yibo Dou,Yuanjian Zhang","doi":"10.1002/anie.202505786","DOIUrl":"https://doi.org/10.1002/anie.202505786","url":null,"abstract":"Chemical upcycling of waste plastics offers a promising way toward achieving a circular economy and alleviating environmental pollution but remains a huge challenge. Inspired by hydrolase enzymes and aiming to overcome their intrinsic limitations, we put forward a design principle for an innovative nanozyme featuring asymmetric metal sites. This nanozyme functions as photocatalyst enabling sustainable valorization of polyester plastics. As a proof of concept, an asymmetric ligand substitution strategy is developed to construct metal-organic frameworks (MOFs) that defective MIL-101(Fe) (D-MIL-101) with asymmetric Fe3-δ/Fe3+ (0< δ <1) sites. The differential electronic configurations inherent to adjacent Fe3-δ/Fe3+ sites endow a high photocatalytic activity for the valorization of polyester plastic. Accordingly, the ester bonds of polyesters can be preferentially cleaved, contributing to the low energy barrier of upcycling plastics. As a result, the D-MIL-101 achieves a high monomer yield with terephthalic acid of ~93.9% and ethylene glycol of ~87.1% for photocatalytic valorization of poly (ethylene terephthalate) (PET), beyond the efficiency of natural enzyme and state-of-the-art photocatalysts. In addition, such a D-MIL-101 is demonstrated to be feasible for the valorization of various real-world polyester plastic wastes in a flow photocatalysis system.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"128 1","pages":"e202505786"},"PeriodicalIF":16.6,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087617","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}

引用次数: 0

Photocatalytic Boron Insertion into Thiaarenes via Boryl Radicals. 光催化硼通过硼基自由基插入硫代芳烃。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202508379

Yubing Pang,Ermeng Wang,Juntao Ye

引用次数: 0

Self-activated heterogeneous Fenton process for accelerated degradation of aromatic pollutants over copper oxide catalysts. 自激活非均相Fenton工艺在铜氧化物催化剂上加速降解芳香族污染物。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202508754

Mingjie Huang,Hong-Zhi Liu,Qing-Qing Huang,Tao Zhou,Xiaohui Wu,Wen-Wei Li,Han-Qing Yu

{"title":"Self-activated heterogeneous Fenton process for accelerated degradation of aromatic pollutants over copper oxide catalysts.","authors":"Mingjie Huang,Hong-Zhi Liu,Qing-Qing Huang,Tao Zhou,Xiaohui Wu,Wen-Wei Li,Han-Qing Yu","doi":"10.1002/anie.202508754","DOIUrl":"https://doi.org/10.1002/anie.202508754","url":null,"abstract":"Metal-based heterogeneous catalysts have been commonly adopted for Fenton-like oxidation of organic pollutants, but generally suffer from inadequate activity in practical water treatment applications due to surface passivation by accumulated pollutants and sluggish redox cycling of active metal. Here, we observed an unusual phenomenon of pollutant-induced activity enhancement for copper oxide (CuO) in H2O2 activation and phenol degradation, which is in sharp contrast to considerable activity decay of Fe2O3 catalyst. The CuO was found to stabilize and activate phenol via ligand-to-metal charge transfer route, generating surface-bound phenoxyl radicals for further mediating the H2O2 activation and enabling a rapid regeneration of low-valent Cu. Based on this principle, a Fe-Cu bimetal oxides catalyst was elaborated to further augment the catalyst-phenol interaction towards self-activated Fenton oxidation. The optimal catalyst achieved 14-time faster pollutant degradation rate and 2 order-of-magnitude higher H2O2 utilization efficiency than the Fe2O3 control. It also demonstrated good adaptability to degradation of diverse substituted benzenes and maintained stable performance for treatment of real lake water during 100-day continuous operation. Our work implies that the catalyst-pollutant interaction may be rationally leveraged and modulated to create highly efficient and stable heterogeneous catalytic systems, thus further unlocking their potential for sustainable water purification application.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"70 1","pages":"e202508754"},"PeriodicalIF":16.6,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087571","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}

引用次数: 0

Proton Driving Mechanism Revealed in Sulfur-Doped Single-Atom FeN2O2 Carbon Dots for Superior Peroxidase Activity. 硫掺杂单原子FeN2O2碳点的质子驱动机制研究

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202504575

Jia Yang,Maolin Wang,Siyu Gao,Meng Zhou,Xiaogang Du,Li Zhang,Ying Wang,Xianxiang Dai,Yuanyuan Jiang,Yunkun Li,Yunsong Zhang,Li Lin

{"title":"Proton Driving Mechanism Revealed in Sulfur-Doped Single-Atom FeN2O2 Carbon Dots for Superior Peroxidase Activity.","authors":"Jia Yang,Maolin Wang,Siyu Gao,Meng Zhou,Xiaogang Du,Li Zhang,Ying Wang,Xianxiang Dai,Yuanyuan Jiang,Yunkun Li,Yunsong Zhang,Li Lin","doi":"10.1002/anie.202504575","DOIUrl":"https://doi.org/10.1002/anie.202504575","url":null,"abstract":"Heteroatom-doped single-atom nanozymes (SAEs) hold great promise as enzyme mimics, yet their catalytic mechanisms remain unclear. This study reveals that the proton driving mechanism induced by sulfur doping in single-atom FeN2O2 carbon dots (S-FeCDs) significantly enhances peroxidase (POD)-like activity. Synthesized via low-temperature carbonization, S-FeCDs exhibit FeN2O2 coordination with sulfur in the second shell, as confirmed by XAFS and AC-STEM. The POD-specific activity of S-FeCDs reached 295 U/mg, which is 11.2-fold higher than that of sulfur-free FeCDs, with natural enzyme-like kinetics. In situ experiments, kinetic and mechanistic studies revealed that sulfur doping promotes H2O dissociation, enhances H+ adsorption, reduces the ΔG for H2O2-to-·OH conversion. DFT revealed a lowered energy barrier for the rate-determining step (2*OH → *O+*H2O) from 2.50 eV to 1.62 eV. In vivo, S-FeCDs demonstrated broad pH efficacy in MRSA-infected wound models, achieving near-complete healing within 7 days. The proton driving mechanism was further validated through nitro compound reduction, demonstrating accelerated N-H bond activation. This work highlights the critical role of sulfur-induced proton dynamics in enhancing SAEs performance, providing a rational strategy for designing multifunctional nanozymes in biomedical and catalytic applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"44 1","pages":"e202504575"},"PeriodicalIF":16.6,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087574","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}

引用次数: 0

Isoreticular Synthesis of Mesoporous Metal-Organic Polyhedra with Permanent Porosity to Gas and Water. 对气体和水具有永久孔隙的介孔金属-有机多面体的等孔合成。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202505682

Alba Cortés-Martínez,Pilar Fernández-Seriñán,Cornelia von Baeckmann,Caterina Caules,Laura Hernández-López,María Susana Gutiérrez Gómez,Yunhui Yang,Roberto Sánchez-Naya,José A Suárez Del Pino,Judith Juanhuix,Inhar Imaz,Arnau Carné-Sánchez,Daniel Maspoch

引用次数: 0

Thermally Gated Covalent Adaptivity in Liquid Crystal Elastomers for Stable Actuation. 液晶弹性体中用于稳定驱动的热门控共价自适应。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202506571

Yixuan Wang,Enjian He,Huan Liang,Yuting Wang,Zhijun Yang,Shuhan Zhang,Yen Wei,Yan Ji

{"title":"Thermally Gated Covalent Adaptivity in Liquid Crystal Elastomers for Stable Actuation.","authors":"Yixuan Wang,Enjian He,Huan Liang,Yuting Wang,Zhijun Yang,Shuhan Zhang,Yen Wei,Yan Ji","doi":"10.1002/anie.202506571","DOIUrl":"https://doi.org/10.1002/anie.202506571","url":null,"abstract":"Liquid crystal elastomers (LCEs), with reversible actuation of large and anisotropic deformation, have surged in smart materials such as soft robotics, sensors and artificial muscles. LCEs incorporating dynamic covalent bonds (DCBs) endowing network with rearranging ability through reversible bond reaction, facilitating the fabrication of soft actuators with tailored actuation modes and reprogrammability. However, unintended activation of DCBs during actuation, particularly under thermal perturbations, remains a critical challenge, as it damages actuation stability which arises catastrophic failure and potential security risks in practical applications. Present strategies in enhancing actuation stability either achieve only temporary stability or sacrificed reprogrammability or actuation performance. Here, we propose a strategy incorporating catalyst-free α-AC/A DCB of high temperature active-threshold to fabricate stable dynamic LCE actuators with thermally gated behavior. This design exhibits a \"thermal gate\" at 120 °C with inert bond exchange below this threshold, yet rapidly activated at 160 °C. The integrated permanent crosslinks further prevent unintended chain slippage, ensuring topological stability. The resulting dynamic LCE could be fabricated to actuators efficiently and exhibiting unprecedented durability at 120 °C (sustaining 10,000 actuation cycles). The switches between reprogrammability and actuation stability are long-standing reversible, meeting the demands of long-term service without compromising its reprogrammability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"131 1","pages":"e202506571"},"PeriodicalIF":16.6,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087616","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}

引用次数: 0

Structural Origin of Spin-Orbit Splitting of 1P Orbitals of Icosahedral Au13 Superatom Protected by Ligands. 配体保护二十面体Au13超原子1P轨道自旋轨道分裂的结构起源。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202508151

Shun Ito,Kiichirou Koyasu,Tatsuya Tsukuda

引用次数: 0

Flow Battery with Remarkably Stable Performance at High Current Density: Development of A Nonfluorinated Separator with Concurrent Rejection and Conductivity. 在高电流密度下具有显著稳定性能的液流电池：一种同时具有阻隔性和导电性的无氟隔膜的研制。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-05-19 DOI: 10.1002/anie.202505383

Wanqiao Liang,Ehsan Ghasemiestahbanati,Nathan T Eden,Durga Acharya,Cara M Doherty,Mainak Majumder,Matthew R Hill

{"title":"Flow Battery with Remarkably Stable Performance at High Current Density: Development of A Nonfluorinated Separator with Concurrent Rejection and Conductivity.","authors":"Wanqiao Liang,Ehsan Ghasemiestahbanati,Nathan T Eden,Durga Acharya,Cara M Doherty,Mainak Majumder,Matthew R Hill","doi":"10.1002/anie.202505383","DOIUrl":"https://doi.org/10.1002/anie.202505383","url":null,"abstract":"Redox flow batteries show promise for large-scale grid stabilisation. Of these, organic redox flow batteries (ORFBs) harbour the potential for sustainable and economic operation due to the materials deployed. Their long-term operation requires exquisite transport control of species across the cell, with movement of cations key for high current density, and anionic rejection needed for cycling stability. Nafion, although promising as a commercial separator, faces cost and sustainability limitations due to its fluorinated nature and per- and polyfluroralkyl substances (PFAS) generation. Here, we report the tailored combination of a hydrophilic mixed-matrix membrane, SPEEK-SX, with sulphonated polydichloroxylene (Sp-DCX) as the additive and sulphonated poly(ether ether ketone) (SPEEK) as the matrix. Compared to Nafion-212, the dense aromatic backbone of SPEEK efficiently rejected the crossover of electrolytes, with sulfonate groups housed within Sp-DCX micropores increasing Na+ mobility. SPEEK-SX2 exhibited 190 times higher Na+/ Fe(CN)6 4- selectivity and 6 times higher Na+/ 2,6-DHAQ2- selectivity compared to Nafion-212. This enabled stable operation for 600 cycles at a high current density of 160 mA cm-2 with only 0.00935% per cycle capacity decay. In contrast, the SPEEK membrane exhibited 0.07% per cycle decay, whereas Nafion-212 failed to run at this high current density.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":"e202505383"},"PeriodicalIF":16.6,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087664","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}

引用次数: 0