Angewandte Chemie International Edition最新文献

{"title":"Homoleptic and Heteroleptic Polyoxotungstate–Organic Cages for Efficient Photocatalytic Hydrogen Evolution","authors":"Wenjun Ruan, Yeqin Feng, Yuan Gao, Kentaro Yonesato, Linjie Lan, Ziteng Guo, Panchao Yin, Ming Wang, Kosuke Suzuki, Hongjin Lv, Xikui Fang","doi":"10.1002/anie.202508797","DOIUrl":"https://doi.org/10.1002/anie.202508797","url":null,"abstract":"Metal–organic cages with polyoxometalate (POM) clusters as nodes are an emerging frontier of coordination‐driven self‐assembly, but they have been limited to homoleptic cages, which are composed of only one type of organic ligands. We show here that, in the construction of POM–organic cages with Keggin‐type {SiW<jats:sub>9</jats:sub>Ni<jats:sub>4</jats:sub>} cluster nodes, introducing a secondary ligand may change the self‐assembly processes in two distinct ways: by coordination or as supramolecular templates. The use of a tetracarboxylate panel L<jats:sup>C</jats:sup>, in complementary to a bent dicarboxylate linker (L<jats:sup>A</jats:sup> or L<jats:sup>B</jats:sup>), allows the integrative self‐sorting to give heteroleptic coordination cages POM<jats:sub>8</jats:sub>L<jats:sup>A/B</jats:sup><jats:sub>4</jats:sub>L<jats:sup>C</jats:sup><jats:sub>4</jats:sub> (3 or 4) that are otherwise not accessible through either ligand alone. The aromatic L<jats:sup>C</jats:sup> can also alter the outcome of the self‐assembly process by acting as a non‐coordinating template, transforming a coordinatively frustrated, homoleptic cage POM<jats:sub>8</jats:sub>L<jats:sup>D</jats:sup><jats:sub>6</jats:sub> (5) to POM<jats:sub>8</jats:sub>L<jats:sup>D</jats:sup><jats:sub>5</jats:sub> (6). These octa‐Keggin cages were all shown to be efficient molecular catalysts for visible‐light‐driven hydrogen production; for 4, in particular, an apparent turnover number of 4910 was achieved in 5 h under minimally optimized conditions. Mechanistic studies confirmed the existence of both reductive and oxidative quenching processes, with the former being dominant.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"15 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747369","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}

{"title":"Rhenium‐Doping to Promote Structural Evolution of Metallic Iridium to Oxides on Platinum Nanowire Bundles for Acidic Oxygen Evolution","authors":"Jiashun Liang, Jiamao Zheng, Dominik Wierzbicki, Shuo Liu, Guofeng Wang, Chaochao Dun, Gang Wu","doi":"10.1002/anie.202512317","DOIUrl":"https://doi.org/10.1002/anie.202512317","url":null,"abstract":"The current high Ir loading (∼2 mg<jats:sub>Ir</jats:sub> cm<jats:sup>−2</jats:sup>) in proton exchange membrane water electrolyzers (PEMWEs) severely hinders their applications for green hydrogen production. Reducing Ir loading while maintaining high performance and durability for the oxygen evolution reaction (OER) anode is critical for the Gigawatt‐scale deployment of PEMWEs. Herein, we report an ultra‐low Ir anode, consisting of Re‐doped Ir nanoparticles anchored on Pt nanowire networks, enabling rational catalyst design at the atomic scale and electrode structure engineering at the nanoscale. The unique doping of Re into Ir was explored as an effective strategy to promote the desirable conversion from metallic Ir to amorphous IrO<jats:italic><jats:sub>x</jats:sub></jats:italic> during the acidic OER, thus benefiting intrinsic activity and stability enhancements. Notably, the Pt nanowire bundles serve as a support to enhance electrical conductivity and provide a high‐surface‐area, robust, and interconnected electrode structure, significantly increasing Ir utilization and electron/mass transport at the device level. Three‐electrode electrochemical tests revealed that the developed Ir catalyst exhibits a 100% increase in electrochemical surface area (ECSA) and a 160% enhancement in intrinsic OER activity compared to commercial Ir black catalysts. The optimized Ir anode achieved a current density of 3.0 A cm<jats:sup>−2</jats:sup> at 1.69 V (0.2 mg<jats:sub>Ir</jats:sub> cm<jats:sup>−2</jats:sup>) and 1.73 V (0.1 mg<jats:sub>Ir</jats:sub> cm<jats:sup>−2</jats:sup>) in membrane electrode assemblies (MEAs), exceeding the US DOE 2026 targets (0.5 mg<jats:sub>PGM</jats:sub> cm<jats:sup>−2</jats:sup> at 1.8 V for 3.0 A cm<jats:sup>−2</jats:sup>). The corresponding MEAs also demonstrated compelling long‐term durability, as evidenced by a low voltage degradation rate of 26 µV h<jats:sup>−1</jats:sup> over 1100 hours of operation and 0.8 µV cycle<jats:sup>−1</jats:sup> during an accelerated stress test.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"15 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747408","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}

{"title":"The Natural Redox Cofactor Pyrroloquinoline Quinone (PQQ) Enables Photocatalytic Radical Cyclizations","authors":"Srishti B. Bahukhandi, Andreas S. Klein, Ghulam Mustafa, Maria Weyh, Alexandra Walter, Erling Thyrhaug, Jürgen Hauer, Golo Storch, Cathleen Zeymer","doi":"10.1002/anie.202505431","DOIUrl":"https://doi.org/10.1002/anie.202505431","url":null,"abstract":"Photoenzymatic catalysis facilitates stereoselective new‐to‐nature chemistry under mild conditions. In addition to the rational design of artificial photoenzymes, naturally occurring redox enzymes can be repurposed to promote photoredox catalysis in the chiral protein environment. Here, we show that enzymes utilizing the pyrroloquinoline quinone (PQQ) cofactor expand the toolbox of photobiocatalysis. PQQ absorbs visible light and is capable of single‐electron transfer. It thus exhibits mechanistic similarities to flavin cofactors, which are widely used for photoenzymatic approaches. First, we established the trimethyl ester PQQMe<jats:sub>3</jats:sub> as a stand‐alone photoredox catalyst in pure organic solvent. Upon excitation, PQQMe<jats:sub>3</jats:sub> enables the redox‐neutral radical cyclization of an <jats:italic>N</jats:italic>‐(bromoalkyl)‐substituted indole. We then tested a panel of PQQ‐dependent sugar and alcohol dehydrogenases for photoenzymatic catalysis in aqueous buffer, focusing on a redox‐neutral radical reaction to form oxindoles. Under optimized reaction conditions, we obtained a 69% yield and an 82:18 enantiomeric ratio. Our work thus demonstrates that PQQ enzymes are capable of stereoselective photoredox catalysis. Future enzyme engineering efforts based on computational modeling and directed evolution will fully unlock their synthetic potential.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"27 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747120","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}

{"title":"Achieving Charge‐Transfer‐Featured Organic Room‐Temperature Phosphorescence with Combined High Efficiency and Long Lifetime via V‐Shaped D–A Dyads","authors":"Kuan Chen, Binhao Li, Chuanhao Liu, Yanju Luo, Kaixin Yu, Mengjiao Jia, Yan Huang, Zhiyun Lu","doi":"10.1002/anie.202508776","DOIUrl":"https://doi.org/10.1002/anie.202508776","url":null,"abstract":"The realization of long‐lived charge‐transfer‐based organic room‐temperature phosphorescence (<jats:sup>3</jats:sup>CT‐RTP, <jats:italic>τ</jats:italic><jats:sub>Ph </jats:sub>= 210 ms) via the construction of U‐shaped donor–acceptor (D–A) dyads is impeded by suboptimal phosphorescence efficiency ( = 6%). Herein, we reveal that modifying the skeleton of D–A dyads from U‐shaped to V‐shaped configurations yields <jats:sup>3</jats:sup>CT‐RTP with both long <jats:italic>τ</jats:italic><jats:sub>Ph</jats:sub> (150–220 ms) and high (13%–25%). This improvement stems from preserving a substantial degree of forbiddenness in the radiative transition process of the compound while simultaneously increasing its D–A dihedral angle, which can promote more efficient spin‐orbit coupling and thus more rapid intersystem crossing. Additionally, augmenting the framework rigidity of a V‐shaped D–A dyad can potentially reduce the non‐radiative transition rate constant of triplet excitons (<jats:italic>k</jats:italic><jats:sub>nr,T</jats:sub>), thereby facilitating the attainment of long <jats:italic>τ</jats:italic><jats:sub>Ph</jats:sub> and high .","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"68 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747371","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}

{"title":"Harnessing Pyridinic N Vacancy Defect in Microporous Structures to Induce the Pre-Adsorption of Oxygen and Boost Oxygen Reduction Reaction Kinetics.","authors":"Binbin Jia,Xuan Xie,Jie Lin,Huiqing Wang,Pengfei Hu,Fengyi Wang,Xiaoyu Fan,Jinlong Zheng,Tianyi Ma,Liqun Ye","doi":"10.1002/anie.202508674","DOIUrl":"https://doi.org/10.1002/anie.202508674","url":null,"abstract":"Defect structures within the carbon matrix play a crucial role in enhancing the oxygen reduction reaction (ORR) activity of Fe single atom and nitrogen-doped catalysts (Fe-N-C SACs). However, overlooking the O2 pre-adsorption process induced by defective structures hampers the precise identification of active sites and the investigation of the reaction mechanism in Fe-N-C SACs. Hence, we report a Fe SAC with abundant pyridinic N vacancy defects in microporous structures (Fe-Nv-C SAC) and propose a synergistic effect between pyridinic N vacancy defects and O2 molecules that promotes the kinetics of ORR. The developed Fe-Nv-C SAC demonstrates exceptional ORR performance, exhibiting superior mass activity and turnover frequency compared to conventional Fe-N-C SACs. The in situ Fourier transform infrared spectroscopy (FTIR) and theoretical calculations indicate that pyridinic N vacancy defects in microporous structures facilitate pre-adsorption of O2 molecules results in the d-band centers of central Fe atoms shifting away from the fermi level. This shift weakens the adsorption strength of *OH species, thereby facilitating the kinetic process of ORR. This work addresses a critical gap in the field of electrocatalysis by providing the experimental validation of pre-adsorption of O2 molecules on Fe single-atom catalysts, a phenomenon previously only speculated through theoretical calculations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"715 1","pages":"e202508674"},"PeriodicalIF":16.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737289","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}

{"title":"Unraveling the Mode of Action of a Neuron-Specific Fluorescent Probe, NeuO: Intracellular Phosphorylation Through PAK6 Kinase.","authors":"Beomsue Kim,Dongwan Ko,Sang-Bum Kim,Songhui Kim,Minji Kim,Na-Kyeong Hong,Sun You Park,Wonju Kim,Byoung-Cheol Lee,Yunbeom Lee,Taebo Sim,Young-Tae Chang","doi":"10.1002/anie.202511160","DOIUrl":"https://doi.org/10.1002/anie.202511160","url":null,"abstract":"NeuO is an intriguing molecular probe capable of selectively labeling live neurons within a heterogeneous population of brain cells. The precise mechanism responsible for this neuronal labeling has remained a longstanding enigma. We investigated four potential mechanisms underlying NeuO's fluorescence, including its interaction with neuronal proteins, transportation into neurons, export from glial cells, and structural alterations within neurons. Our study found that NeuO undergoes structural changes via phosphorylation by the PAK6 kinase, resulting in high fluorescence in neurons, likely due to fluorogenic activation and intracellular retention within neurons. This discovery improves our understanding of the molecular mechanism of NeuO in neurons and facilitates the development of new chemical compounds that can be selectively modified by kinases in living cells.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"216 1","pages":"e202511160"},"PeriodicalIF":16.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737294","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}

{"title":"Electrochemical Polymerization of 1,2-Dithiolane Derivatives at Room Temperature.","authors":"Jun Fang,Chenhao Ji,Yanshan Meng,Pengyuan Ye,Houyu Zhang,Wen Li","doi":"10.1002/anie.202506724","DOIUrl":"https://doi.org/10.1002/anie.202506724","url":null,"abstract":"Recently, 1,2-dithiolanes derived polydisulfides have prompted growing research interests. An innovative polymerization method with convenient operation under mild conditions is needed for improving monomer conversion, polymerization degree, and bulk performance. Here, we report an electrochemically initiated ring-opening polymerization (ROP) of thioctic acid (TA) monomers and its derivatives at room temperature, with high monomer conversion and polymerization degree. The resulting polymer exhibits potential as a transparent and vibration-damping coating. Electrochemical oxidation was the key step for initiating the rapidly polymerization and could completely circumvent the use of chemical initiators or harsh conditions. Cyclic voltammetry experiments identified the oxidation of TA at anode accompanying with an absorption-controlled one-electron transfer process. Together with density functional theory calculations, we proposed a cationic radical-initiated polymerization process. This unique electrochemical polymerization strategy was simple, rapid, efficient, and applicable for diverse TA-derived monomers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":"e202506724"},"PeriodicalIF":16.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737279","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}

{"title":"Improved Ionic Thermoelectric Performance of Adhesive and Self-Healing Cationic High-Entropy Gel Thermocell.","authors":"Lijuan Yang,Jiawei Chen,Wenjun He,Guimei Li,Chunxia Xie,Wei Wang,Dongxue Han,Cheng-Gong Han,Li Niu","doi":"10.1002/anie.202511293","DOIUrl":"https://doi.org/10.1002/anie.202511293","url":null,"abstract":"Gel thermocell can directly convert heat into electricity by ions as energy carriers, capable of low-grade heat harvesting. However, ionic thermoelectric performance, including ionic thermopower, output power density, and energy density, needs to be significantly improved to meet practical applications. To date, it still lacks an effective strategy to focus on gels to achieve the overall high performance. Herein, an adhesive and self-healing cationic high-entropy gel (CHEG) G-FeCN4-/3--K+-Na+-Li+-Gdm+-Cs+ in a multi-ion cooperative chemical environment has been designed by the interaction between multications and anions, improving the entropy change of redox reaction, exchange current density, and ionic conductivity, thereby achieving an overall high ionic thermoelectric performance. The CHEG thermocell using the synergy of thermogalvanic and thermodiffusion effects showed a total ionic thermopower of 41 mV K-1 with 2.3 mV K-1 for the former, and delivered a maximum output power density of 14.3 mW m-2 K-2 and an energy density of 4.5 J m-2 K-2. In addition, an ultrahigh maximum output power density of 4.13 mW m-2 K-2 was obtained in the CHEG device that was assembled by connecting four thermocells in series, which could realize electrocatalytic degradation of rhodamine B. This work demonstrates a feasible way to design high-performance ionic thermoelectric gels and provides a new application in water pollution treatments.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":"e202511293"},"PeriodicalIF":16.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737390","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}

{"title":"Enantioselective Synthesis of ε-Lactams via Rh(I)-Catalyzed C─C Bond Activation.","authors":"Shiyuan Sui,Hao Wu,Yuanyuan Guo,Gongming Chen,Junbiao Chang,Dachang Bai","doi":"10.1002/anie.202509640","DOIUrl":"https://doi.org/10.1002/anie.202509640","url":null,"abstract":"ε-Lactams are important structural motifs in medicinal chemistry, but a fully enantioselective synthesis without byproduct formation represents a challenge that has attracted significant research interest. Herein, we report an atom- and step-economic synthesis of chiral ε-lactams via Rh(I)-catalyzed enantioselective C─C bond activation of aminocyclopropanes. The catalytic C─C bond activation enables a directed generation of chiral rhodacyclobutanes that circumvents β-hydride decomposition. Subsequent enantioselective cycloaddition of the alkene unit and then fragmentation generates chiral ε-lactams. A range of enantioenriched ε-lactams have been obtained with excellent regio- and enantioselectivities, which can undergo several stereospecific transformations. Theoretical calculations are performed to reveal the reaction mechanism and the origin of enantioselectivity control.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"25 1","pages":"e202509640"},"PeriodicalIF":16.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737293","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}

{"title":"Controllable Preparation of Hierarchically Charge-Separated Interface to Effectively Promote the Desolvation and Kinetics of Lithium Ions.","authors":"Qian Chang,Changshui Huang,Zhihui Zhang,Feng He,Xinlong Fu,Yuliang Li","doi":"10.1002/anie.202511502","DOIUrl":"https://doi.org/10.1002/anie.202511502","url":null,"abstract":"Solid-electrolyte interphase (SEI) is one of the key factors to determine the performance of batteries. Electrolyte additives enhance SEI performance for fast charging and long cycle life but introduce system-level uncertainties, including cathode degradation, safety hazards, and cost escalation. In this study, we prepare a composite electrode (BPQDs/GDYNTs) featuring a charge-separated interface structure to improve the SEI directly without auxiliary additives. The BPQDs/GDYNTs are comprised of graphdiyne tubes (GDYNTs) with black phosphorus quantum dots (BPQDs) distributed on the surface. The charge transfer between BPQDs and GDYNTs creates a charge-separated interface, thereby enabling the efficient adsorption of lithium (Li) ions by the electron-rich state of GDYNTs while promoting the adsorption of hexafluorophosphate anion (PF6 -) on the electron-deficient state of BPQDs. That facilitates the in situ formation of a thin and inorganic-rich SEI containing fluorine- and phosphorus-based species, which significantly enhances both the desolvation of Li-ions and their kinetics. When utilized as the anode of Li-ion batteries, the BPQDs/GDYNTs electrode exhibits fast-charging capability and remarkable longevity, demonstrating ultra-stable cycling performance over 50 000 cycles at a high current density of 10 A g-1 with negligible capacity decay.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"718 1","pages":"e202511502"},"PeriodicalIF":16.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737252","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}