Angewandte Chemie International Edition最新文献_第6页

Supramolecular Gels as Active Tools for Reaction Engineering

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-28 DOI: 10.1002/anie.202502053

David K. Smith

{"title":"Supramolecular Gels as Active Tools for Reaction Engineering","authors":"David K. Smith","doi":"10.1002/anie.202502053","DOIUrl":"https://doi.org/10.1002/anie.202502053","url":null,"abstract":"Supramolecular gels assembled from low-molecular-weight gelators (LMWGs) are fascinating soft materials for use in synthesis, combining aspects of hetero- and homogeneous systems. The unique combination of environments within a gel offers the ability to control reactivity in new ways. For example, self-assembly into a gel network can modify the reactivity of catalytic sites on the LMWG. Controlling the assembly of multiple LMWGs can result in integrated gels with orthogonal activities that could not normally co-exist. Enzymes encapsulated within self-assembled gels can exhibit superactivity, extending their use into solvent media more appropriate for organic synthesis. Highly reactive species, such as ligand-free nanoparticles or moisture/air-sensitive organometallics can be protected within the unique environment of a supramolecular gel, facilitating their use in ambient conditions, potentially opening up the use of such species to non-specialist researchers. Beyond fundamental chemistry, performing reactions in gels leads to the emerging concept of gels as ‘nanoreactors’. Smart chemical engineering methods are enabling the fabrication of materials and devices for use in a variety of synthetic workflows, potentially transforming the way synthesis is done. In summary, this review provides an overview of key concepts and signposts the way towards future developments of gels as active tools for reaction engineering.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"4 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734365","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

A Ruthenium(II) Complex Inhibits BRD4 for Synergistic Seno- and Chemo-Immunotherapy in Cisplatin-Resistant Tumor Cells

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-28 DOI: 10.1002/anie.202505689

Jinrong Yang, Fa Wang, Shuqi Huang, Tao Feng, Kai Xiong, Yu Chen, Hui Chao

{"title":"A Ruthenium(II) Complex Inhibits BRD4 for Synergistic Seno- and Chemo-Immunotherapy in Cisplatin-Resistant Tumor Cells","authors":"Jinrong Yang, Fa Wang, Shuqi Huang, Tao Feng, Kai Xiong, Yu Chen, Hui Chao","doi":"10.1002/anie.202505689","DOIUrl":"https://doi.org/10.1002/anie.202505689","url":null,"abstract":"Drug resistance is a significant challenge for tumor therapy. Activating immunity is an effective method to combat drug-resistant tumors. Utilizing metallic chemotherapeutic agents to induce non-apoptotic programmed cell death is a practical approach to stimulate immunity. Besides, triggering tumor cell senescence, named senotherapy, is also an effective but often ignored method to induce immune responses. Despite some progress, reports on metallic immunotherapeutic stimuli are sparse and mainly delve into the level of organelle targeting, with vague drug–target mechanisms. Here, we report a Ru(II) complex (Ru2c) inhibits BRD4 with high affinity at a nanomolar constant. After encapsulated in to biotin-DNA cage, Ru2@biotin-DNA cage was demonstrated to kill drug-resistant cancer cells through a synergistic apoptosis-ferroptosis-senescence pathway, exhibiting 51-fold anticancer activity compared to the commercial inhibitor JQ-1. Ru2c effectively erased drug-resistant tumors and activated innate and acquired immunity in vivo. To the best of our knowledge, Ru2c is the first metal-based BRD4 inhibitor to achieve synergistic seno-immunotherapy and chemo-immunotherapy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723891","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

Hydrogenation of “Readily Activated Molecule” for Glycine Electrosynthesis

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-28 DOI: 10.1002/anie.202505675

Xiaowen Sun, Egon Campos dos Santos, Mingtao Li, Yujie Shi, Kanglei Pang, Miao Zhang, Jiayin Yuan, Hong Liu, Xiaowen Yu

{"title":"Hydrogenation of “Readily Activated Molecule” for Glycine Electrosynthesis","authors":"Xiaowen Sun, Egon Campos dos Santos, Mingtao Li, Yujie Shi, Kanglei Pang, Miao Zhang, Jiayin Yuan, Hong Liu, Xiaowen Yu","doi":"10.1002/anie.202505675","DOIUrl":"https://doi.org/10.1002/anie.202505675","url":null,"abstract":"The hydrogenation of glyoxylate oxime is the energy‐intensive step in glycine electrosynthesis. To date, there has been a lack of rational guidance for catalyst design specific to this step, and the unique characteristics of the oxime molecule have often been overlooked. In this study, we initiate a theoretical framework to elucidate the fundamental mechanisms of glycine electrosynthesis across typical transition metals. By comprehensively analyzing the competitive reactions, proton‐coupled electron transfer processes, and desorption steps, we identify the unique role of the glyoxylate oxime as a “readily activated molecule”. This inherent property positions Ag, featuring weak adsorption characteristics, as the “dream” catalyst for glycine electrosynthesis. Notably, a record‐low onset potential of –0.09 V vs. RHE and an impressive glycine production rate of 1327 μmol h–1 are achieved when using an ultralight Ag foam electrode. This process enables gram‐scale glycine production within 20 hours and can be widely adapted for synthesizing diverse amino acids. Our findings underscore the vital significance of considering the inherent characteristics of reaction intermediates in catalyst design.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723368","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

Outside Back Cover: Giant Bulk Photovoltaic Effect in a Chiral Polar Crystal based on Helical One-dimensional Lead Halide Perovskites

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-27 DOI: 10.1002/anie.202506098

Ayumi Ishii, Ryohei Sone, Tomohide Yamada, Mizuki Noto, Hikari Suzuki, Daiki Nakamura, Kei Murata, Takuya Shiga, Kazuyuki Ishii, Masayuki Nihei

引用次数: 0

Built‐in Electric Field in Freestanding Hydroxide/Sulfide Heterostructures for Industrially Relevant Oxygen Evolution

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-27 DOI: 10.1002/anie.202504972

Wentong Wu, Yueshuai Wang, Shizhen Song, Zhichao Ge, Chunyang Zhang, Jie Huang, Guiren Xu, Ning Wang, Yue Lu, Zhanfeng Deng, Haohong Duan, Maochang Liu, Cheng Tang

{"title":"Built‐in Electric Field in Freestanding Hydroxide/Sulfide Heterostructures for Industrially Relevant Oxygen Evolution","authors":"Wentong Wu, Yueshuai Wang, Shizhen Song, Zhichao Ge, Chunyang Zhang, Jie Huang, Guiren Xu, Ning Wang, Yue Lu, Zhanfeng Deng, Haohong Duan, Maochang Liu, Cheng Tang","doi":"10.1002/anie.202504972","DOIUrl":"https://doi.org/10.1002/anie.202504972","url":null,"abstract":"Alkaline water electrolysis (AWE), as a premier technology to massively produce green hydrogen, hinges on outstanding oxygen evolution reaction (OER) electrodes with high activity and robust stability under high current densities. However, it is often challenged by issues such as catalytic layer shedding, ion dissolution, and inefficient bubble desorption. Herein, a scalable corrosion‐electrodeposition method is presented to synthesize nickel‐iron layered double hydroxide (NiFe‐LDH)/Ni3S2 heterostructures on nickel mesh, tailored to meet the stringent requirements of industrial AWE. The study underscores the critical role of the built‐in electric field (BEF) on optimizing electronic properties, curtailing Fe leaching, and enhancing mass transfer. The resultant NiFe‐LDH/Ni3S2 heterostructure manifests remarkable OER performance, with ultra‐low overpotentials of 202 mV at 10 mA cm–2 and 290 mV at 800 mA cm–2 in 1.0 M KOH at 25°C, alongside superior steady‐state stability and resistance to reverse current under fluctuating conditions. Furthermore, the performance is further validated in alkaline electrolyzer, achieving a large current density of 800 mA cm–2 at a cell voltage of 1.908 V, while maintaining excellent stability. This work advances the understanding of BEF‐induced charge redistribution in hetero‐structured catalysts, offering a blueprint for the design of efficient OER electrodes for industrially relevant AWE applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"61 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713396","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

Non-Carbonized Pd Single-Atom Catalyst Supported on Lignin-Functionalized Phenolic Resin for Potent Catalytic Transfer Hydrogenation of Lignin-Derived Aldehydes

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-27 DOI: 10.1002/anie.202503195

Tairan Pang, Zhenglong Xue, Guanhua Wang, Li Junkai, Wenjie Sui, Chuanling Si

{"title":"Non-Carbonized Pd Single-Atom Catalyst Supported on Lignin-Functionalized Phenolic Resin for Potent Catalytic Transfer Hydrogenation of Lignin-Derived Aldehydes","authors":"Tairan Pang, Zhenglong Xue, Guanhua Wang, Li Junkai, Wenjie Sui, Chuanling Si","doi":"10.1002/anie.202503195","DOIUrl":"https://doi.org/10.1002/anie.202503195","url":null,"abstract":"Single-atom catalysts (SACs) are highly dependent on the properties of their supports, and organic polymers have recently emerged as promising candidates due to their tunable physicochemical properties and diverse functional groups. However, the high-temperature carbonization commonly required for conventional organic polymer-supported SAC fabrication often leads to the loss of these functional groups, thus weakening metal-support interactions and catalytic performance accordingly. Herein, we report a sustainable strategy to synthesize nitrogen-functionalized lignin-based phenolic resin (N-LPR) supports for stabilizing atomically dispersed Pd without carbonization. Using NH3·H2O as both the nitrogen source and catalyst, high molecular weight lignin fractions (L3) were transformed into N-L3PR-50% supports with a unique nano-chain-like structure, high surface area, and abundant amine groups, which can directly anchor Pd sites under room temperature. The resulting Pd@N-L3PR-50% catalyst achieved approximately 100% vanillin conversion and 97.91% selectivity for 2-methoxy-4-methylphenol at 80°C with excellent cycle stability and adaptability to lignin-derived aldehydes, benefiting from the stable Pd-N coordination and the good adsorption capacity provided by the N-L3PR-50% support. Consequently, this work not only demonstrates a straightforward non-carbonation strategy to prepare lignin-based SACs for potent biomass-derived chemical transformations but also provides a novel avenue for the application of conventional multifunctional organic polymers as support for SACs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713676","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

Routes to Pt Derivatives of High-Valent Sulfur Oxofluorides S(=O)2F, S(=O)F2 and S(=O)F3 by Fluorination and Oxygenation

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-27 DOI: 10.1002/anie.202503153

Ruben Jaeger, Ouchan He, Dilcan Dirican, Stefan Sander, Mike Ahrens, Thomas Braun

{"title":"Routes to Pt Derivatives of High-Valent Sulfur Oxofluorides S(=O)2F, S(=O)F2 and S(=O)F3 by Fluorination and Oxygenation","authors":"Ruben Jaeger, Ouchan He, Dilcan Dirican, Stefan Sander, Mike Ahrens, Thomas Braun","doi":"10.1002/anie.202503153","DOIUrl":"https://doi.org/10.1002/anie.202503153","url":null,"abstract":"Metal derivatives of high-valent sulfur fluorides and oxofluorides can provide fluorinated building blocks for materials science and bioactive compounds, but so far, such building blocks are elusive. The paper describes routes to access remarkable metal derivatives of S(=O)2F, S(=O)F2 and S(=O)F3 by oxygenation or fluorination steps. The Pt(II) fluorido complex trans-[Pt(F)(SOF)(PCy3)2] (2) reacts with the Davis reagent (3-phenyl-2-(phenylsulfonyl)-1,2-oxaziridine) to yield the sulfuryl fluorido complex trans-[Pt(F)(SO2F)(PCy3)2] (4). Notably, the electrophilic fluorinating agent NFSI (N-fluorobenzenesulfonimide) reacts with 2 to form trans-[Pt(F)(SOF2)(PCy3)2][NFSO2Ph] (5a). By nucleophilic fluorination with TMAF (Me4NF) it is possible to fluorinate the sulfur center once more to give the complex trans-[Pt(F)(SOF3)(PCy3)2] (6) bearing an unprecedented SOF3 ligand. Above 283 K, complex 6 shows a decomposition of the SOF3 moiety to form trans-[Pt(F)2(PCy3)2] (7) and SOF2. The described complexes could represent a previously unknown class of transfer reagents for high-valent sulfur fluoride units.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713677","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

Enhancing Heterointerface Coupling for Durable Industrial-Level Proton Exchange Membrane Water Electrolysis

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-27 DOI: 10.1002/anie.202502250

Kai Sun, Wei Mao, Lujie Jin, Wenjuan Shi, Wenzhe Niu, Chenyang Wei, Yixiang He, Qisheng Yan, Ruijie Wang, Youyong Li, Bo Zhang

{"title":"Enhancing Heterointerface Coupling for Durable Industrial-Level Proton Exchange Membrane Water Electrolysis","authors":"Kai Sun, Wei Mao, Lujie Jin, Wenjuan Shi, Wenzhe Niu, Chenyang Wei, Yixiang He, Qisheng Yan, Ruijie Wang, Youyong Li, Bo Zhang","doi":"10.1002/anie.202502250","DOIUrl":"https://doi.org/10.1002/anie.202502250","url":null,"abstract":"The industrial-level application of proton exchange membrane water electrolysis (PEMWE) lies in the capacity of operating at high current density in order for higher power density and lower operational cost. However, it poses a significant challenge to the overall performance of catalysts. Heterointerface engineering has emerged as an ideal strategy for addressing the anodic intrinsic activity limitations. Nevertheless, due to the fragile interface structure with weak interactions between different components, it is difficult to maintain the high activity and long-term stability of heterostructured catalysts. Herein, we report a ternary heterostructured catalyst, RuIrOx-CeO2, featuring a strong-coupled interface between RuIrOx phase and CeO2 phase. This strong-coupled interface exhibits both electronic and oxygen interaction, which effectively inhibits the active phase separation. When applied in PEMWE (0.8 mgIr cm-2 for the anode and 0.4 mgPt cm-2 for the cathode), the resultant catalyst expresses impressive activity, achieving a current density of 3.0 A cm-2 at a cell voltage of 1.75 V in PEMWE and demonstrates a stable 2000-h operation at 5.0 A cm-2 with an imperceptible voltage degradation of <1 μV h-1.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"61 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713798","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

Membrane-Bounded Intracellular E3 Ubiquitin Ligase-Targeting Chimeras (MembTACs) for Targeted Membrane Protein Degradation

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-27 DOI: 10.1002/anie.202501857

Zhi Zhu, Mengwu Mo, Feiyu Wang, Huiming Zhang, Ying Zhang, Chaoyong Yang, Jinbiao Shang

引用次数: 0

Electrical Energy Storage by Poly(ionic Liquids)

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-27 DOI: 10.1002/anie.202424185

Jiahui Liu, Tingwei Zhang, Sourav Biswas, Marek W. Urban

引用次数: 0