Angewandte Chemie最新文献

Mechanism-Guided Precision Hydrolysis of Early Transition Metals to Access (Mixed-Metal) Oxo Clusters 机制引导下的早期过渡金属精确水解以获得（混合金属）氧簇

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-02-25 DOI: 10.1002/ange.202525769

Muhammed Jibin Parammal, Jikson Pulparayil Mathew, Alessandro Prescimone, Ajmal Roshan Unniram Parambil, Harry Wilson, Jonathan De Roo

{"title":"Mechanism-Guided Precision Hydrolysis of Early Transition Metals to Access (Mixed-Metal) Oxo Clusters","authors":"Muhammed Jibin Parammal, Jikson Pulparayil Mathew, Alessandro Prescimone, Ajmal Roshan Unniram Parambil, Harry Wilson, Jonathan De Roo","doi":"10.1002/ange.202525769","DOIUrl":"https://doi.org/10.1002/ange.202525769","url":null,"abstract":"Zirconium and hafnium oxo clusters are catalysts, and building blocks for MOFs, 3D-printing and polymer composites. However, their synthesis is often a matter of trial and error, and new structures are hard to design retrosynthetically. Here, we use our recent insight in the formation mechanism of <math></math>(OH)<math></math>(OOCR)<math></math> oxo clusters to redesign their synthesis with higher reaction rates, more economical precursors, more sustainable solvents, and higher atom economy, all at room temperature at gram scale. We add exactly 1.33 equivalents of water for the precision hydrolysis of the metals toward Zr6-carboxylate or Hf6-carboxylate oxo clusters (carboxylate = acetate, oleate, and 2-methylbutanoate). Furthermore, we use precision hydrolysis to synthesize the elusive bimetallic Zr/Hf oxo clusters and to expand rational oxo cluster synthesis to the group 5, accessing the new <math></math>(OEt)<math></math>(OBz)<math></math> and <math></math>(OEt)<math></math>(OBz)<math></math> clusters (OBz = benzoate). Precision hydrolysis allows for a rational design and an economic production of oxo clusters on a multigram scale, with potential to become the workhorse for cluster synthesis.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 15","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202525769","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147708269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Reaction-Based Ratiometric Sensors for Simultaneous Multi-Bio-Analyte Imaging in Living Cells Using Spontaneous Raman Scattering 利用自发拉曼散射在活细胞中同时成像多种生物分析物的基于反应的比率传感器

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2025-12-29 DOI: 10.1002/ange.202522980

Sujit K Das, Heqi Xi, Itsuki Yamamoto, Katsumasa Fujita, Ankona Datta

{"title":"Reaction-Based Ratiometric Sensors for Simultaneous Multi-Bio-Analyte Imaging in Living Cells Using Spontaneous Raman Scattering","authors":"Sujit K Das, Heqi Xi, Itsuki Yamamoto, Katsumasa Fujita, Ankona Datta","doi":"10.1002/ange.202522980","DOIUrl":"https://doi.org/10.1002/ange.202522980","url":null,"abstract":"Raman-scattering comes with the promise of multi-bio-analyte imaging because of narrow peak-widths. This feature combined with alkyne/nitrile tags accessing the cell-silent region, have catalyzed the development of Raman-probes. In this backdrop, Raman-responsive ratiometric sensors will be key players for imaging bio-analytes. A major challenge, however, is low Raman-scattering cross-sections of alkynes/nitriles, leading to probes with low sensitivity and reliance on stimulated Raman which is not widely accessible. Raman-responsive ratiometric sensors for the accessible spontaneous Raman imaging platform still remain elusive. We have leveraged the “push–pull” effect to achieve novel activity-based alkyne-tag Raman sensors (ABATaRs) with high sensitivity. ABATaRs show high computed Raman-scattering activities 12–38 times that of benchmark 5-Ethynyl-2′-deoxyuridine (EdU), significantly high experimental Raman intensity versus EdU between 5 and 22, and relative Raman scattering cross-sections for the alkyne stretching with respect to dimethyl-sulfoxide C-H stretching as high as 466. To demonstrate generality, cell-permeable, ratiometric ABATaRs for pH, hydrogen peroxide, and Cu ions were developed. ABATaRs can image physiological and pathophysiological levels of bio-analytes in live-cells at as low as 1–5 µM sensor concentrations on a spontaneous Raman microscope and distinctly enhance spontaneous Raman imaging-speed. In a key advance, we demonstrate simultaneous multi-analyte Raman-imaging of bio-correlated Cu ions and hydrogen peroxide in live-cells.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 15","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147708388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chiral Mesostructured Mo Doped Bi2WO6 Drives Photocatalytic Urea Synthesis From N2 and CO2 手性介结构Mo掺杂Bi2WO6驱动N2和CO2光催化合成尿素

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-02-25 DOI: 10.1002/ange.202525892

Jiamin Ma, Yang Gao, Wanning Zhang, Lu Han, Shunai Che, Yuxi Fang

{"title":"Chiral Mesostructured Mo Doped Bi2WO6 Drives Photocatalytic Urea Synthesis From N2 and CO2","authors":"Jiamin Ma, Yang Gao, Wanning Zhang, Lu Han, Shunai Che, Yuxi Fang","doi":"10.1002/ange.202525892","DOIUrl":"https://doi.org/10.1002/ange.202525892","url":null,"abstract":"<div>\u0000 \u0000 Direct synthesis of urea through photocatalytic N2 and CO2 reduction (PNCR) offers a sustainable approach to mitigate CO2 emissions and reduce energy consumption from urea production for industry and agriculture. However, achieving high yield of urea is limited by the high energy barrier for co-reduction of N2 and CO2 with subsequent C–N coupling. Herein, we propose that the spin polarization of chiral mesostructured Mo doped Bi2WO6 (CMMB) can facilitate the formation of triplet 3NOH by regulating the parallel electron spin alignment and promote the separation and transfer of photogenerated carriers, leading to enhanced C–N formation. The incorporation of Mo sites into Bi2WO6 promotes the adsorption and activation of N2. A state-of-the-art urea yield was achieved without additives via PNCR on CMMB, surpassing the best-reported inorganic catalyst by a significant margin. This study provides an effective strategy for designing catalyst structures for the green synthesis of organonitrogen compounds.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 15","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147708270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Breaking Activity-Stability Trade-Off by Switching Reaction Pathway for Efficient Electrosynthesis of Glycerate at Industrial-Scale Current Density 在工业规模电流密度下，通过切换反应途径打破活性-稳定性权衡，实现甘油的高效电合成

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-03-05 DOI: 10.1002/ange.3574115

Dingfeng Jin, Tong Li, Jiantao Xu, Jungang Hou

{"title":"Breaking Activity-Stability Trade-Off by Switching Reaction Pathway for Efficient Electrosynthesis of Glycerate at Industrial-Scale Current Density","authors":"Dingfeng Jin, Tong Li, Jiantao Xu, Jungang Hou","doi":"10.1002/ange.3574115","DOIUrl":"https://doi.org/10.1002/ange.3574115","url":null,"abstract":"<div>\u0000 \u0000 The selective electrooxidation of biomass represents a sustainable solution for the synthesis of high-valued chemicals, yet it remains challenging to balance activity, selectivity, and stability. Herein, we report the selective regulation of β-NiCoOOH and γ-NiCoOOH through the precise modulation of precursors, demonstrating β-NiCoOOH as active catalyst exhibit excellent performance for the electrocatalytic valorization of glycerol to glycerate (GLA) with a remarkable selectivity of 78.44% and an industrial-scale current density of 1 A cm−2 in an anion exchange membrane electrolyzer for continuous long-term operation of 1080 h. We revealed that the electrooxidation of glycerol to C3 product is contingent on the generation of β-NiCoOOH phase with Co3+ species as the dominant active center while γ-NiCoOOH phase with a large amount of Co4+ sites is beneficial to the cleavage of C─C bond for C1 product. Mass spectrometry and density functional theory (DFT) calculations elucidate that β-NiCoOOH featuring inert lattice oxygen modulates the electronic configuration of the key glyceraldehyde intermediate, which enhances the stability of C─C bond, suppresses undesired cleavage, and thereby promotes the selective electrosynthesis of GLA via the ∙OH-assisted adsorbate evolution mechanism (AEM). This work provides a scalable strategy and offers deep insights into the phase-dependent reaction mechanisms in electrocatalytic biomass upgrading.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 15","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147708018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanically Planar Chiral Molecules by a SuFEx-Auxiliary Approach 机械平面手性分子的sufex辅助方法

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-03-05 DOI: 10.1002/ange.202525515

Shengtong Niu, Yingying Jiang, Darian W. Lewis, Omotolani E. Owoseeni, Md Mahmudul Hassan, Navamoney Arulsamy, Timothy Stephenson, Kelsey Anderson, Qian Yang, Yi Yao, Alexander Mariscal, Wenqi Liu, Chao Duan, Penghao Li, Xuanye Zhang, Alexander K. Goroncy, Xuesong Li

{"title":"Mechanically Planar Chiral Molecules by a SuFEx-Auxiliary Approach","authors":"Shengtong Niu, Yingying Jiang, Darian W. Lewis, Omotolani E. Owoseeni, Md Mahmudul Hassan, Navamoney Arulsamy, Timothy Stephenson, Kelsey Anderson, Qian Yang, Yi Yao, Alexander Mariscal, Wenqi Liu, Chao Duan, Penghao Li, Xuanye Zhang, Alexander K. Goroncy, Xuesong Li","doi":"10.1002/ange.202525515","DOIUrl":"https://doi.org/10.1002/ange.202525515","url":null,"abstract":"<div>\u0000 \u0000 Mechanical chirality, an emerging paradigm in stereochemistry, arises uniquely from the formation of a mechanical bond between achiral and oriented molecular subcomponents, endowing the resulting mechanically interlocked molecules (MIMs) with broad application potential. Despite its potential, it has remained underexplored largely due to the synthetic challenges in producing enantiopure mechanically planar chiral (MPC) molecules, particularly a scalable approach. Here, we introduce the sulfur(VI) fluoride exchange (SuFEx) click reaction into the MIMs field, reporting to employ SuFEx as a metal-free active template method for the synthesis of MPC rotaxanes (up to gram-scale). Subsequently, enantiopure MPC rotaxanes (ee >99%) can be efficiently obtained after the convenient one-step auxiliary elimination by either removal or oxidation of sulfinyl group. Furthermore, the derivative synthesis that can introduce various functional groups either on the macrocycles or on the dumbbells of rotaxanes enables the preparation of a large variety of enantiopure MPC rotaxanes, including higher-order enantiopure MPC [3]rotaxane and enantiopure co-conformationally MPC [3]rotaxane. Notably, using this strategy, enantiopure MPC catenanes can also be obtained by the transformation of rotaxanes, which preserves the enantiopurity and chiroptical properties of parent rotaxanes and provides a new approach to synthesizing enantiopure MPC catenanes.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 15","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147708019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Kontrollierter Transport und lichtinduzierte Freisetzung von Magic Spot Nukleotiden in Escherichia coli 大肠杆菌中魔点核苷酸的受控运输和光诱导释放

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-03-05 DOI: 10.1002/ange.202523307

Christoph Popp, Patrick Moser, Anselm Schwoerbel, Xinwei Liu, Johannes Freitag, Pinku Sarmah, Isabel Prucker, Robert Zscherp, Xuan Wang, Philipp Klahn, Hans-Georg Koch, Gert Bange, Henning J. Jessen

引用次数: 0

Correspondence on “Carbon-Dot-Based Dual-Emission Nanohybrid Produces a Ratiometric Fluorescent Sensor for in Vivo Imaging of Cellular Copper Ions” “碳点基双发射纳米杂化材料制备用于细胞铜离子体内成像的比例荧光传感器”通讯

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-03-05 DOI: 10.1002/ange.4904466

Mustafa Gharib, Maha Said, Raphaël Lévy

{"title":"Correspondence on “Carbon-Dot-Based Dual-Emission Nanohybrid Produces a Ratiometric Fluorescent Sensor for in Vivo Imaging of Cellular Copper Ions”","authors":"Mustafa Gharib, Maha Said, Raphaël Lévy","doi":"10.1002/ange.4904466","DOIUrl":"https://doi.org/10.1002/ange.4904466","url":null,"abstract":"<div>\u0000 \u0000 The 2012 study by Zhu et al. (DOI: 10.1002/ange.201109089) reporting a hybrid nanosystem composed of carbon and CdSe/ZnS quantum dots functionalized with tris(pyridin-2-ylmethyl)ethane-1,2-diamine (CdSe@C-TPEA) as ratiometric fluorescent sensors for intracellular copper imaging remains highly influential, with 499 citations to date (Web of Science, December 4, 2025). As part of the NanoBubbles replication project, we attempted to reproduce key experimental findings following detailed pre-registered protocols. Despite strict adherence to the reported synthesis procedures, we failed to replicate the central claim of Cu2+-induced fluorescence quenching. Furthermore, our analysis reveals significant data anomalies in the original publication, including spectral overlaps with identical noise patterns inconsistent with independent measurements. These findings raise critical concerns regarding data integrity and reproducibility and cast significant doubt on the reliability of Zhu et al.’s reported results.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 15","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.4904466","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147708037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Outside Back Cover: Reaction-Based Ratiometric Sensors for Simultaneous Multi-Bio-Analyte Imaging in Living Cells Using Spontaneous Raman Scattering (Angew. Chem. 15/2026) 外封底：反应为基础的比例传感器，同时多生物分析成像的活细胞使用自发拉曼散射（新）。化学15/2026)

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-03-09 DOI: 10.1002/ange.2026-m2702055900

Sujit K Das, Heqi Xi, Itsuki Yamamoto, Katsumasa Fujita, Ankona Datta

引用次数: 0

Catalytic & Enantioselective Ring Opening of Azabicyclo[1.1.0]Butyl Carbinols via N-Allylation of Strained Tertiary Amines 叔胺n -烯丙化催化氮杂环[1.1.0]丁基甲醇开环对映选择性研究

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-03-05 DOI: 10.1002/ange.202520548

Debraj Ghorai, Saleha Khatun, William DeSnoo, Swagata Paul, Wang-Yeuk Kong, Rupam Sahoo, Debu Ghorai, Dean J. Tantillo, Santanu Panda

{"title":"Catalytic & Enantioselective Ring Opening of Azabicyclo[1.1.0]Butyl Carbinols via N-Allylation of Strained Tertiary Amines","authors":"Debraj Ghorai, Saleha Khatun, William DeSnoo, Swagata Paul, Wang-Yeuk Kong, Rupam Sahoo, Debu Ghorai, Dean J. Tantillo, Santanu Panda","doi":"10.1002/ange.202520548","DOIUrl":"https://doi.org/10.1002/ange.202520548","url":null,"abstract":"<div>\u0000 \u0000 Bicyclo[1.1.0]butanes (BCBs) & aza-bicyclo[1.1.0]butanes (ABBs) are characterized by significant ring strain, which allows diverse strain-release-driven efficient and atom-economical synthetic approaches to diverse valuable C(sp3)-rich novel skeletons, which are relevant to medicinal chemistry. Catalytic and asymmetric synthetic transformations are crucial in modern chemistry, enabling the efficient and selective production of chiral molecules with applications in pharmaceuticals, agrochemicals, and more. Over the last 2 years, a large number of catalytic and asymmetric strain-release-driven ring-opening transformations of BCBs have been reported to access C(sp3)-rich architecture. Despite significant advances using BCBs, catalytic asymmetric methodologies employing ABBs remain unknown. Herein, we report the enantioselective and catalytic strain release-driven ring-opening of ABB rings, which occurs via palladium-catalyzed asymmetric N-allylation followed by spirocyclization. Quantum chemical calculations shine light on the mechanism of this process.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 15","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147708038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Proteinvermittelte Kupfer-Redoxregulation: Rolle von Disulfidbrücken und allosterischer Modulation 蛋白质介导的铜氧化还原调节：二硫键和变构调节的作用

Angewandte Chemie Pub Date : 2026-04-05 Epub Date: 2026-03-05 DOI: 10.1002/ange.202519673

Rebecca Sternke-Hoffmann, Chang Liu, Xue Wang, Hegne Pupart, Xun Sun, Jan Gui-Hyon Dreiser, Peep Palumaa, Qinghua Liao, Matthias Krack, Jinghui Luo

引用次数: 0