Angewandte Chemie最新文献

{"title":"A Stable Open-Shelled Au26 Nanocluster with Remarkable Performance in Selective Oxidation of Benzyl Alcohol","authors":"Yuan-Yuan Dong,&nbsp;Dr. Chun-Yu Liu,&nbsp;Wan-Qi Shi,&nbsp;Dr. Zong-Jie Guan,&nbsp;Prof. Dr. Quan-Ming Wang","doi":"10.1002/ange.202420314","DOIUrl":"https://doi.org/10.1002/ange.202420314","url":null,"abstract":"<p>Open metal sites are crucial in catalysis. We have used a “loose coordination strategy” (LCS) to preorganize open metal sites in gold cluster catalysts. A gold nanocluster with composition of [Au₂₆(3,4-Me₂-Ph-form)₉(ⁱPr₂-imy)₃(Me₂S)](BF₄)₂ (ⁱPr₂-imy=1,3-Diisopropylimidazolium tetrafluoroborate, 3,4-Me₂-Ph-form=N,N′-Di(3,4-dimethyl-phenyl)formamidine) (<b>Au₂₆</b>) has been obtained by one pot synthesis, i.e. the direct reduction of Me₂SAuCl in the presence of N-heterocyclic carbenes and amidinate ligands. ESI-TOF-MS reveals that the Me₂S ligand is detached from the cluster to form open sites. The accessibility of the exposed Au atoms has been confirmed quantitatively by luminescent titration with 2-naphthalenethiol. Surprisingly, <b>Au₂₆</b> has 15 valence electrons, and the presence of an unpaired electron is confirmed by superconducting quantum interference device (SQUID) and electron paramagnetic resonance (EPR). This open-shelled <b>Au₂₆</b> not only shows unexpected high stability but also exhibits excellent catalytic performance toward the selective oxidation of benzyl alcohol to benzaldehyde, achieving a remarkable turnover number up to 100670.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475754","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}

{"title":"Unlocking HFIP for Fluoroalkylation with Molecular Photoelectrocatalysis","authors":"Yi-Xian Zheng,&nbsp;Dr. Yuxing Gao,&nbsp;Dr. Peng Xiong,&nbsp;Prof. Dr. Hai-Chao Xu","doi":"10.1002/ange.202423241","DOIUrl":"https://doi.org/10.1002/ange.202423241","url":null,"abstract":"<p>Despite the increasing interest in radical-based fluoroalkylation techniques, the organofluorine compounds bearing the partially fluorinated hexafluoroisopropyl group remain extremely scarce due to the lack of appropriate reagents. Herein we report an unprecedented photoelectrocatalytic method for the C−H hexafluoroisopropylation of indoles and tryptophan peptides, utilizing the readily available hexafluoro-2-propanol (HFIP) as the fluoroalkylation reagent. In this process, HFIP is converted into hexafluoroisopropyl radicals, enabling fluoroalkylation reactions. This study broadens the potential applications of molecular photoelectrocatalysis, highlighting its capacity to enable transformations that are difficult to accomplish through traditional electrochemical or photochemical approaches.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475475","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}

{"title":"Dynamic, Single-cell Monitoring of RNA Modifications Response to Viral Infection Using a Genetically Encoded Live-cell RNA Methylation Sensor","authors":"Ting Zhang,&nbsp;Hao Yang,&nbsp;Quanwei Yu,&nbsp;Yong Zhang,&nbsp;Yue Zhang,&nbsp;Xianglin Zhu,&nbsp;Xuhan Xia,&nbsp;Feng Li,&nbsp;Ruijie Deng","doi":"10.1002/ange.202418003","DOIUrl":"https://doi.org/10.1002/ange.202418003","url":null,"abstract":"<p>RNA modifications, such as N6-methylation of adenosine (m⁶A), serve as key regulators of cellular behaviors, and are highly dynamic; however, tools for dynamic monitoring of RNA modifications in live cells are lacking. Here, we develop a genetically encoded live-cell RNA methylation sensor that can dynamically monitor RNA m⁶A level at single-cell resolution. The sensor senses RNA m⁶A in cells via affinity-induced cytoplasmic retention using a nuclear location sequence-fused m⁶A reader. It allows for simultaneously measure RNA m⁶A dynamics and viral invasion at single-cell level. Based on the single-cell analytical tool, we found that SARS-CoV-2 infection enhances host-cell RNA m⁶A level, and high-level RNA m⁶A modification in host cells, in turn, facilitates viral infection. Particularly, Omicron, a variant of SARS-CoV-2, that features as high infection capacity, however, exhibits a reduced facilitation of m⁶A modification in host cells. In addition, the sensor can estimate viral inhibition via measuring cellular m⁶A level, that was explored for screening potential antiviral drugs. The methylation sensor can serve for elucidating the interplay between pathogens and host-cell epigenetics at single-cell level.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475474","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}

{"title":"Enantioselective Trifluoromethylazidation of Styrenyl Olefins Catalyzed by an Engineered Nonheme Iron Enzyme","authors":"Hua He,&nbsp;Jia-Xin Yan,&nbsp;Jian-Xiang Zhu,&nbsp;Si-Jia Liu,&nbsp;Xiao-Qi Liu,&nbsp;Dr. Peng Chen,&nbsp;Dr. Xin Wang,&nbsp;Prof. Dr. Zhi-Jun Jia","doi":"10.1002/ange.202423507","DOIUrl":"https://doi.org/10.1002/ange.202423507","url":null,"abstract":"<p>Organofluorines, particularly those containing trifluoromethyl (CF₃) groups, play a critical role in medicinal chemistry. While trifluoromethylation of alkenes provides a powerful synthetic route to construct CF₃-containing compounds with broad structural and functional diversity, achieving enantioselective control in these reactions remains a formidable challenge. In this study, we engineered a nonheme iron enzyme, quercetin 2,3-dioxygenase from <i>Bacillus subtilis</i> (<i>Bs</i>QueD), for the enantioselective trifluoromethylazidation of alkenes. Through directed evolution, the final variant <i>Bs</i>QueD-CF₃ exhibited excellent enantioselectivity, with an enantiomeric ratio (e.r.) of up to 98 : 2. Preliminary mechanistic studies suggest the involvement of radical intermediates. This work expands biocatalytic organofluorine chemistry by reprogramming metalloenzymes for innovative trifluoromethylation reactions.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475437","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}

{"title":"Next-Generation Photosensitizers: Cyanine-Carborane Salts for Superior Photodynamic Therapy of Metastatic Cancer","authors":"Amir Roshanzadeh,&nbsp;Dr. Hyllana C. D. Medeiros,&nbsp;Dr. Christopher K. Herrera,&nbsp;Carson Malhado,&nbsp;Anton W. Tomich,&nbsp;Steven P. Fisher,&nbsp;Sergio O. Lovera,&nbsp;Dr. Matthew Bates,&nbsp;Prof. Vincent Lavallo,&nbsp;Prof. Richard R. Lunt,&nbsp;Prof. Sophia Y. Lunt","doi":"10.1002/ange.202419759","DOIUrl":"https://doi.org/10.1002/ange.202419759","url":null,"abstract":"<p>Photodynamic therapy (PDT) has emerged as a promising targeted treatment for cancer. However, current PDT is limited by low tissue penetration, insufficient phototoxicity (toxicity with light irradiation), and undesirable cytotoxicity (toxicity without light irradiation). Here, we report the discovery of cyanine-carborane salts as potent photosensitizers (PSs) that harness the near-infrared (NIR) absorbing [cyanine⁺] with the inertness of [carborane⁻]. The implementation of [cyanine⁺] [carborane⁻] salts dramatically enhance cancer targeting of the PSs and decrease cytotoxicity. We characterize the cellular uptake of the cyanine-carborane PSs, organelle localization, generation of reactive oxygen species (ROS) with the ability to cogenerate multiple ROS species, suppression of pro-metastatic pathways, and activation of apoptotic pathways. We further demonstrate the ability of optimized PSs to eliminate tumors <i>in vivo</i> using an orthotopic mouse model of breast cancer. These newly developed [cyanine⁺] [carborane⁻] salt PSs introduce a potent therapeutic approach against aggressive breast cancer while decreasing side effects.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202419759","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475733","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}

{"title":"Frontispiz: A Knowledge–Data Dual-Driven Framework for Predicting the Molecular Properties of Rechargeable Battery Electrolytes","authors":"Yu-Chen Gao,&nbsp;Yu-Hang Yuan,&nbsp;Suozhi Huang,&nbsp;Nan Yao,&nbsp;Legeng Yu,&nbsp;Yao-Peng Chen,&nbsp;Qiang Zhang,&nbsp;Xiang Chen","doi":"10.1002/ange.202580461","DOIUrl":"https://doi.org/10.1002/ange.202580461","url":null,"abstract":"<p>In their Research Article (e202416506), Xiang Chen and co-authors developed a knowledge–data dual-driven framework that incorporates domain expertise into artificial intelligence models, achieving notable accuracy in predicting properties such as melting, boiling, and flash points of battery electrolytes.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202580461","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143117931","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}

{"title":"Frontispiz: Generation of Bis(pentafluorophenyl)boron Enolates from Alkynes and Their Catalyst-Free Alkyne Coupling","authors":"Prof. Masatoshi Shibuya,&nbsp;Souta Yuruka,&nbsp;Prof. Yoshihiko Yamamoto","doi":"10.1002/ange.202580462","DOIUrl":"https://doi.org/10.1002/ange.202580462","url":null,"abstract":"<p>Catalyst-free alkyne couplings using bis(pentafluorophenyl)boron enolates are reported by Masatoshi Shibuya, Souta Yuruka and Yoshihiko Yamamoto in their Communication (e202417910). The strongly Lewis acidic boron center activates a carbon–carbon triple bond, enabling C−C bond formation between the boron enolate and the alkyne.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202580462","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143117936","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}

{"title":"BERICHTIGUNG: Correction to “Catalytic Linkage Engineering of Covalent Organic Frameworks for the Oxygen Reduction Reaction”","authors":"","doi":"10.1002/ange.202424473","DOIUrl":"https://doi.org/10.1002/ange.202424473","url":null,"abstract":"<p>X. Li, S. Yang, M. Liu, X. Yang, Q. Xu, G. Zeng, Z. Jiang, <i>Angew. Chem. Int. Ed</i>. <b>2023</b>, <i>62</i>, e202304356</p><p>DOI: 10.1002/ange.202304356</p><p>Correction 1: In the Supporting Information of this article, Page 15, a wrong version of Figure S11 was inadvertently included. The PXRD patterns depicted for the samples after treatment with boiling water and acid-base treatment were incorrect. The correct version of Figure S11 is shown below.\u0000</p><p>Correction 2: In the Supporting Information, Page 18, the unit of the y-axis of Figure S14 has a typo. The unit should be “J/J₀(%)”. The correct version of Figure S14 is shown below.\u0000</p><p>Correction 3: In the Supporting Information, Page 38, the caption of Table S5 has a typo. The table caption should read: “Table S5. Atomistic coordinates for the AA-stacking mode of amide-COF optimized using DFTB+ method. Lattice type: orthorhombic, Space group: PMMM; α= β = 90° γ = 120°, a = 22.428619 Å, b = 22.524134 Å, c = 3.555884 Å.”</p><p>The original Supporting Information was replaced with a corrected version of the Supporting Information. The authors apologize for these errors which do not affect the data analysis and conclusions of the original Research Article.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 7","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202424473","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380939","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}

{"title":"Light-Driven Stepwise Reduction of Aliphatic Carboxylic Esters to Aldehydes and Alcohols","authors":"Delian Wei,&nbsp;Jiawei Bu,&nbsp;Shengfu Zhang,&nbsp;Shiyu Chen,&nbsp;Ling Yue,&nbsp;Xipan Li,&nbsp;Prof. Kangjiang Liang,&nbsp;Prof. Chengfeng Xia","doi":"10.1002/ange.202420084","DOIUrl":"https://doi.org/10.1002/ange.202420084","url":null,"abstract":"<p>The reduction of carboxylic esters to aldehydes and alcohols is a fundamental functional group transformation in chemistry. However, the inertness of carbonyl group and the instability of ketyl radical anion intermediate impede the reduction of carboxylic esters via photochemical strategy. Herein, we described the reduction of aliphatic carboxylic esters with synergistic dual photocatalysis via phenolate-catalyzed single electron transfer process and thiol-catalyzed hydrogen atom transfer process. The competitive back electron transfer process was effectively inhibited by protonation of the ketyl-type radical anion. This protocol enabled the efficient reduction of carboxylic esters to alcohols under mild conditions. By interruption of the reduction with prolinol, the step-controlled reduction of carboxylic esters to aldehydes was accomplished. The developed process was also successfully applied to the preparation of deuterated alcohols and aldehydes from esters with D₂O as the deuterium source.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475276","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}

{"title":"Converting Fe−N−C Single-atom Catalyst to a New FeNxSey Cluster Catalyst for Proton-exchange Membrane Fuel Cells","authors":"Yang Zhao,&nbsp;Dr. Pengfei Yin,&nbsp;Dr. Yuanyuan Yang,&nbsp;Ruguang Wang,&nbsp;Prof. Cairong Gong,&nbsp;Jisi Li,&nbsp;Jiaxin Guo,&nbsp;Quanlu Wang,&nbsp;Prof. Tao Ling","doi":"10.1002/ange.202419501","DOIUrl":"https://doi.org/10.1002/ange.202419501","url":null,"abstract":"<p>Iron-nitrogen-carbon (Fe−N−C) single-atom catalyst is the most promising alternative to platinum catalyst for proton-exchange membrane fuel cells (PEMFCs), however its high performance cannot be maintained for a long enough time in device operation. The construction of a new Fe coordination environment that is completely different from the square-planar Fe−N₄ configuration in classic Fe−N−C catalyst is expected to break the current stability limits of Pt-free catalysts, which however remains unexplored. Here, we report, for the first time, the conversion of Fe−N−C catalyst to a new FeN_xSe_y cluster catalyst, where the active Fe sites are three-dimensionally (3D) co-coordinated by N and Se atoms. Due to this unique Fe coordination configuration, the FeN_xSe_y catalyst exhibits much better 4e⁻ ORR activity and selectivity than the state-of-the-art Fe−N−C catalyst. Specifically, the yields of hydrogen peroxide (H₂O₂) and ⋅OH radicals on the FeN_xSe_y catalyst are only one-quarter and one-third of that on the Fe−N−C counterpart, respectively. Therefore, the FeN_xSe_y catalyst exhibits outstanding cyclic stability, losing only 10 mV in half-wave potential <i>E</i>_1/2 after 10,000 potential cycles, much smaller than that of the Fe−N−C catalyst (56 mV), representing the most stable Pt-free catalysts ever reported for PEMFCs. More significantly, the 3D co-coordination structure effectively inhibits the Fe demetallization of the FeN_xSe_y catalyst in the presence of H₂O₂. As a result, the FeN_xSe_y based PEMFC shows excellent durability, with the current density attenuation significantly lower than that of the Fe−N−C based device after accelerated durability testing. Our work provides guidance for the development of next-generation Pt-free catalysts for PEMFCs.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 9","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475277","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}