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Catalytic Asymmetric Aza-[2+2] Cyclization Reaction of Simple Ketoimine. 简单酮亚胺的催化不对称Aza-[2+2]环化反应。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-22 DOI: 10.1002/anie.202518427
Linqing Wang,Feiyun Gao,Shixin Li,Xiaoyong Zhang,Jiaming Lv,Tianyi Zhao,Shuyang Xu,Rui Wang,Dongxu Yang
{"title":"Catalytic Asymmetric Aza-[2+2] Cyclization Reaction of Simple Ketoimine.","authors":"Linqing Wang,Feiyun Gao,Shixin Li,Xiaoyong Zhang,Jiaming Lv,Tianyi Zhao,Shuyang Xu,Rui Wang,Dongxu Yang","doi":"10.1002/anie.202518427","DOIUrl":"https://doi.org/10.1002/anie.202518427","url":null,"abstract":"Herein, we report the first catalytic enantioselective aza-[2+2] cyclization of simple ketoimines, thereby addressing a persistent challenge in four-membered aza-ring construction. While the aza-[2+2] cyclization represents the most straightforward approach to azetidine synthesis, previous methodologies have been strictly limited to ketoimines, all with an EWG at the central reactive carbon, and predominantly employing cyclic imine substrates. Through rational design of an in situ-generated magnesium catalytic system and systematic investigation of imine electronic effects, we have successfully developed an asymmetric protocol for simple ketoimines. This breakthrough enables efficient access to enantioenriched monocyclic azetidines with excellent stereocontrol. Moreover, a streamlined one-pot tandem oxidation readily converts these azetidines into valuable quaternary chiral β-lactams-privileged scaffolds that are prominent in numerous pharmaceuticals and bioactive agents. A combination of comparative studies, the calculation results of the HOMO and LUMO energies of different imines, relative control experiments, and a series of detailed NLE analysis revealed the coordination difference and the catalytic cycle. The catalytic protocol was used for the synthesis of a series of β-lactams containing aryl or alkyl groups, as well as for pharmaceutical active molecules' β-lactam-modifications. Importantly, the preliminary attempt to take advantage of the significant ring strain of β-lactam for peptide modifications was also achieved on tryptophan.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"117 6 1","pages":"e202518427"},"PeriodicalIF":16.6,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338541","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
Construction of Tetrasubstituted α-Amino- and α-Alkoxy Phosphine Oxides via Pd-Catalyzed Regio- and Enantioselective Hydrophosphinylation of Dienes. 钯催化二烯区选择性和对映选择性氢膦化构建四取代α-氨基和α-烷氧基膦氧化物。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-22 DOI: 10.1002/anie.202519578
Jiang-Tao Cheng,Xinzhu Yuan,Zhiping Yang,Kexin Liu,Jun Joelle Wang
{"title":"Construction of Tetrasubstituted α-Amino- and α-Alkoxy Phosphine Oxides via Pd-Catalyzed Regio- and Enantioselective Hydrophosphinylation of Dienes.","authors":"Jiang-Tao Cheng,Xinzhu Yuan,Zhiping Yang,Kexin Liu,Jun Joelle Wang","doi":"10.1002/anie.202519578","DOIUrl":"https://doi.org/10.1002/anie.202519578","url":null,"abstract":"Significant progress has been made in the asymmetric hydrofunctionalization of dienes to construct vinylic stereogenic carbon centers. However, achieving enantioselective hydrofunctionalization of substituted dienes with heteroatom nucleophiles to form vinylic tetrasubstituted carbon centers remains a formidable challenge. This difficulty arises primarily from issues of regio-control, steric hindrance, and stereo-discrimination. In this study, we present a palladium-catalyzed regio- and enantioselective hydrophosphinylation of 2-amido and 2-alkoxyl dienes using phosphine oxides. This approach successfully constructs chiral allylic α-aminophosphine oxides and α-alkoxyphosphine oxides with tetrasubstituted carbon centers. Our method demonstrates a broad substrate scope with excellent enantioselectivity (up to > 99% ee) and high yields (up to 99%), achieving exclusive regio-control under mild conditions. Additionally, the versatile post-functionalization of the allyl group facilitates the synthesis of a wide variety of tetrasubstituted carbon centers featuring distinct heteroatom.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"52 1","pages":"e202519578"},"PeriodicalIF":16.6,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338542","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
Arene Ruthenium(II) Carboxylates for C─H Alkylations and Arylations at Near Room Temperature. 芳烃钌(II)羧酸盐在近室温下的C─H烷基化和芳基化。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-22 DOI: 10.1002/anie.202508139
Xiaoyan Hou,Zhipeng Lin,Takuya Michiyuki,Xuexue Chang,Lutz Ackermann
{"title":"Arene Ruthenium(II) Carboxylates for C─H Alkylations and Arylations at Near Room Temperature.","authors":"Xiaoyan Hou,Zhipeng Lin,Takuya Michiyuki,Xuexue Chang,Lutz Ackermann","doi":"10.1002/anie.202508139","DOIUrl":"https://doi.org/10.1002/anie.202508139","url":null,"abstract":"The long-term pursuit for more efficient catalysts has stimulated the development of C─H activations under mild reaction conditions, with the overarching goal to improve their user-friendly nature, selectivity, and synthetic utility. Herein, we report mild C─H alkylations enabled by inexpensive and most user-friendly ruthenium carboxylate complexes. While these bench-stable arene ruthenium carboxylate complexes catalyzed direct alkylations under ambient conditions, detailed kinetic studies demonstrated a high catalytic performance for the [Ru(O2CR)2(p-cymene)] during the steady-state catalytic process. Thus, temperature-dependent kinetic Arrenhius-plot analyses of the ruthenium-catalyzed C─H alkylation revealed a comparable activation enthalpy for [Ru(O2CR)2(p-cymene)] and [Ru(t-BuCN)5(H2O)](BF4)2, hence, implying entropic factors to be of relevance. The robust arene ruthenium(II) carboxylate-catalyzed C─H alkylation showed broad versatility under mild reaction conditions with respect to primary, secondary as well as tertiary alkyl bromides in a position-divergent manner, reflecting a wide tolerance of valuable electrophilic functional groups for late-stage functionalizations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"139 1","pages":"e202508139"},"PeriodicalIF":16.6,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338707","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
Topological Duality: Constructing High-Nuclearity Metal Clusters with Unleashed Active Sites for Efficient and Durable CO2 Electroreduction. 拓扑二元性:构建具有释放活性位点的高核金属团簇,用于高效和持久的CO2电还原。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-22 DOI: 10.1002/anie.202516704
Wei Li,Dongxu Cui,Ao Yang,Changyan Zhu,Yuxiao Zhang,Fanfei Meng,Xinlong Wang,Zhongmin Su,Chi-Ming Che,Chunyi Sun
{"title":"Topological Duality: Constructing High-Nuclearity Metal Clusters with Unleashed Active Sites for Efficient and Durable CO2 Electroreduction.","authors":"Wei Li,Dongxu Cui,Ao Yang,Changyan Zhu,Yuxiao Zhang,Fanfei Meng,Xinlong Wang,Zhongmin Su,Chi-Ming Che,Chunyi Sun","doi":"10.1002/anie.202516704","DOIUrl":"https://doi.org/10.1002/anie.202516704","url":null,"abstract":"Precise control of active sites with atomic resolution in metal nanoclusters (MNCs) presents a promising avenue for catalyst engineering towards CO2 electroreduction. However, effective strategies to construct high-nuclearity MNCs while balancing catalytic stability and active-site exposure remain scarce. Herein, we propose a \"topological-duality-driven\" strategy to construct a high-nuclearity Cu24Ag54 nanocluster, featuring an octahedral {Cu24} shell and a double-truncated cubic {Ag54} core with exposed {Ag3} vertices on {111} facets. Notably, the double-truncated cubic is a previously unexplored concave polyhedron with over twice the number of {111} facets compared to conventional structures. As a catalyst for CO2 electroreduction, Cu24Ag54 delivers exceptional performance including a Faradaic efficiency for CO of ∼98%, catalytic stability exceeding 100 h, and current densities up to 750 mA cm-2 (total current 3 A), ranking among the highest values of the reported MNCs. Dedicated studies show the nested structure and increased electron delocalization underpin the catalyst durability. The facilitated electron transfer from Ag to the key intermediate *COOH and electron delocalization effect significantly reduce the energy barrier for *COOH formation by 50%. This work provides a new perspective on the potential of topological geometries in designing high-nuclearity MNCs for highly efficient and robust CO2 electroreduction at industrial current density.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"224 1","pages":"e202516704"},"PeriodicalIF":16.6,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338543","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
NHC-Terphenyl Radicals and Anions: Tuning Stability and Redox Properties via Substituent Patterning. NHC-Terphenyl自由基和阴离子:通过取代基图调整稳定性和氧化还原性质。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-22 DOI: 10.1002/anie.202520260
Henric Steffenfauseweh,Yury V Vishnevskiy,Beate Neumann,Hans-Georg Stammler,Bas de Bruin,Rajendra S Ghadwal
{"title":"NHC-Terphenyl Radicals and Anions: Tuning Stability and Redox Properties via Substituent Patterning.","authors":"Henric Steffenfauseweh,Yury V Vishnevskiy,Beate Neumann,Hans-Georg Stammler,Bas de Bruin,Rajendra S Ghadwal","doi":"10.1002/anie.202520260","DOIUrl":"https://doi.org/10.1002/anie.202520260","url":null,"abstract":"Herein, we report the influence of C2-terphenyl substitution patterns (i.e., p-terphenyl versus m-terphenyl) on the redox behavior and stability of the corresponding radicals and anions derived from N-heterocyclic carbenes (NHCs). Three well-known NHCs; SIPr (1a), IPr (1b), and Me-IPr (1c) (SIPr = C{N(Dipp)CH2}2, IPr = C{N(Dipp)CH}2; Me-IPr = C{N(Dipp)CCH3}2; Dipp = 2,6-iPr2C6H3); were functionalized at the C2 position using 4-bromo-p-terphenyl (p-TerBr) and 5'-bromo-m-terphenyl (m-TerBr) under nickel catalysis, yielding the corresponding cations [(NHC)p-Ter]Br (2a-c) and [(NHC)m-Ter]Br (3a-c), respectively. Cyclic voltammetry (CV) measurements of 2a-c reveal two distinct reversible redox events, while 3a-c exhibit one reversible and one irreversible or quasi-reversible wave. Reduction of 2a-c and 3a-c with KC8 readily affords stable radicals [(NHC)p-Ter]● (4a-c) and [(NHC-m-Ter]● (5a-c), isolated as crystalline solids. Further reduction of 4a-c produces diamagnetic anions [(NHC)p-Ter]K (6a-c-K), consistent with the electrochemical data. In contrast, 5b and 5c are unreactive toward KC8 under similar conditions, while 5a (derived from the more electrophilic NHC 1a) can be reduced to the corresponding anion [(SIPr)m-Ter]K (7a-K). Selected compounds have been characterized by spectroscopic techniques and single-crystal X-ray diffraction, with computational studies supporting the experimental findings. The results highlight how the NHC and the C2-terphenyl substituent influence the properties and stability of the resulting species.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"136 1","pages":"e202520260"},"PeriodicalIF":16.6,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338706","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
Dual-Engineered DPP Polymers: Synergistic Hydrogen Bonding and Ring-Fusion for High-Mobility Organic Field-Effect Transistors. 双工程DPP聚合物:高迁移率有机场效应晶体管的协同氢键和环融合。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-22 DOI: 10.1002/anie.202514768
Zhaoyang Chen,Rui Li,Qianhui Jia,Junhao Deng,Dongxu Liang,Lan Cao,Jun Zhang,Cheng Wang,Jian Hu,Yongqiang Shi,Haichang Zhang
{"title":"Dual-Engineered DPP Polymers: Synergistic Hydrogen Bonding and Ring-Fusion for High-Mobility Organic Field-Effect Transistors.","authors":"Zhaoyang Chen,Rui Li,Qianhui Jia,Junhao Deng,Dongxu Liang,Lan Cao,Jun Zhang,Cheng Wang,Jian Hu,Yongqiang Shi,Haichang Zhang","doi":"10.1002/anie.202514768","DOIUrl":"https://doi.org/10.1002/anie.202514768","url":null,"abstract":"Developing simple and effective molecular design strategies to optimize charge transport mobility remains a key challenge in high-performance organic semiconductors. In this study, we integrate hydrogen bonding (H-B) and ring-fusion (R-F) into a diketopyrrolopyrrole (DPP)-based polymer, yielding a novel material, P-HF. For comparison, a reference polymer (P-B) and a hydrogen-bonded analogue (P-H) were synthesized. The synergistic effects of H-B and R-F dramatically not only enhance both inter- and intramolecular charge transport but also optimize the frontier orbital levels; H-B strengthens intermolecular interactions, enabling localized ordered molecular packing and tighter π-π stacking, while R-F further amplifies these effects meanwhile improving backbone planarity, extending π-conjugation, and optimizing frontier orbital levels. As a result, P-HF achieves an outstanding hole mobility of 5.02 cm2 V-1 s-1, surpassing P-B (0.71 cm2 V-1 s-1) and P-H (2.13 cm2 V-1 s-1), placing it among the highest-performing DPP-based polymers reported. This work demonstrates that combining R-F and H-B offers a viable strategy for designing high-mobility conjugated materials, potentially advancing organic semiconductor development. This dual-engineering strategy is particularly suitable for π-conjugated polymers containing both hydrogen-bonding sites and ring-fused backbones.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"200 1","pages":"e202514768"},"PeriodicalIF":16.6,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338545","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
Bioorthogonal RNase L Recruitment Enables Targeted Inducible Degradation of SARS-CoV-2 RNA. 生物正交RNase L募集使靶向诱导降解SARS-CoV-2 RNA成为可能
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-22 DOI: 10.1002/anie.202515064
Wei Xiong,Xingyu Liu,Qianqian Qi,Yuanyuan Li,Siqi Huang,Wenjin Zou,Minzhi Dai,Yunjia Ning,Yuanqin Min,Xiang Zhou,Tian Tian
{"title":"Bioorthogonal RNase L Recruitment Enables Targeted Inducible Degradation of SARS-CoV-2 RNA.","authors":"Wei Xiong,Xingyu Liu,Qianqian Qi,Yuanyuan Li,Siqi Huang,Wenjin Zou,Minzhi Dai,Yunjia Ning,Yuanqin Min,Xiang Zhou,Tian Tian","doi":"10.1002/anie.202515064","DOIUrl":"https://doi.org/10.1002/anie.202515064","url":null,"abstract":"RIBOTAC (Ribonuclease Targeting Chimera) is a strategy that employs small molecules to selectively bind disease-associated RNA and recruit endogenous RNase L for targeted RNA degradation. This study advances the concept of bioorthogonal cleavage reactions to develop a novel \"bioorthogonal RIBOTAC\" (boRIBOTAC). Focusing on SARS-CoV-2 viral RNA, we engineered a cleavable \"cage\" protective group into a critical site within the RIBOTAC molecule, rendering it inactive as ProRIBOTAC in its untriggered state. When therapeutic intervention becomes necessary or disease progression demands it, a bioorthogonal cleavage reaction selectively removes the protective group, activating the RIBOTAC and thus facilitating inducible degradation of SARS-CoV-2 RNA. This research not only validates the feasibility of this boRIBOTAC and the inducible SARS-CoV-2 RNA degradation strategy but also demonstrates that the boRIBOTAC approach is poised to construct a controllable and effective RNA degradation platform. This platform is anticipated to provide significant technical reserves and practical prospects for addressing potential viral pandemics, chronic infections, and complex disease progressions, while also offering critical insights for future RNA-targeted drug design.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"32 1","pages":"e202515064"},"PeriodicalIF":16.6,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338546","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
Correspondence on "Taxonomy of Chemical Bondings: Opportunities and Challenges". “化学键的分类:机遇与挑战”函电。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-21 DOI: 10.1002/anie.202517813
Robin Taylor
{"title":"Correspondence on \"Taxonomy of Chemical Bondings: Opportunities and Challenges\".","authors":"Robin Taylor","doi":"10.1002/anie.202517813","DOIUrl":"https://doi.org/10.1002/anie.202517813","url":null,"abstract":"In a recent Scientific Perspective, Pizzi et al. recommend that σ- and π-hole bonds should be named after the Periodic-Table group to which the electrophile belongs or, if greater specificity is required, after the element type of the electrophile. This could easily give rise to dozens of noncovalent bond types. The stated benefits of this naming scheme are of debatable value. In addition, it conceals the strong underlying similarity of the differently named interactions. The obvious alternative is to use the terms that reflect the physical natures of these interactions: σ-hole bond, π-hole bond and, possibly, p-hole bond. The concerns that Pizzi et al. have about these terms are shown here to be unjustified, largely because they are based on irrelevant hypothetical interactions. The benefits of using σ-, π- and p-hole bonds instead of dozens of individual names are simplicity, greater clarity and a lack of ambiguity.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"49 1","pages":"e202517813"},"PeriodicalIF":16.6,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145331788","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
Chiral Discrimination of all Proteinogenic Amino Acid Enantiomers by Nanopore Sensing. 基于纳米孔传感的所有蛋白质原性氨基酸对映体的手性识别。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-21 DOI: 10.1002/anie.202515531
Hanhan Zhang,Kefan Wang,Xiao Zhou,Yifan Wang,Panke Zhang,Wenfei Li,Shuo Huang
{"title":"Chiral Discrimination of all Proteinogenic Amino Acid Enantiomers by Nanopore Sensing.","authors":"Hanhan Zhang,Kefan Wang,Xiao Zhou,Yifan Wang,Panke Zhang,Wenfei Li,Shuo Huang","doi":"10.1002/anie.202515531","DOIUrl":"https://doi.org/10.1002/anie.202515531","url":null,"abstract":"D-amino acids, the stereoisomers of the more prevalent L-forms, are ubiquitously distributed across microorganisms, plants, and mammalian systems. Recent advances have uncovered their indispensable roles in biological processes, yet direct, single-molecule detection of D-amino acids has long been understudied. The simultaneous discrimination of all amino acid enantiomers remains a formidable analytical challenge. Here, we report a nickel-ion chelated hetero-octameric Mycobacterium smegmatis porin A (MspA) (MspA-NTA-Ni) nanopore sensor that achieves simultaneous identification of all 19 D-amino acids corresponding to proteinogenic L-isomers. By integrating supervised machine learning algorithms, this system demonstrated an overall recognition accuracy of 99.5%. The method was further validated in analyzing acid-hydrolyzed D-peptide products, yielding clear compositional profiles of amino acid enantiomers. Notably, the technology enables simultaneous sensing of all 39 amino acid enantiomers with an overall accuracy of 98.9%. This approach not only allows direct characterization of DL-amino acid mixtures but also provides a critical sensor component for nanopore-based exo-sequencing of D-peptides and D-proteins.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"6 1","pages":"e202515531"},"PeriodicalIF":16.6,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145331798","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
Controlled Dual Activation of Rhenium(I) Photosensitizers and Profluorophores/Prodrugs via a Dissociative Bioorthogonal Tetrazine-Isonitrile Reaction. 通过解离生物正交四氮-异腈反应控制铼(I)光敏剂和前荧光基团/前药的双重活化。
IF 16.6 1区 化学
Angewandte Chemie International Edition Pub Date : 2025-10-21 DOI: 10.1002/anie.202516957
Eunice Chiu-Lam Mak,Lawrence Cho-Cheung Lee,Kenneth Kam-Wing Lo
{"title":"Controlled Dual Activation of Rhenium(I) Photosensitizers and Profluorophores/Prodrugs via a Dissociative Bioorthogonal Tetrazine-Isonitrile Reaction.","authors":"Eunice Chiu-Lam Mak,Lawrence Cho-Cheung Lee,Kenneth Kam-Wing Lo","doi":"10.1002/anie.202516957","DOIUrl":"https://doi.org/10.1002/anie.202516957","url":null,"abstract":"Strategies for prodrug activation have been developed to enhance treatment efficacy, with bioorthogonal dissociation reactions emerging as a promising approach due to their remarkable specificity. In this work, we designed three rhenium(I) polypyridine complexes featuring a tetrazylmethyl (TzMe) group capable of bioorthogonal activation by 3-isocyanopropyl (ICPr) or 3-isocyanopropyl-1-carbamoyl (ICPrc) derivatives. This design serves as a dual-release platform, which liberates rhenium(I) 3-hydroxypyridine complexes and functional payloads from rhenium(I) TzMe complexes and ICPr/ICPrc-caged compounds, respectively. Upon incubation with an ICPrc derivative, the TzMe complexes exhibited strong emission in acidic buffers, attributed to the predominant existence of the resulting rhenium(I) 3-hydroxypyridine complexes in their protonated form. Confocal imaging of live cells incubated with a TzMe complex and ICPr-caged fluorescein unveiled intense intracellular emission in distinct channels. Importantly, the therapeutic potential of this approach was underscored by the treatment of cells with a TzMe complex and ICPrc-caged doxorubicin. The anticancer effect was amplified through the synergy between singlet oxygen (1O2) photosensitization and prodrug activation, effectively combining photodynamic therapy with chemotherapy. The more pronounced 1O2 generation of the 3-hydroxypyridine complexes in acidic media and their specific accumulation within the acidic lysosomes of cancer cells highlight the potential of bioorthogonal prodrug activation for effective cancer-targeted therapy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"41 1","pages":"e202516957"},"PeriodicalIF":16.6,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338575","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
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