Journal of the American Chemical Society最新文献_第10页

Total Synthesis of (+)-Mannolide B (+)-Mannolide B 的全合成

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-17 DOI: 10.1021/jacs.4c12767

Peng Chen, Lijun Chen, Hongpeng Lin, Yanxing Jia

引用次数: 0

Non-noble Metal Single-Molecule Photocatalysts for the Overall Photosynthesis of Hydrogen Peroxide

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c09445

Fan Fu, Yongxin Liu, Mingliang Liu, Zhengguang Li, Wanying Zhong, Yaqin Li, Kaixiu Li, Jun Wang, Yongchao Huang, Yiming Li, Wei Liu, Yi Zhang, Kaisong Xiang, Hui Liu, Pingshan Wang, Die Liu

{"title":"Non-noble Metal Single-Molecule Photocatalysts for the Overall Photosynthesis of Hydrogen Peroxide","authors":"Fan Fu, Yongxin Liu, Mingliang Liu, Zhengguang Li, Wanying Zhong, Yaqin Li, Kaixiu Li, Jun Wang, Yongchao Huang, Yiming Li, Wei Liu, Yi Zhang, Kaisong Xiang, Hui Liu, Pingshan Wang, Die Liu","doi":"10.1021/jacs.4c09445","DOIUrl":"https://doi.org/10.1021/jacs.4c09445","url":null,"abstract":"Despite the great progress in molecule photocatalytic solar energy conversion, it is particularly challenging to realize a photocatalytic overall reaction in a non-noble metal complex, which represents a new paradigm for photosynthesis. In this study, a class of novel non-noble metal complexes with head-to-tail geometry were designed and readily synthesized via the coordination of triphenylamine-modified 2,2′: 6′,2″-terpyridine ligands with Zn2+. As expected, these complexes exhibited the desired through-space charge-transfer transition, generating both long-lived excited states (on the order of microseconds) and separate redox centers under visible-light irradiation. These complexes have particularly low exciton binding energies, which make them excellent heterogeneous single molecular photocatalysts for the overall photosynthetic production of H2O2. Remarkably, a high H2O2 evolution rate (8862 μmol g–1 h–1) was achieved in pure H2O under an air atmosphere via precise molecular tailoring, revealing the unparalleled advantages of molecular photocatalysts in improving the catalytic rate of H2O2 production. This is the first time that single-molecule photocatalysts have been used to efficiently complete the photosynthesis of H2O2. This study presents a new paradigm for photocatalytic energy conversion and provides unique insights into the design of molecular photocatalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"12 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832956","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

Single-Carbon Insertion into Single C–C Bonds with Diazirines

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c12632

Valero G. Alfonso, Karen de la Vega-Hernández, Marcos G. Suero

引用次数: 0

Multielectron Redox Chemistry of Ytterbium Complexes Reaching the +1 and Zero Formal Oxidation States

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c14904

Maxime Tricoire, Weronika Sroka, Thayalan Rajeshkumar, Rosario Scopelliti, Andrzej Sienkiewicz, Laurent Maron, Marinella Mazzanti

{"title":"Multielectron Redox Chemistry of Ytterbium Complexes Reaching the +1 and Zero Formal Oxidation States","authors":"Maxime Tricoire, Weronika Sroka, Thayalan Rajeshkumar, Rosario Scopelliti, Andrzej Sienkiewicz, Laurent Maron, Marinella Mazzanti","doi":"10.1021/jacs.4c14904","DOIUrl":"https://doi.org/10.1021/jacs.4c14904","url":null,"abstract":"Lanthanide redox reactivity remains limited to one-electron transfer reactions due to their inability to access a broad range of oxidation states. Here, we show that multielectron reductive chemistry is achieved for ytterbium by using the tripodal tris(siloxide)arene redox-active ligand, which can store two electrons in the arene anchor. Reduction of the Yb(III) complex of the tris(siloxide)arene tripodal ligand affords the Yb(II) analogue by metal-centered reduction. Two subsequent reduction events occur mainly at the ligand with retention of the ligand framework and formation of analogous complexes of Yb in the formal +1 and zero oxidation states. Four complexes of Yb in four different oxidation states were isolated, crystallographically and spectroscopically characterized, and their electronic structure was confirmed by DFT studies. Reactivity studies show that the “Yb(I)” complex can transfer two electrons to organic azides, with retention of its molecular structure, to form highly reactive imido intermediates, providing a rare example of a two-electron transfer at a single lanthanide center that does not involve accessing the +4 oxidation state.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"247 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832658","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

Direct Determination of a Giant Zero-Field Splitting of 5422 cm–1 in a Triplet Organobismuthinidene by Infrared Electron Paramagnetic Resonance

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c14795

Tarek Al Said, Davide Spinnato, Karsten Holldack, Frank Neese, Josep Cornella, Alexander Schnegg

引用次数: 0

Classical View on Nonclassical Crystal Growth in a Biological Setting 生物环境下非经典晶体生长的经典观点

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c11940

Richard Johannes Best, Deborah Stier, Lukas Kuhrts, Igor Zlotnikov

引用次数: 0

Plasma-Catalyst Dynamics: Nonthermal Activation of Strong Metal–Support Interactions

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c12388

Russell J. Clarke, Isaac J. Nice, Jason C. Hicks

{"title":"Plasma-Catalyst Dynamics: Nonthermal Activation of Strong Metal–Support Interactions","authors":"Russell J. Clarke, Isaac J. Nice, Jason C. Hicks","doi":"10.1021/jacs.4c12388","DOIUrl":"https://doi.org/10.1021/jacs.4c12388","url":null,"abstract":"Nonthermal plasma-surface interactions enable transformative advancements in green chemistry, healthcare, materials processing, pollution abatement, and the ever-growing area of plasma catalysis. In the context of plasma catalysis, the fate of the active sites during plasma treatment has remained enigmatic, and observation of low-temperature plasma-catalyst events has been challenging. The induction of strong metal–support interactions (SMSI) through high-temperature hydrogen treatment is a well-documented and established, yet limited, method to impact selectivity and stability of noble metal catalysts on reducible supports. Thermally driven SMSI occurs through reduction and subsequent migration of the support to the surface of exposed metal sites, thus affecting the catalyst both electronically and geometrically and serving as an ideal system to evaluate dynamic plasma-catalyst interactions. In this study, a dielectric barrier discharge of hydrogen was used to successfully induce a plasma-SMSI state (P-SMSI) in niobia-supported platinum particles at bulk-gas temperatures as low as −30 °C, which enhances the selectivity for propane dehydrogenation and offers conclusive evidence of plasma-catalyst interactions. Time-resolved spectroscopic evidence of this phenomenon was obtained in situ using a cryogenically cooled plasma IR transmission cell, which provided evidence of diffusion-controlled surface migration. Collectively, P-SMSI constitutes a promising, low-impact technology for synthesizing SMSI-enhanced catalysts with controllable active sites, and knowledge of the nonthermal plasma-catalyst dynamics is critical in designing materials for specific applications or selecting conditions of operation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"201 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832962","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

Precise Large-Scale Chemical Transformations on Surfaces: Deep Learning Meets Scanning Probe Microscopy with Interpretability

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c14757

Nian Wu, Markus Aapro, Joakim S. Jestilä, Robert Drost, Miguel Martínez García, Tomás Torres, Feifei Xiang, Nan Cao, Zhijie He, Giovanni Bottari, Peter Liljeroth, Adam S. Foster

{"title":"Precise Large-Scale Chemical Transformations on Surfaces: Deep Learning Meets Scanning Probe Microscopy with Interpretability","authors":"Nian Wu, Markus Aapro, Joakim S. Jestilä, Robert Drost, Miguel Martínez García, Tomás Torres, Feifei Xiang, Nan Cao, Zhijie He, Giovanni Bottari, Peter Liljeroth, Adam S. Foster","doi":"10.1021/jacs.4c14757","DOIUrl":"https://doi.org/10.1021/jacs.4c14757","url":null,"abstract":"Scanning probe microscopy (SPM) techniques have shown great potential in fabricating nanoscale structures endowed with exotic quantum properties achieved through various manipulations of atoms and molecules. However, precise control requires extensive domain knowledge, which is not necessarily transferable to new systems and cannot be readily extended to large-scale operations. Therefore, efficient and autonomous SPM techniques are needed to learn optimal strategies for new systems, in particular for the challenge of controlling chemical reactions and hence offering a route to precise atomic and molecular construction. In this paper, we developed a software infrastructure named AutoOSS (Autonomous On-Surface Synthesis) to automate bromine removal from hundreds of Zn(II)-5,15-bis(4-bromo-2,6-dimethylphenyl)porphyrin (ZnBr2Me4DPP) on Au(111), using neural network models to interpret STM outputs and deep reinforcement learning models to optimize manipulation parameters. This is further supported by Bayesian optimization structure search (BOSS) and density functional theory (DFT) computations to explore 3D structures and reaction mechanisms based on STM images.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832655","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

Enzymatic Ring Contraction for the Biosynthesis of Sulfur-Containing Cyclopentachromone

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c11906

Qiuyue Nie, Chunxiao Sun, Shuai Liu, Qiang Li, Maria Zotova, Tong Zhu, Xue Gao

{"title":"Enzymatic Ring Contraction for the Biosynthesis of Sulfur-Containing Cyclopentachromone","authors":"Qiuyue Nie, Chunxiao Sun, Shuai Liu, Qiang Li, Maria Zotova, Tong Zhu, Xue Gao","doi":"10.1021/jacs.4c11906","DOIUrl":"https://doi.org/10.1021/jacs.4c11906","url":null,"abstract":"Cyclopentachromone, distinguished by its 6/6/5 heterotricyclic ring structure, is a key building block in many bioactive natural products, yet its enzymatic origin remains unclear. We identified a new class of cyclopentachromone-containing compounds, termed isochromosulfines, characterized by unique C–S bonds. A distinct FAD-dependent monooxygenase, IscL, was identified to catalyze the formation of the 6/6/5 cyclopentadiene intermediate, 2S-remisporine A, from a 6/6/6 xanthone precursor via benzene ring contraction. The high reactivity of 2S-remisporine A further promotes a spontaneous thiol-Micheal addition reaction with thiol-containing compounds, forming the C–S bond in isochromosulfines. Additionally, we demonstrate that IscL homologues mediate a bifurcated pathway of benzene ring modification in the xanthone intermediate, leading to either ring contraction or cleavage, which is determined by a critical residue at position 230 to be phenylalanine or tyrosine. Our findings highlight the pivotal role of IscL in forming the 6/6/5 cyclopentachromone scaffold and offer deep insights into its catalytic mechanism. Our work lays the foundation for genome mining of cyclopentachromone-containing compounds and shows the potential application of IscL in biocatalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"115 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832961","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

Temperature-Adaptive Organic Scintillators for X-ray Radiography

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-12-16 DOI: 10.1021/jacs.4c12872

Mengyang Dong, Ziyang Wang, Zhenyi Lin, Yushan Zhang, Zhengkang Chen, Yiming Wu, Huili Ma, Zhongfu An, Long Gu, Wei Huang

{"title":"Temperature-Adaptive Organic Scintillators for X-ray Radiography","authors":"Mengyang Dong, Ziyang Wang, Zhenyi Lin, Yushan Zhang, Zhengkang Chen, Yiming Wu, Huili Ma, Zhongfu An, Long Gu, Wei Huang","doi":"10.1021/jacs.4c12872","DOIUrl":"https://doi.org/10.1021/jacs.4c12872","url":null,"abstract":"Organic phosphorescence or thermally activated delayed fluorescence (TADF) scintillators, while effective in utilizing triplet excitons, are sensitive to temperature changes, which can impact radioluminescence performance. In this study, we have developed a type of temperature-adaptive organic scintillator with phosphorescence and TADF dual emission. These scintillators can automatically switch modes with temperature changes, enabling efficient radioluminescence from 77 to 400 K. The highest photoluminescence quantum yield and light yield are 83.2% and 78,229 ± 562 photons MeV–1 excited by a UV lamp and X-ray, respectively. Their detection limit is 51 and 23 nGy·s–1 at room temperature and 77 K, respectively, which is lower than the standard dosage of 5.5 μGy s–1 for X-ray diagnostics. Moreover, given the high spatial resolution of 21.7 l p mm–1, we demonstrate their potential application in multiple-temperature X-ray radiography, offering promising new possibilities. This work opens a new route for developing organic scintillators to adapt to ambient temperature change and paves the way for their use in various temperature-sensitive radiography applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"247 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832964","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