Journal of the American Chemical Society最新文献_第9页

Nitric Oxide Inhibition of Glycyl Radical Enzymes and Their Activases

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.4c14786

Juan Carlos Cáceres, Nathan G. Michellys, Brandon L. Greene

{"title":"Nitric Oxide Inhibition of Glycyl Radical Enzymes and Their Activases","authors":"Juan Carlos Cáceres, Nathan G. Michellys, Brandon L. Greene","doi":"10.1021/jacs.4c14786","DOIUrl":"https://doi.org/10.1021/jacs.4c14786","url":null,"abstract":"Innate immune response cells produce high concentrations of the free radical nitric oxide (NO) in response to pathogen infection. The antimicrobial properties of NO include nonspecific damage to essential biomolecules and specific inactivation of enzymes central to aerobic metabolism. However, the molecular targets of NO in anaerobic metabolism are less understood. Here, we demonstrate that the Escherichia coli glycyl radical enzyme pyruvate formate lyase (PFL), which catalyzes the anaerobic metabolism of pyruvate, is irreversibly inhibited by NO. Using electron paramagnetic resonance and site-directed mutagenesis we show that NO destroys the glycyl radical of PFL. The activation of PFL by its cognate radical S-adenosyl-l-methionine-dependent activating enzyme (PFL-AE) is also inhibited by NO, resulting in the conversion of the essential iron–sulfur cluster to dinitrosyl iron complexes. Whole-cell EPR and metabolic flux analyses of anaerobically growing E. coli show that PFL and PFL-AE are inhibited by physiologically relevant levels of NO in bacterial cell cultures, resulting in diminished growth and a metabolic shift to lactate fermentation. The class III ribonucleotide reductase (RNR) glycyl radical enzyme and its corresponding RNR-AE are also inhibited by NO in a mechanism analogous to those observed in PFL and PFL-AE, which likely contributes to the bacteriostatic effect of NO. Based on the similarities in reactivity of the PFL/RNR and PFL-AE/RNR-AE enzymes with NO, the mechanism of inactivation by NO appears to be general to the respective enzyme classes. The results implicate an immunological role of NO in inhibiting glycyl radical enzyme chemistry in the gut.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"64 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703086","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

In Situ Identification of Zinc Sites as Potential-Dependent Selectivity Switch over Dual-Atom Catalysts for H2O2 Electrosynthesis

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.5c0144910.1021/jacs.5c01449

Qizheng An, Xupeng Qin, Xuan Sun, Xu Zhang, Yuhao Zhang, Jianglong Guo, Jingjing Jiang, Jing Zhang, Baojie Li, Yaling Jiang, Hui Zhang, Xin Chen*, Yuanli Li, Kun Zheng, Weiren Cheng*, Dingsheng Wang and Qinghua Liu*,

{"title":"In Situ Identification of Zinc Sites as Potential-Dependent Selectivity Switch over Dual-Atom Catalysts for H2O2 Electrosynthesis","authors":"Qizheng An, Xupeng Qin, Xuan Sun, Xu Zhang, Yuhao Zhang, Jianglong Guo, Jingjing Jiang, Jing Zhang, Baojie Li, Yaling Jiang, Hui Zhang, Xin Chen*, Yuanli Li, Kun Zheng, Weiren Cheng*, Dingsheng Wang and Qinghua Liu*, ","doi":"10.1021/jacs.5c0144910.1021/jacs.5c01449","DOIUrl":"https://doi.org/10.1021/jacs.5c01449https://doi.org/10.1021/jacs.5c01449","url":null,"abstract":"Controllably breaking the activity–selectivity trade-offs in the electrocatalytic oxygen reduction reaction to produce H2O2 has long been a challenge in renewable energy technologies. Herein, by assigning the activity and selectivity requirements to two independent single-atom sites, we deliberately engineered a Co–Zn DAC for promising H2O2 electrosynthesis, from which the Co sites provided the activity response for oxygen reduction, and the Zn sites regulated the reaction selectivity toward the 2e– pathway. Through multidimensional in situ characterizations, a potential-dependent switching function of the Zn sites was revealed, which made the increase in H2O2 production at various reaction stages controllable. As a result, efficient H2O2 selectivity switching from 11.1% in the single Co atom catalyst to 94.8% in the Co–Zn DAC was realized, with a prominent turnover frequency of 2.7 s–1 among the reported H2O2-producing catalysts. Notably, a similar effect was also observed in M–Zn DACs (M = Pt, Ru, or Ni), which demonstrated the universal switcher role of the Zn sites. The real-time catalytic site behavior insights gained through this integrated experimental and theoretical study are envisioned to be valuable not only for the ORR but also for other energy catalysis reactions involving activity–selectivity trade-off issues.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 13","pages":"11465–11476 11465–11476"},"PeriodicalIF":14.4,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746036","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

Configuration Retention in P-Trifluoromethyl Phosphine Enabled Rh(I)-Catalyzed Decarbonylative Coupling of Carboxylates and Boroxines

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.5c03546

Shouzhi Zhang, Bo Li, Suhua Li

引用次数: 0

Reorganizing the Pt Surface Water Structure for Highly Efficient Alkaline Hydrogen Oxidation Reaction

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.5c00775

Chengzhang Wan, Zisheng Zhang, Sibo Wang, Qiang Sun, Ershuai Liu, Heting Pu, Ao Zhang, Zhengyue Chen, Aamir Hassan Shah, Xiaoyang Fu, Anastassia N. Alexandrova, Qingying Jia, Yu Huang, Xiangfeng Duan

{"title":"Reorganizing the Pt Surface Water Structure for Highly Efficient Alkaline Hydrogen Oxidation Reaction","authors":"Chengzhang Wan, Zisheng Zhang, Sibo Wang, Qiang Sun, Ershuai Liu, Heting Pu, Ao Zhang, Zhengyue Chen, Aamir Hassan Shah, Xiaoyang Fu, Anastassia N. Alexandrova, Qingying Jia, Yu Huang, Xiangfeng Duan","doi":"10.1021/jacs.5c00775","DOIUrl":"https://doi.org/10.1021/jacs.5c00775","url":null,"abstract":"The hydrogen oxidation reaction (HOR) in alkaline electrolytes exhibits markedly slower kinetics than that in acidic electrolytes. This poses a critical challenge for alkaline exchange membrane fuel cells (AEMFCs). The slower kinetics in alkaline electrolytes is often attributed to the more sluggish Volmer step (hydrogen desorption). It has been shown that the alkaline HOR activity on the Pt surface can be considerably enhanced by the presence of oxophilic transition metals (TMs) and surface-adsorbed hydroxyl groups on TMs (TM–OHad), although the exact role of TM–OHad remains a topic of active debates. Herein, using single-atom Rh-tailored Pt nanowires as a model system, we demonstrate that hydroxyl groups adsorbed on the Rh sites (Rh–OHad) can profoundly reorganize the Pt surface water structure to deliver a record-setting alkaline HOR performance. In situ surface characterizations, together with theoretical studies, reveal that surface Rh–OHad could promote the oxygen-down water (H2O↓) that favors more hydrogen bond with Pt surface adsorbed hydrogen (H2O↓···Had-Pt) than the hydrogen-down water (OH2↓). The H2O↓ further serves as the bridge to facilitate the formation of an energetically favorable six-membered-ring transition structure with neighboring Pt–Had and Rh–OHad, thus reducing the Volmer step activation energy and boosting HOR kinetics.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"88 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695869","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

Ligand-Controlled Enantioselective Copper-Catalyzed Hydroboration and Ring-Opening Dihydroboration of Arylidenecyclobutanes

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.5c01729

Wenrui Zheng, Yuhan Cao, Boon Beng Tan, Yifan Wang, Shaozhong Ge, Yixin Lu

{"title":"Ligand-Controlled Enantioselective Copper-Catalyzed Hydroboration and Ring-Opening Dihydroboration of Arylidenecyclobutanes","authors":"Wenrui Zheng, Yuhan Cao, Boon Beng Tan, Yifan Wang, Shaozhong Ge, Yixin Lu","doi":"10.1021/jacs.5c01729","DOIUrl":"https://doi.org/10.1021/jacs.5c01729","url":null,"abstract":"Arylidenecyclobutanes are readily accessible and versatile reagents in synthetic chemistry due to the multifaceted reactivity exhibited by their alkene and strained cyclobutane moieties. However, metal-catalyzed enantioselective functionalization of arylidenecyclobutanes, particularly the controllable ring-retaining and ring-opening reactions, is rarely explored. Considering the versatile synthetic utility of enantioenriched organoboronate compounds, herein we report ligand-controlled enantioselective copper-catalyzed ring-retaining hydroboration and ring-opening dihydroboration reactions of arylidenecyclobutanes that afford chiral α-cyclobutyl benzylboronate and 1,5-diboronate compounds with high enantioselectivity when (S)-DTBM-Segphos and (S,S)-Ph-BPE are employed, respectively. Mechanistic studies reveal that the ring-opening process of arylidenecyclobutanes via β-C elimination is significantly slower than that of arylidenecyclopropanes in the presence of CuOAc and (S,S)-Ph-BPE. The synthetic utility of these two enantioselective protocols is further demonstrated through conducting various stereospecific and site-selective transformations of the enantioenriched organoboron products, including concise synthesis of bioactive molecules.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"61 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695721","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

Synthesis of Amorphous Graphene and Graphene Oxide Analogues

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.5c00548

Tomoki Sakuma, Ryoichi Sato, Akihiro Yamaguchi, Hiroaki Imai, Noriyoshi Arai, Yuya Oaki

引用次数: 0

Dearomative Skeletal Editing of Benzenoids via Diradical

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.5c01983

Xiang-Xin Zhang, Shan-Tong Xu, Xue-Ting Li, Ting-Ting Song, Ding-Wei Ji, Qing-An Chen

{"title":"Dearomative Skeletal Editing of Benzenoids via Diradical","authors":"Xiang-Xin Zhang, Shan-Tong Xu, Xue-Ting Li, Ting-Ting Song, Ding-Wei Ji, Qing-An Chen","doi":"10.1021/jacs.5c01983","DOIUrl":"https://doi.org/10.1021/jacs.5c01983","url":null,"abstract":"Dearomative skeletal editing of benzenoids represents a promising yet challenging strategy for the rapid construction of high-value carbon frameworks from readily accessible starting materials. Büchner reaction is a unique type of expansive skeletal editing that transforms benzenoids into functionalized cycloheptatrienes. However, due to challenges in compatibility and selectivity, achieving seamless integration of this reaction with dearomative cycloaddition within a unified system remains undeveloped. Here, we demonstrated an energy-transfer-induced intermolecular dearomative skeletal editing reaction of benzenoids with a range of electronically diverse alkynes. This protocol employed N-acylimines as diradical precursors to efficiently construct various structurally diverse polycyclic frameworks in high chemo-, regio-, and diastereoselectivities that have been previously inaccessible. The challenges related to general reactivity and selectivity issues were circumvented through the smooth merging of photoinduced skeletal editing with dearomative cycloaddition. Experimental and computational studies were performed to support the diradical mechanism and interpret the origins of the observed chemo-, regio-, and diastereoselectivities.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"65 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695720","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

An Atomically Dispersed Mn Photocatalyst for Vicinal Dichlorination of Nonactivated Alkenes 一种原子分散锰光催化剂用于非活化烯的弧形二氯化反应

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.4c16413

Prakash Kumar Sahoo, Rakesh Maiti, Peng Ren, Juan José Delgado Jaén, Xingchao Dai, Giovanni Barcaro, Susanna Monti, Alina Skorynina, Anna Rokicińska, Aleksander Jaworski, Laura Simonelli, Piotr Kuśtrowski, Jabor Rabeah, Shoubhik Das

{"title":"An Atomically Dispersed Mn Photocatalyst for Vicinal Dichlorination of Nonactivated Alkenes","authors":"Prakash Kumar Sahoo, Rakesh Maiti, Peng Ren, Juan José Delgado Jaén, Xingchao Dai, Giovanni Barcaro, Susanna Monti, Alina Skorynina, Anna Rokicińska, Aleksander Jaworski, Laura Simonelli, Piotr Kuśtrowski, Jabor Rabeah, Shoubhik Das","doi":"10.1021/jacs.4c16413","DOIUrl":"https://doi.org/10.1021/jacs.4c16413","url":null,"abstract":"A novel Mn-based single-atom photocatalyst is disclosed in this study, designed for the dichlorination of alkenes to achieve vicinal dichlorinated products using N-chlorosuccinimide as a mild chlorinating agent, which have widespread applications as pest controlling agents, polymers, flame retardants, and pharmaceuticals. In developing this innovative catalyst, we achieved the atomic dispersion of Mn on aryl-amino-substituted graphitic carbon nitride (f-C3N4). This marks the first instance of a heterogeneous version, offering an operationally simple, sustainable, and efficient pathway for dichlorination of alkenes, including drugs, bioactive compounds, and natural products. This material was extensively characterized by using techniques such as UV–vis spectroscopy, X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), magic-angle spinning (MAS), and solid-state nuclear magnetic resonance (ssNMR) spectroscopy to understand it at the atomic level. Furthermore, mechanistic studies based on multiscale molecular modeling, combining classical reactive molecular dynamics (RMD) simulations and quantum chemistry (QC) calculations, illustrated that the controlled formation of Cl radicals from the in situ formed Mn–Cl bond is responsible for the dichlorination reaction of alkenes. In addition, gram-scale and reusability tests were also performed to demonstrate the applicability of this approach on an industrial scale.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"71 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695868","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

Uridine Embedded within DNA is Repaired by Uracil DNA Glycosylase via a Mechanism Distinct from That of Ribonuclease H2

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.5c0143610.1021/jacs.5c01436

Chaochao Fan, Xuelin Zhan, Fengmin Guo, Qiang Li, Kuan Lu, Xiajing Shan, Yifei Zhou, Mengtian Ren, Marc M. Greenberg*, Yijin Liu* and Chuanzheng Zhou*,

{"title":"Uridine Embedded within DNA is Repaired by Uracil DNA Glycosylase via a Mechanism Distinct from That of Ribonuclease H2","authors":"Chaochao Fan, Xuelin Zhan, Fengmin Guo, Qiang Li, Kuan Lu, Xiajing Shan, Yifei Zhou, Mengtian Ren, Marc M. Greenberg*, Yijin Liu* and Chuanzheng Zhou*, ","doi":"10.1021/jacs.5c0143610.1021/jacs.5c01436","DOIUrl":"https://doi.org/10.1021/jacs.5c01436https://doi.org/10.1021/jacs.5c01436","url":null,"abstract":"Uridine (rU) and 2′-deoxyuridine (dU) are common DNA lesions. dU is repaired through a base excision repair (BER) pathway initiated by uracil DNA glycosylase (UDG), while rU is typically removed from DNA via ribonucleotide excision repair, mediated by RNase H2. In this study, we report that rU is also repaired through the UDG-mediated BER pathway. We found that UDG catalyzes the removal of uracil from rU embedded in DNA, but exhibits no activity toward rU in RNA. Biochemical and crystallographic analyses revealed that the 2′–OH group of rU is effectively accommodated by UDG and directly participates in catalyzing the hydrolysis of the N-glycosidic bond. The abasic site product generated upon removal of uracil from rU by UDG is further processed by downstream BER enzymes to restore undamaged DNA. Our findings suggest that UDG-initiated BER constitutes a previously unrecognized pathway for the repair of rU-specific ribonucleotides. Additionally, we developed a method for selectively quantifying rU content in DNA. Using this method, we determined that rU repair by UDG is not a major pathway in human cells. This discovery expands our understanding of the diverse biological functions of UDG, and inspires further investigation to determine the role of its rU-removal in cells.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 13","pages":"11574–11583 11574–11583"},"PeriodicalIF":14.4,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746003","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

Synthesis of Amorphous Graphene and Graphene Oxide Analogues

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-03-25 DOI: 10.1021/jacs.5c0054810.1021/jacs.5c00548

Tomoki Sakuma, Ryoichi Sato, Akihiro Yamaguchi, Hiroaki Imai, Noriyoshi Arai and Yuya Oaki*,

{"title":"Synthesis of Amorphous Graphene and Graphene Oxide Analogues","authors":"Tomoki Sakuma, Ryoichi Sato, Akihiro Yamaguchi, Hiroaki Imai, Noriyoshi Arai and Yuya Oaki*, ","doi":"10.1021/jacs.5c0054810.1021/jacs.5c00548","DOIUrl":"https://doi.org/10.1021/jacs.5c00548https://doi.org/10.1021/jacs.5c00548","url":null,"abstract":"Graphene and graphene oxide (GO) are promising two-dimensional nanomaterials. An ultimate goal is to achieve large-scale bottom-up syntheses of perfect graphene and GO. However, controlled syntheses of perfect graphitic structures still remain challenges in chemistry and materials science. Moreover, amorphous types have not received much attention. The present work shows syntheses, structures, and applications of amorphous graphene and GO analogues alternative to the ideal ones. The simultaneous multiple reactions of two conjugated monomers provide amorphous conjugated polymer networks containing low-crystalline graphitic domains and their stacking. The stacked amorphous graphene and GO are exfoliated into thin nanosheets including few-layers and monolayers. Moreover, in situ syntheses of the amorphous GO analogues are applied to obtain a reinforced plastic with high mechanical strength. The present work implies that various functional nanocarbons can be designed and synthesized by tailored combinations of conjugated monomers.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 13","pages":"11564–11573 11564–11573"},"PeriodicalIF":14.4,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.5c00548","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0