Journal of the American Chemical Society最新文献_第2页

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23

Jing Liu, Zhihao Zhao, Chenghua Deng, Richard Zanni, Ralph R. Weichselbaum and Wenbin Lin*,

引用次数: 0

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23

Ruixue Zhao*, Sungmin Kim*, Mal-Soon Lee*, Benjamin A. Jackson, Fuli Deng, Xiaomai Chen, Cong Zhou, Konstantin Khivantsev, Yue Liu, Vassiliki-Alexandra Glezakou, Roger Rousseau and Johannes A. Lercher*,

引用次数: 0

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23

Clément Atlan*, Corentin Chatelier, Apinya Ngoipala, Kyle Olson, Arnaud Viola, Ewen Bellec, Michael Grimes, Bruno Gilles, Minaam Qamar, Matous Mrovec, Steven J. Leake, Joël Eymery, Tobias U. Schülli, Matthias Vandichel, Marie-Ingrid Richard* and Frédéric Maillard*,

引用次数: 0

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23

Julian von Hofe, Jatin Abacousnac, Mechi Chen, Moeka Sasazawa, Ida Javér Kristiansen, Soren Westrey, David G. Grier and Saumya Saurabh*,

引用次数: 0

The Electronic Structure of the Superatom Au3. 超原子Au3的电子结构。

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23 DOI: 10.1021/jacs.5c09486

Nikita Kavka,Marko Förstel,Kai Pollow,Taarna Studemund,Roland Mitric,Otto Dopfer

{"title":"The Electronic Structure of the Superatom Au3.","authors":"Nikita Kavka,Marko Förstel,Kai Pollow,Taarna Studemund,Roland Mitric,Otto Dopfer","doi":"10.1021/jacs.5c09486","DOIUrl":"https://doi.org/10.1021/jacs.5c09486","url":null,"abstract":"At the heart of large gold clusters lies Au3+, a key three-ring structure that plays a fundamental role in many gold assemblies. Studying this smallest unit provides valuable insight into the photocatalytic mechanisms of larger gold systems. This study presents the first high-resolution, vibrationally resolved optical spectra of mass-selected Au3+ clusters obtained through photodissociation spectroscopy. The spectra, spanning 2.7-5.0 eV, reveal five band systems with complex and irregular structures. To interpret these spectra, we employ ab initio calculations at the CASSCF level, incorporating spin-orbit coupling to characterize the electronic structure of Au3+. These calculations reveal that the observed spectral features arise from the interplay of closely spaced excited states dominated by d-orbital excitations, a small s-d orbital gap, and significant vibronic and spin-orbit coupling. Our findings emphasize that accurate characterization of the excited states of Au3+, a seemingly simple triatomic molecule with a valence configuration and orbital structure similar to that of the strontium atom, requires sophisticated multireference calculations. Simplified theoretical methods, such as density functional theory (DFT) and those utilizing small HOMO-LUMO active spaces, fail to capture the strong multireference effects driven by d-orbital contributions, underscoring the complexity of excited-state interactions in gold clusters.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"25 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684277","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

Dynamic Modulation of Multicellular Interactions via ATP-Dissipative DNA Assembly. 通过atp耗散DNA组装的多细胞相互作用的动态调制。

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23 DOI: 10.1021/jacs.5c08925

Yi Xu,Yao Luo,Xiaoyun Lu,Jingyi Ye,Zeyu Chen,Yao Hu,Chen Shen,Bin Zhao,Erfeng Kou,Jie Deng,Chunhai Fan,Huan Zhang,Honglu Zhang

{"title":"Dynamic Modulation of Multicellular Interactions via ATP-Dissipative DNA Assembly.","authors":"Yi Xu,Yao Luo,Xiaoyun Lu,Jingyi Ye,Zeyu Chen,Yao Hu,Chen Shen,Bin Zhao,Erfeng Kou,Jie Deng,Chunhai Fan,Huan Zhang,Honglu Zhang","doi":"10.1021/jacs.5c08925","DOIUrl":"https://doi.org/10.1021/jacs.5c08925","url":null,"abstract":"Living cells exhibit dynamic adaptability through ATP-fueled processes that are crucial for tissue development and immune responses. Conventional methods for controlling cell assembly lack the nonequilibrium, reversible behavior of natural systems. Here, we present an ATP-dissipative DNA assembly system that leverages DNA's programmability to enable adaptive, hierarchical structures with spatiotemporal control. By utilizing various DNA monomers, including double-stranded DNA (dsDNA), tetrahedral DNA frameworks, and branched DNA frameworks, we achieve the precise regulation of cell assembly in response to ATP-driven enzymatic reactions. BDF-based condensates, formed through multivalent liquid-liquid phase separation (LLPS), dynamically modulate intercellular interactions, mimicking the extracellular matrix adaptability. This system was successfully applied to regulate cell assembly in Ramos, PC-12, and natural killer (NK) cells. By harnessing endogenous ATP secreted by cells, we enabled real-time reversible control over cell assembly. Furthermore, the ATP-dissipative assembly system enhanced the tumor-killing efficacy of NK cells by modulating their interactions with cancer cells. This work highlights the potential of DNA-based dissipative self-assembly for precise spatiotemporal regulation of cellular interactions, shedding light on advanced applications in intelligent materials and immunotherapy.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"110 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684337","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

Cooperative Photoenzymatic Catalysis for Enantioselective Fluoroalkylation/Cyclization Cascade. 对映选择性氟烷基化/环化级联的协同光酶催化。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23 Epub Date: 2025-07-10 DOI: 10.1021/jacs.5c05656

Dongshan Wu, Sanshan Wang, Haowen Zhang, Han Ke, Zeying Sun, Shuhan Xie, Yihui Gao, Jun Yang, Bingwu Wang, Xiaoguang Lei

{"title":"Cooperative Photoenzymatic Catalysis for Enantioselective Fluoroalkylation/Cyclization Cascade.","authors":"Dongshan Wu, Sanshan Wang, Haowen Zhang, Han Ke, Zeying Sun, Shuhan Xie, Yihui Gao, Jun Yang, Bingwu Wang, Xiaoguang Lei","doi":"10.1021/jacs.5c05656","DOIUrl":"10.1021/jacs.5c05656","url":null,"abstract":"Due to the invaluable properties of organofluorine compounds, incorporating a fluorinated unit has become necessary in pharmaceuticals, agrochemicals, and materials. However, achieving asymmetric fluorination such as trifluoromethylation through chemo- or biocatalysis has been a synthetic challenge. Here, we introduce a unique cooperative photoenzymatic catalysis for the enantioselective fluoroalkylation/cyclization cascade. This method, utilizing the engineered flavin-dependent \"ene\"-reductases (EREDs) and an exogenous photocatalyst (PC), produces a variety of fluorinated cyclic ketones with high yield and enantioselectivity. The discovery of stereocomplementary enzymes that provide access to both enantiomers of the cyclized products further enhances the synthetic applications of our method. The radical-trapping, spectroscopic, and kinetic studies have substantiated the interaction mode between the PC and the enzyme and demonstrated a cascade reaction mechanism involving a unique intermolecular addition of fluorinated radicals and a stereocontrolled intramolecular cyclization. Isotopic labeling experiments support flavin as the source of the hydrogen atom. Molecular dynamics simulations reveal that the binding interaction of the enzyme and the intermediate triggers the photoinduced enantioselective cyclization. This work underscores the potential of enzymes for the asymmetric synthesis of fluorinated compounds.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"25508-25516"},"PeriodicalIF":14.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606851","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

Enhancing CO₂ Electroreduction to Ethylene in Acidic Solution by Optimizing Cation Configuration on the Cu Surface. 通过优化铜表面阳离子构型提高酸性溶液中CO2电还原乙烯的性能。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23 Epub Date: 2025-07-11 DOI: 10.1021/jacs.5c06402

Yaoyu Yin, Zhongnan Ling, Shiqiang Liu, Jiapeng Jiao, Yiyong Wang, Yaguang Peng, Xing Tong, Meng Zhou, Rongjuan Feng, Xueqing Xing, Yi Xu, Qinggong Zhu, Xiaofu Sun, Mingchuan Luo, Xinchen Kang, Buxing Han

{"title":"Enhancing CO2 Electroreduction to Ethylene in Acidic Solution by Optimizing Cation Configuration on the Cu Surface.","authors":"Yaoyu Yin, Zhongnan Ling, Shiqiang Liu, Jiapeng Jiao, Yiyong Wang, Yaguang Peng, Xing Tong, Meng Zhou, Rongjuan Feng, Xueqing Xing, Yi Xu, Qinggong Zhu, Xiaofu Sun, Mingchuan Luo, Xinchen Kang, Buxing Han","doi":"10.1021/jacs.5c06402","DOIUrl":"10.1021/jacs.5c06402","url":null,"abstract":"The electroreduction of CO2 to C2H4 offers a promising avenue for advancing carbon neutrality and promoting sustainable chemical manufacturing. In acidic environments, while long-term operational stability and CO2 utilization efficiency are enhanced, the formation of C-C bonds is hindered due to the weak adsorption of *CO intermediates and the competing hydrogen evolution reaction (HER). Theoretical studies suggest that K+ cations with reduced bound water content can strengthen the adsorption of the critical *CO intermediate, and that elevated K+ concentrations on the Cu electrode surface significantly facilitate CO2 electroreduction to C2H4. In this work, a catalyst termed CuTEA was developed by strategically modifying the Nafion ionomer distribution within the catalyst layer. This structural adjustment effectively lowers the bound water associated with K+ cations and concurrently elevates the surface concentration of K+ on the Cu electrode, thereby promoting C-C coupling for C2H4 formation while suppressing HER. Consequently, CuTEA achieves a Faradaic efficiency of 70.2% for C2H4 production, accompanied by a high partial current density of 561.6 mA cm-2 in an acidic electrolyte (pH = 1).","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"25584-25591"},"PeriodicalIF":14.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144606854","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

Ferrous Iron Metabolism Modulator for Immune Stress Regulation and Its Application in Skin Allograft Models. 亚铁代谢调节剂免疫应激调节及其在同种异体皮肤移植模型中的应用。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23 Epub Date: 2025-07-14 DOI: 10.1021/jacs.5c04246

Zhiting Wu, Liyi Zhang, Xinrui Mao, Jingjing Zhu, Jiaoduan Li, Chengcheng Wang, Weiwei Jiang, Yun Zhang, Xuexue Huang, Hongjun Zhuang, Peng Wei, Tao Yi

{"title":"Ferrous Iron Metabolism Modulator for Immune Stress Regulation and Its Application in Skin Allograft Models.","authors":"Zhiting Wu, Liyi Zhang, Xinrui Mao, Jingjing Zhu, Jiaoduan Li, Chengcheng Wang, Weiwei Jiang, Yun Zhang, Xuexue Huang, Hongjun Zhuang, Peng Wei, Tao Yi","doi":"10.1021/jacs.5c04246","DOIUrl":"10.1021/jacs.5c04246","url":null,"abstract":"The dysregulation of ferrous iron (Fe2+) metabolism, which is closely linked to immune stress, plays a pivotal role in driving pathological processes such as ferroptosis and hyperinflammation. Therefore, it is crucial to modulate Fe2+ metabolism to alleviate iron overload and immune stress. However, current iron chelators, which are commonly used as iron metabolism modulators, primarily target ferric ions (Fe3+), the downstream oxidation product of Fe2+. This approach not only limits their modulation efficacy but also poses a risk of disrupting Fe3+ homeostasis in healthy tissues. Herein, a novel Fe2+ metabolism modulator, DHU-Feex1, was developed by optimizing the electronic structure of iron chelators through theoretical calculations. DHU-Feex1 preferentially recognized Fe2+ and effectively inhibited the iron-mediated Fenton reaction. Additionally, by responding to hydroxyl radicals and sequentially scavenging Fe3+, DHU-Feex1 mitigated the harmful effects of ferroptosis. In vivo validation using a mouse skin allograft model demonstrated the therapeutic potential of DHU-Feex1. The modulator remarkably prolonged graft survival and reduced immune rejection by precisely regulating immune responses. Gene and protein expression analyses further revealed that DHU-Feex1 effectively regulated ferroptosis-related pathways and suppressed inflammation, confirming its role as an immunomodulatory agent. In summary, this study presents DHU-Feex1 as a promising strategy for modulating immune responses, particularly in diseases associated with Fe2+ metabolism disorders.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"25325-25336"},"PeriodicalIF":14.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635736","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

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2025-07-23

Mizuki Hirokawa, Taro Ozaki*, Kento Tsukada, Akihiro Sugawara, Yohei Morishita and Teigo Asai*,

引用次数: 0