JACS Au最新文献

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Photoredox-Catalyzed Radical Cyclization of Unactivated Alkene-Substituted β-Ketoesters Enabled Asymmetric Total Synthesis of Tricyclic Prostaglandin D2 Metabolite Methyl Ester
IF 8.5
JACS Au Pub Date : 2025-03-07 DOI: 10.1021/jacsau.4c0126810.1021/jacsau.4c01268
Miao Xiao, Qiaoli Shang, Liuyang Pu, Zheyuan Wang, Lei Zhu*, Zhen Yang* and Jun Huang*, 
{"title":"Photoredox-Catalyzed Radical Cyclization of Unactivated Alkene-Substituted β-Ketoesters Enabled Asymmetric Total Synthesis of Tricyclic Prostaglandin D2 Metabolite Methyl Ester","authors":"Miao Xiao,&nbsp;Qiaoli Shang,&nbsp;Liuyang Pu,&nbsp;Zheyuan Wang,&nbsp;Lei Zhu*,&nbsp;Zhen Yang* and Jun Huang*,&nbsp;","doi":"10.1021/jacsau.4c0126810.1021/jacsau.4c01268","DOIUrl":"https://doi.org/10.1021/jacsau.4c01268https://doi.org/10.1021/jacsau.4c01268","url":null,"abstract":"<p >Regio- and stereoselective photoredox-catalyzed cyclizations of alkene-substituted β-ketoesters have been accomplished for the synthesis of polyfunctionalized cyclopentanones. This was achieved using 2,3,5,6-tetrakis(carbazol-9-yl)-1,4-dicyanobenzene (4CzTPN) and 2,4,6-triisopropyl-thiophenol as cocatalysts under illumination of a blue-light-emitting-diode at ambient temperature. The developed chemistry was successfully applied in the enantioselective total synthesis of the tricyclic prostaglandin D<sub>2</sub> metabolite (tricyclic-PGDM) methyl ester, which was completed in 9 steps with an overall yield of 7%.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1367–1375 1367–1375"},"PeriodicalIF":8.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c01268","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675847","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}
引用次数: 0
Computational Modeling of the Mobility, Stability, and Al Positioning Ability of Cyclic Cationic Organic Structure-Directing Agents in AEI Zeolite.
IF 8.5
JACS Au Pub Date : 2025-03-07 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.5c00094
Pau Ferri, Pieter Cnudde, Manuel Moliner, Veronique van Speybroeck, Mercedes Boronat
{"title":"Computational Modeling of the Mobility, Stability, and Al Positioning Ability of Cyclic Cationic Organic Structure-Directing Agents in AEI Zeolite.","authors":"Pau Ferri, Pieter Cnudde, Manuel Moliner, Veronique van Speybroeck, Mercedes Boronat","doi":"10.1021/jacsau.5c00094","DOIUrl":"10.1021/jacsau.5c00094","url":null,"abstract":"<p><p>The stability and mobility of a set of organic structure-directing agents (OSDAs) with different molecular geometries and charge distribution confined within the pear-like cavities of neutral and Al-containing models of AEI zeolites have been investigated by using static density functional theory calculations and ab initio molecular dynamics simulations. The objective is to identify the role of electrostatic interactions between the OSDAs' positive charge at N<sup>+</sup> atoms and the anionic framework AlO<sub>4</sub> <sup>-</sup> centers on the preferential stabilization of Al at specific crystallographic positions, opening the possibility to modulate the Al distribution in AEI zeolites. We find that several classical piperidinium-based OSDAs with diverse methyl-substituent patterns in the N-containing ring but a symmetrical charge distribution, as well as bulkier nonclassical azoniabicycle-heptane-based OSDAs with the positive charge asymmetrically located at one side of the molecule, behave similarly. All of them remain almost immobile at the center of the <i>aei</i> cavity along the simulations and always stabilize Al preferentially at the T1 crystallographic position. In contrast, an azabicyclo-octane-based OSDA with the positive charge located outside a cyclo-octane ring lacking substituents exhibits an enhanced mobility that includes full rotation within the <i>aei</i> cage and the ability to reach the regions of the cavity not accessible to the other OSDAs investigated. As a result, this highly mobile OSDA preferentially stabilizes Al in the T3 site, which might lead to differences in catalyst activity and stability for zeolite samples synthesized using this OSDA.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1471-1481"},"PeriodicalIF":8.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11938027/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733648","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}
引用次数: 0
Captodative Approach to Stable Nitrogen-Centered Radicals, Anions, and Cations Exhibiting Near-Infrared Electrochromism
IF 8.5
JACS Au Pub Date : 2025-03-06 DOI: 10.1021/jacsau.5c0003710.1021/jacsau.5c00037
Keita Tajima, Christophe Bucher*, Daiki Shimizu, Norihito Fukui* and Hiroshi Shinokubo*, 
{"title":"Captodative Approach to Stable Nitrogen-Centered Radicals, Anions, and Cations Exhibiting Near-Infrared Electrochromism","authors":"Keita Tajima,&nbsp;Christophe Bucher*,&nbsp;Daiki Shimizu,&nbsp;Norihito Fukui* and Hiroshi Shinokubo*,&nbsp;","doi":"10.1021/jacsau.5c0003710.1021/jacsau.5c00037","DOIUrl":"https://doi.org/10.1021/jacsau.5c00037https://doi.org/10.1021/jacsau.5c00037","url":null,"abstract":"<p >Redox interconversion of the oxidation state of nitrogen via hydrogenation and dehydrogenation represents a powerful strategy for designing stimuli-responsive materials. In sharp contrast, the interconversion of nitrogen centers via electron transfer has been underexplored due to the high reactivity of aminyl radicals (R<sub>2</sub>N<sup>•</sup>), amide anions (R<sub>2</sub>N<sup>–</sup>), and nitrenium cations (R<sub>2</sub>N<sup>+</sup>). Herein, we demonstrate that a captodative approach, i.e., the dual incorporation of electron-donating and electron-accepting units, is effective to stabilize these three classes of nitrogen-centered species within the same molecular scaffold. We synthesized a 9,10-dihydroacridine derivative with nitrogen-doping at the 9-position and imide-substitution at the 2,3- and 6,7-positions. This molecule afforded an aminyl radical upon hydrogen abstraction with PbO<sub>2</sub>. The injection or removal of an electron of the aminyl radical furnished the corresponding amide anion and nitrenium cation, respectively. The aminyl radical, amide anion, and nitrenium cation exhibit significant stability under ambient conditions. Redox interconversion between the amide anion and nitrenium cation results in a drastic change in near-infrared (NIR) absorption due to switching of the local aromaticity of the central six-membered ring. These attractive properties lead to electrochromism in the NIR region (up to 1050 nm) between the closed-shell species.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1421–1428 1421–1428"},"PeriodicalIF":8.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00037","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675789","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}
引用次数: 0
Captodative Approach to Stable Nitrogen-Centered Radicals, Anions, and Cations Exhibiting Near-Infrared Electrochromism. 捕获法获得稳定的以氮为中心的自由基、阴离子和阳离子的近红外电致色性。
IF 8.5
JACS Au Pub Date : 2025-03-06 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.5c00037
Keita Tajima, Christophe Bucher, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo
{"title":"Captodative Approach to Stable Nitrogen-Centered Radicals, Anions, and Cations Exhibiting Near-Infrared Electrochromism.","authors":"Keita Tajima, Christophe Bucher, Daiki Shimizu, Norihito Fukui, Hiroshi Shinokubo","doi":"10.1021/jacsau.5c00037","DOIUrl":"10.1021/jacsau.5c00037","url":null,"abstract":"<p><p>Redox interconversion of the oxidation state of nitrogen via hydrogenation and dehydrogenation represents a powerful strategy for designing stimuli-responsive materials. In sharp contrast, the interconversion of nitrogen centers via electron transfer has been underexplored due to the high reactivity of aminyl radicals (R<sub>2</sub>N<sup>•</sup>), amide anions (R<sub>2</sub>N<sup>-</sup>), and nitrenium cations (R<sub>2</sub>N<sup>+</sup>). Herein, we demonstrate that a captodative approach, i.e., the dual incorporation of electron-donating and electron-accepting units, is effective to stabilize these three classes of nitrogen-centered species within the same molecular scaffold. We synthesized a 9,10-dihydroacridine derivative with nitrogen-doping at the 9-position and imide-substitution at the 2,3- and 6,7-positions. This molecule afforded an aminyl radical upon hydrogen abstraction with PbO<sub>2</sub>. The injection or removal of an electron of the aminyl radical furnished the corresponding amide anion and nitrenium cation, respectively. The aminyl radical, amide anion, and nitrenium cation exhibit significant stability under ambient conditions. Redox interconversion between the amide anion and nitrenium cation results in a drastic change in near-infrared (NIR) absorption due to switching of the local aromaticity of the central six-membered ring. These attractive properties lead to electrochromism in the NIR region (up to 1050 nm) between the closed-shell species.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1421-1428"},"PeriodicalIF":8.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11937969/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733676","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}
引用次数: 0
STD NMR Epitope Perturbation by Mutation Unveils the Mechanism of YM155 as an Arginine-Glycosyltransferases Inhibitor Effective in Treating Enteropathogenic Diseases STD NMR 表位突变扰动揭示了 YM155 作为精氨酸-糖基转移酶抑制剂有效治疗肠道致病性疾病的机制
IF 8.5
JACS Au Pub Date : 2025-03-05 DOI: 10.1021/jacsau.4c0114010.1021/jacsau.4c01140
Jonathan Ramírez-Cárdenas, Víctor Taleb, Valeria Calvaresi, Weston B. Struwe, Samir El Qaidi, Congrui Zhu, Kamrul Hasan, Yingxin Zhang, Philip R. Hardwidge, Billy Veloz, Juan C. Muñoz-García, Ramón Hurtado-Guerrero* and Jesús Angulo*, 
{"title":"STD NMR Epitope Perturbation by Mutation Unveils the Mechanism of YM155 as an Arginine-Glycosyltransferases Inhibitor Effective in Treating Enteropathogenic Diseases","authors":"Jonathan Ramírez-Cárdenas,&nbsp;Víctor Taleb,&nbsp;Valeria Calvaresi,&nbsp;Weston B. Struwe,&nbsp;Samir El Qaidi,&nbsp;Congrui Zhu,&nbsp;Kamrul Hasan,&nbsp;Yingxin Zhang,&nbsp;Philip R. Hardwidge,&nbsp;Billy Veloz,&nbsp;Juan C. Muñoz-García,&nbsp;Ramón Hurtado-Guerrero* and Jesús Angulo*,&nbsp;","doi":"10.1021/jacsau.4c0114010.1021/jacsau.4c01140","DOIUrl":"https://doi.org/10.1021/jacsau.4c01140https://doi.org/10.1021/jacsau.4c01140","url":null,"abstract":"<p >Enteropathogenic arginine-glycosyltransferases (Arg-GTs) alter higher eukaryotic proteins by attaching a GlcNAc residue to arginine acceptor sites, disrupting essential pathways such as NF-κB signaling, which promotes bacterial survival. These enzymes are potential drug targets for treating related diseases. In this study, we present a novel STD NMR Epitope Perturbation by Mutation spectroscopic approach that, in combination with hydrogen–deuterium exchange mass spectrometry (HDX-MS), and molecular dynamics simulations, shows that the highly potent broad-spectrum anticancer drug YM155 serves as a potential noncompetitive inhibitor of these enzymes. It induces a conformation of the arginine acceptor site unfavorable for GlcNAc transfer, which underlies the molecular mechanism by which this compound exerts its inhibitory function. Finally, we also demonstrate that YM155 effectively treats enteropathogenic diseases in a mouse model, highlighting its therapeutic potential. Overall, our data suggest that this compound can be repurposed to not only treat cancer but also infectious diseases.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1279–1288 1279–1288"},"PeriodicalIF":8.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c01140","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675682","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}
引用次数: 0
STD NMR Epitope Perturbation by Mutation Unveils the Mechanism of YM155 as an Arginine-Glycosyltransferases Inhibitor Effective in Treating Enteropathogenic Diseases.
IF 8.5
JACS Au Pub Date : 2025-03-05 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.4c01140
Jonathan Ramírez-Cárdenas, Víctor Taleb, Valeria Calvaresi, Weston B Struwe, Samir El Qaidi, Congrui Zhu, Kamrul Hasan, Yingxin Zhang, Philip R Hardwidge, Billy Veloz, Juan C Muñoz-García, Ramón Hurtado-Guerrero, Jesús Angulo
{"title":"STD NMR Epitope Perturbation by Mutation Unveils the Mechanism of YM155 as an Arginine-Glycosyltransferases Inhibitor Effective in Treating Enteropathogenic Diseases.","authors":"Jonathan Ramírez-Cárdenas, Víctor Taleb, Valeria Calvaresi, Weston B Struwe, Samir El Qaidi, Congrui Zhu, Kamrul Hasan, Yingxin Zhang, Philip R Hardwidge, Billy Veloz, Juan C Muñoz-García, Ramón Hurtado-Guerrero, Jesús Angulo","doi":"10.1021/jacsau.4c01140","DOIUrl":"10.1021/jacsau.4c01140","url":null,"abstract":"<p><p>Enteropathogenic arginine-glycosyltransferases (Arg-GTs) alter higher eukaryotic proteins by attaching a GlcNAc residue to arginine acceptor sites, disrupting essential pathways such as NF-κB signaling, which promotes bacterial survival. These enzymes are potential drug targets for treating related diseases. In this study, we present a novel STD NMR Epitope Perturbation by Mutation spectroscopic approach that, in combination with hydrogen-deuterium exchange mass spectrometry (HDX-MS), and molecular dynamics simulations, shows that the highly potent broad-spectrum anticancer drug YM155 serves as a potential noncompetitive inhibitor of these enzymes. It induces a conformation of the arginine acceptor site unfavorable for GlcNAc transfer, which underlies the molecular mechanism by which this compound exerts its inhibitory function. Finally, we also demonstrate that YM155 effectively treats enteropathogenic diseases in a mouse model, highlighting its therapeutic potential. Overall, our data suggest that this compound can be repurposed to not only treat cancer but also infectious diseases.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1279-1288"},"PeriodicalIF":8.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11937963/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733151","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}
引用次数: 0
Electrochemical Synergistic Ni/Co-Catalyzed Carbonylative Cross-Electrophile Coupling of Aryl and Alkyl Halides with CO.
IF 8.5
JACS Au Pub Date : 2025-03-05 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.5c00031
Shaokun Tao, Yun Yang, Li Chen, Jiaqi Xu, Haiyan Fu, Hua Chen, Weidong Jiang, Ruixiang Li, Weichao Xue, Xueli Zheng
{"title":"Electrochemical Synergistic Ni/Co-Catalyzed Carbonylative Cross-Electrophile Coupling of Aryl and Alkyl Halides with CO.","authors":"Shaokun Tao, Yun Yang, Li Chen, Jiaqi Xu, Haiyan Fu, Hua Chen, Weidong Jiang, Ruixiang Li, Weichao Xue, Xueli Zheng","doi":"10.1021/jacsau.5c00031","DOIUrl":"10.1021/jacsau.5c00031","url":null,"abstract":"<p><p>Accessing unsymmetric ketones and achieving their carbon isotope labeling are crucial yet challenging tasks in both synthetic and medicinal chemistry. We report here an efficient electrochemical nickel-/cobalt-catalyzed carbonylative cross-electrophile coupling reaction. This method allows for the modular synthesis of a library of unsymmetric ketones from simple building blocks, including aryl halides, alkyl halides, and gaseous CO. The simultaneous use of nickel and cobalt salts as concerted catalysts ensures the high efficiency of this three-component carbonylative coupling. Furthermore, electrochemical reduction avoids the use of stoichiometric reductants, making this protocol more sustainable and attractive. The broad substrate scope and late-stage <sup>13</sup>C isotope labeling of complex molecules derived from biologically active compounds highlight the practicality of this method.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1413-1420"},"PeriodicalIF":8.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11937974/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733699","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}
引用次数: 0
Electrochemical Synergistic Ni/Co-Catalyzed Carbonylative Cross-Electrophile Coupling of Aryl and Alkyl Halides with CO
IF 8.5
JACS Au Pub Date : 2025-03-04 DOI: 10.1021/jacsau.5c0003110.1021/jacsau.5c00031
Shaokun Tao, Yun Yang, Li Chen, Jiaqi Xu, Haiyan Fu, Hua Chen, Weidong Jiang, Ruixiang Li, Weichao Xue* and Xueli Zheng*, 
{"title":"Electrochemical Synergistic Ni/Co-Catalyzed Carbonylative Cross-Electrophile Coupling of Aryl and Alkyl Halides with CO","authors":"Shaokun Tao,&nbsp;Yun Yang,&nbsp;Li Chen,&nbsp;Jiaqi Xu,&nbsp;Haiyan Fu,&nbsp;Hua Chen,&nbsp;Weidong Jiang,&nbsp;Ruixiang Li,&nbsp;Weichao Xue* and Xueli Zheng*,&nbsp;","doi":"10.1021/jacsau.5c0003110.1021/jacsau.5c00031","DOIUrl":"https://doi.org/10.1021/jacsau.5c00031https://doi.org/10.1021/jacsau.5c00031","url":null,"abstract":"<p >Accessing unsymmetric ketones and achieving their carbon isotope labeling are crucial yet challenging tasks in both synthetic and medicinal chemistry. We report here an efficient electrochemical nickel-/cobalt-catalyzed carbonylative cross-electrophile coupling reaction. This method allows for the modular synthesis of a library of unsymmetric ketones from simple building blocks, including aryl halides, alkyl halides, and gaseous CO. The simultaneous use of nickel and cobalt salts as concerted catalysts ensures the high efficiency of this three-component carbonylative coupling. Furthermore, electrochemical reduction avoids the use of stoichiometric reductants, making this protocol more sustainable and attractive. The broad substrate scope and late-stage <sup>13</sup>C isotope labeling of complex molecules derived from biologically active compounds highlight the practicality of this method.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1413–1420 1413–1420"},"PeriodicalIF":8.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00031","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675678","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}
引用次数: 0
Automated Microfluidics for Efficient Characterization of Cyclohexanol Electrooxidation for Sustainable Chemical Production 自动化微流控技术用于高效表征环己醇电氧化作用以实现可持续化学品生产
IF 8.5
JACS Au Pub Date : 2025-03-04 DOI: 10.1021/jacsau.4c0120710.1021/jacsau.4c01207
Xiao Liang, Mengzheng Ouyang, Nigel P. Brandon, Jin Xuan and Huizhi Wang*, 
{"title":"Automated Microfluidics for Efficient Characterization of Cyclohexanol Electrooxidation for Sustainable Chemical Production","authors":"Xiao Liang,&nbsp;Mengzheng Ouyang,&nbsp;Nigel P. Brandon,&nbsp;Jin Xuan and Huizhi Wang*,&nbsp;","doi":"10.1021/jacsau.4c0120710.1021/jacsau.4c01207","DOIUrl":"https://doi.org/10.1021/jacsau.4c01207https://doi.org/10.1021/jacsau.4c01207","url":null,"abstract":"<p >The electrochemical conversion of biomass-derived compounds into value-added chemicals using renewable electricity has attracted attention as a promising pathway for sustainable chemical production, with the electrooxidation of cyclohexanol being a typical example. However, optimizing and upscaling these processes have been hindered due to a limited understanding of the underlying mechanisms and limiting factors. To address this, there is a critical need for experimental tools that enable more efficient and reproducible measurements of these complex processes. In this work, we develop an automated microfluidic platform and use it to conduct controlled and efficient measurements of cyclohexanol electrooxidation on nickel electrodes under various electrolyte compositions and flow rates. The platform features microchannel networks integrated with multiple analytical instruments such as pumps, an electrochemical workstation, and a digital microscope to perform laboratory functions including electrolyte preparation, reaction control, microscopy, and electrochemical characterization, all streamlined through automation. Cyclohexanol electrooxidation on nickel is found to follow Fleischmann’s mechanism, with an irreversible heterogeneous reaction as the rate-determining step. The effects of ionic and nonionic surfactant additives are screened, both demonstrating the ability to enhance current densities through different mechanisms. The developed platform is readily transferable for measuring other power-to-chemical processes and is believed to be a powerful tool for accelerating the understanding and development of sustainable electrosynthesis.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1340–1349 1340–1349"},"PeriodicalIF":8.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c01207","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675718","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}
引用次数: 0
Automated Microfluidics for Efficient Characterization of Cyclohexanol Electrooxidation for Sustainable Chemical Production.
IF 8.5
JACS Au Pub Date : 2025-03-04 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.4c01207
Xiao Liang, Mengzheng Ouyang, Nigel P Brandon, Jin Xuan, Huizhi Wang
{"title":"Automated Microfluidics for Efficient Characterization of Cyclohexanol Electrooxidation for Sustainable Chemical Production.","authors":"Xiao Liang, Mengzheng Ouyang, Nigel P Brandon, Jin Xuan, Huizhi Wang","doi":"10.1021/jacsau.4c01207","DOIUrl":"10.1021/jacsau.4c01207","url":null,"abstract":"<p><p>The electrochemical conversion of biomass-derived compounds into value-added chemicals using renewable electricity has attracted attention as a promising pathway for sustainable chemical production, with the electrooxidation of cyclohexanol being a typical example. However, optimizing and upscaling these processes have been hindered due to a limited understanding of the underlying mechanisms and limiting factors. To address this, there is a critical need for experimental tools that enable more efficient and reproducible measurements of these complex processes. In this work, we develop an automated microfluidic platform and use it to conduct controlled and efficient measurements of cyclohexanol electrooxidation on nickel electrodes under various electrolyte compositions and flow rates. The platform features microchannel networks integrated with multiple analytical instruments such as pumps, an electrochemical workstation, and a digital microscope to perform laboratory functions including electrolyte preparation, reaction control, microscopy, and electrochemical characterization, all streamlined through automation. Cyclohexanol electrooxidation on nickel is found to follow Fleischmann's mechanism, with an irreversible heterogeneous reaction as the rate-determining step. The effects of ionic and nonionic surfactant additives are screened, both demonstrating the ability to enhance current densities through different mechanisms. The developed platform is readily transferable for measuring other power-to-chemical processes and is believed to be a powerful tool for accelerating the understanding and development of sustainable electrosynthesis.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1340-1349"},"PeriodicalIF":8.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11937964/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733626","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}
引用次数: 0
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