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Identification of Aberrant Expression of Gemcitabine-Targeting Proteins in Drug-Resistant Cells Using an Activity-Based Gemcitabine Probe 使用基于活性的吉西他滨探针鉴定耐药细胞中吉西他滨靶向蛋白的异常表达
IF 3.5 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-28 DOI: 10.1021/acschembio.4c0044610.1021/acschembio.4c00446
Xiaomei Zhu, YuQing Yuan, Kai Wang, Wei Shen* and Qing Zhu*, 
{"title":"Identification of Aberrant Expression of Gemcitabine-Targeting Proteins in Drug-Resistant Cells Using an Activity-Based Gemcitabine Probe","authors":"Xiaomei Zhu,&nbsp;YuQing Yuan,&nbsp;Kai Wang,&nbsp;Wei Shen* and Qing Zhu*,&nbsp;","doi":"10.1021/acschembio.4c0044610.1021/acschembio.4c00446","DOIUrl":"https://doi.org/10.1021/acschembio.4c00446https://doi.org/10.1021/acschembio.4c00446","url":null,"abstract":"<p >Gemcitabine-based monotherapy or combination therapy has become the standard treatment for locally advanced and metastatic pancreatic cancer. However, the emergence of resistance within weeks of treatment severely compromises therapeutic efficacy. The intricate biological process of gemcitabine resistance in pancreatic cancer presents a complex challenge, as the underlying mechanisms remain unclear. Identifying the target protein of gemcitabine is crucial for studying its drug-resistance mechanism. An activity-based probe is a powerful tool for studying drug target proteins, but the current lack of activity-based gemcitabine probes with robust biological activity hinders research on gemcitabine. In this study, we developed three active probes based on gemcitabine, among which <b>Gem-3</b> demonstrated excellent stability and labeling efficacy. We utilized <b>Gem-3</b> in conjunction with chemical proteomics to identify intracellular target proteins. We identified 79 proteins that interact with gemcitabine, most of which were previously unknown and represented various functional classes. Additionally, we validated the increased expression of IFIT3 and MARCKS in drug-resistant cells, along with the activation of the NF-κB signaling pathway. These findings substantially contribute to our comprehension of gemcitabine’s target proteins and further our understanding of the mechanisms driving gemcitabine resistance in pancreatic cancer cells.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"19 11","pages":"2336–2344 2336–2344"},"PeriodicalIF":3.5,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142641011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Modulation of ABCG2 Transporter Activity by Ko143 Derivatives Ko143 衍生物对 ABCG2 转运体活性的调节
IF 3.5 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-24 DOI: 10.1021/acschembio.4c0035310.1021/acschembio.4c00353
Qin Yu, Sepehr Dehghani-Ghahnaviyeh, Ali Rasouli, Anna Sadurni, Julia Kowal, Rose Bang-Soerensen, Po-Chao Wen, Melanie Tinzl-Zechner, Rossitza N. Irobalieva, Dongchun Ni, Henning Stahlberg, Karl-Heinz Altmann*, Emad Tajkhorshid* and Kaspar P. Locher*, 
{"title":"Modulation of ABCG2 Transporter Activity by Ko143 Derivatives","authors":"Qin Yu,&nbsp;Sepehr Dehghani-Ghahnaviyeh,&nbsp;Ali Rasouli,&nbsp;Anna Sadurni,&nbsp;Julia Kowal,&nbsp;Rose Bang-Soerensen,&nbsp;Po-Chao Wen,&nbsp;Melanie Tinzl-Zechner,&nbsp;Rossitza N. Irobalieva,&nbsp;Dongchun Ni,&nbsp;Henning Stahlberg,&nbsp;Karl-Heinz Altmann*,&nbsp;Emad Tajkhorshid* and Kaspar P. Locher*,&nbsp;","doi":"10.1021/acschembio.4c0035310.1021/acschembio.4c00353","DOIUrl":"https://doi.org/10.1021/acschembio.4c00353https://doi.org/10.1021/acschembio.4c00353","url":null,"abstract":"<p >ABCG2 is a multidrug transporter that protects tissues from xenobiotics, affects drug pharmacokinetics, and contributes to multidrug resistance of cancer cells. Here, we present tetracyclic fumitremorgin C analog Ko143 derivatives, evaluate their <i>in vitro</i> modulation of purified ABCG2, and report four high-resolution cryo-EM structures and computational analyses to elucidate their interactions with ABCG2. We found that Ko143 derivatives that are based on a ring-opened scaffold no longer inhibit ABCG2-mediated transport activity. In contrast, closed-ring, tetracyclic analogs were highly potent inhibitors. Strikingly, the least potent of these compounds, MZ82, bound deeper into the central ABCG2 cavity than the other inhibitors and it led to partial closure of the transmembrane domains and increased flexibility of the nucleotide-binding domains. Minor structural modifications can thus convert a potent inhibitor into a compound that induces conformational changes in ABCG2 similar to those observed during binding of a substrate. Molecular dynamics simulations and free energy binding calculations further supported the correlation between reduced potency and distinct binding pose of the compounds. We introduce the highly potent inhibitor AZ99 that may exhibit improved <i>in vivo</i> stability.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"19 11","pages":"2304–2313 2304–2313"},"PeriodicalIF":3.5,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acschembio.4c00353","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640790","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Analyzing the Temperature Dependence of Titania Photocatalysis: Kinetic Competition between Water Oxidation Catalysis and Back Electron–Hole Recombination 分析二氧化钛光催化的温度依赖性:水氧化催化与背电子孔重组之间的动力学竞争
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-24 DOI: 10.1021/acscatal.4c0368510.1021/acscatal.4c03685
Yohei Cho, Tianhao He, Benjamin Moss, Daniele Benetti, Caiwu Liang, Lei Tian, Lucy Jessica F. Hart, Anna A. Wilson, Yu Taniguchi, Junyi Cui, Mengya Yang, Salvador Eslava, Akira Yamaguchi, Masahiro Miyauchi and James R. Durrant*, 
{"title":"Analyzing the Temperature Dependence of Titania Photocatalysis: Kinetic Competition between Water Oxidation Catalysis and Back Electron–Hole Recombination","authors":"Yohei Cho,&nbsp;Tianhao He,&nbsp;Benjamin Moss,&nbsp;Daniele Benetti,&nbsp;Caiwu Liang,&nbsp;Lei Tian,&nbsp;Lucy Jessica F. Hart,&nbsp;Anna A. Wilson,&nbsp;Yu Taniguchi,&nbsp;Junyi Cui,&nbsp;Mengya Yang,&nbsp;Salvador Eslava,&nbsp;Akira Yamaguchi,&nbsp;Masahiro Miyauchi and James R. Durrant*,&nbsp;","doi":"10.1021/acscatal.4c0368510.1021/acscatal.4c03685","DOIUrl":"https://doi.org/10.1021/acscatal.4c03685https://doi.org/10.1021/acscatal.4c03685","url":null,"abstract":"<p >This study examines the kinetic origins of the temperature dependence of photoelectrochemical water oxidation on nanostructured titania photoanodes. We observe that the photocurrent is enhanced at 50 °C relative to 20 °C, with this enhancement being most pronounced (by up to 70%) at low anodic potentials (&lt;+0.6 V vs RHE). Over this low potential range, the photocurrent magnitude is largely determined by kinetic competition between water oxidation catalysis (WOC) and recombination between surface holes and bulk electrons (back electron–hole recombination, BER). We quantify the BER process by transient photocurrent analyses under pulsed irradiation. Remarkably, we find that the kinetics of BER (∼90 ms half-time) are independent of temperature. In contrast, the kinetics of WOC, determined from the analysis of the photoinduced absorption of accumulated surface holes, are found to accelerate up to 2-fold at 50 °C relative to 20 °C. We conclude that the enhanced photocurrent densities observed in the low-applied potential region result primarily from the accelerated WOC, reducing losses due to the competing BER pathway. At higher applied potentials (&gt;+0.6 V vs RHE), a smaller (∼10%) enhancement in photocurrent density is observed at 50 °C relative to 20 °C. Photoinduced absorption studies, correlated with studies using triethanolamine as a hole scavenger, indicate that this more modest enhancement at anodic potentials primarily results from an enhanced charge separation efficiency. We conclude by discussing the implications of these results for the practical application of photoanodic WOC under solar irradiation, influenced by these temperature-independent and -dependent underlying kinetic processes.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16543–16550 16543–16550"},"PeriodicalIF":11.3,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c03685","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Active Palladium Structures on Ceria Obtained by Tuning Pd–Pd Distance for Efficient Methane Combustion 通过调节 Pd-Pd 间距在铈上形成活性钯结构,实现高效甲烷燃烧
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0498510.1021/acscatal.4c04985
Weiwei Yang, Haohong Song, Lihua Zhang, Junyan Zhang, Felipe Polo-Garzon, Haodong Wang, Harry Meyer III, De-en Jiang*, Zili Wu* and Yuanyuan Li*, 
{"title":"Active Palladium Structures on Ceria Obtained by Tuning Pd–Pd Distance for Efficient Methane Combustion","authors":"Weiwei Yang,&nbsp;Haohong Song,&nbsp;Lihua Zhang,&nbsp;Junyan Zhang,&nbsp;Felipe Polo-Garzon,&nbsp;Haodong Wang,&nbsp;Harry Meyer III,&nbsp;De-en Jiang*,&nbsp;Zili Wu* and Yuanyuan Li*,&nbsp;","doi":"10.1021/acscatal.4c0498510.1021/acscatal.4c04985","DOIUrl":"https://doi.org/10.1021/acscatal.4c04985https://doi.org/10.1021/acscatal.4c04985","url":null,"abstract":"<p >Efficiently removing/converting methane via methane combustion imposes challenges on catalyst design: <i>how to design local structures of a catalytic site so that it has both high intrinsic activity and atomic efficiency</i>? By manipulating the atomic distance of isolated Pd atoms, herein we show that the intrinsic activity of Pd catalysts can be significantly improved for methane combustion via a stable Pd<sub>2</sub> structure on a ceria nanorod support. Guided by theory and confirmed by experiment, we find that the turnover frequency (TOF) of the Pd<sub>2</sub> structure with the Pd–Pd distance of 2.99 Å is higher than that of the Pd<sub>2</sub> structure with the Pd–Pd distance of 2.75 Å; at least 26 times that of ceria supported Pd single atoms and 4 times that of ceria supported PdO nanoparticles. The high intrinsic activity of the 2.99 Å Pd–Pd structure is attributed to the conductive local redox environment from the two O atoms bridging the two Pd<sup>2+</sup> ions, which facilitates both methane adsorption and activation as well as the production of water and carbon dioxide during the methane oxidation process. This work highlights the sensitivity of catalytic behavior on the local structure of active sites and the fine-tuning of the metal–metal distance enabled by a support local environment for guiding the design of efficient catalysts for reactions that highly rely on Pt-group metals.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16459–16468 16459–16468"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560479","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Autocatalytic Activation of a Ruthenium-PNN-Pincer Hydrogenation Catalyst 钌-PNN-钳形氢化催化剂的自动催化活化
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0447510.1021/acscatal.4c04475
Jose Fernando Carbajal Perez, Fallyn L. Kirlin, Eamon F. Reynolds, Cole E. Altomare-Jarczyk, Benjamin T. Joseph, Jason M. Keith* and Anthony R. Chianese*, 
{"title":"Autocatalytic Activation of a Ruthenium-PNN-Pincer Hydrogenation Catalyst","authors":"Jose Fernando Carbajal Perez,&nbsp;Fallyn L. Kirlin,&nbsp;Eamon F. Reynolds,&nbsp;Cole E. Altomare-Jarczyk,&nbsp;Benjamin T. Joseph,&nbsp;Jason M. Keith* and Anthony R. Chianese*,&nbsp;","doi":"10.1021/acscatal.4c0447510.1021/acscatal.4c04475","DOIUrl":"https://doi.org/10.1021/acscatal.4c04475https://doi.org/10.1021/acscatal.4c04475","url":null,"abstract":"<p >In this article, we describe a detailed experimental and computational study of the activation mechanism for a highly active pincer ruthenium(0) precatalyst for the hydrogenation of polar organic compounds. The precatalyst activates by reaction with 2 equiv of hydrogen, resulting in a net oxidative addition to ruthenium and hydrogenation of an imine functional group on the supporting ligand. The kinetics of precatalyst hydrogenation were measured by UV–visible spectroscopy under catalytically relevant conditions (10–39 bar hydrogen, 298 K). The kinetic data, in combination with density functional theory calculations, support an intriguing autocatalytic mechanism, where the product ruthenium(II) complex catalyzes the hydrogenation of the ruthenium(0) precatalyst.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16497–16507 16497–16507"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c04475","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571214","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Unique Electron Donor–Acceptor Complex Conformation Ensures Both the Efficiency and Enantioselectivity of Photoinduced Radical Cyclization in a Non-natural Photoenzyme 独特的电子供体-受体复合物构象确保了非天然光酶中光诱导自由基环化的效率和对映选择性
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0504610.1021/acscatal.4c05046
Matteo Capone, Gianluca Dell’Orletta, Claire G. Page, Todd K. Hyster, Gregory D. Scholes and Isabella Daidone*, 
{"title":"Unique Electron Donor–Acceptor Complex Conformation Ensures Both the Efficiency and Enantioselectivity of Photoinduced Radical Cyclization in a Non-natural Photoenzyme","authors":"Matteo Capone,&nbsp;Gianluca Dell’Orletta,&nbsp;Claire G. Page,&nbsp;Todd K. Hyster,&nbsp;Gregory D. Scholes and Isabella Daidone*,&nbsp;","doi":"10.1021/acscatal.4c0504610.1021/acscatal.4c05046","DOIUrl":"https://doi.org/10.1021/acscatal.4c05046https://doi.org/10.1021/acscatal.4c05046","url":null,"abstract":"<p >Non-natural photoenzymatic catalysis exploits active site tunability for stereoselective radical reactions. In flavoproteins, light absorption promotes the excitation of an electron donor–acceptor (EDA) complex formed between the reduced flavin cofactor and a substrate (α-chloroacetamide in this case). This can trigger chloride mesolytic cleavage, leading to radical cyclization (forming a γ-lactam), or revert to the ground state. While this strategy is feasible using a broad UV/visible/near-infrared spectrum, the low quantum yield presents a significant challenge. Using a multiscale computational approach, we elucidate the mechanisms of the light-driven radical initiation step catalyzed by a Gluconobacter oxydans “ene”-reductase mutant (GluER-G6). The low experimental quantum yield stems from the limited population (&lt;10%) of EDA complexes with a charge transfer state competent for mesolytic cleavage. Accessibility of this state requires substrate bending positioning the chlorine atom near the styrenic group. A subset of these reactive conformers exhibits enhanced cyan/red absorption due to the optimal C–Cl bond alignment with the flavin. Engineering a GluER variant to stabilize this conformation is expected to significantly enhance catalytic efficiency when using cyan/red light. The identified reactive intermediates possess the correct prochirality for enantioselective cyclization. Our findings show that ground-state conformational selection of these EDA complex conformers governs both light-activated mesolytic cleavage and enantioselectivity.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16488–16496 16488–16496"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Tetrahydroxybenzoquinone-Based Two-Dimensional Conductive Metal–Organic Framework via π-d Conjugation Modulation for Enhanced Oxygen Evolution Reaction 通过 π-d 共轭调制实现四羟基苯醌基二维导电金属有机框架,用于增强氧进化反应
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0497710.1021/acscatal.4c04977
Yantao Wang, Xiaowan Bai, Junfeng Huang, Wangzu Li, Jinhua Zhang, Hua Li, Yu Long, Yong Peng* and Cailing Xu*, 
{"title":"Tetrahydroxybenzoquinone-Based Two-Dimensional Conductive Metal–Organic Framework via π-d Conjugation Modulation for Enhanced Oxygen Evolution Reaction","authors":"Yantao Wang,&nbsp;Xiaowan Bai,&nbsp;Junfeng Huang,&nbsp;Wangzu Li,&nbsp;Jinhua Zhang,&nbsp;Hua Li,&nbsp;Yu Long,&nbsp;Yong Peng* and Cailing Xu*,&nbsp;","doi":"10.1021/acscatal.4c0497710.1021/acscatal.4c04977","DOIUrl":"https://doi.org/10.1021/acscatal.4c04977https://doi.org/10.1021/acscatal.4c04977","url":null,"abstract":"<p >2D conductive metal–organic frameworks (2D c-MOFs) have attracted significant interest as efficient electrocatalysts for the oxygen evolution reaction (OER). However, effectively regulating their catalytic activity remains a significant challenge. Herein, density functional theory (DFT) was performed to explore the effect of π-d conjugation modulation on the electronic structure of the tetrahydroxy-1,4-benzoquinone-based 2D c-MOFs. The computational results indicate that the strong π-d conjugation caused by orbital hybridization between Co and Fe widens and enhances the hybridization between the d<sub><i>xz</i></sub>/d<sub><i>yz</i></sub> orbitals at the metal sites and the p orbitals of the ligands, thereby affecting the reconstruction of the MOFs during the OER process. Experimentally, CoFe-THQ with various atomic ratios was synthesized. The results indicated that the synthesized Co<sub>0.6</sub>Fe<sub>0.4</sub>-THQ powders only needs an overpotential of 247 mV to reach a current density of 10 mA cm<sup>–2</sup> for the OER in alkaline medium, which is much lower than most reported transition metal-based electrocatalysts and even better than that of the benchmark RuO<sub>2</sub> electrocatalyst. Furthermore, in situ Raman and in situ Fourier transform infrared spectroscopy analyses revealed that Co<sub>0.6</sub>Fe<sub>0.4</sub>-THQ undergoes a different reconstruction evolution during the OER process compared to Co-THQ, with the mixed (Co, Fe) bimetallic oxides ((Co, Fe)<sub>3</sub>O<sub>4</sub> and α-(Co, Fe)<sub>2</sub>O<sub>3</sub>) formed after reconstruction identified as the true active species. This study opens up an effective avenue for the rational design of high-activity 2D c-MOF electrocatalysts.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16532–16542 16532–16542"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Epoxy Group Modified Atomic Zn–N2O2 for H2O2 Electrosynthesis and Sulfide Oxidation 用于 H2O2 电合成和硫化物氧化的环氧基改性原子 Zn-N2O2
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0472910.1021/acscatal.4c04729
Chengbo Ma, Jun Wang, Xiaomei Liu, Ning Li, Wen Liu, Yang Li, Xiaobin Fan and Wenchao Peng*, 
{"title":"Epoxy Group Modified Atomic Zn–N2O2 for H2O2 Electrosynthesis and Sulfide Oxidation","authors":"Chengbo Ma,&nbsp;Jun Wang,&nbsp;Xiaomei Liu,&nbsp;Ning Li,&nbsp;Wen Liu,&nbsp;Yang Li,&nbsp;Xiaobin Fan and Wenchao Peng*,&nbsp;","doi":"10.1021/acscatal.4c0472910.1021/acscatal.4c04729","DOIUrl":"https://doi.org/10.1021/acscatal.4c04729https://doi.org/10.1021/acscatal.4c04729","url":null,"abstract":"<p >In this study, zinc single-atom catalysts (SACs) (Zn SACs) with Zn–N<sub>2</sub>O<sub>2</sub> as the coordination shell and the epoxy group (C–O–C) as the second coordination structure are synthesized. The obtained Zn SACs exhibit a high 2e<sup>–</sup> ORR selectivity of &gt;85% in a wide potential window of 0–0.65 V vs RHE and achieve a high generation rate of 828.9 mmol g<sub>cat</sub><sup>–1</sup> h<sup>–1</sup> for H<sub>2</sub>O<sub>2</sub>. Experimental and theoretical calculations have confirmed that the second coordination structure of adjacent C–O–C can effectively optimize the adsorption energy of Zn–N<sub>2</sub>O<sub>2</sub> for *OOH and tune the 2e<sup>–</sup> ORR selectivity. In addition, a small onset potential of 0.38 V vs RHE is achieved for sulfides oxidation reaction (SOR) by the obtained Zn SACs. Moreover, a coupled system of anodic SOR and cathodic 2e<sup>–</sup> ORR is fabricated, which can save 45% energy consumption compared to the OER-2e<sup>–</sup> ORR system due to a decreased cell voltage of 2.03 V at 20 mA cm<sup>–2</sup>. This study provides new bifunctional Zn SACs modified by adjacent C–O–C, which are effective as bifunctional catalysts for electrosynthesis of H<sub>2</sub>O<sub>2</sub> and electro-oxidation of sulfides. These two reactions can be performed together in a coupled system with decreased energy cost and thus should have better application potential.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16522–16531 16522–16531"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Unified Enantioselective Allylations and Vinylogous Reactions Enabled by Visible Light-Driven Chiral Lewis Acid Catalysis 通过可见光驱动的手性路易斯酸催化实现统一的对映选择性烯丙基化和乙烯基化反应
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0463810.1021/acscatal.4c04638
Fuyuan Li, Fa-Yu Liu, Xiaowei Zhao*, Yanli Yin, Bin Yu, Junmin Zhang* and Zhiyong Jiang*, 
{"title":"Unified Enantioselective Allylations and Vinylogous Reactions Enabled by Visible Light-Driven Chiral Lewis Acid Catalysis","authors":"Fuyuan Li,&nbsp;Fa-Yu Liu,&nbsp;Xiaowei Zhao*,&nbsp;Yanli Yin,&nbsp;Bin Yu,&nbsp;Junmin Zhang* and Zhiyong Jiang*,&nbsp;","doi":"10.1021/acscatal.4c0463810.1021/acscatal.4c04638","DOIUrl":"https://doi.org/10.1021/acscatal.4c04638https://doi.org/10.1021/acscatal.4c04638","url":null,"abstract":"<p >In contemporary organic synthesis, chemists actively pursue a diverse range of substrates that can be efficiently catalyzed within an integrated system, playing a crucial role in advancing the pharmaceutical industry. However, due to the influence of substituents on reactivity and selectivity, it poses a challenging dilemma to explore different strategies for activating substrates with distinct functional groups. Herein, we have developed an important visible light-driven chiral Lewis acid catalysis platform which facilitates the unified allylations and vinylogous reactions of various allyl bromides and isatins for the highly enantio- and diastereoselective construction of valuable 3-allyl-3-hydroxy oxindoles. The success of this approach lies in utilizing a radical pathway for intermediate formation and stereocenter generation. Moreover, the activation capability of chiral Lewis acids provides an opportunity to achieve sufficient enantiocontrol and enhance regioselectivity. The robustness of this method is demonstrated by its application in precise radical-based propargylation reactions using readily accessible propargyl bromides.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16479–16487 16479–16487"},"PeriodicalIF":11.3,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Functional Nucleic Acid Enzymes: Nucleic Acid-Based Catalytic Factories 功能性核酸酶:基于核酸的催化工厂
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-23 DOI: 10.1021/acscatal.4c0267010.1021/acscatal.4c02670
Min Yang, Yushi Xie, Longjiao Zhu, Xiangyang Li and Wentao Xu*, 
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