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Strain-Triggered Distinct Oxygen Evolution Reaction Pathway in Two-Dimensional Metastable Phase IrO2 via CeO2 Loading 二维可变相 IrO2 中通过 CeO2 负载的应变触发的独特氧气进化反应途径
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c05204
Hao Yu, Yujin Ji, Chenchen Li, Wenxiang Zhu, Yue Wang, Zhiwei Hu, Jing Zhou, Chih-Wen Pao, Wei-Hsiang Huang, Youyong Li, Xiaoqing Huang, Qi Shao
{"title":"Strain-Triggered Distinct Oxygen Evolution Reaction Pathway in Two-Dimensional Metastable Phase IrO2 via CeO2 Loading","authors":"Hao Yu, Yujin Ji, Chenchen Li, Wenxiang Zhu, Yue Wang, Zhiwei Hu, Jing Zhou, Chih-Wen Pao, Wei-Hsiang Huang, Youyong Li, Xiaoqing Huang, Qi Shao","doi":"10.1021/jacs.4c05204","DOIUrl":"https://doi.org/10.1021/jacs.4c05204","url":null,"abstract":"A strain engineering strategy is crucial for designing a high-performance catalyst. However, how to control the strain in metastable phase two-dimensional (2D) materials is technically challenging due to their nanoscale sizes. Here, we report that cerium dioxide (CeO<sub>2</sub>) is an ideal loading material for tuning the in-plane strain in 2D metastable 1T-phase IrO<sub>2</sub> (1T-IrO<sub>2</sub>) via an in situ growth method. Surprisingly, 5% CeO<sub>2</sub> loaded 1T-IrO<sub>2</sub> with 8% compressive strain achieves an overpotential of 194 mV at 10 mA cm<sup>–2</sup> in a three-electrode system. It also retained a high current density of 900 mA cm<sup>–2</sup> at a cell voltage of 1.8 V for a 400 h stability test in the proton-exchange membrane device. More importantly, the Fourier transform infrared measurements and density functional theory calculation reveal that the CeO<sub>2</sub> induced strained 1T-IrO<sub>2</sub> directly undergo the *O–*O radical coupling mechanism for O<sub>2</sub> generation, totally different from the traditional adsorbate evolution mechanism in pure 1T-IrO<sub>2</sub>. These findings illustrate the important role of strain engineering in paving up an optimal catalytic pathway in order to achieve robust electrochemical performance.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":15.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597462","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
Unveiling the Failure Mechanism of Zn Anodes in Zinc Trifluorosulfonate Electrolyte: The Role of Micelle-like Structures 揭示三氟磺酸锌电解液中锌阳极的失效机理:胶束状结构的作用
IF 15 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c07015
Xin Shi, Jianning Zeng, Ang Yi, Fuxin Wang, Xiaoqing Liu, Xihong Lu
{"title":"Unveiling the Failure Mechanism of Zn Anodes in Zinc Trifluorosulfonate Electrolyte: The Role of Micelle-like Structures","authors":"Xin Shi, Jianning Zeng, Ang Yi, Fuxin Wang, Xiaoqing Liu, Xihong Lu","doi":"10.1021/jacs.4c07015","DOIUrl":"https://doi.org/10.1021/jacs.4c07015","url":null,"abstract":"Zinc trifluorosulfonate [Zn(OTf)<sub>2</sub>] is considered as the most suitable zinc salt for aqueous Zn-ion batteries (AZIBs) but cannot support the long-term cycling of the Zn anode. Here, we reveal the micelle-like structure of the Zn(OTf)<sub>2</sub> electrolyte and reunderstand the failing mechanism of the Zn anode. Since the solvated Zn<sup>2+</sup> possesses a positive charge, it can spontaneously attract OTf<sup>–</sup> with the hydrophilic group of –SO<sub>3</sub> and the hydrophobic group of −CF<sub>3</sub> via electrostatic interaction and form a “micelle-like” structure, which is responsible for the poor desolvation kinetics and dendrite growth. To address these issues, an antimicelle-like structure is designed by using ethylene glycol monomethyl ether (EGME) as a cosolvent for highly reversible AZIBs. The modified electrolyte shows lower dissociation ability to Zn(OTf)<sub>2</sub> and higher coordination tendency with Zn<sup>2+</sup> compared to the Zn(OTf)<sub>2</sub> electrolyte, resulting in the unique solvation structure of Zn<sup>2+</sup>(H<sub>2</sub>O)<sub>1.2</sub>(OTf<sup>–</sup>)<sub>2</sub>(EGME)<sub>2.8</sub>, which significantly reduces the charge of micelle, damages the micelle-like structure, and boosts the desolvation kinetics. Moreover, the reduction of EGME and OTf<sup>–</sup> can form a robust dual-layered SEI with high Zn<sup>2+</sup> ion conductivity. Consequently, the Zn/Cu asymmetric coin cell using ZT-EGME can work at a high rate and a capacity of 50 mA cm<sup>–2</sup> and 5 mA h cm<sup>–2</sup> for more than 120 cycles, while its counterparts using ZT can barely work. Moreover, a 505.1 mA h pouch cell with practical parameters including a lean electrolyte supply of 15 mL A h<sup>–1</sup> and an N/P ratio of ∼3.5 can work for 50 cycles.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":15.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597463","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
Reversible Adsorption of Ammonia in the Crystalline Solid of a CO2H-Functionalized Cyclic Oligophenylene. CO2H 功能化环状低聚亚苯基结晶固体对氨的可逆吸附。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c03798
Kosuke Ono, Tomoki Ishikawa, Shion Masano, Hidetoshi Kawai, Kei Goto
{"title":"Reversible Adsorption of Ammonia in the Crystalline Solid of a CO<sub>2</sub>H-Functionalized Cyclic Oligophenylene.","authors":"Kosuke Ono, Tomoki Ishikawa, Shion Masano, Hidetoshi Kawai, Kei Goto","doi":"10.1021/jacs.4c03798","DOIUrl":"https://doi.org/10.1021/jacs.4c03798","url":null,"abstract":"<p><p>Ammonia (NH<sub>3</sub>) is a viable candidate for the storage and distribution of hydrogen (H<sub>2</sub>) due to its exceptional volumetric and gravimetric hydrogen energy density. Therefore, it is desirable to develop NH<sub>3</sub> storage materials that exhibit robust stability across numerous adsorption-desorption cycles. While porous materials with polymeric frameworks are often used for NH<sub>3</sub> capture, achieving reversible NH<sub>3</sub> uptake remains a formidable challenge, primarily due to the high reactivity of NH<sub>3</sub>. Here, we advocate the use of CO<sub>2</sub>H-functionalized cyclic oligophenylene <b>1a</b> with high chemical stability as a novel single-molecule-based adsorbent for NH<sub>3</sub>. Simple reprecipitation of <b>1a</b> selectively yielded microporous crystalline solid <b>1a</b> (<b>N</b>). Crystalline <b>1a</b> (<b>N</b>) adsorbs up to 8.27 mmol/g of NH<sub>3</sub> at 100 kPa and 293 K. Adsorbed NH<sub>3</sub> in the pore of <b>1a</b> (<b>N</b>) has a packing density of 0.533 g/cm<sup>3</sup> at 293 K, which is close to the density of liquid NH<sub>3</sub> (0.681 g/cm<sup>3</sup> at 240 K). Crystalline <b>1a</b> (<b>N</b>) also exhibits reversible NH<sub>3</sub> adsorption over at least nine cycles, sustaining its storage capacity (1st cycle: 8.27 mmol/g; 9th cycle: 8.25 mmol/g at 100 kPa and 293 K) and crystallinity. During each desorption cycle, NH<sub>3</sub> was removed from <b>1a</b> (<b>N</b>) under reduced pressure (∼65 Pa), leaving <3% of the total uptake, and <b>1a</b> (<b>N</b>) was fully purged under dynamic vacuum conditions (∼5 × 10<sup>-4</sup> Pa at 293 K for 1 h) before the subsequent adsorption cycles. Thus, microporous crystalline <b>1a</b> (<b>N</b>) can reliably adsorb and desorb NH<sub>3</sub> repeatedly, which avoids the need for heat-based activation between cycles.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588977","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
Pressure-Dependent CO2 Electroreduction to Methane over Asymmetric Cu-N2 Single-Atom Sites. 通过不对称 Cu-N2 单原子位点电还原成甲烷的压力依赖性 CO2。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c04031
Haoyang Wu, Benqiang Tian, Wenhai Xu, Kovan K Abdalla, Yun Kuang, Jiazhan Li, Xiaoming Sun
{"title":"Pressure-Dependent CO<sub>2</sub> Electroreduction to Methane over Asymmetric Cu-N<sub>2</sub> Single-Atom Sites.","authors":"Haoyang Wu, Benqiang Tian, Wenhai Xu, Kovan K Abdalla, Yun Kuang, Jiazhan Li, Xiaoming Sun","doi":"10.1021/jacs.4c04031","DOIUrl":"https://doi.org/10.1021/jacs.4c04031","url":null,"abstract":"<p><p>Single-atom catalysts (SACs) with unitary active sites hold great promise for realizing high selectivity toward a single product in the CO<sub>2</sub> electroreduction reaction (CO<sub>2</sub>RR). However, achieving high Faradaic efficiency (FE) of multielectron products like methane on SACs is still challenging. Herein, we report a pressure-regulating strategy that achieves 83.5 ± 4% FE for the CO<sub>2</sub>-to-CH<sub>4</sub> conversion on the asymmetric Cu-N<sub>2</sub> sites, representing one of the best CO<sub>2</sub>-to-CH<sub>4</sub> performances. Elevated CO<sub>2</sub> pressure was demonstrated as an efficient way to inhibit the hydrogen evolution reaction via promoting the competing adsorption of reactant CO<sub>2</sub>, regardless of the nature of the active sites. Meanwhile, the asymmetric Cu-N<sub>2</sub> structure could endow the Cu sites with stronger electronic coupling with *CO, thus suppressing the desorption of *CO and facilitating the following hydrogenation of *CO to *CHO. This work provides a synergetic strategy of the pressure-induced reaction environment regulating and the electronic structure modulating for selective CO<sub>2</sub>RR toward targeted products.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597920","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
Enantioconvergent Hydroboration of E/Z-Mixed Trisubstituted Alkenes. E/Z-Mixed Trisubstituted Alkenes 的对映转化氢硼化合。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c06585
Yinwei Bao, Chenggong Zheng, Kangyu Xiong, Chenke Hu, Peng Lu, Yuwen Wang, Zhan Lu
{"title":"Enantioconvergent Hydroboration of <i>E</i>/<i>Z</i>-Mixed Trisubstituted Alkenes.","authors":"Yinwei Bao, Chenggong Zheng, Kangyu Xiong, Chenke Hu, Peng Lu, Yuwen Wang, Zhan Lu","doi":"10.1021/jacs.4c06585","DOIUrl":"https://doi.org/10.1021/jacs.4c06585","url":null,"abstract":"<p><p>The lack of mode for chirality recognition makes it particularly challenging to carry out asymmetric transformations on <i>E</i>/<i>Z</i>-mixed minimally functionalized trisubstituted alkenes. Here, we report a catalytic enantioconvergent hydroboration of minimally functionalized trisubstituted <i>E</i>/<i>Z</i>-mixed alkenes to construct chiral organoboronic esters with excellent enantioselectivity using chiral radical cobalt catalyst. This C(sp<sup>3</sup>)-H borylation protocol showed good functional group tolerance and products could be converted to valuable compounds via C-B derivatizations. The mechanistic studies, which included control experiments, nonlinear effect experiments, deuterated labeling experiments, and X-ray diffraction, demonstrated that the favorable compatibility between the thermodynamically unfavorable isomerization and hydroboration was the key factor in achieving convergent transformation.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588939","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
Regioselective Pyridine to Benzene Edit Inspired by Water-Displacement. 受水置换启发的吡啶到苯的区域选择性编辑。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c05999
Benjamin R Boswell, Zhensheng Zhao, Ryan L Gonciarz, Keyur M Pandya
{"title":"Regioselective Pyridine to Benzene Edit Inspired by Water-Displacement.","authors":"Benjamin R Boswell, Zhensheng Zhao, Ryan L Gonciarz, Keyur M Pandya","doi":"10.1021/jacs.4c05999","DOIUrl":"https://doi.org/10.1021/jacs.4c05999","url":null,"abstract":"<p><p>Late-stage derivatization of drug-like functional groups can accelerate drug discovery efforts by swiftly exchanging hydrogen-bond donors with acceptors, or by modulating key physicochemical properties like logP, solubility, or polar surface area. A proven derivatization strategy to improve ligand potency is to extend the ligand to displace water molecules that are mediating the interactions with a receptor. Inspired by this application, we developed a method to regioselectively transmute the nitrogen atom from pyridine into carbon bearing an ester, a flexible functional group handle. We applied this method to a variety of substituted pyridines, as well as late-stage transformation of FDA-approved drugs.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141597921","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 Evolution and Reversibility of a Single Au25 Nanocluster for the Oxygen Reduction Reaction. 单个 Au25 纳米团簇在氧还原反应中的动态演化和可逆性。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c03939
Zehui Sun, Jia Wang, Lei Su, Zhihao Gu, Xin-Ping Wu, Wei Chen, Wei Ma
{"title":"Dynamic Evolution and Reversibility of a Single Au<sub>25</sub> Nanocluster for the Oxygen Reduction Reaction.","authors":"Zehui Sun, Jia Wang, Lei Su, Zhihao Gu, Xin-Ping Wu, Wei Chen, Wei Ma","doi":"10.1021/jacs.4c03939","DOIUrl":"https://doi.org/10.1021/jacs.4c03939","url":null,"abstract":"<p><p>Ultrasmall metallic nanoclusters (NCs) protected by surface ligands represent the most promising catalytic materials; yet understanding the structure and catalytic activity of these NCs remains a challenge due to dynamic evolution of their active sites under reaction conditions. Herein, we employed a single-nanoparticle collision electrochemistry method for real-time monitoring of the dynamic electrocatalytic activity of a single fully ligand-protected Au<sub>25</sub>(PPh<sub>3</sub>)<sub>10</sub>(SC<sub>2</sub>H<sub>4</sub>Ph)<sub>5</sub>Cl<sub>2</sub><sup>2+</sup> nanocluster (Au<sub>25</sub><sup>2+</sup> NC) at a cavity carbon nanoelectrode toward the oxygen reduction reaction (ORR). Our experimental results and computational simulations indicated that the reversible depassivation and passivation of ligands on the surface of the Au<sub>25</sub><sup>2+</sup> NC, combined with the dynamic conformation evolution of the Au<sub>25</sub><sup>9+</sup> core, led to a characteristic current signal that involves \"ON-OFF\" switches and \"ON\" fluctuations during the ORR process of a single Au<sub>25</sub><sup>2+</sup> NC. Our findings reinvent the new perception and comprehension of the structure-activity correlation of NCs at the atomic level.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588937","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
Polynuclear Cobalt Cluster-Based Coordination Polymers for Efficient Nitrate-to-Ammonia Electroreduction. 基于多核钴簇的配位聚合物用于高效硝酸-氨电解还原。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c06098
Miao Wang, Shufan Li, Yuming Gu, Wenjie Xu, Huaizhu Wang, Jingjie Sun, Shuangming Chen, Zuoxiu Tie, Jing-Lin Zuo, Jing Ma, Jian Su, Zhong Jin
{"title":"Polynuclear Cobalt Cluster-Based Coordination Polymers for Efficient Nitrate-to-Ammonia Electroreduction.","authors":"Miao Wang, Shufan Li, Yuming Gu, Wenjie Xu, Huaizhu Wang, Jingjie Sun, Shuangming Chen, Zuoxiu Tie, Jing-Lin Zuo, Jing Ma, Jian Su, Zhong Jin","doi":"10.1021/jacs.4c06098","DOIUrl":"https://doi.org/10.1021/jacs.4c06098","url":null,"abstract":"<p><p>The electrocatalytic nitrate reduction reaction (NITRR) holds great promise for purifying wastewater and producing valuable ammonia (NH<sub>3</sub>). However, the lack of efficient electrocatalysts has impeded the achievement of highly selective NH<sub>3</sub> synthesis from the NITRR. In this study, we report the design and synthesis of two polynuclear Co-cluster-based coordination polymers, {[Co<sub>2</sub>(TCPPDA)(H<sub>2</sub>O)<sub>5</sub>]·(H<sub>2</sub>O)<sub>9</sub>(DMF)} and {Co<sub>1.5</sub>(TCPPDA)[(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>]·(H<sub>2</sub>O)<sub>6</sub>(DMF)<sub>2</sub>} (namely, <b>NJUZ-2</b> and <b>NJUZ-3</b>), which possess distinct coordination motifs with well-defined porosity, high-density catalytic sites, accessible mass transfer channels, and nanoconfined chemical environments. Benefitting from their intriguing multicore metal-organic coordination framework structures, <b>NJUZ-2</b> and <b>NJUZ-3</b> exhibit remarkable catalytic activities for the NITRR. At a potential of -0.8 V (vs. RHE) in an H-type cell, they achieve an optimal Faradaic efficiency of approximately 98.5% and high long-term durability for selective NH<sub>3</sub> production. Furthermore, the electrocatalytic performance is well maintained even under strongly acidic conditions. When operated under an industrially relevant current density of 469.9 mA cm<sup>-2</sup> in a flow cell, a high NH<sub>3</sub> yield rate of up to 3370.6 mmol h<sup>-1</sup> g<sup>-1</sup><sub>cat.</sub> was observed at -0.5 V (vs. RHE), which is 20.1-fold higher than that obtained in H-type cells under the same conditions. Extensive experimental analyses, in combination with theoretical computations, reveal that the great enhancement of the NITRR activity is attributed to the preferential adsorption of NO<sub>3</sub><sup>-</sup> and the reduction in energy input required for the hydrogenation of *NO<sub>3</sub> and *NO<sub>2</sub> intermediates.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588975","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
High-Throughput Covalent Modifier Screening with Acoustic Ejection Mass Spectrometry. 利用声发射质谱法高通量筛选共价修饰剂
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c02377
Xiujuan Wen, Chang Liu, Kiersten Tovar, Patrick Curran, Matthew Richards, Sony Agrawal, Richard Johnstone, Ryan E Loy, Joey L Methot, My Sam Mansueto, Markus Koglin, Mary Jo Wildey, Lyle Burton, Thomas R Covey, Kevin P Bateman, Michael Kavana, David G McLaren
{"title":"High-Throughput Covalent Modifier Screening with Acoustic Ejection Mass Spectrometry.","authors":"Xiujuan Wen, Chang Liu, Kiersten Tovar, Patrick Curran, Matthew Richards, Sony Agrawal, Richard Johnstone, Ryan E Loy, Joey L Methot, My Sam Mansueto, Markus Koglin, Mary Jo Wildey, Lyle Burton, Thomas R Covey, Kevin P Bateman, Michael Kavana, David G McLaren","doi":"10.1021/jacs.4c02377","DOIUrl":"https://doi.org/10.1021/jacs.4c02377","url":null,"abstract":"<p><p>Interests in covalent drugs have grown in modern drug discovery as they could tackle challenging targets traditionally considered \"undruggable\". The identification of covalent binders to target proteins typically involves directly measuring protein covalent modifications using high-resolution mass spectrometry. With a continually expanding library of compounds, conventional mass spectrometry platforms such as LC-MS and SPE-MS have become limiting factors for high-throughput screening. Here, we introduce a prototype high-resolution acoustic ejection mass spectrometry (AEMS) system for the rapid screening of a covalent modifier library comprising ∼10,000 compounds against a 50 kDa-sized target protein─Werner syndrome helicase. The screening samples were arranged in a 1536-well format. The sample buffer containing high-concentration salts was directly analyzed without any cleanup steps, minimizing sample preparation efforts and ensuring protein stability. The entire AEMS analysis process could be completed within a mere 17 h. An automated data analysis tool facilitated batch processing of the sample data and quantitation of the formation of various covalent protein-ligand adducts. The screening results displayed a high degree of fidelity, with a <i>Z</i>' factor of 0.8 and a hit rate of 2.3%. The identified hits underwent orthogonal testing in a biochemical activity assay, revealing that 75% were functional antagonists of the target protein. Notably, a comparative analysis with LC-MS showcased the AEMS platform's low risk of false positives or false negatives. This innovative platform has enabled robust high-throughput covalent modifier screening, featuring a 10-fold increase in library size and a 10- to 100-fold increase in throughput when compared with similar reports in the existing literature.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141588941","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
Synthetic and Mechanistic Studies into the Reductive Functionalization of Nitro Compounds Catalyzed by an Iron(salen) Complex. 铁(硒)络合物催化硝基化合物还原官能化的合成与机理研究。
IF 14.4 1区 化学
Journal of the American Chemical Society Pub Date : 2024-07-12 DOI: 10.1021/jacs.4c02797
Emily Pocock, Martin Diefenbach, Thomas M Hood, Michael Nunn, Emma Richards, Vera Krewald, Ruth L Webster
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