Journal of the American Chemical Society最新文献_第5页

Scalable Thiol Reactivity Profiling Identifies Azetidinyl Oxadiazoles as Cysteine-Targeting Electrophiles. 可扩展的巯基反应谱分析确定了氮杂环丁基噁二唑作为半胱氨酸靶向电介质。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-27 Epub Date: 2024-11-14 DOI: 10.1021/jacs.4c05711

Fereshte Ghorbani, Shaochen You, Gennadii A Grabovyi, Mannkyu Hong, Garrett Lindsey, Arnab K Chatterjee, Michael J Bollong

{"title":"Scalable Thiol Reactivity Profiling Identifies Azetidinyl Oxadiazoles as Cysteine-Targeting Electrophiles.","authors":"Fereshte Ghorbani, Shaochen You, Gennadii A Grabovyi, Mannkyu Hong, Garrett Lindsey, Arnab K Chatterjee, Michael J Bollong","doi":"10.1021/jacs.4c05711","DOIUrl":"10.1021/jacs.4c05711","url":null,"abstract":"Cysteine reactive groups are a mainstay in the design of covalent drugs and probe molecules, yet only a handful of electrophiles are routinely used to target this amino acid. Here, we report the development of scalable thiol reactivity (STRP), a method which enables the facile interrogation of large chemical libraries for intrinsic reactivity with cysteine. High throughput screening using STRP identified the azetidinyl oxadiazole as a moiety that selectively reacts with cysteine through a ring opening-based mechanism, capable of covalently engaging cysteine residues broadly across the human proteome. We show the utility of this reactive group with the discovery of an azetidinyl oxadiazole containing a small molecule that augments the catalytic activity of the deubiquitinase UCHL1 in vitro and in cells by covalently modifying a cysteine distal to its enzymatic active site. This study adds a novel cysteine targeting group to the electrophilic lexicon and provides robust methodology to rapidly surveil libraries for reactivity with cysteine.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32333-32342"},"PeriodicalIF":14.4,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612690","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

Excited State Dynamics of Geometrical Evolution of α-Substituted Dibenzoylmethanatoboron Difluoride Complex with Aggregation-Induced Emission Property. 具有聚集诱导发射特性的α-取代二苯甲酰甲硼二氟化物配合物几何演化的激发态动力学。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-27 Epub Date: 2024-11-17 DOI: 10.1021/jacs.4c10277

Yushi Fujimoto, Yoshifumi Mochiduki, Hikaru Sotome, Rintaro Shimada, Hajime Okajima, Yasunori Toda, Akira Sakamoto, Hiroshi Miyasaka, Fuyuki Ito

{"title":"Excited State Dynamics of Geometrical Evolution of α-Substituted Dibenzoylmethanatoboron Difluoride Complex with Aggregation-Induced Emission Property.","authors":"Yushi Fujimoto, Yoshifumi Mochiduki, Hikaru Sotome, Rintaro Shimada, Hajime Okajima, Yasunori Toda, Akira Sakamoto, Hiroshi Miyasaka, Fuyuki Ito","doi":"10.1021/jacs.4c10277","DOIUrl":"10.1021/jacs.4c10277","url":null,"abstract":"Organic molecules with an aggregation-induced emission (AIE) property have been attracting much attention from the viewpoint of application to solid state emissive materials. For the AIE mechanism, quantum mechanical studies proposed the restriction of the intramolecular motion (RIM) model with the contribution of the conical intersection (CI) and deduced the importance of the restricted access to a conical intersection (RACI) in the potential energy surface (PES). Although these theoretical studies have contributed to the elucidation of AIE phenomena, direct detection of the reaction dynamics is indispensable to clarify the actual PES and the deactivation mechanism. Along this line, we investigated excited state dynamics of the AIE molecule with dibenzoylmethanatoboron difluoride complexes using time-resolved absorption spectroscopies in both visible and infrared (IR) regions. While the reference system of 1,3-bis(4-methoxyphenyl)methanatoboron difluoride (2aBF2) showed strong emission in solution, the methyl-substituted derivative at the α-position of the dioxaborine ring (2amBF2) led to the very weak fluorescence in solution but strong emission in the solid state. Time-resolved visible absorption measurements revealed a peak shift and broadening of the stimulated emission in the solution of 2amBF2, owing to the rapid change of the molecular geometry. With the temporal evolution of time-resolved IR absorption signals and density functional theory (DFT) calculation of these systems, it was deduced that 2amBF2 has two stable geometries, namely, planar and bending, in the S1 state and the bending geometry in the S1 state led to rapid conversion to the S0 state. These results support the RACI model in the aggregated states, leading to the AIE properties.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32529-32538"},"PeriodicalIF":14.4,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142643291","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

Turning on Low-Temperature Catalytic Conversion of Biomass Derivatives through Teaming Pd₁ and Mo₁ Single-Atom Sites. 通过 Pd1 和 Mo1 单原子位点组合实现生物质衍生物的低温催化转化。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-27 Epub Date: 2024-11-14 DOI: 10.1021/jacs.4c07075

Yu Tang, George Yan, Shiran Zhang, Yuting Li, Luan Nguyen, Yasuhiro Iwasawa, Tomohiro Sakata, Christopher Andolina, Judith C Yang, Philippe Sautet, Franklin Feng Tao

{"title":"Turning on Low-Temperature Catalytic Conversion of Biomass Derivatives through Teaming Pd1 and Mo1 Single-Atom Sites.","authors":"Yu Tang, George Yan, Shiran Zhang, Yuting Li, Luan Nguyen, Yasuhiro Iwasawa, Tomohiro Sakata, Christopher Andolina, Judith C Yang, Philippe Sautet, Franklin Feng Tao","doi":"10.1021/jacs.4c07075","DOIUrl":"10.1021/jacs.4c07075","url":null,"abstract":"On-purpose atomic scale design of catalytic sites, specifically active and selective at low temperature for a target reaction, is a key challenge. Here, we report teamed Pd1 and Mo1 single-atom sites that exhibit high activity and selectivity for anisole hydrodeoxygenation to benzene at low temperatures, 100-150 °C, where a Pd metal nanoparticle catalyst or a MoO3 nanoparticle catalyst is individually inactive. The catalysts built from Pd1 or Mo1 single-atom sites alone are much less effective, although the catalyst with Pd1 sites shows some activity but low selectivity. Similarly, less dispersed nanoparticle catalysts are much less effective. Computational studies show that the Pd1 and Mo1 single-atom sites activate H2 and anisole, respectively, and their combination triggers the hydrodeoxygenation of anisole in this low-temperature range. The Co3O4 support is inactive for anisole hydrodeoxygenation by itself but participates in the chemistry by transferring H atoms from Pd1 to the Mo1 site. This finding opens an avenue for designing catalysts active for a target reaction channel such as conversion of biomass derivatives at a low temperature where neither metal nor oxide nanoparticles are.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32366-32382"},"PeriodicalIF":14.4,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612693","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

Real-Space Spectral Determination of Short Single-Stranded DNA Sequence Structures. 短单链 DNA 序列结构的实空间光谱测定。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-27 DOI: 10.1021/jacs.4c12393

Yu Han, Li Dong, Lu-Yao Zhu, Chun-Rui Hu, Hang Li, Yang Zhang, Chao Zhang, Yao Zhang, Zhen-Chao Dong

{"title":"Real-Space Spectral Determination of Short Single-Stranded DNA Sequence Structures.","authors":"Yu Han, Li Dong, Lu-Yao Zhu, Chun-Rui Hu, Hang Li, Yang Zhang, Chao Zhang, Yao Zhang, Zhen-Chao Dong","doi":"10.1021/jacs.4c12393","DOIUrl":"https://doi.org/10.1021/jacs.4c12393","url":null,"abstract":"Resolving the sequence and structure of flexible biomolecules such as DNA is crucial to understanding their biological mechanisms and functions. Traditional structural biology methods remain challenging for the analysis of small and disordered biomolecules, especially those that are difficult to label or crystallize. Recent development of single-molecule tip-enhanced Raman spectroscopy (TERS) offers a label-free approach to identifying nucleobases in a single DNA chain. However, a clear demonstration of sequencing both spatially and spectrally at single-base resolution is still elusive due to the challenges caused by weak Raman signals and the flexibility of DNA molecules. Here, we report a proof-of-principle demonstration to this end, spectrally resolving in real space individual nucleobases and their sequence structures within a short, single-stranded DNA molecule artificially designed. This breakthrough is achieved through the development of subnanometer-resolved low-temperature TERS methodology for such thermally unstable flexible biomolecules. Further TERS mapping over individual nucleobases provides additional structural information about the molecular configurations and even the locations of functional groups, offering a way to track modification types and binding sites in biomolecules.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142737797","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

Observation of Ferroelectricity in Carbapenem Intermediates Enables Reactive Oxygen Species Generation by Ultrasound. 观察碳青霉烯中间体的铁电性可通过超声波产生活性氧。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-27 Epub Date: 2024-11-15 DOI: 10.1021/jacs.4c09955

Xian-Jiang Song, Wenbo Sun, Long-Xing Zhou, Wei-Xin Mao, Hua-Ming Xu, Jin-Fei Lan, Yao Zhang, Han-Yue Zhang

{"title":"Observation of Ferroelectricity in Carbapenem Intermediates Enables Reactive Oxygen Species Generation by Ultrasound.","authors":"Xian-Jiang Song, Wenbo Sun, Long-Xing Zhou, Wei-Xin Mao, Hua-Ming Xu, Jin-Fei Lan, Yao Zhang, Han-Yue Zhang","doi":"10.1021/jacs.4c09955","DOIUrl":"10.1021/jacs.4c09955","url":null,"abstract":"Organic ferroelectrics show great applications in the fields of biomedicine, including disease treatment, biosensors, and tissue engineering. Organosilicon pharmaceutical intermediates generally include chiral centers and have satisfying biosafety, biocompatibility, or even biodegradability, which provide versatile platforms for the design of ferroelectricity. However, their academic values in ferroelectricity have long been long overlooked. Here, we demonstrated the ferroelectric properties of 4-acetoxy-azacyclic butanone (4-AA), a key synthetic organosilicon-based intermediate of carbapenem drugs. This compound undergoes a 222F2-type ferroelectric-ferroelastic phase transition at 326 K. As an organic piezoelectric material, 4-AA can produce reactive oxygen species when subjected to ultrasonic vibrations. Combined with its desirable biocompatibility, this material may contribute to antimicrobial and wound healing, tumor treatment, etc. This work will provide inspiration for the discovery of multifunctional biomedical ferroelectric materials as well as their related application prospects.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32519-32528"},"PeriodicalIF":14.4,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142638039","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

Structural Insights into the Mechanism of a Polyketide Synthase Thiocysteine Lyase Domain. 多酮类化合物合成酶硫代半胱氨酸裂解酶结构域的机理。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-27 Epub Date: 2024-11-15 DOI: 10.1021/jacs.4c11656

Andrew D Steele, Song Meng, Gengnan Li, Edward Kalkreuter, Changsoo Chang, Ben Shen

{"title":"Structural Insights into the Mechanism of a Polyketide Synthase Thiocysteine Lyase Domain.","authors":"Andrew D Steele, Song Meng, Gengnan Li, Edward Kalkreuter, Changsoo Chang, Ben Shen","doi":"10.1021/jacs.4c11656","DOIUrl":"10.1021/jacs.4c11656","url":null,"abstract":"Polyketide synthases (PKSs) are renowned for the structural diversity of the polyketide natural products they produce, but sulfur-containing functionalities are rarely installed by PKSs. We previously characterized thiocysteine lyase (SH) domains involved in the biosynthesis of the leinamycin (LNM) family of natural products, exemplified by LnmJ-SH and guangnanmycin (GnmT-SH). Here we report a detailed investigation into the PLP-dependent reaction catalyzed by the SH domains, guided by a 1.8 Å resolution crystal structure of GnmT-SH. A series of elaborate substrate mimics were synthesized to answer specific questions garnered from the crystal structure and from the biosynthetic logic of the LNM family of natural products. Through a combination of bioinformatics, molecular modeling, in vitro assays, and mutagenesis, we have developed a detailed model of acyl carrier protein (ACP)-tethered substrate-SH, and interdomain interactions, that contribute to the observed substrate specificity. Comparison of the GnmT-SH structure with archetypical PLP-dependent enzyme structures revealed how Nature, via evolution, has modified a common protein structural motif to accommodate an ACP-tethered substrate, which is significantly larger than any of those previously characterized. Overall, this study demonstrates how PLP-dependent chemistry can be incorporated into the context of PKS assembly lines and sets the stage for engineering PKSs to produce sulfur-containing polyketides.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32605-32617"},"PeriodicalIF":14.4,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142638100","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

Ammonia Synthesis with Visible Light and Quantum Dots. 利用可见光和量子点合成氨。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-27 Epub Date: 2024-11-17 DOI: 10.1021/jacs.4c06713

Vanshika Jain, Shreya Tyagi, Pradyut Roy, Pramod P Pillai

{"title":"Ammonia Synthesis with Visible Light and Quantum Dots.","authors":"Vanshika Jain, Shreya Tyagi, Pradyut Roy, Pramod P Pillai","doi":"10.1021/jacs.4c06713","DOIUrl":"10.1021/jacs.4c06713","url":null,"abstract":"Light-assisted synthesis of ammonia from nitrate and nitrite sources is a sustainable approach to reduce the burden of the energy-intensive Haber-Bosch process. However, poor selectivity and the need for UV-active photocatalysts are the current bottlenecks in the synthesis of ammonia from nitrate and nitrite sources. Herein, we introduce selective visible-light-driven ammonia production from nitrate and nitrite ions with indium phosphide quantum dots (InP QDs) as the photocatalyst. The presence of catalytic indium sites and microenvironment modulation through an interplay of catalyst-reactant interactions resulted in efficient and selective ammonia formation under visible light. Ammonia was produced in an attractive yield of ∼94% in both aqueous and gaseous phases within 2 h of visible-light irradiation at room temperature. A decent formation of ammonia was observed under sunlight as well, strengthening the translational prospects of InP QD photocatalysts. Mechanistic investigations ascertained a negligible role of competing hydrogen evolution in direct nitrate reduction, confirming the active participation of photoexcited charge carriers from InP QDs in the ammonia synthesis. Kinetic studies revealed the energetically challenging nitrate-to-nitrite conversion as the rate-determining step, with subsequent reactions proceeding with ∼100% conversion to yield ammonia. A series of experiments concluded that water is the proton source in the InP QD-photocatalyzed synthesis of ammonia. Our study shows the impact of the rationally designed core and surface of InP QD-based photocatalysts in developing sustainable routes to produce ammonia beyond the Haber-Bosch process.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32356-32365"},"PeriodicalIF":14.4,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646405","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

Why Does a Transition Metal Dichalcogenide Nanoribbon Narrow into a Nanowire under Electron Irradiation? 为什么在电子辐照下过渡金属二卤化物纳米带会变窄成纳米线？

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-26 DOI: 10.1021/jacs.4c12428

Yue Liu, Tian Cui, Da Li

{"title":"Why Does a Transition Metal Dichalcogenide Nanoribbon Narrow into a Nanowire under Electron Irradiation?","authors":"Yue Liu, Tian Cui, Da Li","doi":"10.1021/jacs.4c12428","DOIUrl":"https://doi.org/10.1021/jacs.4c12428","url":null,"abstract":"Transition metal dichalcogenide (TMDC) nanowires have practical applications in 1D electron channels, spintronics, optoelectronics, and catalysis due to their authentic subnanometer width (<1 nm) and intrinsic metallicity. Although narrowing of a TMDC nanoribbon into a nanowire under electron irradiation has been frequently observed in the synthesis of TMDC nanowires, the mechanism underlying this unexpected structural transformation remains a mystery. Here, to reveal the underlying mechanism, we combine first-principles calculations with a global structure search of 1D nanowires and show that a nanoribbon of 1H-phase MoS2 with a width narrower than 6 rings is energetically unfavorable compared with its nanowire counterpart due to the edge–edge interaction. The bending effect induced by S defects under electron irradiation is the major driving force for the transition of MoS2 nanoribbon into a nanowire. We predict that the precursor of the Mo6S6 nanowire is a well-defined Mo11S11-i nanowire with an unexpected stoichiometry. The intrinsic local compressive strain triggers a phase transition from Mo11S11-i to its slightly modified sister nanowire, Mo11S11-ii, which is characterized by the configuration (Mo1S1)5&Mo6S6. Triggered by electron irradiation, the nanoribbon undergoes a step-by-step narrowing process with sequential peeling of a Mo1S1 fragment in each step to form a robust Mo6S6 nanowire. This unique narrowing mechanism is universal for the nanoribbon-to-nanowire transformation of other TMDCs under electron irradiation. Our study highlights a hitherto unexplored mechanism for creating individual M6X6 nanowires and contributes to an in-depth understanding of the narrowing of TMDC nanoribbons under electron irradiation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"8 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719001","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

A Discrete Trialane with a Near-Linear Al3 Axis 具有近线性 Al3 轴的离散试样

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-26 DOI: 10.1021/jacs.4c10967

Debabrata Dhara, Lukas Endres, Aritra Roy, Rian D. Dewhurst, Rüdiger Bertermann, Felipe Fantuzzi, Holger Braunschweig

引用次数: 0

Catalytic Enantioselective Hydrogen Atom Abstraction Enables the Asymmetric Oxidation of Meso Diols 催化不对称选择性氢原子萃取使中二元醇的不对称氧化成为可能

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-26 DOI: 10.1021/jacs.4c13919

Nelson Y. S. Lam, Jyoti Dhankhar, Antti S. K. Lahdenperä, Robert J. Phipps

引用次数: 0