Journal of the American Chemical Society最新文献_第3页

DNA-Regulated Multi-Protein Complement Control DNA 调节的多蛋白补体控制

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-21 DOI: 10.1021/jacs.4c11315

Yinglun Ma, Peter H. Winegar, C. Adrian Figg, Namrata Ramani, Alex J. Anderson, Kathleen Ngo, John F. Ahrens, Nikhil S. Chellam, Young Jun Kim, Chad A. Mirkin

{"title":"DNA-Regulated Multi-Protein Complement Control","authors":"Yinglun Ma, Peter H. Winegar, C. Adrian Figg, Namrata Ramani, Alex J. Anderson, Kathleen Ngo, John F. Ahrens, Nikhil S. Chellam, Young Jun Kim, Chad A. Mirkin","doi":"10.1021/jacs.4c11315","DOIUrl":"https://doi.org/10.1021/jacs.4c11315","url":null,"abstract":"In nature, the interactions between proteins and their complements/substrates can dictate complex functions. Herein, we explore how DNA on nucleic acid modified proteins can be used as scaffolds to deliberately control interactions with a peptide complement (by adjusting length, sequence, and rigidity). As model systems, split GFPs were covalently connected through DNA scaffolds (36–58 bp). Increasing the length or decreasing the rigidity of the DNA scaffold (through removal of the duplex) increases the extent of intramolecular protein binding (up to 7.5-fold) between these GFP fragments. Independent and dynamic control over functional outputs can also be regulated by DNA hybridization; a multi-protein (split CFP and YFP) architecture was synthesized and characterized by fluorescence. This ternary construct shows that DNA displacement strands in different stoichiometric ratios can be used deliberately to regulate competitive binding between two unique sets of proteins. These studies establish a foundation for creating new classes of biological machinery based upon the concept of DNA-regulated multi-protein complement control.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"129 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhancing the Conversion Efficiency of Polyethylene to Methane through Codoping of Mn Atoms into Ru Centers and CeO2 Supports 通过在 Ru 中心和 CeO2 支持物中掺入锰原子提高聚乙烯到甲烷的转化效率

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-21 DOI: 10.1021/jacs.4c10793

Meng Zhao, Xiang Chu, Fei Wang, Yizhu Fang, Lu Sun, Qing Xie, Ling-ling Zhang, Shuyan Song, Hongjie Zhang, Xiao Wang

{"title":"Enhancing the Conversion Efficiency of Polyethylene to Methane through Codoping of Mn Atoms into Ru Centers and CeO2 Supports","authors":"Meng Zhao, Xiang Chu, Fei Wang, Yizhu Fang, Lu Sun, Qing Xie, Ling-ling Zhang, Shuyan Song, Hongjie Zhang, Xiao Wang","doi":"10.1021/jacs.4c10793","DOIUrl":"https://doi.org/10.1021/jacs.4c10793","url":null,"abstract":"Chemical conversion has emerged as an effective approach for disposing waste plastics; however, the product diversity in traditional methods leads to pressing challenges in product separation and purification. As a pioneering advancement, the comprehensive transformation of waste plastics into CH4 presents an attractive prospect: directly yielding high-purity products. Significantly, CH4 is an important hydrogen carrier and an industrial feedstock. However, there is still much room for enhancing the overall efficiency. Herein, we show a new strategy to construct a high-efficiency and robust polyethylene (PE) upgrading catalyst by codoping Mn heteroatoms into both RuO2 and CeO2. We found that these Mn heteroatoms effectively bolster the stability of Ruδ+ species under high-temperature reduction conditions. The harmonious coexistence of Ru0 and Ruδ+ significantly refines the reaction pathway by enhancing the adsorption of the alkane intermediates. Consequently, we achieved an impressive PE conversion rate exceeding >99% with nearly 99% toward CH4 at a moderate temperature of 250 °C within 8 h. Our discovery not only opens a new window for catalyst upgrading but also presents exciting opportunities for the in-depth conversion of waste plastics into complex, high-purity fine chemicals through methane-mediated catalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685125","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

Light, Switch, Action! The Influence of Geometrical Photoisomerization in an Adaptive Self-Assembled System. 光、开关、作用！自适应自组装系统中几何光异构化的影响。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-20 Epub Date: 2024-11-05 DOI: 10.1021/jacs.4c11206

Marco Ovalle, Charlotte N Stindt, Ben L Feringa

{"title":"Light, Switch, Action! The Influence of Geometrical Photoisomerization in an Adaptive Self-Assembled System.","authors":"Marco Ovalle, Charlotte N Stindt, Ben L Feringa","doi":"10.1021/jacs.4c11206","DOIUrl":"10.1021/jacs.4c11206","url":null,"abstract":"The ubiquitous ability of natural dynamic nanostructures to adapt to environmental changes is a highly desirable property for chemical systems, particularly in the development of complex matter, molecular machines, and life-like materials. Designing such systems is challenging due to the generation of complex mixtures with responses that are difficult to predict, characterize, and diversify. Here, we navigate between self-assembled architectures using light by operating an intrinsic photoswitchable building block that governs the state of the system. When complementary units are present, the photoswitch determines the predominant architecture, reversibly adapting between the cage and macrocycles, including (otherwise inaccessible) higher-energy assemblies. Our study showcases this concept with seven different transformations, offering an unprecedented degree of control, diversification, and adaptation by self-selecting complementary units. These findings could enable applications of on-demand dissipative macrocycles based on dynamic bonds. We also envision different transient nanostructures, e.g., reticular and polymeric materials, being explored by fine-tuning the nature of the complementary unit.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"31892-31900"},"PeriodicalIF":14.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580858","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

Selective Oxidation of Polyesters via PdCu-TiO₂ Photocatalysts in Flow. 通过 PdCu-TiO2 光催化剂在流动中选择性氧化聚酯。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-20 Epub Date: 2024-11-05 DOI: 10.1021/jacs.4c11973

Shuai Zhang, Bernt Johannessen, Bingquan Xia, Xintong Gao, Kenneth Davey, Jingrun Ran, Shi-Zhang Qiao

{"title":"Selective Oxidation of Polyesters via PdCu-TiO2 Photocatalysts in Flow.","authors":"Shuai Zhang, Bernt Johannessen, Bingquan Xia, Xintong Gao, Kenneth Davey, Jingrun Ran, Shi-Zhang Qiao","doi":"10.1021/jacs.4c11973","DOIUrl":"10.1021/jacs.4c11973","url":null,"abstract":"Catalytic upcycling of plastic wastes offers a sustainable circular economy. Selective conversion of the most widely used polyester, polyethylene terephthalate (PET), under ambient conditions is practically attractive because of low energy consumption and carbon footprint. Here, we report selective, aerobic conversion of PET in a flow reactor using TiO2 photocatalyst modified with atomic Pd and metallic PdCu (Pd1Cu0.4-TiO2) under ambient conditions. We demonstrate that atomically synergistic Pd1Cu0.4-TiO2 exhibits a formate evolution of 4707 μmol g-1 h-1 with a selectivity of 92.3% together with trace COx released. Importantly, we show that this corresponds to 10-103 times greater activity than reported photocatalytic systems. We confirm that synergy between atomic Pd and metallic PdCu boosts directional charge transfer and oxygen-induced C-C cleavage and inhibits product decomposition. We conclude that photocatalytic waste plastic-to-chemical conversion is sustainable via targeted engineering of atomically synergistic catalysts and reaction systems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32003-32012"},"PeriodicalIF":14.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580862","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

Facile Alkyne Assembly-Enabled Functional Au Nanosheets for Photoacoustic Imaging-Guided Photothermal/Gene Therapy of Orthotopic Glioblastoma 用于光声成像引导的直位胶质母细胞瘤光热/基因治疗的简易炔烃组装功能金纳米片

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-20 DOI: 10.1021/jacs.4c08990

Xixi Hu, Peiling Li, Dongdong Xu, Hua Liu, Qiaoqiao Hao, Mengyang Zhang, Zhaoyin Wang, Tianxiang Wei, Zhihui Dai

{"title":"Facile Alkyne Assembly-Enabled Functional Au Nanosheets for Photoacoustic Imaging-Guided Photothermal/Gene Therapy of Orthotopic Glioblastoma","authors":"Xixi Hu, Peiling Li, Dongdong Xu, Hua Liu, Qiaoqiao Hao, Mengyang Zhang, Zhaoyin Wang, Tianxiang Wei, Zhihui Dai","doi":"10.1021/jacs.4c08990","DOIUrl":"https://doi.org/10.1021/jacs.4c08990","url":null,"abstract":"Treatment of glioblastoma (GBM) remains challenging due to the presence of blood–brain barrier (BBB) and tumor heterogeneity. Herein, Au nanosheets (AuNSs) functionalized with RGD peptides and small interfering RNA (siRNA), referred to as AuNSs-RGD-C≡C-siRNA (ARCR), are prepared to achieve multimodal therapy for GBM. The AuNSs with a large modifiable surface area, intriguing photothermal conversion efficiency (50.26%), and remarkable photothermal stability (44 cycles over 7 h) are created using a well-designed amphiphilic surfactant. Furthermore, alkynyl groups are assembled onto the Au surface within 1 min, enabling strong covalent binding of siRNA to AuNSs and thereby avoiding the interference from biological thiols. Owing to the lipophilicity of the surfactant and the targeting property of RGD, ARCR effectively passes through the BBB and accumulates in GBM tumor regions, allowing near-infrared photoacoustic imaging-guided photothermal/gene therapy. This work proposes a facile strategy to construct theranostic Au-based materials, highlighting the potential of multifunctional nanoagents for GBM therapy.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"69 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673102","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

Origin of the High Catalytic Activity of MoS₂ in Na-S Batteries: Electrochemically Reconstructed Mo Single Atoms. Na-S 电池中 MoS2 高催化活性的起源：电化学重构的 Mo 单原子。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-20 Epub Date: 2024-11-07 DOI: 10.1021/jacs.4c13400

Xue Zhong, Yujie Huang, Jieming Cai, Yujin Li, Zidong He, Dongyang Cai, Zhenglei Geng, Wentao Deng, Guoqiang Zou, Hongshuai Hou, Xiaobo Ji

{"title":"Origin of the High Catalytic Activity of MoS2 in Na-S Batteries: Electrochemically Reconstructed Mo Single Atoms.","authors":"Xue Zhong, Yujie Huang, Jieming Cai, Yujin Li, Zidong He, Dongyang Cai, Zhenglei Geng, Wentao Deng, Guoqiang Zou, Hongshuai Hou, Xiaobo Ji","doi":"10.1021/jacs.4c13400","DOIUrl":"10.1021/jacs.4c13400","url":null,"abstract":"Room-temperature sodium-sulfur (RT Na-S) batteries with high energy density and low cost are considered promising next-generation electrochemical energy storage systems. However, their practical feasibility is seriously impeded by the shuttle effect of sodium polysulfide (NaPSs) resulting from the sluggish reaction kinetics. Introducing a suitable catalyst to accelerate conversion of NaPSs is the most used strategy to inhibit the shuttle effect. Traditional catalytic approaches often want to avoid the irreversible phase transition of the catalyst at a deep discharge. On the contrary, here, we leverage the intrinsic structural tunability of the MoS2 catalyst in the opposite direction and innovatively propose a voltage modulation strategy for in situ generation of trace Mo single atoms (MoSAC) during the first charge-discharge process, leading to the formation of highly active catalytic phases (MoS2/MoSAC) through the self-reconstruction. Theoretical calculations reveal that the incorporation of MoSAC modulates the electronic structure of the Mo d-band center, which not only effectively promotes the d-p orbital hybridization but also accelerates the catalytic intermediate desorption by the bonding transition, the dynamic single-atom synergistic catalytic mechanism enhances the adsorption response between the metal active site and NaPSs, which significantly improves the sulfur redox reaction (SRR), and the initial capacity of the MoS2/MoSAC/CF@S cell at 0.2 A g-1 is increased by 46.58% compared to that of the MoS2/CF@S cell. The discovery of the MoS2/MoSAC/CF catalyst provides new insights into adjusting the structure and function of transition metal disulfide catalysts at the atomic scale, offering hope for the development of high-specific-energy RT Na-S batteries.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32124-32134"},"PeriodicalIF":14.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142602040","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

Spatial Control over Reactions via Localized Transcription within Membraneless DNA Nanostar Droplets 通过无膜 DNA 纳米柱液滴内的局部转录实现对反应的空间控制

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-20 DOI: 10.1021/jacs.4c07274

Eli Kengmana, Elysse Ornelas-Gatdula, Kuan-Lin Chen, Rebecca Schulman

{"title":"Spatial Control over Reactions via Localized Transcription within Membraneless DNA Nanostar Droplets","authors":"Eli Kengmana, Elysse Ornelas-Gatdula, Kuan-Lin Chen, Rebecca Schulman","doi":"10.1021/jacs.4c07274","DOIUrl":"https://doi.org/10.1021/jacs.4c07274","url":null,"abstract":"Biomolecular condensates control where and how fast many chemical reactions occur in cells by partitioning reactants and catalysts, enabling simultaneous reactions in different spatial locations of a cell. Even without a membrane or physical barrier, the partitioning of the reactants can affect the rates of downstream reaction cascades in ways that depend on reaction location. Such effects can enable systems of biomolecular condensates to spatiotemporally orchestrate chemical reaction networks in cells to facilitate complex behaviors such as ribosome assembly. Here, we develop a system for developing such control in synthetic systems. We localize different transcription templates within different phase-separated, membraneless DNA nanostar (NS) droplets─programmable, in vitro liquid–liquid phase separation systems for partitioning of substrates and localization of reactions to membraneless droplets. When RNA produced within such droplets is also degraded in the bulk, droplet-localized transcription creates RNA concentration gradients. Consistent with the formation of these gradients, toehold-mediated strand displacement reactions involving transcripts are 2-fold slower far from the site of transcription than when nearby. We then demonstrate how multiple such gradients can form and be maintained independently by simultaneous transcription reactions occurring in tandem, each localized to different NS droplet types. Our results provide a means for constructing reaction systems in which different reactions are spatially localized and controlled without the need for physical membranes. This system also provides a means for generally studying how localized reactions and the exchange of reaction products might occur between protocells.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"9 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673064","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

Catalytic Asymmetric Reactions of Ketimines and Alkenes via [2 + 2] Cycloaddition: Chemical Reactivity Controlled by Switching a Heteroatom. 通过 [2 + 2] 环加成催化酮亚胺和烯烃的不对称反应：通过切换一个杂原子控制化学反应活性。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-20 Epub Date: 2024-11-08 DOI: 10.1021/jacs.4c13302

Qun Zhao, Yao Li, Zhiyuan Ren, Ying-Bo Shao, Li Chen, Xin Li

{"title":"Catalytic Asymmetric Reactions of Ketimines and Alkenes via [2 + 2] Cycloaddition: Chemical Reactivity Controlled by Switching a Heteroatom.","authors":"Qun Zhao, Yao Li, Zhiyuan Ren, Ying-Bo Shao, Li Chen, Xin Li","doi":"10.1021/jacs.4c13302","DOIUrl":"10.1021/jacs.4c13302","url":null,"abstract":"Azetidine units are commonly found in natural products and biologically active drugs. The [2 + 2] cycloaddition of imines and alkenes has been extensively used in the synthesis of such structures, while enantioselective approaches remain elusive. Herein, an efficient B(C6F5)3/chiral phosphoric acid-catalyzed asymmetric [2 + 2] cycloaddition of ketimines and aryl vinyl selenides was presented, delivering valuable chiral azetidines with excellent stereoselectivities (>20:1 dr and up to 96:4 er). What's even more interesting was that when a \"Se\" atom was switched to an \"S\" atom, the reaction proceeded through a [2 + 2] cycloaddition/ring-opening cascade process, affording a range of chiral thioacetals with high enantioselectivities (up to 98:2 er), which were also important organic sulfur compounds. Mechanistic experiments, coupled with density functional theory (DFT) calculations, shed light on a mechanism involving stepwise [2 + 2] cycloaddition and ring-opening processes, with the initial alkenylation step identified as crucial for achieving stereoselective control.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32088-32097"},"PeriodicalIF":14.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142602033","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

Preserving High Porosity of Covalent Organic Frameworks via Functional Polymer Guest Introduction 通过功能性聚合物客体保持共价有机框架的高孔隙率简介

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-20 DOI: 10.1021/jacs.4c10273

Tianwei Xue, Olga A. Syzgantseva, Li Peng, Ruiqing Li, Yuyu Guo, Chengbin Liu, Tongxin Qiao, Wenli Hao, Jiaran Li, Lilin Zhu, Shuliang Yang, Jun Li, Wendy L. Queen

{"title":"Preserving High Porosity of Covalent Organic Frameworks via Functional Polymer Guest Introduction","authors":"Tianwei Xue, Olga A. Syzgantseva, Li Peng, Ruiqing Li, Yuyu Guo, Chengbin Liu, Tongxin Qiao, Wenli Hao, Jiaran Li, Lilin Zhu, Shuliang Yang, Jun Li, Wendy L. Queen","doi":"10.1021/jacs.4c10273","DOIUrl":"https://doi.org/10.1021/jacs.4c10273","url":null,"abstract":"Due to their high structural tunability, remarkable internal surface areas, readily accessible pore space, and host of possible applications, covalent organic frameworks (COFs) remain at the forefront of materials science research. Unfortunately, many COFs suffer from structural distortions or pore collapse during activation, which can lead to a substantial loss of crystallinity and functionality. Thus, herein, we demonstrate a facile method to address this issue by introducing polymer guests. The polymer adheres to the COF internal pore wall, acting as a supporting pillar during activation and effectively preserving the COF porosity and crystallinity. In fact, the surface area of one COF/polymer composite, known as TAPB-TA/PDA, was boosted by a factor of 16 when compared to the parent COF, TAPB-TA. More importantly, the now robust COF structure was able to resist layer shifting and order loss during both solvent immersion and removal. The introduction of functional polymer guests not only solidifies the COF structure and preserves its high porosity but is also shown to enhance the transport and separation of photogenerated charge carriers, thereby facilitating hydrogen evolution during photocatalytic water splitting. Molecular dynamics simulations further support experimental observations that the incorporation of PDA within the COF pores reinforces the walls, preventing its collapse. The proposed mechanism is based on the adsorption of PDA oligomers along the c direction of the unit cell, fastening the COF layers in place via van der Waals interactions. This kind of interaction locks −N═CH–Ph–CH═N– units in a trans-configuration in the COF pores.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"5 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678805","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

Accelerated Mechanochemical Bond Scission and Stabilization against Heat and Light in Carbamoyloxime Mechanophores. 氨基甲酰肟机械分子中加速的机械化学键断裂和抗热抗光的稳定性。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-20 Epub Date: 2024-11-07 DOI: 10.1021/jacs.4c13319

Simay Aydonat, Davide Campagna, Sourabh Kumar, Sonja Storch, Tim Neudecker, Robert Göstl

{"title":"Accelerated Mechanochemical Bond Scission and Stabilization against Heat and Light in Carbamoyloxime Mechanophores.","authors":"Simay Aydonat, Davide Campagna, Sourabh Kumar, Sonja Storch, Tim Neudecker, Robert Göstl","doi":"10.1021/jacs.4c13319","DOIUrl":"10.1021/jacs.4c13319","url":null,"abstract":"Current approaches to the discovery of mechanochemical reactions in polymers are limited by the interconnection of the zero-force and force-modified potential energy surfaces since most mechanochemical reactions are force-biased thermal reactions. Here, carbamoyloximes are developed as a mechanophore class in which the mechanochemical reaction rates counterintuitively increase together with the thermal stability. All carbamoyloxime mechanophores undergo force-induced homolytic bond scission at the N-O bond, and their mechanochemical scission rate increases with the degree of substitution on the α-substituent. Yet, carbamoylaldoximes react to both heat and light with a pericyclic syn elimination, while carbamoylketoximes undergo thermal decomposition at high temperature and photochemical homolytic scission only from the triplet state. Thereby, the mechanochemical and thermal reaction trajectories are separated, and the thermal stability increases alongside the mechanochemical reaction kinetics. This approach may play an important role in the future of systematic mechanochemical reaction discovery.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"32117-32123"},"PeriodicalIF":14.4,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142602444","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