Journal of the American Chemical Society最新文献

{"title":"","authors":"Yong-Ze Xie, Dong-Sheng Yang, Li-Gang Bai, Jin-Wei Yang, Bo Gu, Meng-Ting Liu, Qi-Yue Wang, Wang Wang, Wen-Bo Liu* and Heng Song*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c09258","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Atomic Trajectories of a Bimolecular Reaction Visualized by Ultrafast Electron Diffraction.","authors":"R Patrick Xian, Stuart A Hayes, Gastón Corthey, Carole A Morrison, Alexander Marx, Hazem Daoud, Cheng Lu, R J Dwayne Miller","doi":"10.1021/jacs.5c07077","DOIUrl":"https://doi.org/10.1021/jacs.5c07077","url":null,"abstract":"<p><p>Bimolecular reactions are ubiquitous in chemistry, but it is exceptionally difficult to resolve the motion of atoms for such processes on the ultrafast time scales that the breaking and creation of chemical bonds occur. Detecting small changes in atom positions requires high temporal and spatial resolution and reliable signal-to-noise characteristics. Here, we have exploited solid-state alignment to track a photoinduced bimolecular disproportionation reaction that transforms two pairs of adjacent triiodide anions (I₃^-) into the metastable tetraiodide molecule and the diiodide fragment. We use ultrafast electron diffraction and dynamical structure refinement, where the atomic displacements are directly reconstructed from the diffraction data with plausible restraints on the atomic trajectories starting from the known ground-state structure. The excited-state structures are supported by theoretical calculations in the solid state and the reaction courses show clear site dependence on the ultrafast time scale. Our results provide a close-up view of the atomic motions involved in this classic reaction in real time, from bond elongation to breaking at the parent ion, to collision and subsequent bond formation of the liberated I atom with the neighboring I₃^-, all within a picosecond.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144751754","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}

{"title":"Two-in-One Flexible Metal-Organic Framework: One-Step C₂H₄ Purification via Inverse C₂H₆-C₂H₄ and C₂H₂-CO₂ Separations.","authors":"Debolina Mukherjee, Shyam Chand Pal, Jia-Xin Wang, Volodymyr Bon, Santanu Chand, Stefan Kaskel, Bin Li, Dirk Volkmer, Madhab C Das","doi":"10.1021/jacs.5c08726","DOIUrl":"https://doi.org/10.1021/jacs.5c08726","url":null,"abstract":"<p><p>Flexible metal-organic frameworks (FMOFs) with \"S-shaped\" stepped isotherms are stimuli-responsive smart materials that exhibit dynamic structural changes in response to guests, offering intrinsic thermal management and excellent regenerability compared to the classical rigid adsorbents. Herein, a 2-fold interpenetrated 3D flexible MOF (FMOF): <b>IITKGP-39</b> is reported whose gate-opening behavior is synchronously intertwined with the pore functionalization strategy, which served as a fascinating tool for simultaneous redressal of highly demanding one-step ethylene (C₂H₄) purification via inverse ethane-ethylene (C₂H₆/C₂H₄) separation (i.e., C₂H₆ trapping) as well as acetylene-carbon dioxide (C₂H₂/CO₂) separation through one-step sorbent separation technology (OSST). Notably, <b>IITKGP-39</b> represents the first FMOF to exhibit inverse C₂H₆/C₂H₄ sorption behavior with outstanding breakthrough separation selectivity of ∼2.3 at room temperature (298 K), accompanied by one-step C₂H₄ purification from ternary C₂ gas mixtures. Further, it excels in C₂H₂/CO₂ separation with a remarkable uptake ratio of ∼18 and high breakthrough selectivity of 8.3. A detailed elucidation into structural dynamics is revealed through <i>in situ</i> X-ray diffraction analysis that manifested the sorbate-induced structural transformation among three distinct phases: as-synthesized (phase-α), activated (phase-β), and gas sorption/gate opened phase (phase-γ). Thus, <b>IITKGP-39</b> is a unique industrially compatible two-in-one physisorbent that serves as a multipurpose molecular separator by virtue of reversible flexibility with outstanding separation performances.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144751790","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}

{"title":"Activation of Anionic Redox for Stoichiometric and Li-Excess Metal Sulfides through Structural Disordering: Joint Experimental and Theoretical Study.","authors":"Miyuki Shinoda, Koki Matsunoshita, Masanobu Nakayama, Satoshi Hiroi, Koji Ohara, Masaki Abe, Nozomu Ishiguro, Yukio Takahashi, Gen Hasegawa, Naoaki Kuwata, Tsukasa Iwama, Takuya Masuda, Kosuke Suzuki, Hirofumi Ishii, Yu-Cheng Shao, Daisuke Shibata, Akinori Irizawa, Toshiaki Ohta, Itsuki Konuma, Teppei Ohno, Yosuke Ugata, Naoaki Yabuuchi","doi":"10.1021/jacs.5c04018","DOIUrl":"10.1021/jacs.5c04018","url":null,"abstract":"<p><p>Extensive research efforts have been dedicated to Li-excess compounds with anionic redox reaction as potential high-capacity positive electrode materials for Li-ion battery applications. The origin of activation on anionic redox is still under debate, and a unified understanding is necessary, especially for sulfide-based compounds without conductive d electrons. Herein, joint experimental and theoretical study is conducted for Li-excess and stoichiometric compounds with different crystal structures, cation-disordered rocksalt, and cation-ordered layered structures. In contrast to the understanding of Li-excess oxides, sulfide-based compounds with ordered layered structures are electrochemically less active compared with the materials with disordered structure. Theoretical study reveals that a unique local structure for a sulfide ion coordinated by 6 Li ions, SLi₆ configuration, is formed, which can be found only for the disordered structure and not for the layered structure. The unique local structure triggers electron delocalization for sulfide 3p orbitals, leading to superior electronic conductivity, as experimentally evidenced, and thus anionic redox is successfully activated. Furthermore, such nonuniform local structures lead to easier structural distortion and efficient S-S dimerization, and even trimerization (S₃^2-), upon delithiation. Although sulfide-based compounds as battery electrode materials suffer from dissolution after oxidation, this practical problem is effectively mitigated by the use of highly concentrated electrolyte solutions with fewer free solvent molecules, leading to superior reversibility for anionic redox. The insights derived can guide the development of high-energy electrode materials with anionic redox with or without transition metal ions possessing conductive d electrons.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"26238-26253"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144641249","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}

{"title":"Radical 1,3-Difunctionalization of β,γ-Unsaturated Ketones via Concomitant 1,2-Carbonyl Migration: An Entrance to β-SF₅-/β-CF₃SF₄ Ketones.","authors":"Jia-Yu Li, Ying Liu, Donglei Sun, Gang Wu, Shuai-Shuai Yue, Hui-Yi Yang, Hao Zhang, Wei Zhang, Meng-Meng Zheng, Xiao-Song Xue, Shuo Guo","doi":"10.1021/jacs.5c09085","DOIUrl":"10.1021/jacs.5c09085","url":null,"abstract":"<p><p>The radical migration (RaM) mechanism via photoinduced transformation is a powerful tool in organic synthesis to construct new molecular scaffolds. Herein we disclose a metal-free, photoinduced 1,2-carbonyl migration of β,γ-unsaturated ketones to afford a wide range of valuable β-SF₅/β-CF₃SF₄ ketones. This transformation exhibits broad functional group tolerance and is suitable for the late-stage modification of complex molecules in up to 93% yield with excellent chemoselectivity and regioselectivity. Furthermore, mechanistic studies reveal that the selective synthesis of 1,3-chloropentafluorosulfanylation can be accomplished via a carbonyl migration followed by a radical chain propagation pathway. Finally, SF₅-containing compound <b>5</b> exhibits potential anticancer activity, underscoring the utility of this approach.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"26124-26132"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647912","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}

{"title":"Diastereo- and Enantioselective Synthesis of Polycyclic Amines by Cascade Cyclization of Aromatic Aldimines with Tethered Alkenes via Scandium-Catalyzed C-H Activation.","authors":"Aniket Mishra, Xiaobin Lin, Kakoli Maji, Masayoshi Nishiura, Xuefeng Cong, Zhaomin Hou","doi":"10.1021/jacs.5c08707","DOIUrl":"10.1021/jacs.5c08707","url":null,"abstract":"<p><p>The development of stereoselective and atom-efficient methods for constructing densely functionalized polycyclic amines bearing multiple stereocenters is of great interest and importance, but remains a significant challenge. Herein, we report an unprecedented regioselective and stereoselective cascade cyclization of aromatic aldimines with tethered alkenes via C-H activation by half-sandwich scandium catalysts. The reaction proceeds through <i>ortho</i>-C-H activation of an alkene-tethered aromatic aldimine by a scandium alkyl (or amido) species in the catalyst followed by intramolecular alkene insertion (<i>exo</i>-selective cyclization) into the resulting scandium-aryl bond and the subsequent intramolecular nucleophilic addition (cyclization) to the imine unit. The use of a chiral half-sandwich scandium catalyst enabled the asymmetric cascade cyclization with a high level of enantioselectivity (up to 98:2 e.r.) and diastereoselectivity (>19:1 d.r.). This protocol offers a straightforward route for the efficient and selective synthesis of a unique family of multisubstituted benzo-fused polycyclic amines, featuring 100% atom-efficiency, broad substrate scope, and excellent diastereo- and enantioselectivity.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"26116-26123"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144648004","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}

{"title":"Origin of Selectivity in Alternating Current-Enabled Partial Reduction of (Hetero)Arenes: A Case Study of Two Consecutive Irreversible Electrochemical Steps.","authors":"Sreesaila Sreekumar, Joshua A Beeler, Diptangshu Datta Mal, Henry S White, Long Luo","doi":"10.1021/jacs.5c08873","DOIUrl":"10.1021/jacs.5c08873","url":null,"abstract":"<p><p>Herein, we investigate the origin of selectivity in the alternating current (AC)-enabled partial reduction of (hetero)arenes to cyclic alkenes. Reduction of (hetero)arenes can be considered as a reaction involving two consecutive irreversible electrochemical steps: the first generates the desired cyclic alkene, while the second leads to its undesired overreduction. Conventional constant current or voltage (DC) electrolysis results in poor selectivity toward the partial reduction products, originating from overreduction and base-induced decomposition of the desired product. Fast-scan cyclic voltammetry shows that the rate constant for the first reduction (<i>k</i>₁) exceeds that of the second one (<i>k</i>₂). Finite element simulations based on this experimental finding semiquantitatively capture the frequency-dependent selectivity observed in AC electrolysis experiments (i.e., increasing the AC frequency enhances selectivity). The results further reveal that AC electrolysis mitigates the low selectivity by only collecting the products at the initial stage of the reduction reaction, which is mostly under a kinetically controlled regime. We then extend the finite element model and introduce Δ<i>E</i>_FOW, the foot-of-the-wave potential difference between cyclic voltammograms of substrate and partial reduction product, as an accessible proxy for <i>k</i>₂/<i>k</i>₁. A Δ<i>E</i>_FOW > 80 mV predicts synthetically useful selectivity (>30%) toward the partial reduction product below 100 Hz.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"26917-26925"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144673363","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}

{"title":"Inhibitor-Dependent Tolerance of New Delhi Metallo-β-Lactamase Driven by Single Mutation-Induced Conformational Changes.","authors":"Liwen Huang, Tsz-Fung Wong, Qipeng Cheng, Pui-Kin So, Ming Liu, Xuechen Li, Sheng Chen, Zhong-Ping Yao","doi":"10.1021/jacs.5c05669","DOIUrl":"10.1021/jacs.5c05669","url":null,"abstract":"<p><p>The emergence of metallo-β-lactamases as formidable adversaries in the antimicrobial resistance crisis stems from their unparalleled capacity to hydrolyze β-lactam antibiotics. This study deciphers the evolutionary strategy of New Delhi metallo-β-lactamase (NDM) variants through studies of conformational dynamics. We employ hydrogen/deuterium exchange mass spectrometry (HDX-MS) to map conformational landscapes of NDM in the ligand-free state and in the bound states with inhibitors l-captopril, d-captopril, ebselen, and aspergillomarasmine A (AMA), respectively. Crucially, our findings reveal similar allosteric fingerprints corresponding to different inhibition mechanisms; that is, inhibition induces pronounced dynamic perturbations in the α3-L8-β8 region─a previously under-characterized region. Strikingly, the clinically prevalent M154L mutation in this region reshapes conformational flexibility, amplifying inhibitor-specific conformational responses without altering the l/d-captopril binding dynamics. This study demonstrates how a single mutation can be critical for antibiotic resistance evolution where zinc is scarce in the presence of AMA and ebselen, as indicated by more protected HDX patterns of the α3-L8 region and several active-site loop (ASL) regions. Our results establish three key advances: (1) identification of α3-L8 as a cryptic allosteric region governing conformational adaptability, (2) demonstration of a single mutation M154L rewiring long-range dynamic communication, and (3) proposal of conformation-guided inhibitor design as a viable strategy against NDM. Overall, this work unveils a novel perspective─resistance mutations function not merely as chemical optimizers but as allosteric modulators that exploit inherent protein plasticity. These insights position the α3-L8 region as a compelling target for developing novel inhibitors, providing a blueprint for combating the next frontier of antimicrobial resistance.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"26389-26401"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144681676","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}

{"title":"Deciphering SN2-Type Nucleophilic Substitution via Halogen-Free Intermediates for High-Energy Zinc-Iodine Batteries.","authors":"Zhehan Yi, Hengyue Xu, Jin-Lin Yang, Jia Li, Tao Xiao, Hao Chen, Cheng Jiang, Hong Li, Seok Woo Lee, Hong Jin Fan","doi":"10.1021/jacs.5c08469","DOIUrl":"10.1021/jacs.5c08469","url":null,"abstract":"<p><p>High-valence halogen conversion reactions are promising for realizing high-energy-density aqueous batteries. It has been more challenging to realize a stable and reversible <i>I</i>⁰/<i>I</i>⁺ conversion than the facile <i>I</i>^-/<i>I</i>⁰ conversion. While interhalogen chemistry has been employed to realize a reversible <i>I</i>^-/I⁰/<i>I</i>⁺ (i.e., four-electron) redox couple, the introduction of additional halide species raises corrosion and toxicity issues. Herein, we propose an SN2-type nucleophilic substitution mechanism for the activation of the <i>I</i>⁰/<i>I</i>⁺ redox process. A series of halogen-free intermediates containing imide groups is proven effective in promoting four-electron halogen reactions due to conjugation-stabilized nitrogen anions. A structure-kinetics relationship among various imide-containing molecules is elucidated using two descriptors: the hydrogen dissociation energy (<i>E</i>_d) of the imide group and the local nucleophilicity (LN) of the corresponding nitrogen anion. A Zn-I₂ battery with a theobromine intermediate exhibits stable cycling (a capacity retention of 93.9% at 5 A g^-1 over 1000 cycles). This work provides new insights into the mechanism of the <i>I</i>⁰/<i>I</i>⁺ redox process and a new avenue to the development of high-capacity multielectron iodine cathodes.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"26889-26897"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688372","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}

{"title":"","authors":"Yandong Ma,&nbsp;Yakui Deng,&nbsp;Wei Xue,&nbsp;Xin Ji* and Min-Hui Li*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 30","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":15.6,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c06533","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144720413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}