Journal of the American Chemical Society最新文献_第2页

Nonreciprocal Circularly Polarized Lasing from Organic Achiral Microcrystals 有机非手性微晶体的非互易圆偏振激光

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.5c05118

Shiyang Ji, Yifan Zhou, Lin Xiong, Xinyu Liu, Tong Zhu, Xiuqin Zhan, Yongli Yan, Jiannian Yao, Kang Wang, Yong Sheng Zhao

{"title":"Nonreciprocal Circularly Polarized Lasing from Organic Achiral Microcrystals","authors":"Shiyang Ji, Yifan Zhou, Lin Xiong, Xinyu Liu, Tong Zhu, Xiuqin Zhan, Yongli Yan, Jiannian Yao, Kang Wang, Yong Sheng Zhao","doi":"10.1021/jacs.5c05118","DOIUrl":"https://doi.org/10.1021/jacs.5c05118","url":null,"abstract":"Organic materials are particularly appealing for circularly polarized (CP) lasers due to their remarkable chiroptical activities and exceptional optical gain properties. However, conventional organic CP lasers based on chiral molecules or microstructures typically exhibit reciprocal behavior, which complicates material synthesis and device fabrication for practical applications. In this study, we present nonreciprocal CP lasing from achiral organic microcrystals through the coupling between fluorescence linear anisotropy (f) and linear birefringence (LB), known as f-LB effect. By carefully controlling the crystallization process, we prepared triclinic and orthorhombic polymorphs with distinct molecular packing arrangements, which unlock the precise manipulation of f-LB coupling for efficient polarization state conversion of photons. The triclinic crystals exhibited stronger f-LB effect owing to the suitable angle between the emission plane and birefringence axis, resulting in robust nonreciprocal CP luminescence. More importantly, this coupling was further amplified during lasing oscillation, ultimately enabling nonreciprocal CP lasing with a dissymmetry factor of ∼1.0. These findings provide a novel approach to exploring high-performance nonreciprocal CP lasers and offer new insights into chiral photonics and optoelectronics.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"12 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893567","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

Cation–Anion Regulation Engineering in a Flame-Retardant Electrolyte toward Safe Na-Ion Batteries with Appealing Stability 阻燃电解液中的正负离子调节工程，以实现具有吸引力稳定性的安全钠离子电池

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.4c18326

Yi-Hu Feng, Chengye Lin, Hanwen Qin, Guang-Xu Wei, Chao Yang, Yongwei Tang, Xu Zhu, Shuai Sun, Tian-Ling Chen, Mengting Liu, Hong Zheng, Xiao Ji, Ya You, Peng-Fei Wang

{"title":"Cation–Anion Regulation Engineering in a Flame-Retardant Electrolyte toward Safe Na-Ion Batteries with Appealing Stability","authors":"Yi-Hu Feng, Chengye Lin, Hanwen Qin, Guang-Xu Wei, Chao Yang, Yongwei Tang, Xu Zhu, Shuai Sun, Tian-Ling Chen, Mengting Liu, Hong Zheng, Xiao Ji, Ya You, Peng-Fei Wang","doi":"10.1021/jacs.4c18326","DOIUrl":"https://doi.org/10.1021/jacs.4c18326","url":null,"abstract":"Great electrochemical stability and intrinsic safety are of critical significance in realizing large-scale applications of Na-ion batteries (NIBs). Unfortunately, the notorious decomposition of the electrolyte and undesirable side reactions on the cathode–electrolyte interphase (CEI) pose major obstacles to the practical implementation of NIBs. Besides, the flammability of traditional carbonate-based electrolytes raises increasing safety concerns about the batteries. Herein, a flame-retardant all-fluorinated electrolyte is proposed to achieve an anion-aggregated inner solvation shell by modulating cation–anion interactions through a low-coordination number cosolvent. The more electrochemically antioxidant fluorinated solvents and anion-dominated interfacial chemistry contribute to the construction of both mechanically and chemically stable F-rich CEI. Such thin, homogeneous interphase effectively inhibits the parasitic reaction, strengthens the interfacial stability, and enables fast Na+ diffusion kinetics on the interface. When employing this electrolyte, the Na0.95Ni0.4Fe0.15Mn0.3Ti0.15O2 (NFMT) cathode delivers remarkable discharge capacity up to 169.7 mAh g–1, with stable cycling at 1C for 500 cycles. Impressively, NFMT//hard carbon pouch cells with such electrolyte also achieve a steady operation for 100 cycles at 0.5C with 86.8% capacity remaining. This study offers a practical reference for developing high-performance and flame-retardant electrolytes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"224 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893565","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

The Role of Cu3+ in the Oxygen Evolution Activity of Copper Oxides Cu3+在铜氧化物析氧活性中的作用

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.4c18147

Pooja Basera, Yang Zhao, Angel T. Garcia-Esparza, Finn Babbe, Neha Bothra, John Vinson, Dimosthenis Sokaras, Junko Yano, Shannon W. Boettcher, Michal Bajdich

{"title":"The Role of Cu3+ in the Oxygen Evolution Activity of Copper Oxides","authors":"Pooja Basera, Yang Zhao, Angel T. Garcia-Esparza, Finn Babbe, Neha Bothra, John Vinson, Dimosthenis Sokaras, Junko Yano, Shannon W. Boettcher, Michal Bajdich","doi":"10.1021/jacs.4c18147","DOIUrl":"https://doi.org/10.1021/jacs.4c18147","url":null,"abstract":"Cu-based oxides and hydroxides represent an important class of materials from a catalytic and corrosion perspective. In this study, we investigate the formation of bulk and surface Cu3+ species that are stable under water oxidation catalysis in alkaline media. So far, no direct evidence existed for the presence of hydroxides (CuOOH) or oxides, which were primarily proposed by theory. This work directly places CuOOH in the oxygen evolution reaction (OER) Pourbaix stability region with a calculated free energy of −208.68 kJ/mol, necessitating a revision of known Cu–H2O phase diagrams. We also predict that the active sites of CuOOH for the OER are consistent with a bridge O* site between the two Cu3+ atoms with onset at ≥1.6 V vs the reversible hydrogen electrode (RHE), aligning with experimentally observed Cu2+/3+ oxidation waves in cyclic voltammetry of Fe-free and Fe-spiked copper in alkaline media. Trace amounts of Fe (2 μg/mL (ppm) to 5 μg/mL) in the solution measurably enhance the catalytic activity of the OER, likely due to the adsorption of Fe species that serve as the active sites . Importantly, modulation excitation X-ray absorption spectroscopy (ME-XAS) of a Cu thin-film electrode shows a distinct Cu3+ fingerprint under OER conditions at 1.8 V vs RHE. Additionally, in situ Raman spectroscopy of polycrystalline Cu in 0.1 mol/L (M) KOH revealed features consistent with those calculated for CuOOH in addition to CuO. Overall, this work provides direct evidence of bulk electrochemical Cu3+ species under OER conditions and expands our longstanding understanding of the oxidation mechanism and catalytic activity of copper.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"9 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898112","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

Solvent-Controlled Enantioselective Allylic C–H Alkylation of 2,5-Dihydrofuran via Synergistic Palladium/Nickel Catalysis 溶剂控制对映选择性2,5-二氢呋喃烯丙基C-H烷基化协同钯/镍催化

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.5c01228

Fule Wu, Hongkai Wang, Zhenwei Wu, Yangbin Liu, Xiaoming Feng

引用次数: 0

Unraveling Atomic-Level Mechanisms of Structural Transitions in Lithium Cobalt Oxide under High-Voltage Conditions 高压条件下钴酸锂结构跃迁的原子水平机制研究

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.4c17362

Weiguang Lin, Wei Su, Ting Lin, Qiu Fang, Shiyu Wang, Jing Chen, Yuzhou He, Dongxiao Wang, Dongdong Xiao, Yingchun Lyu, Qinghua Zhang, Dong Su, Lin Gu

{"title":"Unraveling Atomic-Level Mechanisms of Structural Transitions in Lithium Cobalt Oxide under High-Voltage Conditions","authors":"Weiguang Lin, Wei Su, Ting Lin, Qiu Fang, Shiyu Wang, Jing Chen, Yuzhou He, Dongxiao Wang, Dongdong Xiao, Yingchun Lyu, Qinghua Zhang, Dong Su, Lin Gu","doi":"10.1021/jacs.4c17362","DOIUrl":"https://doi.org/10.1021/jacs.4c17362","url":null,"abstract":"High-voltage cycling of layered cathode materials in lithium-ion batteries presents challenges related to structural instability. Deciphering atomic-scale structural degradation mechanisms is essential for improving their electrochemical performance at high voltages. This study utilized advanced electron microscopy and principal component analysis to detect subtle spinel-like structure induced by the migration of cobalt atoms within LiCoO2 subjected to high-voltage cycling at charge voltages of 4.6 and 4.8 V. The formation of the spinel-like configuration was accompanied by the emergence of a densified O1 phase beneath thin spinel-like layer on the (003) facets during charging, along with an intriguing local O3- to P3-type oxygen stacking transition observed in LiCoO2 charged to 4.8 V. Upon discharge, an enlarged and defective spinel phase preferentially formed on the non-(003) facets, and the migrated cobalt atoms cannot fully return to their original lattice sites, leading to the irreversible structural changes in LiCoO2. Long-term cycling revealed that the initial extended spinel phase underwent voltage-dependent evolution pathways, which contributed to accelerated capacity fading observed at the cutoff voltage of 4.8 V. Our findings provide new insights into the atomic-level structural transitions in LiCoO2 under high-voltage conditions, offering guidance for the development of more structurally robust LiCoO2 for high-voltage applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"49 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898071","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

Elucidating the Iterative Elongation Mechanism in a Type III Polyketide Synthase III型聚酮合酶的迭代延伸机制研究

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.5c05635

Rebecca N. Re, James J. La Clair, Joseph P. Noel, Michael D. Burkart

{"title":"Elucidating the Iterative Elongation Mechanism in a Type III Polyketide Synthase","authors":"Rebecca N. Re, James J. La Clair, Joseph P. Noel, Michael D. Burkart","doi":"10.1021/jacs.5c05635","DOIUrl":"https://doi.org/10.1021/jacs.5c05635","url":null,"abstract":"Type III polyketide synthases (PKSs) have a much simpler three-dimensional architecture compared with their type I and type II counterparts, yet they catalyze iterative polyketide elongation to generate a myriad of products in plants, fungi, and eubacteria. Despite this mechanistic complexity occurring within a single active site, the mechanism by which type III PKSs stabilize and direct their highly reactive keto and enolate intermediates has yet to be fully understood. Here, we report the synthesis and deployment of stable polyketone CoA analogues for each putative intermediate involved in the biphenyl synthase (BIS) mechanism together with three high-resolution crystal structures of each in complex with BIS from Malus domestica. This set of structures reveals key mechanistic features that control the number of iterative elongation steps and that shape the static architectural features responsible for organization of a water-mediated hydrogen bonding network necessary for termination of the elongation reaction by an intramolecular aldol cyclization and production of the 3,5-dihydroxybiphenyl BIS product. Elucidating these protein–substrate interactions provides a foundation for using polyketone CoA analogues to further unravel the control mechanisms of PKS catalysis and gain the insight necessary for predictive engineering of these enzymes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"43 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898120","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 Highly Efficient Molecular Iron(II) Photocatalyst for Concurrent CO2 Reduction and Organic Synthesis 用于CO2还原和有机合成的高效分子铁（II）光催化剂

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.5c01698

Yan-Nan Jing, Hai-Xu Wang, Cheng Wang, Chen Ye, Chen-Ho Tung, Li-Zhu Wu

引用次数: 0

Microdroplet Cascade Catalysis for Highly Selective Production of Propylene Glycol under Ambient Conditions 微滴级联催化在环境条件下高选择性生产丙二醇

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.4c17760

Jianing Dong, Jiajia Xu, Zhao-Dong Meng, Zi-Ang Nan, Weixin Li, Richard N. Zare, Zhong-Qun Tian, Feng Ru Fan

{"title":"Microdroplet Cascade Catalysis for Highly Selective Production of Propylene Glycol under Ambient Conditions","authors":"Jianing Dong, Jiajia Xu, Zhao-Dong Meng, Zi-Ang Nan, Weixin Li, Richard N. Zare, Zhong-Qun Tian, Feng Ru Fan","doi":"10.1021/jacs.4c17760","DOIUrl":"https://doi.org/10.1021/jacs.4c17760","url":null,"abstract":"Conventional propylene glycol (PG) production relies on an energy-intensive two-step thermocatalytic process, contributing significantly to CO2 emissions. A sustainable alternative under ambient conditions remains elusive, hindered by challenges in selectivity and energy efficiency. Here, we present a cascade catalysis strategy for efficient and selective PG production within water microdroplets under ambient conditions. Propylene (CH3CH═CH2) is converted to PG (CH3CH(OH)CH2OH) at the microdroplet/titanium silicalite-1 (TS-1) interface, driven by in situ generated hydrogen peroxide (H2O2) via methyl viologen catalysis. This approach harnesses the water microdroplet interface to confine the reaction, enhancing catalytic activity and increasing selectivity. Our system achieves a PG production efficiency of 680 μM and a selectivity of 88%, while minimizing unwanted side products and energy demands. This innovative method offers a sustainable pathway for PG synthesis and highlights the transformative potential of water microdroplet technology in advancing green chemistry and industrial applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"22 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898111","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

Discrete Brush Polymers Enhance 19F MRI Performance through Architectural Precision 离散刷状聚合物通过结构精度提高19F MRI性能

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.5c00938

Nduka D. Ogbonna, Parikshit Guragain, Venkatesh Mayandi, Cyrus Sadrinia, Raman Danrad, Seetharama Jois, Jimmy Lawrence

{"title":"Discrete Brush Polymers Enhance 19F MRI Performance through Architectural Precision","authors":"Nduka D. Ogbonna, Parikshit Guragain, Venkatesh Mayandi, Cyrus Sadrinia, Raman Danrad, Seetharama Jois, Jimmy Lawrence","doi":"10.1021/jacs.5c00938","DOIUrl":"https://doi.org/10.1021/jacs.5c00938","url":null,"abstract":"The development of metal-free magnetic resonance imaging (MRI) agents demands precise control over molecular architecture to achieve optimal performance. Current fluorine-based contrast agents rely on maximizing fluorine content (>20 wt %) for sensitivity, requiring extensive solubilizing groups that lead to signal-diminishing aggregation. Here we show that discrete brush polymers (Đ = 1.0) with precise backbone lengths and a single terminal fluorine group achieve superior imaging performance through architectural control rather than high fluorine content. This design prevents both intra- and intermolecular fluorine aggregation while maintaining high aqueous solubility, enabling sharper signals and higher sensitivity than conventional systems despite containing less than 7 wt % fluorine. Systematic investigation reveals how backbone length controls fluorine mobility and signal generation, establishing clear structure–property relationships previously obscured by molecular heterogeneity. This work demonstrates how precise architectural control can enhance functional performance beyond traditional approaches, providing new strategies for designing imaging materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"111 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898114","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

Cs2AgSbI6 Nanocrystals: a New Air-Stable Iodide Double-Perovskite (Elpasolite) Semiconductor Cs2AgSbI6纳米晶体：一种新型空气稳定的碘化双钙钛矿（Elpasolite）半导体

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-01 DOI: 10.1021/jacs.5c03942

Faris Horani, Daniel R. Gamelin

引用次数: 0