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

Divergent Mechanisms of SSZ-39 Crystallization Using Structurally Similar but Chemically Distinct Organic Structure-Directing Agents 结构相似但化学性质不同的有机结构导向剂对SSZ-39结晶机理的影响

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c03712

Zhiyin Niu, Taimin Yang, Alyssa McNarney, Luke Tufaro, Simon M. Vornholt, Hadi Bourji, Jia Lv, Michael P. Harold, Jeremy C. Palmer, Bradley F. Chmelka, Karena W. Chapman, Roger Moulton, Jeffrey D. Rimer

{"title":"Divergent Mechanisms of SSZ-39 Crystallization Using Structurally Similar but Chemically Distinct Organic Structure-Directing Agents","authors":"Zhiyin Niu, Taimin Yang, Alyssa McNarney, Luke Tufaro, Simon M. Vornholt, Hadi Bourji, Jia Lv, Michael P. Harold, Jeremy C. Palmer, Bradley F. Chmelka, Karena W. Chapman, Roger Moulton, Jeffrey D. Rimer","doi":"10.1021/jacs.5c03712","DOIUrl":"https://doi.org/10.1021/jacs.5c03712","url":null,"abstract":"The role of an organic structure-directing agent on zeolite crystallization is conventionally interpreted based on the final, bulk crystal structure. However, few studies have examined their effect on the dynamics of zeolite crystal growth and restructuring, particularly with respect to the interzeolite transformations that are increasingly being exploited in zeolite synthesis. Herein, we compare two organic structure-directing agents that both direct the formation of the small-pore zeolite SSZ-39 (AEI). The organics have nearly identical molecular structures but exhibit distinct chemical compositions by virtue of a single heteroatom substitution. Our findings reveal that the organics have a dramatic impact on the crystallization kinetics, physicochemical properties, and catalytic performance of zeolite AEI prepared by the transformation of zeolite FAU parent crystals. The conventional quaternary ammonium structure-directing agent, “Pippy”, produces a distinct intermediate metastable structure with defects and anisotropic crystal shape that transitions into relatively thick zeolite AEI platelets with compromised hydrothermal stability. This transition is accompanied by an unusual morphological evolution from rod-like to platelet crystals that defies common Ostwald ripening processes. We demonstrate that a new quaternary ammonium-ether structure-directing agent, “Morphy”, produces thinner platelets of zeolite AEI and bypasses the defective intermediate observed for the conventional organic. Syntheses with Morphy produce a more hydrothermally stable product, which exhibits superior activity in the NH3 selective catalytic reduction of NOx used as a benchmark reaction for assessing structure–performance relationships.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"49 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144193308","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 Nitrilium-Type N-Heterocyclic Aryne 氮型n -杂环芳烃

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c05146

Marisol Alvarado, Lauren Tran, Christina Tönshoff, Bo Li, Clovis Darrigan, Hugues Preud’homme, Anna Chrostowska, Holger F. Bettinger, Shih-Yuan Liu

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Lithium-Mediated Ammonia Electrosynthesis over Orderly Arranged Dipoles Regulated Solid-Electrolyte Interphase 有序偶极调节固-电解质界面上锂介导的氨电合成

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c00551

Fangying Duan, Junwu Chen, Mengfei Zhang, Yiming Liu, Hao Xue, Yu Sun, Qiongguang Li, Xuehua Zhang, Zijian Gao, Zongjing Lu, Philippe Schwaller, Guangjin Zhang, Jian Zhang, Menglei Yuan

{"title":"Lithium-Mediated Ammonia Electrosynthesis over Orderly Arranged Dipoles Regulated Solid-Electrolyte Interphase","authors":"Fangying Duan, Junwu Chen, Mengfei Zhang, Yiming Liu, Hao Xue, Yu Sun, Qiongguang Li, Xuehua Zhang, Zijian Gao, Zongjing Lu, Philippe Schwaller, Guangjin Zhang, Jian Zhang, Menglei Yuan","doi":"10.1021/jacs.5c00551","DOIUrl":"https://doi.org/10.1021/jacs.5c00551","url":null,"abstract":"The electrocatalytic lithium-mediated nitrogen reduction reaction (Li-NRR) is considered as a promising alternative to the energy-intensive Haber-Bosch route. However, the solid electrolyte interphase that is derived from the electrolyte easily hinders the diffusion and nucleation of Li+, which ultimately suppresses N2 activation and the subsequent protonation process. Herein, we successfully construct surface oxygen vacancies (Ov) on commercial BaTiO3 (BTO) nanoparticles and further drive the phase transition from cubic/tetragonal to rhombohedral, which enhances the ferroelectricity of Ov-enriched BaTiO3 (BTOV) and produces orderly arranged dipoles. Systematic experimental and computational results validate that Ov-induced orderly arranged dipoles readily bind anions in the electrolyte and promote their reduction to form a LiF-rich SEI. The optimized anion-derived SEI enhances the Li+ transfer kinetics and effectively facilitates the uniform nucleation of Li+, which enables lower energy of Li+ desolvation and the reactant crossing the SEI. Thus, the as-prepared BTOV delivers a faradaic efficiency of 93.01% and an NH3 yield rate of 6.94 nmol s–1 cm–2 at −0.5 V which achieves more than a 45-fold performance improvement compared to the BTO counterpart. This work opens new horizons for the introduction of orderly arranged dipoles to modulate SEI chemistry and further enhance the intrinsic activity of the Li-NRR.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"54 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202268","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 Molecule Assembly Route to Simultaneously Detoxify Platinum Sites and Disentangle Reactant Transport Paths in Proton Exchange Membrane Fuel Cells 质子交换膜燃料电池中同时解毒铂位点和解缠反应物运输路径的分子组装路线

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c04479

Meihua Tang, Huangli Yan, Zhenying Zheng, Hao Zhang, Chengwen Yu, Bin Liu, Shengli Chen

{"title":"A Molecule Assembly Route to Simultaneously Detoxify Platinum Sites and Disentangle Reactant Transport Paths in Proton Exchange Membrane Fuel Cells","authors":"Meihua Tang, Huangli Yan, Zhenying Zheng, Hao Zhang, Chengwen Yu, Bin Liu, Shengli Chen","doi":"10.1021/jacs.5c04479","DOIUrl":"https://doi.org/10.1021/jacs.5c04479","url":null,"abstract":"Substantially reducing the platinum (Pt) usage is essential for large-scale application of proton exchange membrane fuel cells (PEMFCs), a key hydrogen-energy technology promising a carbon-neutral future. Currently, the low-Pt PEMFCs suffer from sluggish reaction and transport kinetics in the cathodic catalyst layers (CCLs) caused by the adsorption of perfluorinated sulfonic acid (PFSA) ionomers to Pt via the side chains and the accompanying uneven PFSA aggregation. Herein, we demonstrate, through detailed physical and electrochemical characterizations and molecular dynamics simulations, that β-cyclodextrin with a unique chemical and geometric structure can effectively address these issues through a molecule assembly route. On one side, β-cyclodextrin forms a hydrogen-bonded molecular assembly with PFSA, which effectively mitigates sulfonate poisoning to Pt, produces ordered hydrophilic domains for rapid proton transport, and at the same time increases the porosity crossing CCL. On the other side, the hydrophobic β-cyclodextrin nanocavities provide ideal O2 diffusion paths. The thus formed CCL and Pt/ionomer interface with enriched catalytic sites, and well-segregated and ordered O2 and proton transport channels, remarkably boost the fuel cell performance.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144193310","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

Pushing the Boundaries of Resolution in Solid-State Nuclear Magnetic Resonance of Biomolecules with 160 kHz Magic-Angle Spinning 用160千赫魔角旋转推动生物分子固态核磁共振分辨率的极限

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c02466

Zhiyu Sun, Claire Ollier, Adrienn Rancz, Batiste Thienpont, Kristof Grohe, Lukas Becker, Armin Purea, Frank Engelke, Sebastian Wegner, James Sturgis, Tatyana Polenova, Tanguy Le Marchand, Guido Pintacuda

引用次数: 0

Cooperative Organosulfur/Photoredox Catalysis Enables Radical-Polar Crossover C(sp3)–N Coupling via Inner-Sphere Electron Shuttling 协同有机硫/光氧化还原催化通过球内电子穿梭实现自由基-极性交叉C(sp3) -N耦合

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c00352

Youngeun Hong, Changkyu Park, Junseong Jang, Minseok Oh, Dongwook Kim, Seunghoon Lee, Seung Youn Hong

{"title":"Cooperative Organosulfur/Photoredox Catalysis Enables Radical-Polar Crossover C(sp3)–N Coupling via Inner-Sphere Electron Shuttling","authors":"Youngeun Hong, Changkyu Park, Junseong Jang, Minseok Oh, Dongwook Kim, Seunghoon Lee, Seung Youn Hong","doi":"10.1021/jacs.5c00352","DOIUrl":"https://doi.org/10.1021/jacs.5c00352","url":null,"abstract":"Radical-polar crossover (RPC) is a valuable mechanistic tool for revitalizing traditional radical and polar chemistries by integrating them. However, transitioning from radical to polar pathways across multiple redox events requires precise redox potential matching between the reaction components (catalysts and substrates), which inherently limits the scope of these transformations. Here, we present a cooperative catalytic platform that diverts the key RPC mechanism from outer-sphere to inner-sphere manifolds, enabling C(sp3)–N coupling of redox active esters with otherwise oxidizable (hetero)arylamines. The key to success is the identification of organosulfur catalyst capable of selectively shuttling electrons between the photocatalyst and the incipient radical in preference to competing arylamine oxidation. Experimental and computational studies reveal that the tailored organosulfur catalyst plays a crucial role in steering the post-radical generation steps to guide the desired reaction trajectory for C(sp3)–N bond formation. This method displays good functional group compatibility and chemoselectivity, providing an efficient route to functionally rich secondary and tertiary arylamines. The virtue of this method was further demonstrated by late-stage applications for synthesizing medically relevant nitrogen-containing compounds.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"246 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202267","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

Divergent Total Syntheses of Rearranged Steroids Swinhoeisterols A–C 重排甾体A-C的发散性全合成

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c07053

Ganlin Huang, Xinliang Zhang, Yu-Cheng Gu, Jinghan Gui

引用次数: 0

Correction to “Electrocatalytic Oxidation of Ammonia by (Salen)ruthenium(III) Ammine Complexes: Direct Evidence for a Ruthenium(VI) Nitrido Active Intermediate” 更正“（Salen）钌（III）胺配合物对氨的电催化氧化：钌（VI）氮的活性中间体的直接证据”

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c08147

Jianhui Xie, Tingting Yang, Longzhu Hong, Hui Li, Bing Li, Zhenguo Guo, Yingying Liu, Tai-Chu Lau

引用次数: 0

The Intricate Nonribosomal Assembly of a Potent Antifungal Lipopeptide from the Burkholderia cepacia Complex 来自洋葱伯克霍尔德菌复合体的有效抗真菌脂肽的复杂非核糖体组装

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-02 DOI: 10.1021/jacs.5c04167

Lei Zhong, Agnes Mühlenweg, Dou Hong, Sarah Yammine, Annette Poch, Dingchang Xu, Yasemin Kirimlioglu, Lisa Großgloß, Malo Boulanger, Franziska Graeger, Maria Seidel, Manuel Gemander, Grit Walther, Sebastian Kemper, Tam Dang, Monique Royer, Andi Mainz, Stéphane Cociancich, Roderich D. Süssmuth

{"title":"The Intricate Nonribosomal Assembly of a Potent Antifungal Lipopeptide from the Burkholderia cepacia Complex","authors":"Lei Zhong, Agnes Mühlenweg, Dou Hong, Sarah Yammine, Annette Poch, Dingchang Xu, Yasemin Kirimlioglu, Lisa Großgloß, Malo Boulanger, Franziska Graeger, Maria Seidel, Manuel Gemander, Grit Walther, Sebastian Kemper, Tam Dang, Monique Royer, Andi Mainz, Stéphane Cociancich, Roderich D. Süssmuth","doi":"10.1021/jacs.5c04167","DOIUrl":"https://doi.org/10.1021/jacs.5c04167","url":null,"abstract":"The Burkholderia cepacia complex (BCC) is a group of Gram-negative bacteria known for their pathogenicity to patients suffering from cystic fibrosis (CF). The BCC-belonging strain B. pyrrocinia BC11 (formerly B. cepacia BC11) produces AFC-BC11, a compound with strong activity against phytopathogenic fungi. In this contribution, we report on the unprecedented N-acyl-tetrapeptide structure and antifungal potency of this natural product. We further provide insights into central steps of its biosynthesis mediated by a nonclassical nonribosomal peptide synthesis machinery lacking condensation domains. With the involvement of a sole acyl/peptidyl carrier protein AfcK, an acyltransferase AfcL and coenzyme A, the growing acyl-peptide chain is shuffled between different thioester carriers during the intricate biosynthetic assembly. The knowledge of the AFC-BC11 structure may contribute to the development of antifungals against phytopathogens and, with the afc gene cluster being conserved in various Burkholderia strains, possibly to an understanding of the human pathogenesis of the BCC.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"37 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144193307","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

Microdroplet Surface Drives and Accelerates Proton-Controlled, Size-Dependent Nitrate Photolysis 微液滴表面驱动和加速质子控制，大小依赖的硝酸盐光解

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-06-01 DOI: 10.1021/jacs.5c00720

Xiaowu Zhang, Qishen Huang, Yu-Xin Liu, Jiayi Yin, Shu-Feng Pang, Pai Liu, Yun-Hong Zhang, Maofa Ge

{"title":"Microdroplet Surface Drives and Accelerates Proton-Controlled, Size-Dependent Nitrate Photolysis","authors":"Xiaowu Zhang, Qishen Huang, Yu-Xin Liu, Jiayi Yin, Shu-Feng Pang, Pai Liu, Yun-Hong Zhang, Maofa Ge","doi":"10.1021/jacs.5c00720","DOIUrl":"https://doi.org/10.1021/jacs.5c00720","url":null,"abstract":"Particulate nitrate photolysis regenerates reactive oxidized nitrogen species (HONO and NOx) in the atmosphere, influencing tropospheric ozone, atmospheric oxidation capacity, and particulate matter formation. However, reported nitrate photolysis rates vary by orders of magnitude, and the roles of protons and the air–water interface in accelerating nitrate photolysis in deliquesced aerosols (i.e., microdroplets) remain unclear. Using confocal Raman spectroscopy and aerosol optical tweezer, we measured nitrate photolysis rate coefficients (j) in microdroplets, ranging from 5.28 × 10–8 to 9.07 × 10–6 s–1, depending on pH (3.2–7.4) and radius (3.7 μm to 6.0 mm). j remained pH-independent under proton-sufficient conditions (pH < 6.5) but decreased with increasing pH under proton-deficient conditions (pH > 6.5), resolving discrepancies in previous studies. Moreover, we identified a tipping-point radius (r* = 706 μm), below which j scales inversely with the droplet radius and above which j plateaus at the aqueous bulk value (6.73 ± 2.12 × 10–8 s–1). These findings demonstrate that nitrate photolysis occurs predominantly at the air–water interface in microdroplets. With the atmospheric aerosol pH and radii typically below these tipping points (pH* = 6.5, r* = 706 μm), the surface-driven size-dependent photolysis likely explains the variations in atmospheric particulate nitrate photolysis rates.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144193312","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