Journal of the American Chemical Society最新文献_第10页

Diversity-Oriented C-H Activation Reactions of the Naphthalene Scaffold. 萘支架的C-H活化反应。

IF 15.6 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-09 DOI: 10.1021/jacs.5c10482

Zhoulong Fan, Md Emdadul Hoque, Kevin Wu, Maximilian D Palkowitz, Upender Velaparthi, Kevin W Gillman, Jennifer X Qiao, Jin-Quan Yu

{"title":"Diversity-Oriented C-H Activation Reactions of the Naphthalene Scaffold.","authors":"Zhoulong Fan, Md Emdadul Hoque, Kevin Wu, Maximilian D Palkowitz, Upender Velaparthi, Kevin W Gillman, Jennifer X Qiao, Jin-Quan Yu","doi":"10.1021/jacs.5c10482","DOIUrl":"https://doi.org/10.1021/jacs.5c10482","url":null,"abstract":"Diversity-oriented synthesis (DOS) has emerged as an efficient strategy for constructing diverse compound libraries, facilitating hit or lead identification in the drug discovery process. In parallel, developing diverse transformations at different sites is an appealing strategy to expand the diversity of appendages on scaffolds. Owing to the availability of C-H bonds at multiple sites of pharmacophores, diversity-oriented C-H activation reactions are an ideal approach to realize this goal. Given the pharmacophoric significance of the naphthalene scaffold in clinical drugs, diversity-oriented C-H functionalization reactions on this scaffold would be useful for drug discovery. Direct C-H activation at the challenging C6 and C7 positions has remained unexplored due to electronic similarity, remote distance from the directing group, and interference from geometrically identical positions (C7 vs C3, C6 vs C4). Herein, we report two types of templates designed to differentiate the C6 and C7 positions on the naphthalene scaffold. The success is attributed to manipulation of the distance parameter in the template and the utilization of an oligopeptide ligand. Notably, the utility of this diversity-oriented C-H activation is showcased through the divergent modification of naphthalene-containing complex molecules.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022486","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

Harnessing Dynamic Heteroleptic Complexation for Self-Assembly of Robust Nested Metallo-Supramolecular Cages. 利用动态异差络合进行鲁棒嵌套金属超分子笼的自组装。

IF 15.6 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-09 DOI: 10.1021/jacs.5c10891

Soumyakanta Prusty, Hung-Kai Hsu, Mahesh Madasu, Alisha Rani, Jun-Hao Fu, Lin-Ting Lin, Ming-Hao Lee, Ming-Wen Chu, Chun-Hong Kuo, Yi-Tsu Chan

{"title":"Harnessing Dynamic Heteroleptic Complexation for Self-Assembly of Robust Nested Metallo-Supramolecular Cages.","authors":"Soumyakanta Prusty, Hung-Kai Hsu, Mahesh Madasu, Alisha Rani, Jun-Hao Fu, Lin-Ting Lin, Ming-Hao Lee, Ming-Wen Chu, Chun-Hong Kuo, Yi-Tsu Chan","doi":"10.1021/jacs.5c10891","DOIUrl":"https://doi.org/10.1021/jacs.5c10891","url":null,"abstract":"The exclusive formation of artificial multicomponent assemblies remains a significant challenge, in contrast to the well-established organization observed in natural systems, due to intrinsic entropic constraints. To overcome this limitation, recent efforts have been focused on developing precision self-assembly strategies for the rational construction of such architectures. Here, we construct an ideal complementary pair of 2,2':6',2″-terpyridine (tpy)-based ligands by fine-tuning the substituent bulkiness, which enables the quantitative formation of robust nested cages through efficient dynamic heteroleptic complexation with multivalent coordination. The multivalent ligand design proves essential for successful self-assembly, as the smaller incarcerated cage cannot be independently synthesized in an exclusive manner. Notably, the improved solubility and exceptional stability of the nested cage even at low concentrations allow for structural characterization by high-field nuclear magnetic resonance (NMR) spectroscopy, solution-based small-angle X-ray scattering (SAXS), and scanning transmission electron microscopy (STEM). Moreover, its well-defined internal cavity permits the in situ reductive formation of gold nanoparticles, demonstrating its potential as a functional nanoreactor.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022496","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 Macroporous Cyclodextrin Monolith for Continuous Removal of Per- and Polyfluoroalkyl Substances from Water 用于连续去除水中全氟烷基和多氟烷基物质的大孔环糊精整体体

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-08 DOI: 10.1021/jacs.5c09865

Zhi-Wei Lin, Subeen Kim, Yaryna Dyakiv, Eden Frances P. Gedangoni, Aaron I. Packman, Damian E. Helbling, Gordon J. Getzinger, William R. Dichtel

{"title":"A Macroporous Cyclodextrin Monolith for Continuous Removal of Per- and Polyfluoroalkyl Substances from Water","authors":"Zhi-Wei Lin, Subeen Kim, Yaryna Dyakiv, Eden Frances P. Gedangoni, Aaron I. Packman, Damian E. Helbling, Gordon J. Getzinger, William R. Dichtel","doi":"10.1021/jacs.5c09865","DOIUrl":"https://doi.org/10.1021/jacs.5c09865","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFASs) are environmentally persistent, bioaccumulative, and toxic chemicals that contaminate global drinking water resources. Their ubiquity and potential impact on human health motivate large-scale remediation. Conventional materials used to remove PFASs during drinking water production are functionally inefficient or energetically expensive, motivating the discovery of new materials and technologies. Here, we introduce cyclodextrin-based monoliths, featuring a highly permeable, mechanically robust porous architecture that enables rapid and continuous PFAS removal from water. The monolith was directly polymerized into flow-through columns and showed water permeability similar to packed sand due to its interconnected macroporous structure. Compared to leading benchmarks under equivalent sorbent mass or contact time, the monolith demonstrated superior PFAS sorption with later breakthroughs for most PFASs. We show the hierarchical morphology of a monolith is more efficient use of sorbent mass than particle-based sorbents, as its macropores enable facile diffusion of PFAS to meso- and microporous sorption sites. The significance of hierarchical pore design was demonstrated by instant PFAS breakthrough passing through the pulverized monolith, where the water primarily flows through interparticle pathways with limited access to sorption sites. After treating 150 L of water spiked with 25 PFAS for 37 days, 47 mg of monolith was regenerated through alcohol wash, with near-complete mass balance of adsorbed PFASs. The regenerated monolithic sorbent treated another 170 L of water for 39 days with comparable removal. The monolith offers a novel morphology with simple and direct synthesis in columns for water treatment and provides superior PFAS removal, regeneration and reuse.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009206","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

Synthesis of Bicyclo[2.1.0]pentanes and Vinylcyclopropanes Using Palladium Carbenes: Ligand-Controlled Carbene Reactivity 钯卡宾合成双环[2.1.0]戊烷和乙烯基环丙烷：配体控制的卡宾反应性

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-08 DOI: 10.1021/jacs.5c10617

Isaiah K. Eckart-Frank, Emily S. Arnold, Liam P. Murphy, Sidney M. Wilkerson-Hill

{"title":"Synthesis of Bicyclo[2.1.0]pentanes and Vinylcyclopropanes Using Palladium Carbenes: Ligand-Controlled Carbene Reactivity","authors":"Isaiah K. Eckart-Frank, Emily S. Arnold, Liam P. Murphy, Sidney M. Wilkerson-Hill","doi":"10.1021/jacs.5c10617","DOIUrl":"https://doi.org/10.1021/jacs.5c10617","url":null,"abstract":"Once physical organic curiosities, bicyclo[2.1.0]pentanes (colloquially termed housanes) are useful strain-release reagents and are unique structural motifs for medicinal chemistry campaigns because of their high Fsp3 content. Despite this, methods to synthesize housanes are lacking due to their highly strained nature. Herein, we report an intramolecular cyclopropanation strategy to obtain functionalized housanes using palladium carbenes (20 substrates, up to 89% yield). Key to the success of this reaction was the insight that the reactivity of Pd(0) carbenes is controlled by the supporting ligand. Strongly donating N-heterocyclic carbene ligands promote cyclopropanation reactivity, while some π-accepting phosphoramidite ligands (e.g., rac-MonoPhos) afford C–H insertion products (8 examples, up to 20:1 selectivity). Deuterium-labeling studies revealed a KIE of 2.1 at 80 °C, suggesting a palladium carbene is involved in the C–H insertion step, and the independent synthesis of alkyldiazenes confirms that they are not relevant intermediates in this reaction. The housane products were amenable to late-stage cross-coupling reactions and ring-opening reactions to provide cyclopentanes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"103 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009204","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 Basis for 3-Amino-3-carboxypropyl Transfer in Nocardicin Biosynthesis 诺卡菌生物合成中3-氨基-3-羧基转移的结构基础

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-08 DOI: 10.1021/jacs.5c08367

Yaojie Gao, Masayuki Karasawa, Zhiyang Quan, Takahiro Mori, Masahiro Kanaida, Craig A. Townsend, Tohru Terada, Ikuro Abe, Takayoshi Awakawa

引用次数: 0

Photocatalytic Oxidative Dimerization of Electronically Diverse Phenols Using Borate to Prevent Overoxidation. 利用硼酸盐光催化氧化二聚化防止过氧化。

IF 15.6 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-08 DOI: 10.1021/jacs.5c12438

Jingze Wu, Yoshito Koga, Gang Hong, Madeline E Rotella, Marisa C Kozlowski

引用次数: 0

Ruthenium-Catalyzed Intermolecular [2 + 2] Cycloaddition of Unactivated Allenes and Alkynes with Unusual Regioselectivity 钌催化具有特殊区域选择性的非活化烯和炔的分子间[2 + 2]环加成

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-08 DOI: 10.1021/jacs.5c11285

Chaoshen Zhang, Herman H. Y. Sung, Ian D. Williams, Yun-Dong Wu, Jianwei Sun

引用次数: 0

Ubiquitous Chiral Symmetry Breaking of Conjugated Polymers via Liquid–Liquid Phase Separation 通过液-液相分离共轭聚合物的普遍手性对称性破缺

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-08 DOI: 10.1021/jacs.5c07995

Zhuang Xu, Ziming Wang, Rui Zhang, Archana Verma, Justin S. Neu, Priyotosh Bairagya, Sanghyun Jeon, Alec M. Damron, Joshua M. Rinehart, Justine S. Wagner, Sina Sabury, Xuyi Luo, Anna M. Österholm, Jianguo Mei, Jeffrey S. Moore, Wei You, John R. Reynolds, Nicholas E. Jackson, Ying Diao

{"title":"Ubiquitous Chiral Symmetry Breaking of Conjugated Polymers via Liquid–Liquid Phase Separation","authors":"Zhuang Xu, Ziming Wang, Rui Zhang, Archana Verma, Justin S. Neu, Priyotosh Bairagya, Sanghyun Jeon, Alec M. Damron, Joshua M. Rinehart, Justine S. Wagner, Sina Sabury, Xuyi Luo, Anna M. Österholm, Jianguo Mei, Jeffrey S. Moore, Wei You, John R. Reynolds, Nicholas E. Jackson, Ying Diao","doi":"10.1021/jacs.5c07995","DOIUrl":"https://doi.org/10.1021/jacs.5c07995","url":null,"abstract":"Spontaneous chiral symmetry breaking remains a fascination in chemistry, biology, materials science, and even astronomy. Chiral symmetry breaking usually requires intrinsic molecular chirality or extrinsic chiral sources but remains rare in nonchiral systems. Here, we reveal a ubiquitous, entropy-driven chiral symmetry breaking mechanism observed in 22 out of 35 conjugated polymers in the absence of any chiral source─a phenomenon overlooked for decades. Chiral assemblies spontaneously occur through liquid–liquid phase separation (LLPS) of lyotropic mesophases from isotropic solutions upon a concentration increase. Machine learning identifies the underpinning molecular features validated by further molecular design. The universality of this phenomenon hints at a possible link between LLPS and chiral symmetry breaking in the origin of life, while paving the way for an emerging frontier of chiral electronics.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"14 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009208","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

Oxophilic Sites Mediated Dynamic Oxygen Replenishment to Stabilize Lattice Oxygen Catalysis in Acidic Water Oxidation. 亲氧位点介导的动态氧补充以稳定酸性水氧化中的晶格氧催化。

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-08 DOI: 10.1021/jacs.5c09939

Shaoxiong Li,Sheng Zhao,Sung-Fu Hung,Liming Deng,Luqi Wang,Fuke Shi,Ao Dong,Ying Zhang,Tsung-Yi Chen,Feng Hu,Linlin Li,Seeram Ramakrishna,Yuping Wu,Shengjie Peng

{"title":"Oxophilic Sites Mediated Dynamic Oxygen Replenishment to Stabilize Lattice Oxygen Catalysis in Acidic Water Oxidation.","authors":"Shaoxiong Li,Sheng Zhao,Sung-Fu Hung,Liming Deng,Luqi Wang,Fuke Shi,Ao Dong,Ying Zhang,Tsung-Yi Chen,Feng Hu,Linlin Li,Seeram Ramakrishna,Yuping Wu,Shengjie Peng","doi":"10.1021/jacs.5c09939","DOIUrl":"https://doi.org/10.1021/jacs.5c09939","url":null,"abstract":"Developing efficient and durable catalysts for the oxygen evolution reaction (OER) in acidic media is essential for advancing proton exchange membrane water electrolysis (PEMWE). However, catalyst instability caused by lattice oxygen (OL) depletion and metal dissolution remains a critical barrier. Here, we propose an oxophilic-site-mediated dynamic oxygen replenishment mechanism (DORM), in which OL actively participates in O-O bond formation and is continuously refilled by water-derived species. Oxophilic dopants modulate the local electronic structure, lower the energy barrier for oxygen vacancy healing, and reorganize the interfacial hydrogen-bond network to enhance water mobility, orientation, and proton accessibility, collectively promoting water dissociation and stabilizing OL catalysis. The optimized catalyst achieves a low overpotential of 289 mV and exceptional durability, operating continuously for 650 h at 10 mA cm-2 in acidic electrolyte and maintaining stable performance for 280 h at 1 A cm-2 in a PEMWE. This work establishes a mechanistic framework for dynamic OL redox and provides a rational strategy for designing robust, noble-metal-free acidic OER electrocatalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"35 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145008809","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 Quantitative Molecular Analysis at Single-Molecule Resolution. 单分子分辨率的实时空间定量分子分析。

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-09-08 DOI: 10.1021/jacs.5c08253

Jiale Feng,Wenbo Li,Mengmeng Ma,Jiayi Zhang,Tongyu He,Tao Cheng,Sheng Dai,Bin Song,Boyuan Shen

{"title":"Real-Space Quantitative Molecular Analysis at Single-Molecule Resolution.","authors":"Jiale Feng,Wenbo Li,Mengmeng Ma,Jiayi Zhang,Tongyu He,Tao Cheng,Sheng Dai,Bin Song,Boyuan Shen","doi":"10.1021/jacs.5c08253","DOIUrl":"https://doi.org/10.1021/jacs.5c08253","url":null,"abstract":"Advances in molecular analysis and characterization techniques should revolutionize the methods for scientific exploration across physics, chemistry, and biology, fundamentally overturning our understanding of interactions and processes that govern molecular behavior at the microscopic level. Currently, the absence of a molecular analysis method that can both quantify molecules and achieve single-molecule spatial resolution hinders our study of complex molecular systems in sorption and catalysis. Here, we propose a quantitative analysis strategy for small molecules confined in ZSM-5, a zeolite material extensively used in catalysis and gas separation, based on low-dose transmission electron microscopy. This approach enables the visualization of molecular structures with angstrom spatial resolution and facilitates their identification through detailed molecular imaging. By integrating experimental and simulated images with adsorption data, the quantity of small molecules within each zeolite channel is precisely calibrated, thereby advancing the study of the molecular sorption, transport, and reaction dynamics in ZSM-5 channels. The quantitative insights into these processes enhance our understanding of microscale mechanisms, elucidating the roles of host-guest interactions, molecular geometry, and external stimulus. This work expands the application of low-dose electron microscopy in molecular imaging and analysis, establishing it as a spatially resolved and quantitative tool for studying molecular behaviors in real space that is previously inaccessible.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"14 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145008817","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