化学最新文献_第10页

Polar π stacking for metal-free near, remote, and ultra-remote C–H coupling with aryliodanes

IF 23.5 1区化学

Chem Pub Date : 2025-04-18 DOI: 10.1016/j.chempr.2025.102546

Jorge D. Martín-Bernardos, Katrin Golob, Wei W. Chen, Orsola A. Luongo, Inés Sedó, Ana B. Cuenca, Alexandr Shafir

{"title":"Polar π stacking for metal-free near, remote, and ultra-remote C–H coupling with aryliodanes","authors":"Jorge D. Martín-Bernardos, Katrin Golob, Wei W. Chen, Orsola A. Luongo, Inés Sedó, Ana B. Cuenca, Alexandr Shafir","doi":"10.1016/j.chempr.2025.102546","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102546","url":null,"abstract":"We introduce a C–H coupling process in which an aromatic C–I position serves as trampoline for targeting various aromatic C–H positions. The reaction is set in motion by an interaction between the λ3-iodane ArI(OAc)2 and the π system of polyunsaturated organosilanes. In particular, the silyl-terminated enynes engage in fully regioselective ortho and para C–H functionalization, with selectivity switch achieved by reversing the order of the substrate’s ene and yne fragments. Density functional theory (DFT) calculations show that the ortho selectivity is governed by a [3,3] sigmatropic rearrangement, while the para coupling occurs through a directional three-point π interaction of the enyne-derived cationic π system, giving rise to an essentially barrierless [5,5] sigmatropic rearrangement. Furthermore, iodane-guided C–H functionalization of 2-iodonaphthalene could be directed to the ultra-remote C6 position through further π extension of the organosilanes partner. The latter reaction represents a nearly unprecedented example of a formal [7,7] sigmatropic rearrangement.","PeriodicalId":268,"journal":{"name":"Chem","volume":"30 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846495","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 and regenerable Ir1–Cu1 dual-atom catalyst for low-temperature alkane dehydrogenation

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-04-18 DOI: 10.1038/s41929-025-01328-3

Xiaowen Chen, Maolin Wang, Yurong He, Mi Peng, Jiangyong Diao, Dequan Xiao, Ning Wang, Xiangbin Cai, Hongyang Liu, Ding Ma

{"title":"A highly efficient and regenerable Ir1–Cu1 dual-atom catalyst for low-temperature alkane dehydrogenation","authors":"Xiaowen Chen, Maolin Wang, Yurong He, Mi Peng, Jiangyong Diao, Dequan Xiao, Ning Wang, Xiangbin Cai, Hongyang Liu, Ding Ma","doi":"10.1038/s41929-025-01328-3","DOIUrl":"https://doi.org/10.1038/s41929-025-01328-3","url":null,"abstract":"Alkane dehydrogenation as a direct route to produce olefins receives widespread attention from industry and academia. However, high temperatures (>550 °C) are often needed to break C–H bonds, leading to deleterious side reactions in the alkane dehydrogenation process. Here we reduce the reaction temperature of n-butane dehydrogenation by fabricating a robust and regenerable Ir1–Cu1 dual-atom catalyst. The so-prepared system shows a turnover frequency of 2.45 s−1 at 450 °C, which is 6.3 times higher than the single-atom Ir1/ND@G catalyst, while, at he same time, achieving a high C4 olefin selectivity of 98%. Importantly, key for the success of the Ir1–Cu1 dual-atom catalyst are the sterically favourable geometric configuration and the modulated electronic property, which can lower the reaction barrier for C–H activation, shift the rate-determining step and facilitate the desorption of the product. Thus, a remarkable activity can be achieved for n-butane dehydrogenation at relatively low temperature (≤450 °C).<figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"263 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846671","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

Solid-Liquid Interfacial Hydrogen Bond Mediated Mass Transfer toward Industrial Water Electrolysis

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-18 DOI: 10.1002/anie.202502151

Yu Lin, Bowen Chen, Danji Huang, Zhenhong Yang, Ang Lu, Zhaoyang Shi, Youwen Liu, Jiakun Fang, Huiqiao Li, Tianyou Zhai

引用次数: 0

Self-assembled nanoprobes for cancer phototheranostics

IF 20.3 1区化学

Coordination Chemistry Reviews Pub Date : 2025-04-18 DOI: 10.1016/j.ccr.2025.216643

Sondavid Nandanwar , Van Kieu Thuy Nguyen , Dai Lam Tran , Thanh Chung Pham , Songyi Lee

{"title":"Self-assembled nanoprobes for cancer phototheranostics","authors":"Sondavid Nandanwar , Van Kieu Thuy Nguyen , Dai Lam Tran , Thanh Chung Pham , Songyi Lee","doi":"10.1016/j.ccr.2025.216643","DOIUrl":"10.1016/j.ccr.2025.216643","url":null,"abstract":"<div><div>Self-assembled nanoprobes have emerged as an advanced cancer treatment, offering a unified platform that integrates both diagnostic and therapeutic capabilities. This paper highlights recent advancements in self-assembled nanoprobes designed for cancer phototheranostics, combining photodynamic therapy (PDT) and/or photothermal therapy (PTT) with imaging such as fluorescence imaging (FI) and/or photoacoustic imaging (PAI) for precise tumor targeting. Combinations with chemotherapy (CMT), chemodynamic therapy (CDT), surgical therapy (ST), and photoimmunotherapy (PIT) were also considered. By leveraging key features of the tumor microenvironment, such as acidic condition, high glutathione levels, and hypoxia, these nanoprobes facilitate stimuli-responsive activation, improving therapeutic precision while reducing unintended side effects. Nanoprobes are based on various types of chromophores including porphyrin, cyanine, xanthene, BODIPY derivatives, and aggregation-induced emission luminogens. These designs exhibit an improved photothermal conversion efficiency (PCE), enhanced reactive oxygen species (ROS) generation, and compatibility with multimodal imaging such as near-infrared FI and PAI. This report provides an overview of the design principles, activation mechanisms, and therapeutic efficacy of these advanced nanoprobes, emphasizing their potential for cancer phototheranostics.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"538 ","pages":"Article 216643"},"PeriodicalIF":20.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842758","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 Systems Biology Toolkit (SSBtoolkit): From Molecular Structure to Subcellular Signaling Pathways.

IF 5.6 2区化学

Journal of Chemical Information and Modeling Pub Date : 2025-04-18 DOI: 10.1021/acs.jcim.5c00165

Rui Pedro Ribeiro,Jonas Goßen,Giulia Rossetti,Alejandro Giorgetti

引用次数: 0

Structural Insight into a Human H Ferritin@Gold-Monocarbene Adduct: Aurophilicity Revealed in a Biological Context

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-18 DOI: 10.1002/anie.202503778

Lucrezia Cosottini, Andrea Giachetti, Annalisa Guerri, Ane Martinez-Castillo, Andrea Geri, Stefano Zineddu, Nicola G.A. Abrescia, Luigi Messori, Paola Turano, Antonio Rosato

{"title":"Structural Insight into a Human H Ferritin@Gold-Monocarbene Adduct: Aurophilicity Revealed in a Biological Context","authors":"Lucrezia Cosottini, Andrea Giachetti, Annalisa Guerri, Ane Martinez-Castillo, Andrea Geri, Stefano Zineddu, Nicola G.A. Abrescia, Luigi Messori, Paola Turano, Antonio Rosato","doi":"10.1002/anie.202503778","DOIUrl":"https://doi.org/10.1002/anie.202503778","url":null,"abstract":"Human H ferritin (HuHf) has excellent potential as a nanocarrier for the selective delivery of anticancer metal-based drugs to tumour cells. Here, we addressed the interaction of the gold monocarbene compound Au(NHC)Cl with HuHf by electrospray ionization-mass spectrometry (ESI-MS) measurements, which provide the metalation state of the protein subunits and demonstrate the involvement of protein cysteines in gold binding. The adduct between Au(NHC)Cl and HuHf was studied by cryo-EM measurements, resulting in a high-resolution 3D density map at 1.51 Å. The cryo-EM structure shows a novel tetranuclear gold(I) cluster, located in a surface pocket of each subunit where it is bound to Cys90 and Cys102. The short inter-metal distances are diagnostic of the occurrence of aurophilic interactions. The present work demonstrates the usefulness of cryo-EM to investigate the interactions between metal-based drugs and their protein targets/carriers also leveraging the strong signal of transition metal ions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849460","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

On-Demand Regulation of Catalytic DNA Circuits Using Phosphorylated Charge Reversal Peptides

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-04-18 DOI: 10.1002/anie.202425113

Qingqing Zhang, Shanshan Yu, Shizhen He, Yuqiu He, Xiaoqing Liu, Fuan Wang

{"title":"On-Demand Regulation of Catalytic DNA Circuits Using Phosphorylated Charge Reversal Peptides","authors":"Qingqing Zhang, Shanshan Yu, Shizhen He, Yuqiu He, Xiaoqing Liu, Fuan Wang","doi":"10.1002/anie.202425113","DOIUrl":"https://doi.org/10.1002/anie.202425113","url":null,"abstract":"Catalytic DNA circuits have emerged as a powerful tool for high-performance biosensing application; however, the establishment of a safe and efficient in vivo delivery system remains a critical bottleneck. Peptides serve as attractive carriers due to their rich chemical diversity, excellent biocompatibility, high loading capacity, and specific binding ability, making them ideal candidates for the on-demand regulation of DNA circuits—yet remains largely unexplored. In this study, we developed a multifunctional enzyme-responsive peptide (ERP) for the efficient loading and specific intracellular delivery and release of catalytic circuitry probes through a phosphorylation-based charge reversal procedure. This ERP-programmed catalytic DNA circuit enables the precise, spatially controllable in vivo imaging of microRNA (miRNA). The multifunctional cationic peptide formed a stable nanocomplex with anionic DNA cargo via strong electrostatic interactions, thus protecting the DNA probes from degradation in biological environments. Moreover, with the ability to actively targeting tumor cells and facilitate endogenous phosphorylation-guided release of DNA probes, this multifunctional peptide could significantly reduce the nonspecific delivery of probes to healthy tissues, thereby minimizing unwanted off-site signal leakage. By the integration of cell-selective delivery and site-specific stimulation, this endogenously regulated and multiply guaranteed DNA circuit system paves a simple yet effective way for disease diagnosis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"40 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846907","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 high strength, high elasticity, self-healing deep eutectic ionic elastomers based on multiple non-covalent interactions by using biomass glycerol monomer HPA for strain sensors

IF 4.6 2区化学

Polymer Pub Date : 2025-04-18 DOI: 10.1016/j.polymer.2025.128423

Deyang Wang, Jinqing Qu

{"title":"Synthesis of high strength, high elasticity, self-healing deep eutectic ionic elastomers based on multiple non-covalent interactions by using biomass glycerol monomer HPA for strain sensors","authors":"Deyang Wang, Jinqing Qu","doi":"10.1016/j.polymer.2025.128423","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128423","url":null,"abstract":"Deep eutectic ionic elastomers (DEIEs) have emerged as a research focus in flexible ionic conductors due to their advantages, including rapid and convenient preparation processes, excellent mechanical and electrical properties. However, there remains an obvious research gap in developing DEIEs with superior comprehensive mechanical properties using greener biomass monomers and the simplest formulations. In this study, two novel LiTFSI(lithium bis(trifluoromethane sulfonimide))-based polymerizable deep eutectic solvents systems: HPA(2-hydroxy-3-phenoxypropyl acrylate)/LiTFSI and HEA(2-hydroxyethyl acrylate)/LiTFSI were successfully discovered. Notably, the biomass monomer HPA was utilized for the first time in constructing PDES(polymerizable deep eutectic solvent),and then DEIEs were successfully prepared by UV-initiated free radical random copolymerization using these 2 kinds of PDESs. The DEIEs’ polymer network exhibit various non-covalent interactions, such as hydrogen bonds, dipole-dipole interactions, and π-π interactions, which endow them with high mechanical strength (2.76 MPa), good stretchability (687%), and high elasticity. These abundant physical interactions also confer the material with good self-healing capabilities. Moreover, the DEIEs demonstrates good transparency, sufficient ionic conductivity, and a wide operating temperature range. This material can not only be used for sensing and detecting conventional human physiological activities but also maintains stable sensing performance under complex conditions, such as mechanical damage and low-temperature environments, showcasing significant potential in flexible sensing applications.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

PolyA-Bridged Capture Probe Architecture Enables High-Efficiency DNA Hybridization for Multiplex Biosensing Applications

IF 7.4 1区化学

Analytical Chemistry Pub Date : 2025-04-18 DOI: 10.1021/acs.analchem.5c01752

Jiaqi Yang, Lele Wang, Yanli Wen, Ruiyan Guo, Yinbo Huo, Haoran Zhao, Lanying Li, Juan Yan, Gang Liu

{"title":"PolyA-Bridged Capture Probe Architecture Enables High-Efficiency DNA Hybridization for Multiplex Biosensing Applications","authors":"Jiaqi Yang, Lele Wang, Yanli Wen, Ruiyan Guo, Yinbo Huo, Haoran Zhao, Lanying Li, Juan Yan, Gang Liu","doi":"10.1021/acs.analchem.5c01752","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c01752","url":null,"abstract":"DNA target-probe hybridization is a critical recognition and combination process for establishing high-performance biosensors. However, in conventional self-assembly strategies, surface-anchored capture probes exhibit heterogeneous molecular conformations and limit the kinetics of DNA hybridization at the interface. As a result, the response speed and practicability of electrochemical biosensors are quite limited, especially in real samples. Interfacial regulation of the molecular conformation using artificial DNA nanostructures has been widely recognized as a promising strategy to improve the accessibility and activity of capture probes. This study introduces a significantly simplified molecular regulatory structure on the surface of the gold electrode consisting of a probe-polyA-probe (PAP) sequence and a capture probe (CP). The PAP sequence has a central polyA fragment anchoring to the gold electrode and two flanking probes for hybridization with the two ends of the capture probe, forming a bridged CP (BCP). Upon dual-terminal hybridization with PAP, the capture probe underwent structural linearization through opposing directional extension, thereby markedly enhancing the steric accessibility and subsequent hybridization efficiency. By establishing a BCP biosensor, we achieved rapid and sensitive detection of DNA hybridization from 1 fM to 1 nM. More importantly, the platform demonstrated valuable versatility in the construction of both a gap hybridization biosensor for microRNA and a DNAzyme biosensor for Pb2+. The BCP biosensor exhibited exceptional biorecognition capability, achieving rapid DNA hybridization kinetics in only 3 min and a remarkable hybridization efficiency of 95.56%. Based on its high sensitivity, operational simplicity, and broad applicability, our BCP biosensor has shown an avenue for the development of novel electrochemical biosensors for molecular diagnostics and environmental monitoring.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"10 1","pages":""},"PeriodicalIF":7.4,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847012","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

Refining Electrocatalyst Design for 5-Hydroxymethylfurfural Oxidation: Insights into Electrooxidation Mechanisms, Structure–Property Correlations, and Optimization Strategies

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-04-18 DOI: 10.1021/acscatal.4c06577

Xupo Liu, Jiashu Tang, Ye Chen, Xiangjia Song, Junpo Guo, Gongke Wang, Shixing Han, Xin Chen, Congcong Zhang, Shixue Dou, Huaiyu Shao, Deli Wang

{"title":"Refining Electrocatalyst Design for 5-Hydroxymethylfurfural Oxidation: Insights into Electrooxidation Mechanisms, Structure–Property Correlations, and Optimization Strategies","authors":"Xupo Liu, Jiashu Tang, Ye Chen, Xiangjia Song, Junpo Guo, Gongke Wang, Shixing Han, Xin Chen, Congcong Zhang, Shixue Dou, Huaiyu Shao, Deli Wang","doi":"10.1021/acscatal.4c06577","DOIUrl":"https://doi.org/10.1021/acscatal.4c06577","url":null,"abstract":"Electrooxidation of biomass-derived 5-hydroxymethylfurfural (HMF) is a green and economically viable approach to produce the valuable chemical 2,5-furandicarboxylic acid (FDCA). Given the significance of this transformation, there is a pressing demand for efficient electrocatalysts to expedite the HMF electrooxidation. This article provides a comprehensive overview of the electrooxidation mechanisms, structure–property correlations, and optimization strategies for catalysts involved in converting HMF into FDCA. Initially, the selectivity of reaction pathways, electrooxidation mechanisms, and thermodynamic and kinetic principles governing HMF oxidation are discussed, along with strategies to hinder the competitive oxygen evolution reaction. Subsequently, the structure–property correlations of electrocatalysts based on precious metals and transition metals are introduced in detail, emphasizing the promotion effects of various metal elements on the HMF oxidation process. Furthermore, an in-depth analysis of performance optimization strategies for electrocatalysts is also conducted, including tailoring surface adsorption, regulating dehydrogenation, accelerating proton transfer, integrating catalytic sites, and regenerating active species. Additionally, we critically assess the current challenges faced in developing highly effective HMF electrooxidation catalysts and propose future directions for overcoming these obstacles. This review article aims to provide insightful inspiration for developing high-efficiency electrocatalysts to expedite biomass conversion applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"75 5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846738","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