Chemical Science最新文献_第8页

Recent advances in catalytic asymmetric alkenyl C(sp2)–H bond functionalizations

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-10 DOI: 10.1039/d5sc00623f

Xiao-Ju Si, Tian-Ci Wang, Teck Peng Loh, Ming-Zhu Lu

{"title":"Recent advances in catalytic asymmetric alkenyl C(sp2)–H bond functionalizations","authors":"Xiao-Ju Si, Tian-Ci Wang, Teck Peng Loh, Ming-Zhu Lu","doi":"10.1039/d5sc00623f","DOIUrl":"https://doi.org/10.1039/d5sc00623f","url":null,"abstract":"Alkenes and their derivatives are widespread in numerous bioactive natural products and pharmaceutically relevant molecules. They are also synthetically versatile building blocks that have found broad applications in a plethora of organic transformations. The asymmetric alkenyl C(sp2)–H functionalization of readily available olefinic feedstocks allows the practical and straightforward synthesis of structurally diverse chiral compounds. As such, an ever-increasing number of robust and versatile strategies have been established to selectively functionalize the olefinic C(sp2)−H bonds in recent years. The current review provides a concise overview of these impressive achievements in the realm of asymmetric alkenyl C–H functionalization reactions, with a particular emphasis on substrate scopes, limitations, mechanistic studies, as well as their applications in the precise synthesis of diversely functionalized chiral molecules. Challenges and future opportunities regarding this area of research are also discussed. Through this review, we aim to inspire continuous efforts toward further development of more practical and broadly applicable strategies to advance this burgeoning field.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143589932","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

Contrasting effects of mismatch locations on Z-DNA formation under bending force

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-10 DOI: 10.1039/d5sc00749f

SoJung Park, Jaehun Yi, Nam Ki Lee

引用次数: 0

Eight-Electron Copper-Hydride Nanoclusters: Synthesis, Structure, Alloying Chemistry and Photoluminescence

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-10 DOI: 10.1039/d4sc08547g

Jing Sun, Jiahe Liu, Hai-Feng Su, Simin Li, Xiongkai Tang, Zhenlang Xie, Zhen Xu, Wenya Jiang, Jianyu Wei, Xuekun Gong, Ayisha He, Song Wang, De-En Jiang, Nanfeng Zheng, Hui Shen

{"title":"Eight-Electron Copper-Hydride Nanoclusters: Synthesis, Structure, Alloying Chemistry and Photoluminescence","authors":"Jing Sun, Jiahe Liu, Hai-Feng Su, Simin Li, Xiongkai Tang, Zhenlang Xie, Zhen Xu, Wenya Jiang, Jianyu Wei, Xuekun Gong, Ayisha He, Song Wang, De-En Jiang, Nanfeng Zheng, Hui Shen","doi":"10.1039/d4sc08547g","DOIUrl":"https://doi.org/10.1039/d4sc08547g","url":null,"abstract":"The first copper-hydride nanocluster, featuring eight free valence electrons, has been successfully isolated and characterized spectroscopically. The structure of the nanocluster, represented by the chemical formula [Cu47(PhSe)15(PPh3)5(CF3COO)12H12] (referred to as Cu47H12, where PPh3 denotes triphenylphosphine), has been precisely determined through single crystal X-ray diffraction analysis. Several distinguishing features differentiate the Cu47H12 clusters from previously reported examples. In terms of composition, these clusters represent a rare instance of high-nuclearity Cu nanoclusters containing hydride and stabilized by selenolate ligands. From an electronic standpoint, the stabilization of the nanocluster is achieved through its eight free valence electrons, marking it as the first copper-hydride cluster with this configuration. The alloying chemistry of the nanocluster also introduces unexpected findings in the field. The incorporation of silver atoms leads to the formation of [(CuAg)47(PhSe)18(PPh3)6(CF3COO)12H6]3+ clusters, which exhibit significant structural differences from the parent cluster. Both the homo and alloy clusters display dual-emission properties at 298 K, with the clusters additionally showcasing triple or even quadruple emission at 77 K. This work is anticipated to stimulate research interest in hydride-containing metal nanoclusters, focusing not only on compositional tailoring and structural engineering, but also on electronic structure details and potential applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582943","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

Carbon-based iontronics – current state and future perspectives

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-10 DOI: 10.1039/d4sc06817c

Panlong Li, Przemyslaw Galek, Julia Grothe, Stefan Kaskel

{"title":"Carbon-based iontronics – current state and future perspectives","authors":"Panlong Li, Przemyslaw Galek, Julia Grothe, Stefan Kaskel","doi":"10.1039/d4sc06817c","DOIUrl":"https://doi.org/10.1039/d4sc06817c","url":null,"abstract":"Over the past decades, carbon materials, including fullerenes, carbon nanotubes, graphene, and porous carbons, have achieved tremendous achievement and success in the fields of energy, environment, medicine, and beyond, through their development and application. Due to their unique physical and chemical characteristics for enabling simultaneous interaction with ions and transport of electrons, carbon materials have been attracting increasing attention in the emerging field of iontronics in recent years. In this review, we firstly summarize the recent progress and achievements of carbon-based iontronics (ionic sensors, ionic transistors, ionic diodes, ionic pumps, and ionic actuators) for multiple bioinspired applications ranging from information sensing, processing, and actuation, and further simple and basic artificial intelligent reflex arc units for the construction of smart and autonomous iontronics. Additionally, the promising potentials of carbon materials for smart iontronics are highlighted and prospects are provided in this review, which provide new insights for the further development of nanostructured carbon materials and carbon-based smart iontronics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"68 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582938","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

Nitrene-mediated Aminative N–N–N Coupling: Facile Access to Triazene 1-Oxides

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-10 DOI: 10.1039/d5sc00064e

Shi-Yang Zhu, Hai-Ruo Zhang, Bo-Yang Sun, Zi-Qian Bai, Gang He, Gong Chen, Hao Wang

引用次数: 0

CO2-Enhanced TADF of an Ultra-Stable Cu(I) Cluster via Guest-Host π‒π Interaction

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-10 DOI: 10.1039/d4sc07949c

Hong-Jin Zhang, Zong-Ren Chen, Ji-Tong Xu, Jia-Wen Ye, Ling Chen, Xiao-Ming Chen

{"title":"CO2-Enhanced TADF of an Ultra-Stable Cu(I) Cluster via Guest-Host π‒π Interaction","authors":"Hong-Jin Zhang, Zong-Ren Chen, Ji-Tong Xu, Jia-Wen Ye, Ling Chen, Xiao-Ming Chen","doi":"10.1039/d4sc07949c","DOIUrl":"https://doi.org/10.1039/d4sc07949c","url":null,"abstract":"Efficient and reversible luminescence detection for CO2 without solvent assistance is of great significance but still remains challenging to achieve, due to the lack of efficient interaction between CO2 molecules and the host emitting center. Benefiting from the abundant host-guest interactions, metal clusters provide a platform for detecting small molecules. However, the insufficient chemical stability of most metal clusters limits the practical applications. Here, we report a hydrophobic Cu(I) cluster (denoted as CuIDPO) with one-dimensional channels. Notably, it displays exceptional chemical stability in both acidic and alkaline aqueous solutions (pH = 1-14). More importantly, CuIDPO shows remarkable CO2-induced luminescence enhancement (up to 385% in 1 bar CO2), which can be applied to analyze CO2 content (LOD = 7.7 mbar). Crystallographic analysis and theoretical calculations suggest the mechanism of CO2-locking rotation of the phenyl groups in the Cu(I) cluster through guest-host π‒π interaction, which is quite unique when compared to the known acid-base neutralization and framework flexibility adjustment mechanisms. Such luminescence CO2 sensing shows advantages like ultrafast response and well reversibility. Additionally, CuIDPO-loaded membranes were fabricated for spatially resolved 2D visual detection.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"104 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582939","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

Modeling Thermocatalytic Systems for CO2 Hydrogenation to Methanol

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-10 DOI: 10.1039/d5sc00211g

Jikai Sun, Jianzhong Wu

{"title":"Modeling Thermocatalytic Systems for CO2 Hydrogenation to Methanol","authors":"Jikai Sun, Jianzhong Wu","doi":"10.1039/d5sc00211g","DOIUrl":"https://doi.org/10.1039/d5sc00211g","url":null,"abstract":"The hydrogenation of CO2 to CH3OH over Cu-based catalysts holds significant potential for advancing carbon sequestration and sustainable chemical processes. While numerous studies have focused on catalyst development, the environmental effects on underlying reaction mechanisms have yet to be fully understood. In this work, we develop a grand potential theory for a comprehensive analysis of CO2 hydrogenation to CH3OH over Cu (111) and Cu (211) surfaces. By integrating electronic and classical density functional calculations to bridge the “pressure gap”, the theoretical results revealed that the HCOO* formation rate may vary by several orders of magnitude depending on reaction conditions. The grand potential theory enables us to elucidate the molecular mechanisms underlying the need for high H2 pressure, the prevalence of saturated CO2 adsorption, and the important roles of CO and H2O in hydrogenation. Moreover, this study addressed and clarified controversies over CO2 versus CO adsorption and hydrogenation, the formate versus carboxy pathways, and the difference in HCOO* hydrogenation activity between Cu (111) and Cu (211) surfaces. The theoretical analysis offers a new perspective for optimizing reaction conditions and catalyst performance in methanol synthesis and can be generalized to enhance our understanding of heterogeneous catalysis under industrially relevant conditions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143589930","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

Unraveling the Effect of Alkali Cation on Fe Single Atom Catalysts with High Coordination Number

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-08 DOI: 10.1039/d5sc00581g

Yecheng Li, Songjie Meng, Zihong Wang, Hehe Zhang, Xin Zhao, Qingshun Nian, Digen Ruan, Lianfeng Zou, Zhansheng Lu, Xiaodi Ren

{"title":"Unraveling the Effect of Alkali Cation on Fe Single Atom Catalysts with High Coordination Number","authors":"Yecheng Li, Songjie Meng, Zihong Wang, Hehe Zhang, Xin Zhao, Qingshun Nian, Digen Ruan, Lianfeng Zou, Zhansheng Lu, Xiaodi Ren","doi":"10.1039/d5sc00581g","DOIUrl":"https://doi.org/10.1039/d5sc00581g","url":null,"abstract":"Fe single atom catalysts (SACs) with high coordination number have emerged as high-performance catalysts for the conversion of CO2 to CO. However, the influence of alkali cation at the catalyst-electrolyte interface has not yet been understood clearly. Here, we investigate the role of the various alkali metal cations (Na+, K+, Rb+) on catalytic CO2 reduction reaction (CO2RR) behavior on high coordination number Fe SACs (FeN5 and FeN6) obtained from a facile hard template method. We find that larger cations can greatly promote CO2RR and such effects are enhanced with increasing cation concentration. Nevertheless, hydrogen evolution side reaction (HER) on co-existing N heteroatom sites will be worsened. This trade-off highlights the importance of manipulating the reactive sites for SACs. From theoretical simulation and in-situ spectroscopy results, we confirm the functioning mechanism of cations on Fe SACs lies in the enhancement of the adsorption of key intermediates through direct coordination and indirect hydrogen bonding effects. With the rationally designed Fe SACs (FeN5) and the electrolyte condition (1 M KOH), our flow cell test demonstrate a maximum Farady efficiency of CO (FECO) of approximately 100% at 100 mA cm-2. This research provides significant insights for future SACs and electrolyte design.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"18 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575222","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

Bifunctional Additive-Driven Shape Transitions of Block Copolymer Particles through Synergistic Quaternization and Protonation

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-08 DOI: 10.1039/d5sc00259a

Zhengping Tan, Soohyun Ban, Younghyeon Ahn, Kang Hee Ku, Bumjoon Kim

{"title":"Bifunctional Additive-Driven Shape Transitions of Block Copolymer Particles through Synergistic Quaternization and Protonation","authors":"Zhengping Tan, Soohyun Ban, Younghyeon Ahn, Kang Hee Ku, Bumjoon Kim","doi":"10.1039/d5sc00259a","DOIUrl":"https://doi.org/10.1039/d5sc00259a","url":null,"abstract":"Block copolymer (BCP) particles with tailored shapes and nanostructures hold promise for applications in cell adhesion, photonic system, and energy storage due to their unique optical and rheological properties. Conventional approaches relying on surfactant-mediated self-assembly often limit particle geometries to simple structures. Herein, we present a versatile approach to expand the morphology of poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) BCP particles through the incorporation of 9-bromononanoic acid (BNA), a bifunctional additive that facilitates synergistic quaternization and protonation. Increasing the BNA-to-2VP molar ratio enhances P2VP hydrophilicity and reduces the pH value, driving dramatic shape transitions from onion-like spheres to tulip bulbs, ellipsoids, discs, and Janus cups. This morphological diversity is attributed to synergetic interfacial instability-driven water infiltration and pH-induced repulsion of protonated P2VP chains. Additives with a single functional group, however, yield limited morphologies, such as tulip bulbs or onion-like spheres. Notably, Janus cups fabricated via this strategy exhibit selective cargo-loading capabilities, highlighting the importance of precise control over the internal composition and structure of BCP particles.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"91 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575219","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

Mechanism and dynamics of photoswitchable flavoprotein charge-transfer complexes

IF 8.4 1区化学

Chemical Science Pub Date : 2025-03-07 DOI: 10.1039/d4sc08614g

Bo Zhuang, Guangliu Ran, Wenkai Zhang, Feng Gai

{"title":"Mechanism and dynamics of photoswitchable flavoprotein charge-transfer complexes","authors":"Bo Zhuang, Guangliu Ran, Wenkai Zhang, Feng Gai","doi":"10.1039/d4sc08614g","DOIUrl":"https://doi.org/10.1039/d4sc08614g","url":null,"abstract":"Because of their diverse uses in biological science and engineering, continued effort has been made to expand the pool of photoswitchable protein systems. A recent study demonstrated that in monomeric sarcosine oxidase (MSOX), photoexcitation of a charge-transfer (CT) complex formed by a flavin cofactor and a nonreactive ligand (e.g., methylthioacetate) induces the ligand to reversibly change conformation, with implications for the development of flavin-dependent fast photochromic proteins. However, the factors that control the underlying switching mechanism and dynamics remain largely unexplored. Herein, combining extensive protein mutagenesis, ultrafast laser spectroscopic measurements and classical and quantum computational approaches, we assess those factors in a range of protein variants, including those of MSOX and another flavoenzyme, N-methyltryptophan oxidase (MTOX), where we find that a similar photoswitching cycle can occur. We demonstrate that (1) the kinetic behaviors of the photoswitching cycle are protein- and ligand-dependent; (2) the photoswitching and backward thermal recovery rates can be tuned by mutation of a specific active-site residue (Met245 and Thr239 in MSOX and MTOX, respectively), with recovery rates spanning over an order of magnitude, and (3) modifications of the protein environment alter the conformational energy landscape of the ligand–flavin complex, consequently regulating the photocycle. Taken together, these findings highlight the versatility of such photoswitchable systems, providing a molecular basis for fine-tuning their photophysical properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143589933","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