Chemical Science最新文献_第9页

O-Trifluoromethylation of ketones: an alternative straightforward route to alkenyl trifluoromethyl ethers 酮的o -三氟甲基化：制备烯基三氟甲基醚的一种直接途径

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-09 DOI: 10.1039/d5sc01073j

Chi Gao, Yang Liu, Cheng-Sheng Li, He Guo, Sheng-Han Wang, Cong Xu, Mang Wang

{"title":"O-Trifluoromethylation of ketones: an alternative straightforward route to alkenyl trifluoromethyl ethers","authors":"Chi Gao, Yang Liu, Cheng-Sheng Li, He Guo, Sheng-Han Wang, Cong Xu, Mang Wang","doi":"10.1039/d5sc01073j","DOIUrl":"https://doi.org/10.1039/d5sc01073j","url":null,"abstract":"Here we report an unprecedented O-trifluoromethylation of ketones using chloro(phenyl)trifluoromethyl-λ3-iodane (CPTFI). Our method provides a new strategy for the facile synthesis of various synthetically valuable alkenyl trifluoromethyl ethers, particularly those CF3O-substituted terminal alkenes and cyclic alkenes that have been elusive until now, from simple aromatic, aliphatic, and cyclic ketones. The success of this reaction is attributed to the full utilization of the multifunctionality of CPTFI: 1) its strong Lewis acid activation ability, which enables weak nucleophile such as Cl anion to attack the carbonyl group; 2) its bifunctionality, which allows for the introduction of CF3 and Cl into the carbonyl in one step, thus enabling the obtainment of alkenyl trifluoromethyl ethers by further removal of HCl. The further transformation in the synthesis of CF3O-cyclopropanes, which were previously largely unexplored, reveals the significant potential of alkenyl trifluoromethyl ethers as valuable CF3O-containing building blocks in the discovery of innovative materials, pharmaceuticals, and agrochemicals.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806228","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

Precise positioning of Au islands within mesoporous Pd–Pt nanoparticles for plasmon-enhanced methanol oxidation 等离子体增强甲醇氧化介孔Pd-Pt纳米颗粒中Au岛的精确定位

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-09 DOI: 10.1039/d4sc07345b

Liyang Zhu, Yunqing Kang, Miharu Eguchi, Yingji Zhao, Dong Jiang, Xiaoqian Wei, Xingtao Xu, Kenta Nakagawa, Toru Asahi, Tokihiko Yokoshima, Yusuke Yamauchi

{"title":"Precise positioning of Au islands within mesoporous Pd–Pt nanoparticles for plasmon-enhanced methanol oxidation","authors":"Liyang Zhu, Yunqing Kang, Miharu Eguchi, Yingji Zhao, Dong Jiang, Xiaoqian Wei, Xingtao Xu, Kenta Nakagawa, Toru Asahi, Tokihiko Yokoshima, Yusuke Yamauchi","doi":"10.1039/d4sc07345b","DOIUrl":"https://doi.org/10.1039/d4sc07345b","url":null,"abstract":"Trimetallic systems have garnered considerable attention in (electro)catalysis due to the synergistic effects resulting from the combination of three different metals. However, achieving precise control over the positioning of various metals and understanding the relationship between structure and performance remains challenging. This study introduces an approach for synthesizing Pd@Pt@Au mesoporous nanoparticles (MNPs) with distinct core–shell Pd@Pt structures, featuring well-dispersed isolated Au islands on the outer shell, improving the plasmonic effect. The electrocatalytic performance of Pd@Pt@Au MNPs in the methanol oxidation reaction (MOR) is assessed under light-induced and light-independent conditions. The results indicate significantly enhanced activity compared to commercial Pt black, with catalytic activity during MOR increasing approximately 7.5-fold under light irradiation. The external placement of Au on the shell of Pd@Pt@Au MNPs provides superior plasmonic enhancement, thereby contributing to improved catalytic performance under light irradiation. This investigation sheds light on the controlled synthesis of trimetallic MNPs and their catalytic applications, underscoring the importance of precise Au positioning for optimizing performance.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"75 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806229","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

Design of Cellulosic Poly(Ionic Liquid)s with Hydrogen Bond/Ion Dual Regulation Mechanism for Highly Reversible Zn Anode† 具有氢键/离子双调控机制的纤维素聚离子液体用于高可逆锌阳极的设计

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-09 DOI: 10.1039/d5sc01555c

Kui Chen, Yongzhen Xu, Hebang Li, Yue Li, Lihua Zhang, Yuanlong Guo, Qinqin Xu, Yunqi Li, Haibo Xie

{"title":"Design of Cellulosic Poly(Ionic Liquid)s with Hydrogen Bond/Ion Dual Regulation Mechanism for Highly Reversible Zn Anode†","authors":"Kui Chen, Yongzhen Xu, Hebang Li, Yue Li, Lihua Zhang, Yuanlong Guo, Qinqin Xu, Yunqi Li, Haibo Xie","doi":"10.1039/d5sc01555c","DOIUrl":"https://doi.org/10.1039/d5sc01555c","url":null,"abstract":"The unstable electrode/electrolyte interface with erratic zinc (Zn) deposition, severe dendritic growth and parasitic side reactions deteriorates the reversibility, tolerance and sustainability of aqueous Zn ion batteries (AZIBs). Herein, a imidazolium-based cellulosic poly(ionic liquid)s ([CellMim]+) additive with hydrogen bond/ion dual regulation mechanism for aqueous electrolyte was designed and prepared via a transesterification reaction by taking the particular solvent properties. The water-rich Zn anode interface significantly optimized by hydrogen bond (HB) formation and preferential adsorption of [CellMim]+. Additionally, the overfed Zn2+ ions are modulated by [CellMim]+ cations though electrostatic repulsion, fostering uniform Zn deposition and solid electrolyte interface (SEI). Notably, the Zn||Zn cells with [CellMim]+ modified Zn(OTf)2 electrolyte exhibit a long cycle life over 1800 h at 1 mA cm-2 and a high cumulative capacity of 3700 mAh cm-2 at 10 mA cm-2 with 56.9% Zn utilization rate (ZUR). Intriguingly, this electrolyte demonstrates a remarkable durability of 260 h at 8 mA cm-2 with 22.77% ZUR for a 9 cm2 pouch cell. These results highlight the great potential of cellulosic derivatives in battery applications and offer valuable insights into the design of sustainable aqueous electrolyte additives for AZIBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"38 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806231","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

Asymmetric Total Synthesis of Penicilfuranone A through NHC-Catalyzed Umpolung nhc催化Umpolung不对称合成青霉素呋喃酮A

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-08 DOI: 10.1039/d5sc01508a

Yiming Ding, Xianwen Long, Jingwei Zhang, Qu Chunlei, Peng Wang, Xiaodong Yang, Pema-Tenzin Puno, Jun Deng

引用次数: 0

Discovery of a molecular adsorbent for efficient CO2/CH4 separation using a computation-ready experimental database of porous molecular materials 利用可计算的多孔分子材料实验数据库，发现一种用于CO2/CH4高效分离的分子吸附剂

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-08 DOI: 10.1039/d5sc01532d

Siyuan Yang, Qianqian Mao, Heng Ji, Dingyue Hu, Jinjin Zhang, Linjiang Chen, Ming Liu

{"title":"Discovery of a molecular adsorbent for efficient CO2/CH4 separation using a computation-ready experimental database of porous molecular materials","authors":"Siyuan Yang, Qianqian Mao, Heng Ji, Dingyue Hu, Jinjin Zhang, Linjiang Chen, Ming Liu","doi":"10.1039/d5sc01532d","DOIUrl":"https://doi.org/10.1039/d5sc01532d","url":null,"abstract":"The development and sharing of computational databases for metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have significantly accelerated the exploration and application of these materials. Recently, molecular materials have emerged as a notable subclass of porous materials, characterized by their crystallinity, modularity, and processability. Among these, macrocycles and cages stand out as representative molecules. Experimentally discovery of a target molecular material from a vast possibility of structures for defined applications is generally impractical due to high experimental costs. This study presents the most extensive Computation-ready Experimental (CoRE) database of macrocycles and cages (MCD) to date, comprising 7,939 structures. Using the MCD, we conducted simulations of binary CO2/CH4 competitive adsorption under conditions relevant to industrial applications. These simulations established a structure-property-function relationship, enabling the identification of materials with potential for CO2/CH4 separation. Among them, a macrocycle, NDI-Δ, exhibited promising CO2 adsorption capacity and selectivity, as confirmed by gas sorption and breakthrough experiments.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797709","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

Redox Mediated Dimerisation of a cyclo-As8 Complex 氧化还原介导的环as8复合物二聚化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-08 DOI: 10.1039/d5sc01685a

Christoph Riesinger, Manfred Scheer

引用次数: 0

Pyridine-N-oxide Catalyzed Asymmetric N-Acylative Desymmetrization of Sulfonimidamides 吡啶- n -氧化物催化磺胺酰化不对称脱对称反应

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-08 DOI: 10.1039/d5sc01270h

Cui-Mei Guo, Fang-Yuan Zhang, Yin Tian, Ming-Sheng Xie, Hai-Ming Guo

引用次数: 0

Fluorine-rich interface for garnet-based high-performance all-solid-state lithium batteries 基于石榴石的高性能全固态锂电池的富氟界面

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-08 DOI: 10.1039/d5sc01107h

Shruti Suriyakumar, Indu M. Santhakumari, Souvik Ghosh, Anju Vakakuzhiyil Gopinathan, Sooraj Kunnikuruvan, Manikoth M. Shaijumon

{"title":"Fluorine-rich interface for garnet-based high-performance all-solid-state lithium batteries","authors":"Shruti Suriyakumar, Indu M. Santhakumari, Souvik Ghosh, Anju Vakakuzhiyil Gopinathan, Sooraj Kunnikuruvan, Manikoth M. Shaijumon","doi":"10.1039/d5sc01107h","DOIUrl":"https://doi.org/10.1039/d5sc01107h","url":null,"abstract":"Solid-state batteries present a promising avenue that offers improved safety and energy density, effectively addressing the limitations of state-of-the-art lithium-ion batteries. Among different solid electrolytes, composite polymer electrolytes (CPEs) offer versatile multi-component solutions to distinct challenges posed by inorganic solid and organic polymer electrolytes. However, the polymer–filler interface issues significantly hamper their performance when higher ceramic (>20%) loading occurs. Here, we demonstrate an efficient strategy to introduce an in situ-formed fluorine-rich interface for the lithium anode and the ceramic fillers in the CPE. The rationally designed CPE comprises a high ceramic loading of 40% and exhibits significantly high Li-ionic conductivity (10−4 S cm−1 @ 55 °C) and compatibility, along with impressive long cycling performance of the Li|Li symmetric cell for over 2000 cycles at 0.1 mA cm−2. We fabricated all-solid-state Li//LFP full cells that delivered a discharge capacity of 140 mA h g−1 at a 0.1C-rate when cycled at 70 °C and showed good cycling stability. The role of fluorine-containing additives in enhancing conductivity was validated using computations. Furthermore, we extended the applicability of the optimised CPE as an interface modifier in Li//LFP full cells, resulting in improved capacity and long-term cycling.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"72 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797675","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

RIBOsensor for FRET-based, real-time ribose measurements in live cells 核糖传感器，基于fret，实时核糖测量活细胞

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-08 DOI: 10.1039/d5sc00244c

Mina Ahmadi, Zhuangyu Zhao, Ivan J. Dmochowski

引用次数: 0

Point defect formation at finite temperatures with machine-learning force fields 用机器学习力场在有限温度下形成点缺陷

IF 8.4 1区化学

Chemical Science Pub Date : 2025-04-08 DOI: 10.1039/d4sc08582e

Irea Mosquera-Lois, Johan Klarbring, Aron Walsh

{"title":"Point defect formation at finite temperatures with machine-learning force fields","authors":"Irea Mosquera-Lois, Johan Klarbring, Aron Walsh","doi":"10.1039/d4sc08582e","DOIUrl":"https://doi.org/10.1039/d4sc08582e","url":null,"abstract":"Point defects dictate the properties of many functional materials. The standard approach to modelling the thermodynamics of defects relies on a static description, where the change in Gibbs free energy is approximated by the internal energy. This approach has a low computational cost, but ignores contributions from atomic vibrations and structural configurations that can be accessed at finite temperatures. We train a machine learning force field (MLFF) to explore dynamic defect behaviour using Te_i +1 and V_Te +2 in CdTe as exemplars. We consider the different entropic contributions (e.g., electronic, spin, vibrational, orientational, and configurational) and compare methods to compute the defect free energies, ranging from a harmonic treatment to a fully anharmonic approach based on thermodynamic integration. We find that metastable configurations are populated at room temperature and thermal effects increase the predicted concentration of Te_i +1 by two orders of magnitude --- and can thus significantly affect the predicted properties. Overall, our study underscores the importance of finite-temperature effects and the potential of MLFFs to model defect dynamics at both synthesis and device operating temperatures.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797723","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