Chemical Science最新文献_第3页

Correction: Hydroxy-directed iridium-catalyzed enantioselective formal β-C(sp2)–H allylic alkylation of α,β-unsaturated carbonyls 更正：羟基定向铱催化α，β-不饱和羰基的对映选择性正式β-C(sp2) -H烯丙基烷基化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-11 DOI: 10.1039/d5sc90128f

Sankash Mitra, Rahul Sarkar, Aditya Chakrabarty, Santanu Mukherjee

引用次数: 0

Reversible surface reconstruction of metal–organic frameworks for durable oxygen evolution reaction 用于持久析氧反应的金属-有机骨架的可逆表面重构

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-11 DOI: 10.1039/d5sc02536b

Shulin Li, Zhaoxin Zhou, Jiahui Li, Yang Xiao, Ye Yuan, He Zhu, Fengchao Cui, Xiaofei Jing, Guangshan Zhu

{"title":"Reversible surface reconstruction of metal–organic frameworks for durable oxygen evolution reaction","authors":"Shulin Li, Zhaoxin Zhou, Jiahui Li, Yang Xiao, Ye Yuan, He Zhu, Fengchao Cui, Xiaofei Jing, Guangshan Zhu","doi":"10.1039/d5sc02536b","DOIUrl":"https://doi.org/10.1039/d5sc02536b","url":null,"abstract":"Metal–organic frameworks (MOFs) are regarded as prospective electrocatalysts for the oxygen evolution reaction (OER). Nevertheless, controllably reversible reconstruction of MOFs, yielding highly active catalytic sites for durable OER, has not been extensively studied. Herein, Ni-BPM (BPM = 4,4′-dihydroxybiphenyl-3,3′-dicarboxylic acid) equipped with open metal sites was selected as a potential electrocatalyst, and orientated MOF electrodes were fabricated via a sacrificial lattice-matched-template method. Surface reconstruction of Ni-BPM to active γ-NiOOH was detected during the OER, and reconstructed Ni-BPM can also be repaired in the reduction process, resulting in durable OER properties: continuous operation at 100 mA cm−2 for 130 h followed by another 70 h at 500 mA cm−2, surpassing those of most single Ni-based catalysts. The electronic configuration transformation of Ni sites at the interface of Ni-BPM and γ-NiOOH is confirmed using in situ Raman and X-ray absorption spectra together with density functional theory (DFT) calculations. This work has investigated the reversible structural transformation of MOFs during the OER and thereby would help establish a theoretical foundation for the development of durable MOF electrocatalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260568","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

Dual-engine-driven synthesis of unsaturated esters over channel-expanding Cu-Cs catalysts 双引擎驱动的扩张型Cu-Cs催化剂上不饱和酯的合成

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-11 DOI: 10.1039/d5sc02896e

Jiaqi Fan, Lishu Shao, Weizhe Gao, Yitong Han, Wenjie Xiang, Hao Huang, Zhihao Liu, chufeng liu, Bo Wang, Kangzhou Wang, Guangbo Liu, Jiancai Sui, Qiang Liu, Tao Li, Tao Xing, Shuhei Yasuda, Zhixin Yu, Guohui Yang, Peipei Zhang, Noritatsu Tsubaki

{"title":"Dual-engine-driven synthesis of unsaturated esters over channel-expanding Cu-Cs catalysts","authors":"Jiaqi Fan, Lishu Shao, Weizhe Gao, Yitong Han, Wenjie Xiang, Hao Huang, Zhihao Liu, chufeng liu, Bo Wang, Kangzhou Wang, Guangbo Liu, Jiancai Sui, Qiang Liu, Tao Li, Tao Xing, Shuhei Yasuda, Zhixin Yu, Guohui Yang, Peipei Zhang, Noritatsu Tsubaki","doi":"10.1039/d5sc02896e","DOIUrl":"https://doi.org/10.1039/d5sc02896e","url":null,"abstract":"This study presents a one-step catalytic synthesis of unsaturated esters (methyl acrylate, MA; methyl methacrylate, MMA) from methanol (MeOH, C1 source) and methyl acetate (MAc) via a Cu-Cs dual-engine-driven (DED) system that integrates four sequential steps—dehydrogenation, aldol condensation, hydrogenation, and secondary aldol condensation. The Cu-engine facilitates proton transfer by capturing protons during MeOH dehydrogenation and donating them in methyl acrylate (MA) hydrogenation, while the Cs-engine activates saturated esters for formaldehyde-mediated aldol condensation. Through systematic optimization of Cu loading methods, deposition sequences, and Cu/Cs ratios, we developed a silicon carrier channel-expanding strategy, enlarging mesopores from 14 nm to 20 nm (30 % specific surface area extension) via copper phyllosilicate-induced corrosion. Catalytic performance hinges on balanced medium-strength acid-base sites, a 10:7 Cs/Cu ratio, and sequential Cu/Cs loading via ammonia evaporation method. The optimized 10Cs/7Cu/Q10 catalyst, combined with a downstream Cs-Al/Q10 system, achieves 64.0 % unsaturated ester selectivity (55.3 % MeOH and 59.8 % methyl acetate conversion). This work establishes a design framework for efficient Cu-Cs catalysts in one-step ester synthesis, emphasizing pore engineering, acid-base synergy, and dual-site cooperativity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260570","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

Self-supplying coreactant radical and structural distortion induced by carbonate ligand in metal–organic framework for anomalous deep-red Self-electrochemiluminescence 金属-有机骨架中碳酸盐配体引起的异常深红色自致电化学发光的自供反应物自由基和结构畸变

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-10 DOI: 10.1039/d5sc02359a

Lu Zhao, Zhenjie Xu, Xianzhen Song, Caifeng Ding, Huangxian Ju

{"title":"Self-supplying coreactant radical and structural distortion induced by carbonate ligand in metal–organic framework for anomalous deep-red Self-electrochemiluminescence","authors":"Lu Zhao, Zhenjie Xu, Xianzhen Song, Caifeng Ding, Huangxian Ju","doi":"10.1039/d5sc02359a","DOIUrl":"https://doi.org/10.1039/d5sc02359a","url":null,"abstract":"Self-electrochemiluminescence (self-ECL) can deal with the problems of limited electron transport efficiency, reduced signal stability, and redundant ECL processes. A feasible solution is to assemble the luminescent components and coreactant radicals together. Here a self-ECL material was designed relying on a europium-based metal–organic framework (Eu-MOF, ZL-2) with 1,10-phenanthroline and CO32− as ligands under strong alkaline conditions. Upon oxidation of the CO32− ligand to produce C2O62−, OH˙ could be generated to act as a coreactant radical, which reacted with the luminophore radical of oxidized ZL-2 to realize self-ECL without an extra coreactant. The coordination of the CO32− ligand induced Eu3+ to occupy some sites in the tetrakaidecahedron structure of ZL-2, which caused the structure to distort, and thus triggered the unusual electric-dipole transfer transition 5D0–7F4. Therefore, ZL-2 was endowed with deep-red luminescence in the first near-infrared (NIR-I) region, which filled a gap in self-NIR-ECL applications. This discovery suggested a novel promising dual-function mechanism of the CO32− ligand, undoubtedly broadening the application and development of MOFs in the ECL field.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252196","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

Surface Inclusion and Dynamics of Cucurbit[7]uril-Based Supramolecular Complexes 瓜bbbbl基超分子配合物的表面包裹和动力学

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-10 DOI: 10.1039/d5sc03152d

Carina Santos, Guillaume Bastien, Doroteja Lončarić, Martin Dracinsky, Ivana Cisarova, Eric Masson, Jiří Kaleta

引用次数: 0

Molecular Engineering of Bis(triphenylamine)-Modified Fluorene Luminophore for Immensely Enriching Anisotropic Force-Triggered High-Contrast Tricolor Fluorescent Molecular Switches Library 用于丰富各向异性力触发高对比度三色荧光分子开关库的双（三苯胺）修饰芴发光团的分子工程

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-10 DOI: 10.1039/d5sc02314a

Zhao Chen, Yijie Zou, Ya Yin, Dian-Dian Deng, Yue Yang, Congbin Fan, Shouzhi Pu, Gang Liu

{"title":"Molecular Engineering of Bis(triphenylamine)-Modified Fluorene Luminophore for Immensely Enriching Anisotropic Force-Triggered High-Contrast Tricolor Fluorescent Molecular Switches Library","authors":"Zhao Chen, Yijie Zou, Ya Yin, Dian-Dian Deng, Yue Yang, Congbin Fan, Shouzhi Pu, Gang Liu","doi":"10.1039/d5sc02314a","DOIUrl":"https://doi.org/10.1039/d5sc02314a","url":null,"abstract":"The preparation of anisotropic mechanical force-triggering high-contrast tricolor fluorescent solid switches is very significative yet extremely challenging. Herein, we report a high-efficiency molecular engineering strategy to develop mechanochromic compounds capable of showing infrequent contrasting three-color fluorescence switching feature. Notably, 14 new symmetric fluorescent molecules by introducing a variety of substituents on either side of the central organic moiety involving 4,4'-((9H-fluoren-9-ylidene)methylene)bis(N,N-diphenylaniline) are successfully obtained, and 10 new fluorogenic compounds have been discovered to exhibit seldom-observed tricolored mechanofluorochromic phenomena. Impressively, among them, 8 luminogens demonstrate exceptionally scarce anisotropic force-triggered high-contrast three-color fluorescence responses, which is a commendable achievement, fully verifying the effectiveness of our molecular engineering strategy presented in this study. Furthermore, based on two newly developed representational mechanically responsive tricolor fluorescence switches, three advanced information anticounterfeiting systems are skillfully constructed.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"51 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252197","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

Three-state molecular switch based on terarylene photo- or redox-induced reversible isomerisation 基于三元乙烯光或氧化还原诱导可逆异构化的分子开关

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-10 DOI: 10.1039/d5sc02845k

Nicolò Baggi, Anne Léaustic, Jean-Noël Rebilly, François Mavré, Eric Rivière, Christian Herrero, François Maurel, Pei Yu

{"title":"Three-state molecular switch based on terarylene photo- or redox-induced reversible isomerisation","authors":"Nicolò Baggi, Anne Léaustic, Jean-Noël Rebilly, François Mavré, Eric Rivière, Christian Herrero, François Maurel, Pei Yu","doi":"10.1039/d5sc02845k","DOIUrl":"https://doi.org/10.1039/d5sc02845k","url":null,"abstract":"Multi-addressable molecular photoswitches whose isomerisation can be triggered not only by light, but also by other stimuli are appealing for the development of novel smart materials as well as for broadening the areas for their potential application. Diarylethenes (DAEs) are among the most studied switches for this purpose, since tailored functionalisation can make them responsive not only to UV or visible light, but also to other inputs, such as an electrochemical one. In this work, we synthesised five terarylene-based switches and investigated their photochemical and redox properties. Unlike their DAEs analogues, whose cyclisation upon an oxidation-reduction sequence is well-established, our systems undergo a similar oxidative ring-closing of the neutral open form to a doubly charged closed form while the subsequent reduction leads to ring-opening to the neutral open form. Moreover, the neutral closed form can also be re-opened by a catalytic amount of oxidant. With the support of theoretical modelling and cyclic voltammetry simulations, a general mechanism is proposed to rationalise this original bidirectional dual-responsive behaviour.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252483","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

Molecular Machine Learning Approach to Enantioselective C–H Bond Activation Reactions: From Generative AI to Experimental Validation 分子机器学习方法对映选择性C-H键激活反应：从生成人工智能到实验验证

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-10 DOI: 10.1039/d5sc01098e

Ajnabiul Hoque, Taiwei Chang, Jin-Quan Yu, Raghavan B. Sunoj

{"title":"Molecular Machine Learning Approach to Enantioselective C–H Bond Activation Reactions: From Generative AI to Experimental Validation","authors":"Ajnabiul Hoque, Taiwei Chang, Jin-Quan Yu, Raghavan B. Sunoj","doi":"10.1039/d5sc01098e","DOIUrl":"https://doi.org/10.1039/d5sc01098e","url":null,"abstract":"Molecular machine learning (ML) has gained considerable attention in recent years. Developing ML algorithms for chemical reaction prediction is a formidable task, due to the small-sized reaction data it often presents, besides the sparsity and skewed distribution. While previous ML studies offered effective predictions on known reactions, efforts in using deep generative models for guiding new reactions and their prospective validation are rare. We harness both predictive and explorative abilities of deep learning on an important catalytic asymmetric β-C(sp3)–H activation reaction, consisting of 220 experimentally reported examples that differs primarily in terms of the substrate, catalyst, and coupling partner. A transfer learning approach using a chemical language model, pretrained on 1 million unlabeled molecules followed by fine-tuning on this reaction data set, is adopted. Our ensemble prediction (EnP) model, where 30 fine-tuned CLMs concurrently predict the %ee of test set reactions, is highly reliable. Another language model, fine-tuned on the 77 known chiral ligands as used in the above reactions, is employed for generating novel ligands of high validity and novelty. A proof of concept wet-lab experimental validation reveals that most of the ML-generated reactions are in excellent agreement with the EnP predictions. Results also caution the prospects of ML-driven reaction development for ligand design and emphasize the importance of domain experts in key decisions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"458 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252486","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

Enhanced Recyclability of Methacrylic Resins by Copolymerization or Pendant Modification Using Trityl Esters 三烷基酯共聚或悬垂改性提高甲基丙烯酸树脂的可回收性

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-10 DOI: 10.1039/d5sc03190g

Yota Chiba, Shoji Hirabayashi, Yasuhiro Kohsaka

引用次数: 0

Multi-STEM MePCR: a bisulfite-free, multiplex, high-sensitive and high-specific assay to measure DNA methylation Multi-STEM MePCR：一种不含亚硫酸盐，多重，高灵敏度和高特异性的测定DNA甲基化的方法

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-10 DOI: 10.1039/d5sc01429h

Hao Yang, Jiani Qiu, Yaping Xu, Wei Ren, LinQing Zhen, Gaolian Xu, Hongchen Gu, Hong Xu

{"title":"Multi-STEM MePCR: a bisulfite-free, multiplex, high-sensitive and high-specific assay to measure DNA methylation","authors":"Hao Yang, Jiani Qiu, Yaping Xu, Wei Ren, LinQing Zhen, Gaolian Xu, Hongchen Gu, Hong Xu","doi":"10.1039/d5sc01429h","DOIUrl":"https://doi.org/10.1039/d5sc01429h","url":null,"abstract":"Aberrant CpG island methylation serves as a pivotal biomarker for cancer diagnostics, with accuracy substantially enhanced by analyzing multiple loci. Current techniques, such as bisulfite conversion or restriction enzyme-based methods, often fall short in delivering efficient multiplexed genomic methylation analysis using standard PCR platforms. Here, we introduce an innovative bisulfite-free, multiplex assay—Multiple Specific Terminal Mediated Methylation PCR (multi-STEM MePCR). This assay integrates a methylation-dependent restriction endonuclease (MDRE) with a novel multiplex PCR, leveraging innovative stem-loop structured assays for simultaneous detection of multiple CpG sites. For proof of concept, the multi-STEM MePCR platform achieves quantification of three methylation model sites simultaneously down to 10 copies per tube, accompanied by a broader linear dynamic range, and attaining a sensitivity of 0.1% against a background of 10,000 unmethylated gene copies. Crucially, by markedly minimizing cross-reactivity and reducing competition among targets, this technique adeptly distinguishes between sites exhibiting significant variations in methylation abundances. Additionally, this method effectively detects digestion products of various sizes, demonstrating clinical precision comparable to bisulfite sequencing, yet with simpler operation, shorter time, and lower cost. This multi-STEM PCR technology pioneers an advanced strategy for multiplexed methylation analysis, essential for epigenetic research and clinical DNA methylation diagnostics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144252199","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