Chemical Science最新文献_第9页

Correction: Recent advances in MOF-based single-atom photocatalysts for CO2 to solar fuel conversion under sunlight irradiation 更正：基于mof的单原子光催化剂在阳光照射下将二氧化碳转化为太阳能燃料的最新进展

IF 7.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/D6SC90091G

Adnan Majeed, Minh-Khoa Duong, Van-Duc Nguyen and Trong-On Do

引用次数: 0

Beyond the Two-Conformer Model: The Role of Boat Conformers in the Stereoselectivity of SN1-Type Glycosylations 超越双构象模型：船形构象在sn1型糖基化立体选择性中的作用

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/d6sc02312f

Wouter Adriaan Remmerswaal, Daan Hoogers, Joeri Schoenmakers, F. Matthias Bickelhaupt, Thomas Hansen, Jeroen D Codee

{"title":"Beyond the Two-Conformer Model: The Role of Boat Conformers in the Stereoselectivity of SN1-Type Glycosylations","authors":"Wouter Adriaan Remmerswaal, Daan Hoogers, Joeri Schoenmakers, F. Matthias Bickelhaupt, Thomas Hansen, Jeroen D Codee","doi":"10.1039/d6sc02312f","DOIUrl":"https://doi.org/10.1039/d6sc02312f","url":null,"abstract":"Oxocarbenium ions play a central role in shaping the stereochemical outcome of SN1-type glycosylation reactions. Generally, glycosylations involving 4 H3-like glycosyl cations proceed with α-selectivity, whereas those involving 3 H4-like cations furnish β-products, reflecting favorable chair-like transition states. While this analysis holds for many glycosyl cations, it breaks down for mannosyl donors. Although the mannosyl 3 H4 cation is significantly more stable than its 4 H3 counterpart, addition of weak carbon nucleophiles predominantly yields α-products. To elucidate the origin of this deviation from the predictive two-conformer model, we examined C-allylation reactions of nucleophiles spanning three orders of magnitude in reactivity with a series of glucosyl and mannosyl-type donors (mannose, rhamnose, and mannuronic acid). Quantum chemical calculations of the competing reaction pathways show that, for mannose, glycosylation proceeds under Curtin-Hammett control via α-attack on a B2,5-like (boat) oxocarbenium ion through an OS2-type transition state that avoids the severe steric (Pauli) repulsion present along the β-1 C4 trajectory. Activation-strain and energy-decomposition analyses quantify the steric and electronic effects and explain why rhamnose, with reduced C6 steric demand, provides slightly more β-selective glycosylation reactions and mannuronic acid, of which the 3 H4 is exceptionally favorable, shows β-selectivity. The mechanistic framework provides a quantitative basis for understanding and designing stereoselective SN1-type glycosylations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"126 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147709073","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

Recent Progress in Iodate Based Nonlinear Optical Crystals 基于碘酸盐的非线性光学晶体研究进展

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/d5sc10104b

Yuwei Kang, Chun-Li Hu, Cai-Chun Zhang, Jiang-Gao Mao

{"title":"Recent Progress in Iodate Based Nonlinear Optical Crystals","authors":"Yuwei Kang, Chun-Li Hu, Cai-Chun Zhang, Jiang-Gao Mao","doi":"10.1039/d5sc10104b","DOIUrl":"https://doi.org/10.1039/d5sc10104b","url":null,"abstract":"Nonlinear optical (NLO) crystals are essential components in modern laser technology. For middle and far-infrared applications, iodates are regarded as highly promising materials due to their intrinsic non‑centrosymmetric (NCS) structures, broad optical transparency, pronounced second‑order NLO responses, and relatively high laser‑induced damage thresholds (LIDTs). However, the tendency of spontaneous crystallization in favor of thermodynamically stable centrosymmetric (CS) phases poses a significant challenge to the rational design of iodates with a macroscopic NCS framework. This review systematically summarizes recent advances over the past decade in the rational designs and controlled syntheses of NCS iodates with significant SHG responses. Emphasis is focused on five key structural‑modulation strategies: polymerization of different iodate anions, aliovalent substitution, fluorine substitution, and the synergistic integration of iodate anions with either planar π‑conjugated units or tetrahedral building blocks. These approaches collectively enhance local polarization, tune electronic structure, and optimize crystal‑growth kinetics, thereby increasing the probability of forming NCS structure and promoting the development of high‑performance iodate NLO crystals. Finally, future research directions and emerging trends in this field are outlined to provide a reference for the continued advancement of related research areas.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147709243","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

Time-resolved spectroscopy of a photoactive dinuclear W/Ru complex: spectroscopic evidence for a metastable intermediate with side-on coordinated carbonyl ligand 光活性双核W/Ru配合物的时间分辨光谱：具有侧配羰基配体的亚稳中间体的光谱证据

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/d6sc00998k

Jan-Hendrik Borter, Sayan Kangsa Banik, Kristian Kunze, Stephan Kupfer, Dirk Schwarzer, Wolfram W. Seidel

{"title":"Time-resolved spectroscopy of a photoactive dinuclear W/Ru complex: spectroscopic evidence for a metastable intermediate with side-on coordinated carbonyl ligand","authors":"Jan-Hendrik Borter, Sayan Kangsa Banik, Kristian Kunze, Stephan Kupfer, Dirk Schwarzer, Wolfram W. Seidel","doi":"10.1039/d6sc00998k","DOIUrl":"https://doi.org/10.1039/d6sc00998k","url":null,"abstract":"The photo-induced dynamics of a redox-active dinuclear W(II)/Ru(II) complex, [Tp*W(CO)Br(PyC<img alt=\"[triple bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e002.gif\"/>CCH2)–Ru(bpy)2](PF6) (2-PF6), is revealed by femtosecond infrared and UV-vis pump-probe spectroscopy in combination with quantum chemical calculations. The use of the mononuclear tungsten alkyne complex [Tp*W(CO)Br(PyC<img alt=\"[triple bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e002.gif\"/>CCH3)] (1) as a benchmark allowed an in-depth analysis of the excited state kinetics of 2-PF6. Excitation of the dinuclear complex at 400 nm produces predominantly a triplet metal-to-ligand charge transfer state localised at the Ru(bpy)2 chromophore (3MLCTbpy) with a lifetime of 6 ps. The following transformation into a tungsten-centered triplet state (3MCW) is accompanied by significant charge transfer and rearrangement of the W–C–O geometry. Subsequent intersysten crossing back to the ground state on a timescale of 12 ps produces a vibrationally excited molecule with up to 3 quanta in the CO stretching vibration. A minor fraction of 10% of the population reacts to an intermediate exhibiting a lifetime of 140 ps and a CO stretching frequency of 1703 cm−1. Our quantum chemical calculations disclose that this species corresponds to an isomer trapped in a metastable state of the S0 potential surface, with the CO bound side-on to the W centre.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"64 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696123","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

Photoinduced deacylative epoxidation of ketone derivatives with allylic peroxides 烯丙基过氧化物酮衍生物的光诱导脱酰环氧化反应

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/d6sc00898d

Jiangtao Lin, Mingqian Zhou, Ziyang Li, Jiang Duan, Xiaoyu Liu, Yue Wang, Chao Shu

引用次数: 0

A Robotic Approach to Polymerization Kinetics: A Case Study on Copolymerization Parameter Estimation 聚合动力学的机器人方法：共聚参数估计的案例研究

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/d6sc02232d

Lachlan Alexander, Vianna F Jafari, Tanja Junkers

{"title":"A Robotic Approach to Polymerization Kinetics: A Case Study on Copolymerization Parameter Estimation","authors":"Lachlan Alexander, Vianna F Jafari, Tanja Junkers","doi":"10.1039/d6sc02232d","DOIUrl":"https://doi.org/10.1039/d6sc02232d","url":null,"abstract":"Automation and high-throughput (HTP) experimentation are transforming chemistry, yet the high cost of robotic platforms limits accessibility. Pipetting robots such as the Opentrons OT-2 provide a cost-effective, open-source alternative, but their application to radical polymerization in well plates has been restricted by challenges such as deoxygenation at microliter scale. Here, we establish a robust workflow for thermal radical polymerization in 96-well plates using the OT-2, supported by custom 3D-printed components for automated NMR sample preparation. This system enables rapid and reproducible data generation while eliminating human bias from experimentation. We demonstrate its utility through the study of copolymerization kinetics, where inconsistent methods, reporting, and model selection have created significant data gaps for predictive modeling. By combining robotic HTP experimentation with IUPAC-recommended evaluation methodology, we provide standardized datasets for predicting reactivity ratios of six monomer pairs: BMA-BA (r1=2.33, r2=0.78), BMA-St (r1=0.61, r2=1.67), St-BA (r1=2.01, r2=0.40), St-MMA (r1=0.80, r2=1.02), GMA-BA (r1=1.42, r2=0.55), and GMA-St (r1 = 0.66, r2 = 1.60). Each dataset can be generated and analyzed within hours, offering a powerful automated platform for systematic polymerization studies. This work establishes the OT-2 as a practical, accessible tool for accelerating polymer research and enabling data-driven chemical discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147709247","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

Unlocking the Potential of Bi₂S₃ for Photocatalysis: A Roadmap for Next-Generation Solar Catalysts 释放Bi₂S₃光催化的潜力：下一代太阳能催化剂的路线图

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/d6sc01361a

Wei Zhao, Qing Chen, Lifeng Cai, Jie Liang, Fangxing Xiao

{"title":"Unlocking the Potential of Bi₂S₃ for Photocatalysis: A Roadmap for Next-Generation Solar Catalysts","authors":"Wei Zhao, Qing Chen, Lifeng Cai, Jie Liang, Fangxing Xiao","doi":"10.1039/d6sc01361a","DOIUrl":"https://doi.org/10.1039/d6sc01361a","url":null,"abstract":"Photocatalysis enables the direct conversion of solar energy into chemical fuels, presenting a compelling strategy to mitigate the global energy crisis and environmental pollution. However, traditional photocatalysts are severely hampered by inefficient visible-light harvesting and undesirably rapid recombination of photogenerated carriers, which bottlenecks their large-scale practical deployment. Thus, developing efficient, stable, and broadband-responsive photocatalytic materials remains a paramount research imperative. Bismuth sulfide (Bi₂S₃), a prototypical narrow-bandgap semiconductor, has recently garnered immense interest. Its judiciously positioned band edges and strong visible-light absorption confer distinct advantages for solar-driven photoredox reactions. Despite significant advances, the field still lacks a comprehensive and timely review consolidating Bi₂S₃-based artificial photosystems. This review systematically summarizes the latest progress in Bi₂S₃-based photocatalysts, with a particular focus on morphology control, heterojunction construction, elemental doping, and defect engineering. We elucidate how these strategies precisely manipulate the electronic structure, facilitate charge separation, broaden light absorption, and enhance material stability. Furthermore, we outline critical future perspectives: (i) designing novel multicomponent architectures, (ii) unraveling the kinetic mechanisms of interfacial carrier transfer, and (iii) validating scalable performance under realistic environmental conditions. This review provides a holistic roadmap for Bi₂S₃-mediated photoredox catalysis, serving as a vital resource for researchers advancing solar energy conversion technologies.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"7 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147720066","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

The mechanochemical activation of a pyrimidine dimer 嘧啶二聚体的机械化学活化

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/d6sc02165d

Xiang Gao, Gurudas Chakraborty, Felix Joel Urhahne, Marcus Lantzius-Beninga, Regina Lennarz, Jilin Fan, Kara Stappert, Jan Meisner, Robert Göstl, Andreas Herrmann

引用次数: 0

Through-space donor–acceptor homoconjugation strategies for emissive radical species 发射基种的空间给受体同偶联策略

IF 8.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/d6sc00981f

Ashton R. Davis, Yujie Zhao, Robert N. Sansone, Colleen H. McAloon, Robert G. Griffin, Timothy M. Swager

引用次数: 0

Correction: Theoretical insights into site-specific heavy-atom effects on MR-TADF emitters: modulation of spin–orbit coupling and color purity 修正：对MR-TADF发射体的特定位重原子效应的理论见解：自旋轨道耦合和颜色纯度的调制

IF 7.4 1区化学

Chemical Science Pub Date : 2026-04-17 DOI: 10.1039/D6SC90086K

Shi-Jie Ge, Jian-Rong Wu and Zuo-Quan Jiang

引用次数: 0