Chemical Science最新文献

Highly Efficient Heteronuclear Polarization Transfer by Dipolar-Echo Edited R-Symmetry Sequences in Solid-State NMR

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-21 DOI: 10.1039/d4sc07965e

Guangjin Hou, Lixin Liang, Kuizhi Chen

引用次数: 0

Role of exciton delocalization in chiroptical properties of benzothiadiazole carbon nanohoops

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-20 DOI: 10.1039/d4sc07333a

Kovida Kovida, Juraj Malinčík, Carlos M. Cruz, Araceli G. Campaña, Tomáš Šolomek

{"title":"Role of exciton delocalization in chiroptical properties of benzothiadiazole carbon nanohoops","authors":"Kovida Kovida, Juraj Malinčík, Carlos M. Cruz, Araceli G. Campaña, Tomáš Šolomek","doi":"10.1039/d4sc07333a","DOIUrl":"https://doi.org/10.1039/d4sc07333a","url":null,"abstract":"Development of chiral organic materials with a strong chiroptical response is crucial to advance technologies based on circularly polarized luminescence, enantioselective sensing, or unique optical signatures in anti-counterfeiting. The progress in the field is hampered by the lack of structure–property relationships that would help designing new chiral molecules. Here, we address this challenge by synthesis and investigation of two chiral macrocycles that integrate in their structure a pseudo-meta [2.2]paracyclophane with planar chirality and a highly fluorescent benzothiadiazole. Both compounds display remarkably red-shifted fluorescence with high quantum yields and large Stokes shifts. They differ in the extent of π-electron conjugation that allowed, for the first time, systematic examination of the effect of exciton delocalization on the absorption and luminescence of circularly polarized light. By a combination of steady-state spectroscopy and quantum chemical calculations, we constructed a unique structure–property relationship offering critical insights that will aid and abet the development of robust design guidelines for materials with strong electronic circular dichroism or circularly polarized luminescence of exceptional brightness.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858163","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 inductive eﬀect does not explain electron density in haloacetates: Are our textbooks wrong? 归纳效应无法解释卤乙酸盐中的电子密度：我们的教科书错了吗？

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-19 DOI: 10.1039/d4sc04832f

Edwin C. Johnson, Kasimir P Gregory, Hayden Robertson, Isaac Gresham, Andrew R. J. Nelson, Vincent S. J. Craig, Stuart W Prescott, Alister J Page, Grant Bruce Webber, Erica J Wanless

{"title":"The inductive eﬀect does not explain electron density in haloacetates: Are our textbooks wrong?","authors":"Edwin C. Johnson, Kasimir P Gregory, Hayden Robertson, Isaac Gresham, Andrew R. J. Nelson, Vincent S. J. Craig, Stuart W Prescott, Alister J Page, Grant Bruce Webber, Erica J Wanless","doi":"10.1039/d4sc04832f","DOIUrl":"https://doi.org/10.1039/d4sc04832f","url":null,"abstract":"The inductive effect is a central concept in chemistry and is often exemplified by the pKa values of acetic acid derivatives. The reduction in pKa is canonically attributed to the electron density of the carboxylate group being reduced through the inductive effect. However, wave functional theory calculations presented herein reveal that the charge density of the carboxylate group is not explained by the inductive effect. For a series of trihaloacetates (trichloro-, chlorodifluoro- and trifluoro-) we find that the trichloro group has the greatest reduction on the charge density of the carboxylate oxygen atoms; change in charge density is inversely related to substituent electronegativity. These puzzling results are experimentally supported by investigating three independent systems: literature gas phase acidities, specific ion effects in a model thermoresponsive polymer system, and nuclear magnetic resonance (NMR) spectroscopy of haloalkanes. Changes in the solubility of poly(N-isopropylacrylamide), PNIPAM due to the presence of different (substituted) acetates allows for ionic charge densities to be examined. These studies confirmed the unexpected charge density and substituent-electronegativity relationship. Further analysis of literature showed anomalous charge densities for haloalkanes with 13C NMR spectroscopy and gas phase acidity of polyatomic acids. In summary, these independent results show that the induction effect does not explain pKa trends across the haloacetic acids.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849330","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

Correction: FragGen: towards 3D geometry reliable fragment-based molecular generation 更正：FragGen：实现可靠的基于片段的三维几何分子生成

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-19 DOI: 10.1039/d4sc90252a

Odin Zhang, Yufei Huang, Shicheng Chen, Mengyao Yu, Xujun Zhang, Haitao Lin, Yundian Zeng, Mingyang Wang, Zhenxing Wu, Huifeng Zhao, Zaixi Zhang, Chenqing Hua, Yu Kang, Sunliang Cui, Peichen Pan, Chang-Yu Hsieh, Tingjun Hou

引用次数: 0

A Perspective on Field-effect in Energy and Environmental Catalysis

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-18 DOI: 10.1039/d4sc07740g

HuangJingWei Li, Hongmei Li, Mengzhen Du, Erjun Zhou, Wan Ru Leow, Min Liu

{"title":"A Perspective on Field-effect in Energy and Environmental Catalysis","authors":"HuangJingWei Li, Hongmei Li, Mengzhen Du, Erjun Zhou, Wan Ru Leow, Min Liu","doi":"10.1039/d4sc07740g","DOIUrl":"https://doi.org/10.1039/d4sc07740g","url":null,"abstract":"The development of catalytic technologies for sustainable energy conversion is a critical step toward addressing fossil fuel depletion and associated environmental challenges. High-efficiency catalysts are fundamental to advancing these technologies. Recently, field-effect facilitated catalytic processes have emerged as a promising approach in energy and environmental applications, including water splitting, CO₂ reduction, nitrogen reduction, organic electrosynthesis, and biomass recycling. Field-effect catalysis offers multiple advantages, such as enhancing localized reactant concentration, facilitating mass transfer, improving reactant adsorption, modifying electronic excitation and work functions, and enabling efficient charge transfer and separation. This review begins by defining and classifying field effects in catalysis, followed by an in-depth discussion on their roles and potential to guide further exploration of field-effect catalysis. To elucidate the theory-structure-activity relationship, we explore corresponding reaction mechanisms, modification strategies, and catalytic properties, highlighting their relevance to sustainable energy and environmental catalysis applications. Lastly, we offer perspectives on potential challenges that field-effect catalysis may face, aiming to provide a comprehensive understanding and future direction for this emerging area.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"64 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841662","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

Long oligos: direct chemical synthesis of genes with up to 1,728 nucleotides

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-18 DOI: 10.1039/d4sc06958g

Yipeng Yin, Reed Arneson, Yinan Yuan, Shiyue Fang

{"title":"Long oligos: direct chemical synthesis of genes with up to 1,728 nucleotides","authors":"Yipeng Yin, Reed Arneson, Yinan Yuan, Shiyue Fang","doi":"10.1039/d4sc06958g","DOIUrl":"https://doi.org/10.1039/d4sc06958g","url":null,"abstract":"The longest oligos that can be chemically synthesized are considered to be 200-mers. Here, we report direct synthesis of an 800-mer green fluorescent protein gene and a 1,728-mer Φ29 DNA polymerase gene on an automated synthesizer. Key innovations that enabled the breakthrough include conducting the synthesis on a smooth surface rather than within the pores of traditional supports, and the use of the powerful catching-by-polymerization (CBP) method for isolating the full-length oligos from complex mixture. Conducting synthesis on smooth surface not only eliminated the steric hindrance that would otherwise prevent long oligo assembly, but also, surprisingly, drastically reduced synthesis errors. Compared with the benchmark PCR assembly gene synthesis method, the direct long oligo synthesis method has the advanges of higer probability to succeed, less sequence restrictions, and being able to synthesize long oligos containing difficult elements such as unusually stable higher-order structures, long repeats, and site-specific modifications. The method is expected to open doors for various projects in areas such as synthetic biology, gene editing, and protein engineering.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"83 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841661","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

Advanced Fabrication Techniques for Polymer-Metal Nanocomposite Films: State-of-the-Art Innovations in Energy and Electronic Applications

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-18 DOI: 10.1039/d4sc04600e

MUHAMMAD tayyab, Liu Zizhe, Sajid Rauf, Zixuan Xu, Rizwan Ur Rehman Sagar, Faiz Faisal, Zuhra Tayyab, Rashid Ur Rehman, muhammad imran, anjam waheed, Rida Javed, Arunpandiyan Surulinathan, Zulakha Zafar, Xian-Zhu Fu, Jing-Li Luo

引用次数: 0

Correction: Enhanced catalytic activity of solubilised species obtained by counter-cation exchange of K{CoII1.5[FeII(CN)6]} for water oxidation

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-18 DOI: 10.1039/d4sc90243b

Yusuke Seki, Takashi Nakazono, Hiroyasu Tabe, Yusuke Yamada

引用次数: 0

Metathesis chemistry of inorganic cumulenes driven by B–O bond formation 由 B-O 键形成驱动的无机积雪烯的复分解化学

IF 8.4 1区化学

Chemical Science Pub Date : 2024-12-18 DOI: 10.1039/d4sc07487d

Jianqin Tang, Chenyang Hu, Agamemnon Crumpton, Liam Griffin, Jose M. Goicoechea, Simon Aldridge

引用次数: 0

Rational Design of a Series of Non-centrosymmetric Antiperovskite and double Antiperovskite Borate Fluorides