Chemical Science最新文献_第9页

Backbone editing and deconstruction of polyethylene by Beckmann rearrangement and hydrogenolysis 贝克曼重排和氢解对聚乙烯骨架的编辑和解构

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-02 DOI: 10.1039/d5sc02684a

Jake X. Shi, Diane D. Kim, Nicodemo R. Ciccia, Pierre Lahaie-Boivin, John F. Hartwig

引用次数: 0

Atmosphere-Directed Reconstruction of Cu-based Metal-Organic Frameworks toward Efficient CO2 Electroreduction cu基金属有机骨架的大气定向重构及其高效CO2电还原

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-02 DOI: 10.1039/d5sc02601f

Jiye Feng, Danni Shi, Fei Wang, Yiming Zou, Weicheng Li, Wenbiao Zhang, Huai-Jun Lin, Yuying Meng, Qingsheng Gao

{"title":"Atmosphere-Directed Reconstruction of Cu-based Metal-Organic Frameworks toward Efficient CO2 Electroreduction","authors":"Jiye Feng, Danni Shi, Fei Wang, Yiming Zou, Weicheng Li, Wenbiao Zhang, Huai-Jun Lin, Yuying Meng, Qingsheng Gao","doi":"10.1039/d5sc02601f","DOIUrl":"https://doi.org/10.1039/d5sc02601f","url":null,"abstract":"The electrochemical reconstruction of metal-organic frameworks (MOFs) offers a promising approach for in situ fabrication of high-performance electrocatalysts. However, this innovation is often hindered by unpredictable structural transformations due to the complex thermodynamic and kinetic interplay of such multiple electrochemical and chemical processes. Herein, the reaction-atmosphere (Ar or CO2) guided reconstruction of Cu-based MOFs to Cu nanoparticles with mix-valence surface/interfaces was for the first time investigated to unravel the kinetic contribution made by intermediate chemisorption. As shown, Cu-1,3,5-benzenetricarboxylate (HKUST-1) with frangible Cu-O4 nodes undergoes thermodynamically favored reduction quickly upon applying cathodic potentials, followed by the varied surface changes kinetically governed by the intermediates of hydrogen evolution or CO2 reduction reactions (HER or CO2RR). Under an Ar atmosphere, the predominant HER increases the [OH-] of the microenvironment near cathodes and thereby boosts the re-oxidation of in-situ formed Cu toward Cu/Cu2O interfaces. Conversely, the CO2RR facilitates the strong adsorption of *CO on Cu surfaces, effectively preserving Cu(0) species. Thanks to the rich Cu/Cu2O interfaces with the lowered energy barrier for *CO-*CO coupling during the subsequent CO2RR test, the restructured electrocatalysts under Ar affords the obviously improved CO2-to-C2H4 conversion as compared with the counterpart restructured under CO2. Such atmosphere-controlled reconstruction strategy is further validated using CuBDC (BDC = 1,4-benzenedicarboxylate) with labile Cu-O4 nodes, while CuPz2 (Pz = pyrazole) with robust Cu-N4 coordination remains stable, highlighting the framework-dependent nature. These findings establish atmosphere-controlled reconstruction of metastable MOFs as a powerful tool for rational electrocatalyst design.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"44 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144192838","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}

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Oriented Design and Engineering of Advanced Metal-Organic Frameworks for Light Hydrocarbon Separations 用于轻烃分离的先进金属-有机框架定向设计与工程

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-02 DOI: 10.1039/d5sc01755f

Hujun Hujun Zhang, Jie Tang, Chunze Yu, Muyu Zhang, Jiaqi Wang, Jingui Duan

{"title":"Oriented Design and Engineering of Advanced Metal-Organic Frameworks for Light Hydrocarbon Separations","authors":"Hujun Hujun Zhang, Jie Tang, Chunze Yu, Muyu Zhang, Jiaqi Wang, Jingui Duan","doi":"10.1039/d5sc01755f","DOIUrl":"https://doi.org/10.1039/d5sc01755f","url":null,"abstract":"Light olefins, such as ethylene (C2H4) and propylene (C3H6), are essential feedstocks for the production of chemical products. However, the current purification strategy of distillation is energy-intensive and results in high carbon emissions. Adsorptive separation, the selective capture of gas from mixtures by porous materials, is considered a promising alternative or transitional technology. Metal-organic frameworks (MOFs), a kind of porous materials with highly tunable nature, have emerged as an innovative chemistry in the past two decades, offering solutions for separating these small gases. This review highlights recent advances in the design and engineering of advanced MOFs, with a focus on precise control over their pore structure and functionality for the adsorption-based purification of C2H4 and C3H6 from corresponding hydrocarbons with the same carbon number. The importance of rational design in achieving specific functionalities, such as functional sites and molecular sieving in rigid MOFs, local/global dynamics in soft MOFs, is underscored, with examples demonstrating enhanced performance in selective adsorption separation. Additionally, methods and examples of large-scale synthesis of MOFs are briefly described. The goal is to present the state-of-art chemistry and application of MOFs and to offer an outlook towards discovering and designing further new materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"134 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144192839","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

Bioorthogonal Probes for L-Form Conversion Visualization and Insights into Antimicrobial Resistance l型转化可视化的生物正交探针及抗菌药物耐药性研究

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-31 DOI: 10.1039/d5sc01586c

Yunzhe Tao, Yongwei Feng, Yu Peng, Xiang Wang, Xiangchuan Meng, Youjun Xu, Xiaowan Han, Qingyang Zhang, Hai-Yu Hu

{"title":"Bioorthogonal Probes for L-Form Conversion Visualization and Insights into Antimicrobial Resistance","authors":"Yunzhe Tao, Yongwei Feng, Yu Peng, Xiang Wang, Xiangchuan Meng, Youjun Xu, Xiaowan Han, Qingyang Zhang, Hai-Yu Hu","doi":"10.1039/d5sc01586c","DOIUrl":"https://doi.org/10.1039/d5sc01586c","url":null,"abstract":"Cell wall-deficient bacteria (CWDB) are key contributors to antimicrobial resistance (AMR), enabling persistent infections by evading antibiotics through their transition to L-form states. Therefore, molecular tools for detecting L-form conversion and AMR mechanisms are crucial for developing novel strategies against bacterial infections. Herein, we present the development of small-sized, peptidoglycan-specific fluorogenic probes employing a two-step bioorthogonal strategy that enables real-time visualization of CWDB formation. Tz-FL-S rapidly reacts with the novel D-alanine derivative TCO-D-Ala at a rate of (2.61 ± 0.07) × 103 M-1∙s-1, resulting in a 4.9-fold increase in fluorescence intensity. This platform exhibited excellent labeling of peptidoglycan in both Gram-positive and Gram-negative bacteria (Signal-to-noise ratio: 15 to 305), effectively capturing the transition from N-form to L-form. Furthermore, we investigated the impact of 14 kinds of antibiotics on L-form conversion and found 13 of them induced CWDB. Besides, we explored the relationship between L-form conversion and AMR. This research enhances our understanding of bacterial adaptations and resistance mechanisms, paving the way for innovative strategies to combat drug-resistant infections.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144184029","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

Solvent-free construction of Cr(III)-sulfonate coordination polymers Cr(III)-磺酸盐配位聚合物的无溶剂构建

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-31 DOI: 10.1039/d5sc03014e

Fan Yang, Xiang-Jing Kong, Tao He, Zhengqing Zhang, Ke Wang, Honglin Du, Guohong Cai, Jing Ju, Xiaoge Wang, Jian-Rong Li, Junliang Sun, Chongli Zhong

{"title":"Solvent-free construction of Cr(III)-sulfonate coordination polymers","authors":"Fan Yang, Xiang-Jing Kong, Tao He, Zhengqing Zhang, Ke Wang, Honglin Du, Guohong Cai, Jing Ju, Xiaoge Wang, Jian-Rong Li, Junliang Sun, Chongli Zhong","doi":"10.1039/d5sc03014e","DOIUrl":"https://doi.org/10.1039/d5sc03014e","url":null,"abstract":"Constructing sulfonate-coordinated coordination polymers (CPs) with high stability remains a significant challenge due to the relatively weak coordination ability of the sulfonate group, especially when paired with highly inert Cr3+ ion. In this study, we designed solvent-free methods to enhance Cr(III)-sulfonate coordination and further advances its reticular chemistry. For the first time, two Cr(III)-sulfonate-coordinated CPs, TGU-9 and TGU-10, were successfully constructed, along with two supramolecules, TGU-7 and TGU-8. All structures were elucidated by the 3D electron diffraction technique. Through solvent-free methods, Cr(III)-sulfonate coordination was achieved by a double displacement reaction between Cr salts and –SO3H groups. Especially, this method resulted in a counterintuitive coordination reversal from –COO– > –SO3– to –SO3– > –COO–. Reaction mechanism analysis revealed that the higher acidity of the –SO3H group, compared to the –COOH group, leads to its preferential deprotonation, thereby facilitating the kinetics of Cr-sulfonate self-assembly. Furthermore, both TGU-9 and TGU-10 exhibited exceptional long-term stability under ambient condition and over a wide pH range. They also showed high proton conductivity exceeding 10–2 S cm–1, ranking top two among the reported sulfonate-coordinated CPs. The designed solvent-free method demonstrated a generally applicable and simple strategy in designing novel metal-ligand coordination and constructing reticular chemistry, beyond the limitations of conventional solvent-based methods.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144184030","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

Extraordinary kinetic inertness of lanthanide(III) complexes of pyridine-rigidified 18-membered hexaazamacrocycle with four acetate pendant arms 吡啶刚性十八元六杂环四乙酸垂臂镧系配合物的异常动力学惰性

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-30 DOI: 10.1039/d5sc01893e

Jan Faltejsek, Peter Urbanovský, Vojtech Kubicek, Jana Havlickova, Ivana Cisarova, Jan Kotek, Petr Hermann

{"title":"Extraordinary kinetic inertness of lanthanide(III) complexes of pyridine-rigidified 18-membered hexaazamacrocycle with four acetate pendant arms","authors":"Jan Faltejsek, Peter Urbanovský, Vojtech Kubicek, Jana Havlickova, Ivana Cisarova, Jan Kotek, Petr Hermann","doi":"10.1039/d5sc01893e","DOIUrl":"https://doi.org/10.1039/d5sc01893e","url":null,"abstract":"Large polyazamacrocycles are used for the complexation of large metal ions. However, their coordination chemistry has not been frequently studied until now. An eighteen-membered macrocycle with two rigidifing pyridine rings and four aliphatic amino groups substituted with four acetic acid pendants, H4pyta, provides a large ligand cavity and coordination number (CN) up to 10. Trivalent lanthanides were chosen to study effect of metal ion size on the properties of H4pyta complexes. The complexes are formed under relatively mild conditions and two isomers were observed, depending on the Ln(III) ion, in different mutual ratios during the synthesis. Going to smaller Ln(III) ions, the CN decreases from 10 to 9. Stability constants of Ln(III)–H4pyta complexes with CN 10 are comparable with those of Ln(III)–H4dota complexes despite the lower overall basicity of H4pyta. In the ten-coordinated isomers, Ln(III) ions are perfectly 3D-wrapped inside the ligand cavity and the ligand is minimally distorted. It leads to an extreme kinetic inertness of the complexes. Dissociation of the Ln(III)–H4pyta complexes in 5 M HClO4 and at 90 C is very slow and requires up to several hours; the inertness is 102–104-times higher than that of the Ln(III)–H4dota complexes. The solid-state structures point to that the symmetric wrapping of metal ions and CN 10 are responsible for the stability of species multiply protonated on the coordinated acetate groups. The results suggest that H4pyta can be considered a leading scaffold for the future development of ligands intended for large metal ions binding in nuclear medicine, e.g. for -emitting radioisotopes from the bottom of the Periodic Table.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144184032","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

Role of Chemistry in Nature-Inspired Skin Adhesives 化学在自然皮肤粘合剂中的作用

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-30 DOI: 10.1039/d5sc01777g

Xiao Yang, Xiaonan Liu, Yeung Yeung Chau, Xuezhi Qin, Hong Zhu, Liang Peng, Kannie Wai Yan Chan, Zuankai Wang

{"title":"Role of Chemistry in Nature-Inspired Skin Adhesives","authors":"Xiao Yang, Xiaonan Liu, Yeung Yeung Chau, Xuezhi Qin, Hong Zhu, Liang Peng, Kannie Wai Yan Chan, Zuankai Wang","doi":"10.1039/d5sc01777g","DOIUrl":"https://doi.org/10.1039/d5sc01777g","url":null,"abstract":"As an essential component of wearable technology, skin adhesion plays a critical role in a wide range of wearable device applications. To maintain effectiveness and safety in daily use, skin adhesives must exhibit strong wet adhesion and high biocompatibility, particularly for devices that remain in contact with the skin for extended periods under humid and dynamic conditions. A comprehensive understanding of skin adhesion's chemical mechanisms is fundamental to advancing this technology. Nature offers valuable inspiration, as numerous organisms have evolved sophisticated chemical and physical adhesion strategies that enable strong and reversible bonding. This review begins by exploring the historical development of nature-inspired skin adhesives, followed by a detailed examination of their performance in moist environments. Particular emphasis is placed on the covalent and non-covalent interactions between adhesive materials and skin surface functional groups, considering both biocompatibility and wet adhesion properties. Additionally, we discuss strategies to mitigate hydration-related challenges alongside an overview of characterization techniques, including mechanical, chemical, and biological testing methods. The classification of nature-inspired skin adhesives into chemical and physical approaches is presented, highlighting their applications in thermal management, energy harvesting, wound care, and transdermal drug delivery. Finally, we identify current limitations and propose design strategies to guide the development of next-generation skin adhesives, providing a clear trajectory for future research.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"41 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144183888","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: Iron-catalyzed three-component 1,2-azidoalkylation of conjugated dienes via activation of aliphatic C–H bonds 修正：通过激活脂肪碳-氢键，铁催化共轭二烯的三组分1,2-叠氮烷基化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-30 DOI: 10.1039/d5sc90119g

Zhen-Yao Dai, Chenxi Lin, Derek B. Hu, Jennifer M. Schomaker

引用次数: 0

Molecular beam scattering of neon from flat jets of cold salty water 冷盐水平喷流对氖的分子束散射

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-30 DOI: 10.1039/d5sc01636c

Walt Yang, Madison M. Foreman, Tiffany C. Ly, Kevin R. Wilson, Daniel M. Neumark

{"title":"Molecular beam scattering of neon from flat jets of cold salty water","authors":"Walt Yang, Madison M. Foreman, Tiffany C. Ly, Kevin R. Wilson, Daniel M. Neumark","doi":"10.1039/d5sc01636c","DOIUrl":"https://doi.org/10.1039/d5sc01636c","url":null,"abstract":"Molecular beam scattering experiments are carried out to study collisions between Ne atoms (Ei = 24.3 kJ mol−1) and the surface of a cold salty water (8 m LiBr(aq), 230 K) flat jet. Translational energy distributions are collected as a function of scattering angle using a rotatable mass spectrometer. Impulsive scattering and thermal desorption contribute to the overall scattering distributions, but impulsive scattering dominates at all three incidence angles explored. Highly super-specular scattering is observed in the impulsive scattering channel that is attributed to anisotropic momentum transfer to the liquid surface. The thermal desorption channel exhibits a cos θ angular distribution. Compared to Ne scattering from dodecane, fractional energy loss in the impulsive scattering channel is much larger across a wide range of deflection angles. A soft-sphere model is applied to investigate the kinematics of energy transfer between the scatterer and liquid surface. Fitting to this model yields an effective surface mass of 250−60+100 amu and internal excitation of 11.8 ± 1.6 kJ mol−1, both of which are considerably larger than for Ne/dodecane. It thus appears that energy transfer to cold salty water is more efficient than to a dodecane liquid surface, a result attributed to the extensive hydrogen-bonded network of liquid water and roughness of the liquid surface.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144183889","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}

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General Palladium-Catalyzed Cross Coupling of Cyclopropenyl Esters 钯催化环丙烯酯的交叉偶联

IF 8.4 1区化学

Chemical Science Pub Date : 2025-05-30 DOI: 10.1039/d5sc03096j

Zachary P. Sercel, Ilan Marek

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