Chemical Science最新文献

{"title":"Enantioselective [5 + 1] cycloaddition of sulfur ylides and vinylethylene carbonates via synergistic palladium/chiral phosphonic acid catalysis","authors":"Miaolin Ke, Jinying Zheng, Jiayi Zong, Keshuang Tang, Jiahao Wang, Guohui Zheng, Boxuan Zhang, Dang Cheng, Zhiran Ju, Fener Chen","doi":"10.1039/d5sc01050k","DOIUrl":"https://doi.org/10.1039/d5sc01050k","url":null,"abstract":"An effective method for the synthesis of dihydropyrans through synergistic palladium and chiral phosphonic acid catalysis was reported. This protocol proceeded under mild reactions and provided dihydropyrans in up to 87% yield and up to 97% ee. Meanwhile, various derivations such as oxidation, Wittig-reaction, reductions, nucleophilic substitution, and Baeyer–Villiger were accomplished to furnish interesting compounds. To gain insight into the reaction mechanism, nonlinear relationship experiments and Hammett plot experiments were carried out. In addition, a range of products (<strong>3i</strong>, <strong>4b</strong>, <strong>4f</strong>, <strong>4g</strong>, and <strong>4j</strong>) accessible from this method exhibit various anti-inflammatory activities on NO and ROS inhibition.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"34 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797680","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}

{"title":"Unraveling microenvironment modification in an atomically dispersed bimetallic FeCu catalyst in the oxygen reduction reaction","authors":"Lingmin Wu, Yinghua Wang, Chunfeng Shao, Fanfei Sun, Liming Wang, Baitao Li","doi":"10.1039/d5sc00944h","DOIUrl":"https://doi.org/10.1039/d5sc00944h","url":null,"abstract":"The important effect of microstructure in Fe–Cu bimetallic catalysts on the mechanism of the oxygen reduction reaction (ORR) was theoretically and experimentally investigated. Three types of Fe sites regulated by Cu were constructed: Fe clusters modified with Cu–N<small>₄</small>, Fe–Cu dimers, and isolated Fe/Cu single atoms. A theoretical study revealed that although copper could reduce the d-band center of Fe, the Fe–Cu dimer displayed unique attributes. Notably, the dimer increased the energy of *π antibonding orbitals combined with Fe<small>²⁺</small>/Fe<small>³⁺</small>-3d and *OH-2p, accelerated *OH removal and produced the lowest predicted overpotential (0.48 V). Three catalysts featuring the above models were experimentally embedded on porous nitrogen-doped carbon. FeCu-NC-2 with Fe–Cu dimers exhibited the most positive half-wave potentials of 0.904 V in alkaline and 0.720 V in neutral solutions. A Zn–air battery and a microbial fuel cell equipped with FeCu-NC-2 as the cathodic catalyst produced stable and high power densities of 568.6 mW cm<small>⁻²</small> and 2467 mW m<small>⁻²</small>, respectively.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"59 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797708","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}

{"title":"Tailored Engineering of Primary Catalytic Sites and Secondary Coordination Spheres in Metalloenzyme-Mimetic MOF Catalysts for Boosting Efficient CO2 Conversion","authors":"Jiawei Li, Fan Yang, Benling Yu, Zhongke Dai, Shiyuan Wei, Ying Wu, Liuqing He, Fa Zhou, Jianhan Huang, You-Nian Liu","doi":"10.1039/d5sc01004g","DOIUrl":"https://doi.org/10.1039/d5sc01004g","url":null,"abstract":"The fabrication of metalloenzyme-mimetic artificial catalyst is a promising approach to achieve maximum catalytic efficiency, but the rational integration of sophisticatedly optimized primary catalytic sites (PCS) and secondary coordination spheres (SCS) for specific transformation poses a grand challenge. Here in this work, we reported the tailored engineering of Cu PCS and perfluoroalkyl SCS onto zircounium-based framework [UiO-67-(BPY-Cu)-F<small>_x</small> (x = 3, 5, 7, 11)] [BPY=2,2′-bipyridine-5,5′-dicarboxylate] that can be utilized in the highly efficient carboxylic cyclization reaction between propargylamines and flue gas CO<small>₂</small>. The perfluoroalkyl groups act as tunable SCS that can facilely adjust the surface electronegativity, hydrophobicity, as well as the CO<small>₂</small> affinity and water vapor-resistance by simply varying the chain length. Meanwhile, the synergy between the Cu PCS and perfluoroalkyl SCS significantly facilitated the cyclization step by stabilizing the critical transition state, leading to the fast cyclization to oxazolidinone ring. Owing to these features, UiO-67-(BPY-Cu)-F<small>₇</small> exhibited remarkable metalloenzyme-mimetic catalytic behavior by greatly facilitating the binding of propargylamines and CO<small>₂</small>, promoting the stabilization of the critical transition state to cyclization, and boosting the releasing of oxazolidinones, which have been systematically investigated by the combination of substrates adsorption tests, <em>in situ </em>Fourier Transform Infrared Spectra, Grand Canonical Monte Carlo simulations, density functional theory calculations, etc. Consequently, UiO-67-(BPY-Cu)-F<small>₇</small> showed outstanding catalytic performance in the carboxylic cyclization of propargylamines and flue gas CO<small>₂</small> under ambient conditions, exhibiting 64 times higher turnover frequency (TOF) than that of homogeneous or other MOF catalysts, and exhibiting the highest TOF under similar conditions. The present work not only provides an alternative strategy for the construction of advanced carboxylic cyclization system, but also paves a new direction to the development of CO<small>₂</small> conversion with exceptional activity through the tailored engineering of PCS and SCS in metalloenzyme-mimetic artificial catalyst.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797711","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}

{"title":"Switchable Colossal Anisotropic Thermal Expansion in a Spin Crossover Framework","authors":"Si-Guo Wu, Wen Cui, Ze-Yu Ruan, Zhao-Ping Ni, Ming-Liang Tong","doi":"10.1039/d4sc08032g","DOIUrl":"https://doi.org/10.1039/d4sc08032g","url":null,"abstract":"Advanced materials with tunable thermal expansion properties have garnered significant attention due to their potential applications in thermomechanical sensing and resistance to thermal stress. Here, switchable colossal anisotropic thermal expansion (ATE) behaviors are realized in a Hofmann-type framework [Fe(bpy-NH2){Au(CN)2}2]·iPrOH (Fe·iPrOH, bpy-NH2 = [4,4'-Bipyridin]-3-amine) through a three-in-one strategy: vibrational mechanism, electronic mechanism and molecular motion. Spin crossover (SCO) centers coordinate with dicyanoaurate linkers to form flexible wine-rack frameworks, which exhibits structural deformations driven by host-guest interactions with iPrOH molecules. By means of vibrational mechanism, a scissor-like motion driven by the rotation of dicyanoaurate is observed within the rhombic grids, resulting in the emergence of colossal ATE in the high temperature region. When spin transition comes into play, electronic mechanism is predominant to form reverse ATE behavior, which is associated with host-guest cooperation involving significant molecular motion of iPrOH guest and adaptive deformation of host clathrate. A remarkably high negative thermal expansion coefficient up to −7.49×105 MK−1 accompanied with abrupt SCO behavior is observed. As a proof of concept, this study opens a novel perspective for designing dynamic crystal materials with tunable thermomechanical property by integrating various ATE-related elements into a unified platform.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"36 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797707","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}

{"title":"Tuning the Electrochemical Redox Mediated Mechanism of Oxygen Evolution on Cobalt sites by Hydroxide ions Coupling","authors":"Wenjuan Song, Xiaoyue Duan, Poe Ei Phyu Win, Xiang Huang, Jiong Wang","doi":"10.1039/d5sc01674f","DOIUrl":"https://doi.org/10.1039/d5sc01674f","url":null,"abstract":"Heterogeneous molecular catalysts (HMCs) with cobalt (Co) active sites are potent for electrochemical oxygen evolution reaction (OER) in the energy conversion applications. Such catalysts are typically operative through the classical redox mediated mechanism, where dynamic equilibriums of Co<small>^2+/3+</small> and Co<small>^3+/4+</small>redox are present before and throughout the OER cycle. The generation of low-valent Co<small>²⁺</small> sites is however disadvantageous for proceeding the catalysis. To this end, sulfate groups embedded in graphene were developed to link a model Co-2, 2'-bipyridine complex toward synthesis of a novel Co based HMC, generating a specific CoN<small>₂</small>O<small>₄</small>S<small>₁</small> coordination moiety. Such molecular Co sites were induced to convert from +2 to +3 oxidation state at the open circuit condition through their proton coupled electron transfer nature. This process ultimately eliminated the generation of Co<small>²⁺</small> state from its redox equilibrium, and efficiently improved the turnover frequencies of Co sites toward OER with two-order dependence on the concentrations of OH<small>⁻</small> ions. This work provides a novel mechanistic perspective for the rational design of high-performance HMCs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"18 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797678","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}

{"title":"External Electric Field Drives the Formation of P🡪C Dative Bonds","authors":"Tingting Ma, Xubin Wang, Xinru Peng, Jiayao Li, Shiwei Yin, Yirong Mo, Changwei Wang","doi":"10.1039/d5sc01701g","DOIUrl":"https://doi.org/10.1039/d5sc01701g","url":null,"abstract":"Chemical interactions driven by external electric fields (EFs) can serve as a catalytic force for molecular machines and linkers for smart materials. In this context, the EF-driven dative bond is demonstrated through the study of interactions between PH3<small></small> and curved carbon-based nanostructures. The P→C dative bonds emerge only in the presence of EFs, whereas the interactions in the absence of EFs lead to van der Waals (vdW) complexes. The formation of EF-driven dative bonds can be verified with distinctive signals in vibrational, carbon-13 NMR, and UV/Vis spectra. The nature of EF-driven dative bonds was theoretically analyzed with the block-localized wavefunction (BLW) method and its associated energy decomposition (BLW-ED) approach. It was found that the charge transfer interaction plays a dominating role and that even in the presence of EFs, complexes dissociate to monomers once the charge transfer interaction is “turned off”. Notably, the inter-fragment orbital mixing stabilizes the complexes and alters their multipoles, leading to additional stability through field-multipole interactions. This conclusion was supported by further decomposition of the charge transfer energy component, clarifying the precise role of orbital mixing. The inter-fragment orbital mixing, which occurs exclusively in the presence of EFs, was elucidated using “in-situ” orbital correlation diagrams. Specifically, both external EFs and intermolecular perturbations remarkably reduce the energy gap between the frontier orbitals of the monomers, thereby facilitating inter-fragment orbital interactions. Significant covalency was confirmed through ab initio valence bond (VB) theory calculations of the EF-driven dative bonds, aligning with the crucial role of the charge transfer interaction. This pronounced covalency emerges as a key feature of EF-driven interactions, setting them apart from traditional dative bonds studied in parallel throughout this work.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"35 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797679","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}

{"title":"Computational framework for discovery of degradation mechanisms of organic flow battery electrolytes","authors":"Xiaotong Zhang, Piotr de Silva","doi":"10.1039/d4sc07640k","DOIUrl":"https://doi.org/10.1039/d4sc07640k","url":null,"abstract":"The stability of organic redox-active molecules is a key challenge for the long-term viability of organic redox flow batteries (ORFBs). Electrolyte degradation leads to capacity fade, reducing the efficiency and lifespan of ORFBs. To systematically investigate degradation mechanisms, we present a computational framework that automates the exploration of degradation pathways. The approach integrates local reactivity descriptors to generate reactive complexes and employs a single-ended process search to discover elementary reaction steps, including transition states and intermediates. The resulting reaction network is iteratively refined with heuristics and human-guided validation. The framework is applied to study the degradation mechanisms of quinone- and quinoxaline-based electrolytes under acidic and basic aqueous conditions. The predicted reaction pathways and degradation products align with experimental observations, highlighting key degradation modes such as Michael addition, disproportionation, dimerization, and electrochemical transformation. The framework provides a valuable tool for <em>in silico</em> screening of stable electrolyte candidates and guiding the molecular design of next-generation ORFBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"108 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819254","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}

{"title":"Machine-learning based classification of 2D-IR liquid biopsies enables stratification of melanoma relapse risk","authors":"Kelly Brown, Amy Farmer, Sabina Gurung, Matthew J. Baker, Ruth Board, Neil T. Hunt","doi":"10.1039/d5sc01526j","DOIUrl":"https://doi.org/10.1039/d5sc01526j","url":null,"abstract":"Non-linear laser spectroscopy methods such as two-dimensional infrared (2D-IR) produce large, information-rich datasets, while developments in laser technology have brought substantial increases in data collection rates. This combination of data depth and quantity creates the opportunity to unite advanced data science approaches, such as Machine Learning (ML), with 2D-IR to reveal insights that surpass those from established data interpretation methods. To demonstrate this, we show that ML and 2D-IR spectroscopy can classify blood serum samples collected from patients with melanoma according to diagnostically-relevant groupings. Using just 20 μL samples, 2D-IR measures ‘protein amide I fingerprints’, which reflect the protein profile of blood serum. A hyphenated Partial Least Squares-Support Vector Machine (PLS-SVM) model was able to classify 2D-protein fingerprints taken from 40 patients with melanoma according to the presence, absence or later development of metastatic disease. Area under the receiver operating characteristic curve (AUROC) values of 0.75 and 0.86 were obtained when identifying samples from patients who were radiologically cancer free and with metastatic disease respectively. The model was also able to classify (AUROC = 0.80) samples from a third group of patients who were radiologically cancer-free at the point of testing but would go on to develop metastatic disease within five years. This ability to identify post-treatment patients at higher risk of relapse from a spectroscopic measurement of biofluid protein content shows the potential for hybrid 2D-IR-ML analyses and raises the prospect of a new route to an optical blood-based test capable of risk stratification for melanoma patients.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"59 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813700","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}

{"title":"A Universal Strategy for Bridging Prussian Blue Analogues and Sodium Layered Oxide Cathodes: Direct Fast Conversion, Dynamic Structural Evolution, and Sodium Storage Mechanisms","authors":"Hong-Wei Li, Jingqiang Wang, Jing Yu, Jia-Yang Li, Yan-Fang Zhu, Huanhuan Dong, Zhijia Zhang, Yong Jiang, Shi Xue Dou, Yao Xiao","doi":"10.1039/d5sc01550b","DOIUrl":"https://doi.org/10.1039/d5sc01550b","url":null,"abstract":"Prussian blue analogues (PBAs) are widely recognized as one of the most promising cathode materials for sodium-ion batteries (SIBs). However, many unqualified PBAs with unsatisfactory electrochemical performance are difficult to dispose of and pose a risk of environmental contamination. Additionally, the production process of layered oxides, another popular cathode material for SIBs, requires prolonged high-temperature sintering, resulting in significant energy consumption. To address the aforementioned issues, a \"two birds with one stone\" strategy is proposed. This approach not only demonstrates the feasibility of directly preparing layered oxides with PBAs as precursors through a fast sintering process but also simultaneously addresses the challenge of treating unqualified PBAs while minimizing excessive energy consumption during the preparation of layered oxides. Furthermore, a series of binary, ternary, and quaternary layered oxides were synthesized directly by utilizing PBAs with varying compositions, showcasing the universality of this strategy. This innovative approach breaks the boundaries between different types of sodium cathode materials and builds a distinctive bridge for the direct conversion of PBAs into layered oxides, thereby widening the feasibility of the cathode for SIBs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782938","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}

{"title":"Interlayer Engineering-Induced Charge Redistribution in Bi2Te3 toward Efficient Zn2+ and NH4+ Storage","authors":"Xiaojie Liang, Fangzhong Liu, Haonan Yue, Yaoyong Dong, Lijuan Chen, Ting Song, Yong Pei, Xianyou Wang, Bei Long, Yao Xiao, Xiong-Wei Wu","doi":"10.1039/d5sc01210d","DOIUrl":"https://doi.org/10.1039/d5sc01210d","url":null,"abstract":"Bismuth-based materials show promise for aqueous energy storage systems due to their unique layered structures and high storage capacity. Some bismuth-based materials have been applied to storage Zn2+ or NH4+, indicating that one bismuth-based compound may be innovatively used in both zinc-ion and ammonium-ion batteries (ZIBs and AIBs). Herein, we successfully design a poly(3,4-ethylenedioxythiophene) (PEDOT) coated and embedded Bi2Te3 (Bi2Te3@PEDOT). Theoretical calculations and experimental researches demonstrate that the PEDOT coating and its intercalation into the interlayer enhance the structural stability of Bi2Te3 and significantly improve the storage capacities for Zn2+ and NH4+. The PEDOT intercalation results in an increased interlayer spacing and a charge redistribution in the interlayer, facilitating the charge transfer. Additionally, the insertion-type mechanism of Zn2+ and NH4+ in Bi2Te3@PEDOT is revealed through ex-situ tests. The optimized electrode (5 mg cm−2) exhibits high discharge capacities of 385 mA h g−1 in ZIBs and 235 mA h g−1 in AIBs at 0.2 A g−1 and a long-term cycle stability. Bi2Te3@PEDOT performs robustly even at a high mass loading of 10 mg cm−2. Bi2Te3@PEDOT//MnO2 (ZIBs) and Bi2Te3@PEDOT//ZnMn2O4 (AIBs) full cells offer high reversible capacities. This work provides a reference for designing bifunctional energy storage materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"234 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782889","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}