Chemical Science最新文献

Facile N-C Bond Cleavage and Arene Reduction by a Transient Uranium (II) Complex 瞬态铀（II）配合物的易溶N-C键裂解和芳烃还原

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-02 DOI: 10.1039/d5sc03694a

R. A. Keerthi Shivaraam, Leonor Maria, Thayalan Rajeshkumar, Rosario Scopelliti, Ivica Zivkovic, andrzej sienkiewicz, Laurent Maron, Marinella Mazzanti

{"title":"Facile N-C Bond Cleavage and Arene Reduction by a Transient Uranium (II) Complex","authors":"R. A. Keerthi Shivaraam, Leonor Maria, Thayalan Rajeshkumar, Rosario Scopelliti, Ivica Zivkovic, andrzej sienkiewicz, Laurent Maron, Marinella Mazzanti","doi":"10.1039/d5sc03694a","DOIUrl":"https://doi.org/10.1039/d5sc03694a","url":null,"abstract":"Complexes of uranium(II) remain extremely rare and their reactivity is practically unexplored. Here we report that the reduction of the heteroleptic bis-aryloxide U(III) complex [U(κ6-{(tBu2ArO)2Me2-cyclam})I], A, yields a rare and highly reactive U(II) intermediate that enables a rare example of intramolecular uranium mediated N-C cleavage and effects arene reduction resulting in the isolation of the U(IV) complex [U(κ7-{(tBu2ArO)(tBu2ArO-κ2-N,C)Me2-cyclam})] (2) and of the inverse-sandwich complex [{U(κ5-{(tBu2ArO)2Me2-cyclam})}2(μ-η6:η6-benzene)] (3) respectively. Moreover, the U(II) solvent-dependent reactivity results in the formation of a putative U-N2 complex in diethyl ether. Computational, EPR and magnetic studies indicate the electronic structure of 3 to be an equilibrium between two possible electronic structures very close in energy: (U(IV) -arene4- -U(IV) and U(III) -arene2- -U(III)). These results indicate that polydentate amine-phenolate ligands can be used to access highly reactive U(II) intermediates and that provides evidence that U(II) species are involved in the formation of inverse sandwich complexes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"10 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533805","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

Thermal proteome profiling of itaconate interactome in macrophages 巨噬细胞衣康酸相互作用蛋白的热蛋白质组学分析

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-02 DOI: 10.1039/d5sc02378e

Yunzhu Meng, Tiantian Wei, Chenlin Zhang, Anqi Yu, Yuan Liu, Junyu Xiao, Chu Wang

{"title":"Thermal proteome profiling of itaconate interactome in macrophages","authors":"Yunzhu Meng, Tiantian Wei, Chenlin Zhang, Anqi Yu, Yuan Liu, Junyu Xiao, Chu Wang","doi":"10.1039/d5sc02378e","DOIUrl":"https://doi.org/10.1039/d5sc02378e","url":null,"abstract":"Itaconate (ITA) is an upregulated immunometabolite in macrophages during pathogen infection. It is known to influence oxidation stress, cellular metabolism, programmed cell death and many other biological processes to regulate the immune response via interaction with proteins. Previous studies capture covalently ITA-modified proteins by activity-based proteome profiling with bioorthogonal chemical probes; however, how itaconate interacts non-covalently with other proteins at the proteome level remains unexplored. Here we applied thermal proteome profiling (TPP) to globally identify a large number of ITA-interacting proteins in macrophage proteomes. Among these targets, we verified mitochondrial branched-chain aminotransferase (BCAT2) as a novel non-covalent binding target of itaconate via biochemical and structural experiments. The binding of itaconate could inhibit transamination activity of BCAT and regulate the metabolism of branched-chain amino acids (BCAAs) in lipopolysaccharide (LPS)-activated inflammatory macrophages. This study offers a valuable resource that helps decipher novel and comprehensive functions of ITA in macrophages during the immune response and other related biological processes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533804","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

A perspective of Emerging trends in integrated PFAS detection and remediation technologies with data driven approaches 综合PFAS检测和修复技术与数据驱动方法的新兴趋势的观点

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-02 DOI: 10.1039/d5sc01624j

Samaneh Yaghoobian, Manuel Alejandro Ramirez Ubillus, Lei Zhai, Jae-Hoon Hwang

{"title":"A perspective of Emerging trends in integrated PFAS detection and remediation technologies with data driven approaches","authors":"Samaneh Yaghoobian, Manuel Alejandro Ramirez Ubillus, Lei Zhai, Jae-Hoon Hwang","doi":"10.1039/d5sc01624j","DOIUrl":"https://doi.org/10.1039/d5sc01624j","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) are highly persistent synthetic chemicals that pose severe environmental and health risks, prompting increasingly stringent regulations. The recent crises caused by PFAS contamination underscore the urgent need for rapid, sensitive, and on-site monitoring, along with effective removal and degradation from water sources. To address these challenges, a key future direction involves integrating detection with remediation, shifting from a singular focus to a comprehensive approach that facilitates both monitoring and elimination. This integration enhances cost-effectiveness, real-time process control, and treatment efficiency, ensuring proactive PFAS mitigation. Additionally, artificial intelligence (AI) and machine learning (ML) are emerging as powerful data-driven tools for optimizing detection sensitivity and treatment performance, offering new opportunities for improving integrated PFAS management systems. This perspective critically evaluates the advancements, challenges, and future potential of integrated detection-remediation strategies for scalable PFAS management in water systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"92 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533802","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

Electrochemical Ammonia Oxidation with a Homogeneous Molecular Redox Mediator 均相分子氧化还原介质的电化学氨氧化研究

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-02 DOI: 10.1039/d5sc00730e

Tarisha Gupta, Sanyam ., Shivani Saraswat, Anirban Mondal, Biswajit Mondal

引用次数: 0

Correction: A planar pentacoordinate oxygen in the experimentally observed [Be5O6]2− dianion 修正：在实验中观察到的[Be5O6]2−离子中的一个平面五座标氧

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-02 DOI: 10.1039/d5sc90136g

Rui Sun, Yang Yang, Xin Wu, Hua-Jin Zhai, Caixia Yuan, Yan-Bo Wu

引用次数: 0

Macrocyclization of backbone N-methylated peptides by a prolyl oligopeptidase with a distinctive substrate recognition mechanism 具有独特底物识别机制的脯氨酸寡肽酶对主干n -甲基化肽的大环化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-02 DOI: 10.1039/d5sc03723a

Emmanuel Matabaro, Haigang Song, Lukas Sonderegger, Fabio Gherlone, Andrew Giltrap, Samuel Liver, Alvar Gossert, Markus Künzler, James H Naismith

{"title":"Macrocyclization of backbone N-methylated peptides by a prolyl oligopeptidase with a distinctive substrate recognition mechanism","authors":"Emmanuel Matabaro, Haigang Song, Lukas Sonderegger, Fabio Gherlone, Andrew Giltrap, Samuel Liver, Alvar Gossert, Markus Künzler, James H Naismith","doi":"10.1039/d5sc03723a","DOIUrl":"https://doi.org/10.1039/d5sc03723a","url":null,"abstract":"Macrocyclization and multiple backbone N-methylations can significantly improve the pharmacological properties of peptides. Since chemical synthesis of such compounds is often challenging, enzyme-based production platforms are an interesting option. Here, we characterized OphP, a serine peptidase involved in the cyclization of omphalotins, a group of ribosomally produced dodecapeptides with multiple backbone N-methylations. OphP displays robust peptidase and macrocyclase activity towards multiply α-N-methylated peptides of various lengths and composition derived from the omphalotin precursor protein OphMA. In addition, OphP processes, with lower efficiency, peptides unrelated to OphMA, containing a MeGly, MeAla or Pro residue at the P1 site. Structural analysis reveals that OphP adopts a canonical prolyl oligopeptidase fold but, unlike other enzymes of this enzyme family, recognizes its substrates by their hydrophobic and multiply backbone N-methylated core rather than by the follower peptide. The activity of OphP could be harnessed for the enzymatic production of therapeutic peptides.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"68 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533850","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

Probing substrate binding and release events in iridium-catalysed hydrogen isotope exchange reactions 探测铱催化氢同位素交换反应中的底物结合和释放事件

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-01 DOI: 10.1039/d5sc00759c

Daria S. Timofeeva, William J. Kerr, David M. Lindsay, David J. Nelson

{"title":"Probing substrate binding and release events in iridium-catalysed hydrogen isotope exchange reactions","authors":"Daria S. Timofeeva, William J. Kerr, David M. Lindsay, David J. Nelson","doi":"10.1039/d5sc00759c","DOIUrl":"https://doi.org/10.1039/d5sc00759c","url":null,"abstract":"Directed, metal-catalysed C–H activation reactions rely on the binding of a Lewis basic functional group to the metal centre to ensure precise control of regioselectivity. However, groups that bind the metal centre too strongly have the potential to decrease turnover frequency and inhibit productive catalysis. Herein, we have used kinetic studies of iridium-catalysed hydrogen isotope exchange reactions, with NMR spectroscopy and mass spectrometry as the analytical techniques, to investigate the binding and release behaviour of a representative series of monosubsituted aromatic systems bearing a Lewis basic directing group. It was found that pyridine and pyrimidine exhibit anomalous behaviour, with a single-binding/dual labelling process dominating, or at least being competitive with, a binding/labelling/dissociation pathway. In contrast, with other directing groups (e.g. ketone, nitro, ester) initial formation of an appreciable population of d1-isotopologue is observed, and this is subsequently converted to the corresponding d2-isotopologue, suggesting a mainly binding/labelling/dissociation pathway. These data reveal three classes of substrate with rather different behaviour and for which reaction design and optimisation needs to be approached rather differently.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"87 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521318","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

High throughput screening for the design of protein binding polymers 高通量筛选设计蛋白质结合聚合物

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-01 DOI: 10.1039/d5sc04391c

Carolin Bapp, Ahmed Z. Mustafa, Cheng Cao, Erica J. Wanless, Martina H. Stenzel, Robert Chapman

{"title":"High throughput screening for the design of protein binding polymers","authors":"Carolin Bapp, Ahmed Z. Mustafa, Cheng Cao, Erica J. Wanless, Martina H. Stenzel, Robert Chapman","doi":"10.1039/d5sc04391c","DOIUrl":"https://doi.org/10.1039/d5sc04391c","url":null,"abstract":"Using polymers for protein encapsulation can enhance stability in processing environments and prolong activity and half-life in vivo. However, finding the best polymer structure for a target protein can be difficult, labour- and cost-intensive. In this study we introduce a high throughput screening approach to identify strong polymer–protein interactions by use of Förster Resonance Energy Transfer (FRET), enabling a rapid read out. We iteratively screened a total of 288 polymers containing varying hydrophilic, hydrophobic, anionic and cationic monomers against a panel of eight different enzymes (glucose oxidase, uricase, manganese peroxidase, bovine serum albumin, carbonic anhydrase, lysozyme, trypsin and casein). By optimisation of the assay conditions it was possible to read out strongly binding polymers at protein concentrations down to 0.1 μM. We were able to use the screening data to locate moderately selective polymer binders in most cases, and elucidate general trends in polymer design that lead to strong binding. Interestingly, these trends are not consistent across proteins, underscoring the value of a screening approach for identification of the best polymers. We applied this technique to identify lead polymers suitable for encapsulation of the important therapeutic protein TNF-related apoptosis-inducing ligand (TRAIL), at a concentration of 0.25 μM (5 μg mL−1). This approach should be valuable in the design of polymers for either selective protein binding, or for universal protein repulsion, particularly where the protein is too expensive to work with at high concentrations and large volumes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521245","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

Ensembles of cationic conjugated polymer and anionic platinum(II) complexes: from FRET properties to application studies in E. coli imaging and singlet oxygen generation 阳离子共轭聚合物和阴离子铂（II）配合物的集合：从FRET性质到大肠杆菌成像和单线态氧生成的应用研究

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-01 DOI: 10.1039/d5sc01244a

Angela Lok-Yin So, Jungu Guo, Huanxiang Yuan, Qi Shen, Eric Ka-Ho Wong, Shu Wang, Vivian Wing-Wah Yam

{"title":"Ensembles of cationic conjugated polymer and anionic platinum(II) complexes: from FRET properties to application studies in E. coli imaging and singlet oxygen generation","authors":"Angela Lok-Yin So, Jungu Guo, Huanxiang Yuan, Qi Shen, Eric Ka-Ho Wong, Shu Wang, Vivian Wing-Wah Yam","doi":"10.1039/d5sc01244a","DOIUrl":"https://doi.org/10.1039/d5sc01244a","url":null,"abstract":"A series of anionic alkynylplatinum(II) complexes with terpyridine (tpy) or 2,6-bis(benzimidazol-2′-yl)pyridine (bzimpy) as the tridentate N-donor pincer ligand has been synthesized and characterized. These complexes are found to form ensembles with a cationic poly(fluorene-co-phenylene) derivative (PFP-NMe3+) through electrostatic, Pt(II)⋯Pt(II) and π–π stacking interactions. Förster resonance energy transfer (FRET) has been found to take place, consequently gave rise to fluorescence quenching of the polymer donor and the emergence of low-energy emission from the platinum(II) complex assemblies. The spectroscopic and FRET properties of the two-component systems have been investigated by UV-vis absorption, emission and Stern–Volmer quenching studies. Pathogen imaging and photodynamic therapy (PDT) studies using the polymer–platinum(II) complex ensembles have demonstrated better performance compared to that using PFP-NMe3+ only, which highlights the potential of this class of ensembles for various biological applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521313","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

Electrochemical promoted defluorinative sulfoximination and fluorosulfonylation of non-activated aryl fluorides at room temperature 电化学促进非活化芳基氟化物在室温下的去氟亚胺化和氟磺化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-07-01 DOI: 10.1039/d5sc03674g

Xianqiang Kong, Yiyi Chen, Shuangquan Zhang, Kun Feng, Xiaohui Chen, Lin-Hui Dong, Meng-Hua Li, Yuanqing Xu, ZhongYan Cao

{"title":"Electrochemical promoted defluorinative sulfoximination and fluorosulfonylation of non-activated aryl fluorides at room temperature","authors":"Xianqiang Kong, Yiyi Chen, Shuangquan Zhang, Kun Feng, Xiaohui Chen, Lin-Hui Dong, Meng-Hua Li, Yuanqing Xu, ZhongYan Cao","doi":"10.1039/d5sc03674g","DOIUrl":"https://doi.org/10.1039/d5sc03674g","url":null,"abstract":"Due to the high bond dissociation energy and kinetic inertness of the C–F bond, direct activation of inert aryl fluorides for new transformations under mild conditions remains a significant challenge. Although it has been known that single electron reduction can be applied for the activation of inert aryl fluorides at room temperature, the need for very strong reduction conditions along with the competitive side reactions during the reduction process limits the synthetic applications. Herein, by leveraging the advantages of electrosynthesis and the versatile transformation nature of aryl radicals, two types of challenging defluorinative transformations of non-activated aryl fluorides which include the sulfoximination via cheap nickel catalysis and the transition metal catalyst-free fluorosulfonylation at room temperature have been disclosed for the first time. These reactions show good functional group tolerance and can be applied for the late-stage modifications of bioactive derivatives. As for the practical nickel-catalyzed defluorinative sulfoximination, detailed mechanistic studies reveal that after the cathodic reduction of aryl fluorides to form the key aryl radical, a subsequent nickel-promoted C–N bond formation via paired electrolysis is responsible for the success.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521315","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