Chemical Science最新文献_第2页

Insights into bifunctional active sites of Pt-MoO3/TiO2 catalyst enabling selective hydrogenation of amino acid Pt-MoO3/TiO2催化氨基酸选择性加氢的双功能活性位点研究

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-09 DOI: 10.1039/d5sc05792b

Yundao Jing, Xiaohu Ge, Rui Song, Ningchao Zhu, Jinquan Ming, Nihong An, Yueqiang Cao, Gang Qian, Xuezhi Duan, Xing-Gui Zhou

{"title":"Insights into bifunctional active sites of Pt-MoO3/TiO2 catalyst enabling selective hydrogenation of amino acid","authors":"Yundao Jing, Xiaohu Ge, Rui Song, Ningchao Zhu, Jinquan Ming, Nihong An, Yueqiang Cao, Gang Qian, Xuezhi Duan, Xing-Gui Zhou","doi":"10.1039/d5sc05792b","DOIUrl":"https://doi.org/10.1039/d5sc05792b","url":null,"abstract":"Selective hydrogenation of amino acids to amino alcohols is a valuable transformation in the synthesis of pharmaceuticals, fine chemicals, and chiral building blocks. However, achieving high activity and selectivity under mild conditions remains challenging due to the need for simultaneous hydrogen activation and substrate coordination. Here, we report a series of Pt–MoO3 bifunctional catalysts for the hydrogenation of L-alanine (Ala) to alaninol (AlaOH), with a focus on tuning metal–oxide synergy. Structural and electronic characterization by high-angle annular dark-field scanning transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy reveal strong Pt–MoO3 interactions, characterized by partial electron transfer. Catalytic tests reveal a volcano-type dependence on Pt/Mo ratio, with the 4-Pt-MoO3 catalyst achieving the highest performance. The experiments of H2 temperature programmed desorption and in-situ diffuse reflectance infrared Fourier transform spectroscopy combined with theoretical calculations support a bifunctional mechanism, in which Pt serves as the primary site for H2 activation, while MoO3 facilitates adsorption and stabilization of polar alanine. Further tuning via thermal treatments show that the moderate treatment at 500 °C optimally balances the redox state of MoO3 without compromising Pt dispersion, leading to enhanced hydrogenation performance. This work not only advances understanding of metal-oxide interfacial catalysis but also provides a rational design strategy for efficient and selective hydrogenation amino acid.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247399","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 reflection on modelling and examination of paramagnetic molecules for magnetic storage and molecular spintronics 磁存储和分子自旋电子学中顺磁分子的建模和检验的思考

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-09 DOI: 10.1039/d5sc90219c

Mihail Atanasov, Shashank Vittal Rao, Frank Neese

引用次数: 0

Engineering Pd-based Charge-Asymmetrical Metal Pair Sites to Promote *CHO-CHO Coupling for Selective CO2 Photoreduction to C2H4 工程钯基电荷-不对称金属对位点促进*CHO-CHO偶联选择性CO2光还原为C2H4

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-09 DOI: 10.1039/d5sc05310b

Yi Zhu, Zhijie Pan, Wenbin Liao, Wenbiao Zhang, Qun Liao, Yuanming Zhang, Qingsheng Gao, Xionghui Fu, Mingyao Zhao

{"title":"Engineering Pd-based Charge-Asymmetrical Metal Pair Sites to Promote *CHO-CHO Coupling for Selective CO2 Photoreduction to C2H4","authors":"Yi Zhu, Zhijie Pan, Wenbin Liao, Wenbiao Zhang, Qun Liao, Yuanming Zhang, Qingsheng Gao, Xionghui Fu, Mingyao Zhao","doi":"10.1039/d5sc05310b","DOIUrl":"https://doi.org/10.1039/d5sc05310b","url":null,"abstract":"The photoreduction of CO2 to C2+ products is primarily limited by the kinetic challenges of C-C coupling. Here, we engineer Pd-based charge-asymmetrical metal pair sites to accommodate the energetically favourable CHO-CHO coupling pathway, accomplishing the topmost activity and selectivity toward C2H4. The as-designed Pd-loaded CdS nanospheres Pd/CdS-Sv) featured the Pd-Cd charge-asymmetrical sites co-manipulated by variable Pd loading and sulfur vacancies. They afford the C2H4 evolution rate as high as 14.2 μmol·g-1·h-1, with a selectivity of up to 81.6%, which outperform most of reported photocatalysts. In situ diffuse reflectance infrared Fourier transform spectra distinctly identify the favourable CHO-CHO coupling pathway on Pd/CdS-Sv, which benefits from the obviously shortened C-C bond of 1.453 Å on the Pd-Cd sites as compared to that in CO dimerization 3.508 Å) according to theoretical calculations. The introduction of Pd promotes water dissociation and provides sufficient H to enable the conversion of CO to CHO, and more importantly lowers the energy barrier of the CHO-CHO coupling on the charge-asymmetrical pair sites from 0.37 eV to -0.29 eV, thereby avoiding the sluggish CO-CO dimerization. Gaining new insights into engineering charge-asymmetrical sites to effectively perform C-C coupling pathways, this work will expedite the catalyst exploitation for CO2 photoreduction.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"52 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247400","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

Towards automatically verifying chemical structures: the powerful combination of 1H NMR and IR spectroscopy 自动验证化学结构：1H NMR和IR光谱的强大结合

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-09 DOI: 10.1039/d5sc06866e

J. Benji Rowlands, Lina Jonsson, Jonathan Goodman, Peter Howe, Werngard Czechtizky, Tomas Leek, Richard James Lewis

{"title":"Towards automatically verifying chemical structures: the powerful combination of 1H NMR and IR spectroscopy","authors":"J. Benji Rowlands, Lina Jonsson, Jonathan Goodman, Peter Howe, Werngard Czechtizky, Tomas Leek, Richard James Lewis","doi":"10.1039/d5sc06866e","DOIUrl":"https://doi.org/10.1039/d5sc06866e","url":null,"abstract":"Human interpretation of spectroscopic data remains key to confirming newly synthesised chemical structures. Whilst there have been advances in automated spectral interpretation, the false positive and false negative rates remain too high to replace human interpretation. One approach, Automated Structure Verification (ASV), scores observed nuclear magnetic resonance (NMR) spectra against predicted NMR spectra. We describe a method to extend this approach to infrared (IR) spectra and apply it alongside proton NMR spectra to distinguish between a challenging set of 99 similar isomer pairs. Based on relative scores, we classify each as correct, incorrect or unsolved. Our results show that IR can be used as an efficient automated method to distinguish similar isomers with an accuracy close to that of proton NMR. We further introduce a method to combine NMR and IR results and show that the combination significantly outperforms either technique alone. At a true positive rate of 90%, unsolved pairs are reduced to 0-15% using NMR and IR together compared to 27-49% using individual techniques alone. At a true positive rate of 95%, they are reduced to 15-30% from 39-70%. These results are a significant step towards efficient automated structure verification based on easily measured spectroscopy data.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"17 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247395","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

Photocatalytic Synthesis of Homoallylic Amines via Nucleophilic Addition of Nickel Allyl Complexes to Imines 镍烯丙基配合物在亚胺上亲核加成的光催化合成同丙烯基胺

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-09 DOI: 10.1039/d5sc06916e

Christoph Nopper, Niclas Müller, Beloslava Goycheva, Felix Himmelsbach, Felix Bauer, Bernhard Breit

引用次数: 0

Antioxidant Activity at the Molecular Level: Exploring Ways of Action and Computational Tools to Investigate them 分子水平的抗氧化活性：探索作用方式和研究它们的计算工具

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-09 DOI: 10.1039/d5sc05463j

Annia Galano

{"title":"Antioxidant Activity at the Molecular Level: Exploring Ways of Action and Computational Tools to Investigate them","authors":"Annia Galano","doi":"10.1039/d5sc05463j","DOIUrl":"https://doi.org/10.1039/d5sc05463j","url":null,"abstract":"Despite their apparent simplicity, antioxidants are involved in numerous and complex processes. Several key aspects of antioxidant chemistry are covered in this review. (I) Their ways of action, which include scavenging free radicals; inhibition of the •OH production via Fenton-like reactions by chelating redox metals; the repair of oxidatively-damaged biomolecules; and modulation of the antioxidant/oxidant enzymatic system. (II) The main mechanisms involved in those ways of action, such as formal hydrogen atom transfer (f-HAT), single electron transfer (SET), sequential proton lost electron transfer (SPLET), coupled-deprotonation-chelation mechanism (CDCM), oxidant-enzyme inhibition, and antioxidant-enzyme activation. (III) Computational tools aiming to explore antioxidant activity (AOX). They are roughly grouped into four categories, depending on the used strategy (calculated properties) in: reactivity descriptors, thermochemistry, kinetics and ligand-receptor interactions. The approaches used to estimate them include calculations based on activity-structure relationships, quantum mechanical calculations, and molecular docking. The limitations and advantages of using these strategies and approaches are discussed, as well as some key points related to mimicking the associated chemical reactions (e.g. the importance of solvent polarity, pH, and diffusion). (IV) Some future research directions in the field, like the computational design of new (more efficient) antioxidants, and the emerging role of machine learning (ML) and artificial intelligence (AI) as efficient strategies to address AOX. , can contribute to gain a more complete picture about the complex chemical behavior usually involved in the health benefits offered by antioxidants.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145247398","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

Quantitative and spatially defined functionalization of nanostructures by overcoming the strong steric hindrance through bioinspired nucleobase interactions 通过生物激发的核碱基相互作用克服强位阻，定量和空间定义的纳米结构功能化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05777a

Huijuan Chen, Yuan Xue, Nan Yao, Rong Cheng, Jia Liu, Jiawen Bao, Zan Hua

{"title":"Quantitative and spatially defined functionalization of nanostructures by overcoming the strong steric hindrance through bioinspired nucleobase interactions","authors":"Huijuan Chen, Yuan Xue, Nan Yao, Rong Cheng, Jia Liu, Jiawen Bao, Zan Hua","doi":"10.1039/d5sc05777a","DOIUrl":"https://doi.org/10.1039/d5sc05777a","url":null,"abstract":"Polymer nanostructures with controlled and uniform sizes, tunable surface properties, and spatially defined functionalities are highly pursued by scientists. However, precise control of tailored nanostructures still represents a formidable challenge. Herein, we have successfully developed an efficient and modular route for elegantly functionalizing polymer nanostructures by harnessing robust bioinspired nucleobase interactions of polymers for overcoming the strong steric hindrance. Adenine-containing core-crosslinked nanostructures were rationally designed and fabricated with numerous pendant adenines in the hydrophobic shell layer. Although the adenine-containing hydrophobic shell layer was effectively stabilized by the hydrophilic corona layer, extraordinary multiple hydrogen bonds between bioinspired complementary nucleobase-containing polymers are capable of overcoming the strong steric hindrance for efficient binding. Bioinspired hydrogen bonding interactions of nucleobases display excellent selectivity, superior efficiency, and high association constants. Therefore, it is facile and feasible to tailor the sizes, surface properties, and functionalities of polymer nanostructures through bioinspired nucleobase interactions. Meanwhile, the modular strong interactions of complementary nucleobases enable us to achieve the quantitative core and surface functionalization of synthetic polymer nanostructures. Thus, this work provides a novel and modular strategy for fabricating well-defined nanostructures, which is promising to furnish scalable and elegant nanomaterials for various biological applications such as precise nanovaccines and nanomedicines.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241611","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

Design and Synthesis of Single-Atom Layer Bimetallic Clusters for Dehydrogenative Silylation of Water and Alcohols 水和醇脱氢硅基化单原子层双金属团簇的设计与合成

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05053g

Chunying Chen, Qijie Mo, Fuzhen Li, Haili Song, Qingsheng Gao, Li Zhang

{"title":"Design and Synthesis of Single-Atom Layer Bimetallic Clusters for Dehydrogenative Silylation of Water and Alcohols","authors":"Chunying Chen, Qijie Mo, Fuzhen Li, Haili Song, Qingsheng Gao, Li Zhang","doi":"10.1039/d5sc05053g","DOIUrl":"https://doi.org/10.1039/d5sc05053g","url":null,"abstract":"Single-atom layer clusters (SLCs) have demonstrated high catalytic potentials owing to the fully exposed metal sites, alloying effects and unique electronic structures. However, it is challenging for the precise fabrication of bimetallic SLCs on a support. Herein, a range of bimetallic M1M2-SLCs (M1M2 = PdNi, PtCu, PtNi) with abundant and high-density diatomic alloy sites were precisely anchored onto the carboxyl-functionalized carbon nanotubes (CNTs). Catalytic results showed that the resultant composite of PdNi-SLCs/CNTs was efficient for catalytic dehydrogenative silylation of H2O and alcohols, giving rise to diverse silanols and alkoxysilanes, respectively, in high yields. Especially, the turnover frequency and maximum turnover number of PdNi-SLCs/CNTs-catalyzed dehydrogenative silylation of water were up to 187 s–1 and 964,737 based on Pd, respectively. Reaction mechanism studies revealed that the high catalytic performance was primarily attributed to fully exposed structure of PdNi-SLCs and the cooperation between the Pdδ- – Niδ+ bimetallic clusters with asymmetric charge distribution, in which Pd rapidly dissociated the Si-H bond of silane, and meanwhile the adjacent Ni-mediated H2O activation promoted the cleavage of O–H bond, thereby facilitating the formation of silanol.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"475 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241612","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

Interstellar Formation of 1,2-Propanediol (CH3CH(OH)CH2OH) and 1,2-Ethenediol (HOCHCHOH) — Key Precursors to Sugars and Sugar Derivatives 1,2-丙二醇（CH3CH(OH)CH2OH）和1,2-乙二醇（HOCHCHOH）的星际形成-糖和糖衍生物的关键前体

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05315c

Jia Wang, Chaojiang Zhang, André K. Eckhardt, Ralf I. Kaiser

{"title":"Interstellar Formation of 1,2-Propanediol (CH3CH(OH)CH2OH) and 1,2-Ethenediol (HOCHCHOH) — Key Precursors to Sugars and Sugar Derivatives","authors":"Jia Wang, Chaojiang Zhang, André K. Eckhardt, Ralf I. Kaiser","doi":"10.1039/d5sc05315c","DOIUrl":"https://doi.org/10.1039/d5sc05315c","url":null,"abstract":"Although sugars and sugar derivatives—molecules critical to the origins of life—have been identified in carbonaceous meteorites with total abundances typically higher than that of amino acids, their underlying formation mechanisms in interstellar environments remain poorly understood. This study reports the first formation of 1,2-propanediol (CH3CH(OH)CH2OH) and 1,2-ethenediol (HOCHCHOH) in low-temperature model interstellar ices composed of methane (CH4) and ethylene glycol (HOCH2CH2OH). 1,2-Propanediol forms via the barrierless radical−radical recombination of the methyl (ĊH3) with the 1,2-dihydroxyethyl (HOĊHCH2OH), while 1,2-ethenediol is produced through the decomposition of ethylene glycol. Utilizing vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and isotopic substitution experiments, 1,2-propanediol and its isomer 2-methoxyethanol (CH3OCH2CH2OH), along with enols 1,2-ethenediol and vinyl alcohol (CH2CHOH) were identified in the gas phase during temperature-programmed desorption based on their adiabatic ionization energies and mass-to-charge ratios. Among these compounds, only 1,2-propanediol has not yet been observed in the interstellar medium; these results suggest that it is a promising target for future astronomical detection. Our findings reveal viable abiotic pathways for the formation of biorelevant 1,2-propanediol and 1,2-ethenediol via non-equilibrium chemistry in ethylene glycol-containing interstellar ices, advancing our understanding of the fundamental formation mechanisms of sugars and sugar derivatives in deep space.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241618","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

Rhodamine-functionalised rhodium(III) complexes: dual role as bioimaging agents and controllable reactive oxygen species photosensitisers for photocytotoxicity applications 罗丹明功能化铑（III）配合物：作为生物显像剂和光细胞毒性应用的可控活性氧光敏剂的双重作用

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05257b

Gui-Min Jiang, Fangfang Wei, Kam Keung Leung, Siye Wu, Kenneth Kam-Wing Lo, Keith Man-Chung Wong

{"title":"Rhodamine-functionalised rhodium(III) complexes: dual role as bioimaging agents and controllable reactive oxygen species photosensitisers for photocytotoxicity applications","authors":"Gui-Min Jiang, Fangfang Wei, Kam Keung Leung, Siye Wu, Kenneth Kam-Wing Lo, Keith Man-Chung Wong","doi":"10.1039/d5sc05257b","DOIUrl":"https://doi.org/10.1039/d5sc05257b","url":null,"abstract":"Compared to well-developed iridium(III) complexes, cyclometallated rhodium(III) complexes are underexplored as bioimaging reagents and photosensitisers, primarily due to the presence of non-emissive low-lying d–d excited states that limit their photophysical properties. In this work, a series of rhodamine-containing rhodium(III) complexes [Rh(N^C)2(bpy-Rho)](PF6)2 was designed and synthesised to circumvent this problem. The incorporation of a rhodamine unit into cyclometallated rhodium(III) complexes endowed them with effective bioimaging and considerable reactive oxygen species (ROS) sensitisation capabilities upon low-energy photoexcitation. Time-resolved transient absorption spectroscopy of the complexes revealed a long-lived dark triplet state of rhodamine that was responsible for the enhanced ROS photosensitisation. An energy cascade pathway was proposed for the complexes, involving energy transfer from a rhodamine singlet excited state (S1) to a Rh(N^C)2-based triplet excited state (T1’), and ultimately to the lowest-lying rhodamine-based triplet excited state (T1). Through a judicious choice of cyclometallating ligands, the energy cascade efficiency can be modulated to achieve a delicate balance between fluorescence and ROS photosensitisation. Furthermore, the complexes specifically accumulated in the mitochondria and showed excellent photocytotoxicity via inducing pyroptosis, highlighting their potential as theranostic agents for bioimaging and photodynamic therapy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"112 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241614","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