Chemical Science最新文献

{"title":"π-Extended Diphosphonium-Bridged Ladder Stilbenes: Water-Soluble Fluorophores with up to Eight Annulated Rings","authors":"Sebastian Senn, Jean-Marc Mörsdorf, Maria-Sophie Bertrams, Christoph Kerzig, Joachim Ballmann","doi":"10.1039/d5sc03752b","DOIUrl":"https://doi.org/10.1039/d5sc03752b","url":null,"abstract":"Diphosphapentalene-derived <em>P</em>-heterocyclic materials with two directly fused phospholes are fairly scarce, at least in comparison to their simpler congeners containing only one phosphole entity. To fill that void, <em>π</em>-conjugated naphtho-fused phospholo[3,2-<em>b</em>]phosphole dications were prepared via <em>in-situ</em> oxidation of the corresponding diphosphines. In the case of one specific naphtho-annulation pattern, a hitherto unprecedented bis-(Δ<small>²</small>-phosphetene) dication was formed selectively and isolated as a colorless powder. DFT modelling studies revealed that this bis-(Δ<small>²</small>-phosphetenium) salt is produced via single electron transfer steps, while all the phospholo[3,2-<em>b</em>]phosphole salts may either be generated via their <em>P</em>-diylidic counterparts or via similar radical mechanisms. Exploiting this knowledge, the dicationic phospholo[3,2-<em>b</em>]phosphole isomer of the bis-(Δ<small>²</small>-phosphetenium) salt was isolated as well. In view of the high fluorescence quantum yields of these naphtho-fused phospholo[3,2-<em>b</em>]phosphole salts in aqueous solution, linearly <em>π</em>-extended anthraceno-fused derivatives were developed in order to bathochromically shift their emissions into the biological window. While detailed optoelectronic studies confirmed our expectations, the utmost remarkable observation is that even the anthraceno-fused materials were found to be sufficiently soluble in water, despite the fact that these fluorophores comprise up to eight fused rings.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183372","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":"Oxidation states in solids from data-driven paradigms","authors":"Yue Yin, Hai Xiao","doi":"10.1039/d5sc05694b","DOIUrl":"https://doi.org/10.1039/d5sc05694b","url":null,"abstract":"The oxidation state (OS) is an essential chemical concept that embodies chemical intuition but cannot be computed with well-defined physical laws. We establish a data-driven paradigm, with its implementation as Tsinghua Oxidation States in Solids (TOSS), to explicitly compute OSs in crystal structures as the emergent properties from large-sized datasets based on Bayesian maximum <em>a posteriori</em> probability (MAP). TOSS employs two looping structures over the large-sized dataset of crystal structures to obtain an emergent library of distance distributions as the foundation for chemically intuitive understanding and then determine the OSs by minimizing a loss function for each structure based on MAP and distance distributions in the whole dataset. We apply TOSS to a dataset of over one million crystal structures, achieving a superior success rate, and use the resulting OS dataset to train a graph convolutional network (GCN) model as an alternative. Both TOSS and the GCN model are benchmarked against a curated ICSD dataset of structures with human-assigned OSs, yielding high accuracies of 96.09% and 97.24%, respectively. We expect TOSS and the ML-model-based alternative to find a wide spectrum of applications, and this work also demonstrates an encouraging example for data-driven paradigms to explicitly compute the chemical intuition for tackling complex problems in chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"118 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183055","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":"Gas-Mediated Reinforcement of Cancer Therapies: Emerging Strategies and Future Perspectives","authors":"Fang Yuan, Lu Wang, Lulu Ning, Jianjian Zhang, Yuan Guo","doi":"10.1039/d5sc04798f","DOIUrl":"https://doi.org/10.1039/d5sc04798f","url":null,"abstract":"Cancer therapy has made strike progress and moving towards more precise, intelligent and personalized treatment modes. However, current approaches such as chemotherapy, phototherapy, sonodynamic therapy, immune therapy still suffer from limitation hinder their application in clinical. Gasotransmitters have long been recognized as key regulators in cancer pathology and the development of novel therapeutic agents with gas releasing ability aiming to establish new therapeutic modes have garnering considerable attention. In this perspective, we aim to summarize the critical roles of gaseous molecules in cancer biology and the potential mechanisms for enhancing the efficacy of dominant treatment modalities. We also provide insights into recent advances in integrating gas therapy with conventional treatments to overcome current challenges and improve therapeutic outcomes, ultimately paving the way for the development of next-generation treatment paradigms.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183054","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":"Bisphosphine Ligand Conformer Selection to Enhance Descriptor Database Representation: Improving Statistical Modelling Outcomes","authors":"Jamie Cadge, Sierra D Hart, Richard C Walroth, Matthew S. Sigman, Kyle Mack","doi":"10.1039/d5sc04691b","DOIUrl":"https://doi.org/10.1039/d5sc04691b","url":null,"abstract":"A foundational consideration in the development of computationally derived molecular feature libraries is the generation and selection of conformers. It has been shown that several feature values have a degree of conformer depencency -which may have significant mechanistic implications, partiticulary in the field of homogeneous enantioselective catalysis. However, the computational cost of calculating conformers often prohibits this analysis from being performed, especially when large flexible systems are involved. We report here a a practical, chemically-intutive conformer selection tool for bisphosphineligated palladium(II) dichloride complexes that provide a good balance between representation and computational cost.Conformer-weighted features generated from this method were applied to two previous statistical modelling case studies, where weighted features improve model quality with respect to predictive power. This selection methodology has the potential to be applied to a range of complex molecular systems beyond bisphosphine-ligated organometallic complexes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183366","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":"Dynamic Structural Engineering of Ferrocene-Functionalized Ag20 Nanoclusters for Enhanced CO2 Electroreduction Performance","authors":"Hong-Yan Zhu, Xiao-Wei Wang, Xinyu Chen, Lanyan Li, Yixin Li, Wei-Dong Yu, Jun Yan, Chao Liu","doi":"10.1039/d5sc06306j","DOIUrl":"https://doi.org/10.1039/d5sc06306j","url":null,"abstract":"The integration of organometallic motifs with metal nanoclusters offers a powerful strategy for constructing hybrid catalysts with precisely tunable active sites. Here, we report the synthesis of a 20-silver nanocluster, Ag20-Fc, via cooperative coordination between thiacalix[4]arene (TC4A) and ferrocenylacetylene ligands. The cluster adopts a distinctive sandwich-like architecture, featuring two Ag5@TC4A units flanking a ferrocenyl-stabilized Ag10 core, and exhibits excellent structural tunability. Ligand engineering allows replacement of the ferrocenylacetylene units with methoxyphenylacetylene (Ag20-OPh) or phenylacetylene (Ag20-Ph), while preserving the core framework. Electrospray ionization mass spectrometry reveals dynamic structural reorganization in solution, where Ag₅@TC4A fragments are capable of capturing Ag–alkyne species and reassembling into sandwich-type clusters—a process substantiated by the structural features of Ag24, Ag12, and Cu2Ag11. Ag20-Fc generates a locally electron-rich environment and conjugated ethynyl bridges that facilitate directional charge transfer, delivering outstanding electrocatalytic CO2 reduction. It achieves over 98% Faradaic efficiency for CO across a wide potential range (–1.0 to –1.8 V vs. RHE) and maintains operational stability for 48 h, significantly outperforming Ag20-OPh and Ag20-Ph. Density functional theory calculations uncover a dual enhancement mechanism in which orbital hybridization between ferrocenyl groups and silver atoms tunes the electronic structure at active sites, resulting in a 0.28 eV reduction in the energy barrier for *OCHO intermediate formation compared to Ag20-Ph.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"327 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183052","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":"Thiol-mediated uptake of phosphorothioate liposomes, visualized with fluorescent flippers","authors":"Jules Bouffard, Felix Bayard, Naomi Sakai, Stefan Matile","doi":"10.1039/d5sc05796e","DOIUrl":"https://doi.org/10.1039/d5sc05796e","url":null,"abstract":"Liposomes made from phosphorothioate lipids are shown to penetrate cells better and differently than conventional phosphodiester liposomes. DSP<small>_S</small>C phosphorothioate liposomes are synthesized, characterized and labeled with either internal doxorubicin or membrane-bound flippers. Inhibition experiments reveal that their penetration of HK cells is independent of endocytosis and occurs by thiol-mediated uptake (TMU). Dynamic covalent exchange with phosphorothioate sulfurs as pseudo-thiolates is confirmed and explored to modify liposomes and activate TMU. Mechanosensitive flipper probes and colocalization experiments reveal that phosphorothioate liposomes cross the plasma membrane in intact form with negligible endocytosis and little fusion. In the cytosol, fast-emitting flipper probes and non-released doxorubicin in punctate objects that partially co-localize with lipid droplets but not lysosomes suggest that the liposomes apparently stay at least partially intact and incorporate disorganizing lipid components from lipid droplets. In clear contrast, conventional DSPC liposomes bind to the cell surface in intact form and neither fuse nor cross the plasma membrane. These results support and translate recent insights from cell-penetrating oligonucleotides to phosphorothioate lipids, highlight the importance of understanding the dynamic covalent chemistry of phosphorothioates, and identify flipper dendrons as promising tools to elucidate liposomal delivery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183053","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":"O-B←N Perturbed Polycyclic Aromatic Hydrocarbons: A Straightforward Synthesis Strategy, Photophysical, and Optical Waveguide Properties","authors":"Jinying Jianhua Zhao, Qihang Qihang Yang, Weibin Chen, Nuo Xu, Qing Zhang, Wenhao Zhao, Geng-Geng Luo, Qiuhong Cui, Jianhua Huang","doi":"10.1039/d5sc05407a","DOIUrl":"https://doi.org/10.1039/d5sc05407a","url":null,"abstract":"Polycyclic aromatic hydrocarbons (PAHs) containing O-B←N groups in the backbone have been demonstrated excellent optical properties but two-dimensionally (2D) extended O-B←N perturbed PAHs have been rarely disclosed due to the synthetic difficulties. Moreover, the applications of these O-B←N perturbed PAHs are primarily limited to electroluminescent devices and opening up novel functions of this class of heteroaromatic molecules is urgent. This work develops a straightforward synthesis strategy toward O-B←N perturbed PAHs through 2~3 steps, creating a series of tetra-cycle, octa-cycle, and deca-cycle fused molecules. Photophysical characterizations and theoretical simulations to these O-B←N perturbed PAHs reveal several distinct properties, e.g., high fluorescence quantum yields (70%), aggregation induced emission (AIE) effects, and anti-Kasha emission. Then, through classic solvent diffusion or volatilization methods, these O-B←N perturbed PAHs are further self-assembled to 1D microstructures, e.g., rod or sheet shaped microwires in solutions. These microwires are unprecedentedly subjected to optical waveguide measurements and low optical loss coefficients of 10<small>^-2</small>~10<small>^-3</small> dB/μm are found. This work develops an efficient synthesis strategy toward 2D extended O-B←N perturbed PAHs and performs pioneering applications to optical waveguide, demonstrating the great potential of these O-B←N perturbed PAHs for micro/nanophotonics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"105 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183057","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":"Identifying Inorganic Solids for Harsh Environments via Machine Learning","authors":"Jacob C Hickey, Arman M Karimaghaei, Matt Flores, Sally Hoang, Roy Arrieta, Amit Kumar, Gonzalo Cuervo, Peter Zhu, Jakoah Brgoch","doi":"10.1039/d5sc05800g","DOIUrl":"https://doi.org/10.1039/d5sc05800g","url":null,"abstract":"Developing multifunctional materials with superior mechanical properties, including high hardness and oxidation resistance, remains essential for aerospace, defense, and industrial applications. Machine learning offers a powerful, data-driven pathway for discovering new hard, oxidation-resistant materials for these uses, providing an efficient and scalable alternative to conventional materials discovery methods. Here, we present a pair of extreme gradient boosting (XGBoost) models, trained on compositional and structural descriptors. A Vickers hardness (<em>H<small>_V</small></em>) model was developed using a curated dataset of 1,225 while a model for predicting the oxidation temperature (<em>Tp</em>) was constructed using 348 compounds. The model was subsequently validated against a diverse dataset of 18 inorganic compounds, including borides, silicides, and intermetallics, with previously unmeasured oxidation temperatures. Integrating the updated structure-informed hardness model with the new oxidation model enabled the identification of multifunctional materials that simultaneously exhibit superior hardness and enhanced oxidation resistance. This work highlights the potential of machine learning to accelerate materials discovery and provides a robust framework for identifying compounds capable of withstanding extreme environments.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"105 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183368","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":"Magnetic hysteresis in 1D organometallic lanthanide chain compounds containing 4,4′-bipyridine","authors":"Ernesto Castellanos, Florian Benner, Saroshan Deshapriya, Selvan Demir","doi":"10.1039/d5sc05460e","DOIUrl":"https://doi.org/10.1039/d5sc05460e","url":null,"abstract":"The assembly of multinuclear complexes bearing highly anisotropic building blocks remains an attractive approach to developing advanced functional materials. However, incorporating lanthanide-based metallocenium moieties, [Cp<small>^R</small><small>₂</small>Ln]<small>⁺</small>, into higher-order systems remains a significant synthetic challenge and their targeted isolation is exceedingly rare. Presented herein are organometallic lanthanide chain compounds bearing bridging 4,4′-bipyridine ligands, <img align=\"middle\" alt=\"Image ID:d5sc05460e-t1.gif\" src=\"https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/SC/D5SC05460E/d5sc05460e-t1.gif\"/> (where Ln = Gd (<strong>1</strong>), Tb (<strong>2</strong>), Dy (<strong>3</strong>); Cp* = pentamethylcyclopentadienyl; bpy = 4,4′-bipyridine). This constitutes the first report of a crystallographically characterised 1D organometallic network of lanthanide metallocenium units connected to one another through organic bridges. Each metallocenium moiety is ligated by two bipyridyl ligands, giving rise to zigzag-shaped chains, where tetraphenylborate anions reside in between the nitrogen ligands. The formation of the compounds from <img align=\"middle\" alt=\"Image ID:d5sc05460e-t55.gif\" src=\"https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/SC/D5SC05460E/d5sc05460e-t55.gif\"/> and 4,4′-bipyridine is very fast, leading to an immediate precipitation in the polar solvent THF. Thus, a judicious synthetic route was developed to ensure crystallisation and pure isolation which involved the use of an H-tube. Dc magnetic susceptibility measurements for <strong>1–3</strong> allude to the presence of uncoupled lanthanide ions, which is consistent with the experimental cw-EPR spectrum as well as the calculated magnetic exchange coupling constant, <em>J</em>, for the gadolinium congener, <strong>1</strong>, obtained through broken-symmetry DFT. The dysprosium analogue, <strong>3</strong>, is a single-molecule magnet (SMM) which was confirmed through both out-of-phase ac magnetic susceptibility signals under a zero applied dc field, indicative of slow magnetic relaxation, and isothermal, variable-field dc measurements, revealing open magnetic hysteresis loops up to 8 K. The lack of intra- and interchain magnetic exchange suggests that the origin of single-molecule magnetism in <strong>3</strong> arises from single-ion anisotropy and crystal field, which is further supported <em>via ab initio</em> calculations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"91 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189300","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":"Strain-Dependent Multicolor Mechanochromism of 3H-Bis-Naphthopyran in Solid Polymeric Materials","authors":"Skylar K. Osler, Audrey V. Conner, Molly E. McFadden, Maxwell J. Robb","doi":"10.1039/d5sc05757d","DOIUrl":"https://doi.org/10.1039/d5sc05757d","url":null,"abstract":"Multimodal mechanophores are important targets for the design of complex stress-sensing materials due to their multicolor mechanochromic properties, which potentially enable discrete visual outputs under varying levels of stress and/or strain. We have developed a novel 3H-bis-naphthopyran mechanophore that imbues solid polymeric materials with force-dependent colorimetric sensing capabilities. Polydimethylsiloxane (PDMS) elastomers incorporating a 3H-bis-naphthopyran crosslinker were synthesized and deformed under uniaxial tension. The relative distribution of two distinctly colored merocyanine dyes is systematically biased under varying levels of applied stress and/or strain, resulting in the appearance of distinct coloration, which is characterized by pronounced changes in visible absorption spectra. This work demonstrates that judiciously designed bis-naphthopyran mechanophores can function as force sensors that visually report on the magnitude of applied force in elastomeric materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183369","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}