Chemical Science最新文献

{"title":"Radical Photochemical Difluorosulfoximination of Alkenes and Propellanes","authors":"Simone Baldon, Luca Dell'Amico, Julien Paut, Elsa Anselmi, Guillaume Dagousset, Beatrice Tuccio, Giorgio Pelosi, Sara Cuadros, Emmanuel Magnier","doi":"10.1039/d5sc01068c","DOIUrl":"https://doi.org/10.1039/d5sc01068c","url":null,"abstract":"Herein, we report a metal-free divergent visible-light driven method for the synthesis of fluorinated sulfoximines. Both olefins and propellanes efficiently undergo difluorosulfoximination with yields up to 77% (65 examples). The process is general and robust and tolerates diverse functional groups, including esters, ethers, ketones, silyl groups, silyl ethers or boronic esters. The functionalization of diverse bioactive ingredients (8 examples), as well as various products manipulations demonstrate the synthetic usefulness of the developed synthetic platform. Finally, we rationalized the divergent reaction mechanism performing Stern-Volmer quenching and EPR experiments, that revealed the key activity of a difluoroalkyl sulfoximine radical.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"183 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618910","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-Driven Global Optimization Reveals Nanometre-Scale Mixed Phases of Borophene on Ag(100)","authors":"Yunlei Wang, Xiaojun Wu, Haifeng Lv","doi":"10.1039/d4sc08616c","DOIUrl":"https://doi.org/10.1039/d4sc08616c","url":null,"abstract":"Metal-supported borophene exhibits significant polymorphism and an inherently complex potential energy landscape, posing challenges to exploring its structural diversity. In this study, we integrate a neural network-driven machine learning potential with stochastic surface walking global optimization and an active learning framework to comprehensively map the potential energy surface (PES) of large-size borophene on an Ag(100) substrate. Our exhaustive search identifies 59,857 local minima across 556 distinct supercells, revealing a PES segmented into multiple energy basins and three major funnels. Among the low-energy configurations, 1,391 low-energy structures extend to the nanometre scale, showcasing a diverse array of mixed-phase borophene architectures, including monolayer ribbons (β12 and χ3) and bilayer fragments (BL-α5, BL-α7, BL-α1, BL-α6, and BL-α1α6). Notably, the global minimum structures feature monolayers composed of alternating χ3 and β12 ribbons and bilayers formed from BL-α5, BL-α1α6, and BL-α1 fragments. All mixed-phases borophenes exhibit metallic properties, and their simulated scanning tunneling microscopy (STM) images are provided to facilitate future experimental validation. These findings highlight the extraordinary structural complexity and rich polymorphism of borophene on extended metal surfaces, offering valuable insight into their formation, stability, and potential for tunable electronic properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618821","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":"Ultrafast excited-state dynamics and “three-in-one” phototheranostic properties of a phenanthroline-carbolong photosensitizer","authors":"Haixia Chang, Jiang Feng, Xin-Ao Liu, Rong Miao, Taihong Liu, Liping Ding, Yu Fang","doi":"10.1039/d5sc00013k","DOIUrl":"https://doi.org/10.1039/d5sc00013k","url":null,"abstract":"The favorable excited-state dynamics, nonlinear optics, and extraordinary phototheranostic capabilities of conjugated metallaaromatics are attractive topics of research. A promising and multifunctional photosensitizer, double-phenanthroline-carbolong DPC, was investigated comparatively. It featured strong two-photon absorption (2PA) properties within the near-infrared (NIR) range and a maximum 2PA cross section ~7417 GM at 770 nm in MeOH. Time-dependent density functional theory and ultrafast excited-state dynamics illustrated that fast charge transfer coupled with intersystem crossing to the stable triplet state outcompeted the radiative decays. The “three-in-one” phototherapeutic effect owned the NIR-wavelength 2PA excitation, photodynamic therapy, and photothermal therapy in DPC were illustrated subsequently. The significant contribution from the intrinsic intramolecular charge communication along the DPC skeleton provided the possibility for moderate photothermal conversion (η=36.8%) and photodynamic synergistic therapy (ΦΔ=8.4%). Interestingly, the singlet oxygen generation from DPC was also endowed when irradiated at two-photon exciting wavelengths. In vitro experiments demonstrated the synergistic phototoxicity of DPC in 4T1 cancer cells. Present work offers insights into the extraordinary carbolong metallaaromatics and highlights their potential applications in the fields of nonlinear optics and multifunctional phototheranostics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618912","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":"Modular access to nucleobase GFP-surrogates: pH-responsive smart probes for ratiometric nucleic acid diagnostics","authors":"Keenan T. Regan, Austin Pounder, Ryan E. Johnson, Makay T. Murray, Hannah X. Glowacki, Stacey D. Wetmore, Richard A. Manderville","doi":"10.1039/d4sc07994a","DOIUrl":"https://doi.org/10.1039/d4sc07994a","url":null,"abstract":"We have utilized a modular on-strand Aldol approach to synthesize chalcone-based fluorescent molecular rotors (FMRs) bearing phenolic oxygen donors that mimic the natural tyrosine (Tyr66) chromophore 4-hydroxybenzylidene-imidazolinone (HBI) within green fluorescent proteins (GFPs). Leveraging the FMRs’ propensity to undergo non-radiative decay <em>via</em> twisted intramolecular charge transfer upon excitation within certain microenvironments, we have addressed the longstanding issues of poor brightness (ϵ<small>_max</small>•Φ<small>_<em>fl</em></small>) and weak turn-on responses for GFP-surrogates within nucleic acids. To demonstrate its potential and lay the groundwork for future applications, these FMRs were incorporated into <em>NarI</em>12 and TBA15 oligonucleotides with canonical (A, C, T, G) or locked nucleic acids (LNAs) (T<small>_L</small>, A<small>_L</small>) as flanking bases. The resulting duplexes and G-quadruplexes (GQs) were studied using fluorescence spectroscopy, molecular dynamics simulations, and quantum mechanical calculations, yielding a comprehensive understanding of their structural and photophysical properties in DNA, DNA:RNA, and GQ contexts. Electron-rich chalcones favor neutral phenol excitation (ROH) to afford both phenol (ROH*) and phenolate (RO<small>^‒</small>*) emission, with the latter generated through an intermolecular excited-state proton transfer process, while electron-deficient chalcones serve as ratiometric excitation indicators, due to their photoacidity. The surrogates display strong turn-on responses (up to 154-fold) in a GQ → duplex topology switch with flanked LNAs, giving Φ<small>_<em>fl</em></small> up to 0.58 and molar brightness ~ 15,000 cm<small>^-1</small>M<small>^-1</small> in the duplex. By synergizing the NA sequence and probe, we achieve a switchable <em>ON-to-OFF</em> photoinduced electron transfer, resulting in a 134-fold turn-on emission response to pH. Our findings are the first to optimize the performance of GFP-surrogates as internal nucleobase replacements and suggest multiple ways in which they may be useful tools for NA diagnostics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"63 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618524","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":"Revealing the Nature of the Second Branch Point in the Catalytic Mechanism of the Fe(II)/2OG-Dependent Ethylene Forming Enzyme","authors":"Simahudeen Bathir Jaber Sathik Rifayee, Midhun George Thomas, Christo Christov","doi":"10.1039/d4sc08378d","DOIUrl":"https://doi.org/10.1039/d4sc08378d","url":null,"abstract":"Ethylene-forming enzyme (EFE) has economic importance due to its ability to catalyze the formation of ethylene and 3-hydroxypropionate (3HP). Understanding the catalytic mechanism of EFE is essential for optimizing the biological production of these important industrial chemicals. In this study, we implemented molecular dynamics (MD) and quantum mechanics/molecular mechanics (QM/MM) to elucidate the pathways leading to ethylene and 3HP formation. Our results suggest that ethylene formation occurs from the propion-3-yl radical intermediate rather than the (2-carboxyethyl)carbonato-Fe(II) intermediate (EFIV), which conclusively acts as a precursor for 3HP formation. The results also explain the role of the hydrophobic environment surrounding the 2OG binding site in stabilizing the propion-3-yl radical, which defines their conversion to either ethylene or 3HP. Our simulations on the A198L EFE variant, which produces more 3HP than wild-type (WT) EFE based on experimental observations, predict that the formation of EFIV intermediate is more favored than WT. Also, MD simulations on EFIV intermediate in both WT and A198L EFE predicted that the water molecules approach the Fe center, which suggests a role of water molecules in the breakdown of EFIV intermediate. QM/MM simulations on the EFIV intermediate of WT and A198L EFE predicted that the Fe-bound water molecule could provide a proton for the 3HP formation from EFIV. The study underscores the critical influence of the enzyme’s hydrophobic environment and second coordination sphere residues in determining product distribution between ethylene and 3HP. These mechanistic insights lay a foundation for targeted enzyme engineering, aiming to improve the selectivity and catalytic efficiency of EFE in biological ethylene and 3HP production.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"205 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608134","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":"Drug Binding Disrupts Chiral Water Structures in the DNA First Hydration Shell","authors":"Ty Santiago, Daniel Konstantinovsky, Matthew Tremblay, Ethan A. Perets, Sharon Hammes-Schiffer, Elsa C. Y. Yan","doi":"10.1039/d4sc08372e","DOIUrl":"https://doi.org/10.1039/d4sc08372e","url":null,"abstract":"Knowledge of how intermolecular interactions change hydration structures surrounding DNA will heighten understanding of DNA biology and advance drug development. However, probing changes in DNA hydration structures in response to molecular interactions and drug binding in situ under ambient conditions has remained challenging. Here, we apply a combined experimental and computational approach of chiral-selective vibrational sum frequency generation spectroscopy (chiral SFG) to probe changes of DNA hydration structures when a small-molecule drug, netropsin, binds the minor groove of DNA. Our results show that chiral SFG can detect water being displaced from the minor groove of DNA due to netropsin binding. Additionally, we observe that chiral SFG distinguishes between weakly and strongly hydrogen-bonded water hydrating DNA. Chiral SFG spectra show that netropsin binding, instead of displacing weakly hydrogen-bonded water, preferentially displaces water molecules strongly hydrogen-bonded to thymine carbonyl groups in the DNA minor groove, revealing the roles of water in modulating site-specificity of netropsin binding to duplex DNA rich in adenine-thymine sequences. The results convey the promise of chiral SFG to offer mechanistic insights into roles of water in drug development targeting DNA.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"886 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618520","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":"Anion Endowed High Dielectric Water-Deficient Interface towards Ultrastable Zn Metal Battery","authors":"Xiangjie Liu, Xiaoxin Nie, Yujiao Yang, Meng Yao, Jiaxian Zheng, Hanfeng Liang, Mi Zhou, Jin Zhao, Du Yuan","doi":"10.1039/d5sc00364d","DOIUrl":"https://doi.org/10.1039/d5sc00364d","url":null,"abstract":"Towards reversible metallic Zn anode for aqueous rechargeable zinc battery, regulating electrolyte-Zn interface serves as the key to address the side reactions on Zn. Besides possessing water-deficiency, design rules for constructing the highly efficient electrochemical interface is still vague. As primary electrolyte constituents, not only the roles of anions on solvation structure are being perceived, but also their influence on electrolyte-Zn interface. Here, the characteristics of representative anions are surveyed across current aqueous zinc electrolytes. The candidate reconciling polarizability, H-bond tuning ability and high solubility, is proposed to construct high dielectric water-deficient electrolyte-Zn interface, regulating the interfacial chemistry on Zn. The anion-dominated electrochemical interface promotes Zn deposition kinetics and achieves uniform Zn deposition with high stability, which further renders the in situ formation of SEI towards highly stable Zn stripping/plating, e.g. at 20 mA cm-2 and 20 mAh cm-2. Further, this built-in interface exhibits its function on stabilizing V2O5 cathode, empowering the V2O5/Zn cell with ultra-stable long-term cycling, e.g. 10000 cycles at 10 A g-1 with a high retention rate of 89.7%. Our design offers insight into guidelines for the development of novel electrolytes towards rationalizing electrochemical interface.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608136","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":"Coordination Isomerism in Dioxophosphorane Cyanides","authors":"Ayu Afiqah Nasrullah, Edgar Zander, Fabian Dankert, Andrey Petrov, Jonas Surkau, Eszter Barath, Christian Hering-Junghans","doi":"10.1039/d4sc07636b","DOIUrl":"https://doi.org/10.1039/d4sc07636b","url":null,"abstract":"The 1,3-Phosphaazaallene DippTerP=C=NtBu (DippTer = 2,6-(2,6-iPr2C6H2)-C6H3) is thermally labile towards iso-butene elimination and formation of the corresponding cyanophosphine DippTerP(H)CN (1). In previous work we have shown facile deprotonation of 1 with K[N(SiMe3)2 and formation of cyanophosphide [(DippTerPCN)K]. We now present the alkali metal tethered cyanophosphides [(DippTerPCN)M(crown)] (M = Na, K; crown = 15-c-5, 18-c-6) and their structural diversity in the solid state depending on the metal M and the crown ether. Facile oxidation of [DippTerPCN][M(crown)] with O2 yields the formal cyanide adducts of dioxophosphoranes [DippTerPO2(CN)]−. Interestingly, [DippTerPO2(CN)]− is obtained as a mixture of the cyanide and isocyanide isomers, indicating a coordination isomerism. This phenomenon is corroborated by experimental and theoretical studies revealing the cyanide isomer to be thermodynamically more stable. The oxidation with elemental sulphur gave the corresponding dithiophosphorane cyanide adduct [DippTerPS2(CN)]−, in which no isomerism was observed. This points to a crucial role of triplet oxygen in the isomerisation process. Monooxidation occurs when [DippTerPO2(CN)]− salts were treated with N2O, giving formal anionic phoshinidene monoxide adducts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608169","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":"Spectra-descriptor-based machine learning for predicting protein–ligand interactions","authors":"Cheng Chen, Ledu Wang, Yi Feng, Wencheng Yao, Jiahe Liu, Zifan Jiang, Luyuan Zhao, Letian Zhang, Jun Jiang, Shuo Feng","doi":"10.1039/d5sc00451a","DOIUrl":"https://doi.org/10.1039/d5sc00451a","url":null,"abstract":"Machine learning models have emerged as powerful tools for drug discovery of lead compounds. Nevertheless, despite notable advances in model architectures, research on more reliable and physicochemical-based descriptors for molecules and proteins remains limited. To address this gap, we introduce the Fragment Integral Spectrum Descriptor (FISD), aimed at utilizing the spatial configuration and electronic structure information of molecules and proteins, as a novel physicochemical descriptor for virtual screening models. Validation demonstrates that the combination of FISD and a classical neural network model achieves performance comparable to that of complex models paired with conventional structural descriptors. Furthermore, we successfully predict and screen potential binding ligands for two given protein targets, showcasing the broad applicability and practicality of FISD. This research enriches the molecular and protein representation strategies of machine learning and accelerates the process of drug discovery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"68 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608259","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":"Anisotropy-Dependent Chirality Transfer from Cellulose Nanocrystals to β-FeOOH Nanowhiskers","authors":"Jinyu Tang, Shouhua Feng, Ming Yang","doi":"10.1039/d4sc07747d","DOIUrl":"https://doi.org/10.1039/d4sc07747d","url":null,"abstract":"Chiral iron oxides and hydroxides have garnered considerable interest owing to the unique combination of chirality and magnetism. However, it remains elusive how to improve their g-factor, which is critical for optimizing the chiral magneto-optical response. We demonstrated that the g-factor of β-FeOOH could be boosted by enhancing the anisotropy of nanostructures during a biomimetic mineralization process. Cellulose nanocrystals were used as both mineralization templates and chiral ligands, driving oriented attachment of β-FeOOH nanoparticles and inducing the formation of highly aligned chiral nanowhiskers. Circular dichroism spectra and time-dependent density-functional theory proved induced chirality transfer from cellulose nanocrystals to β-FeOOH through the ligand-metal charge transfer. Interestingly, chirality transfer is significantly enhanced during the elongation of nanowhiskers. A nearly 34-fold increase in g-factor was observed when the aspect ratio of nanowhiskers increased from 2.6 to 4.4, reaching a g-factor of 5.7*10-3, superior to existing dispersions of chiral iron oxides and hydroxides. Semi-empirical quantum calculations unveiled that such remarkable improvement of g-factor could be attributed to the enhanced dipolar interactions. Cellulose nanocrystals exert vicinal actions on highly anisotropic β-FeOOH with a large dipole moment, increasing structural distortions of coordination geometry. This mechanism is accorded with the one-electron theory's static coupling principle, highlighting the large interaction potential from supramolecular templates. Furthermore, paramagnetic β-FeOOH nanowhiskers alter the magnetic anisotropy of cellulose nanocrystals, leading to a reverse response of helical photonic films to magnetic fields, promising for the real-time optical modulation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600081","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}