Chemical Science最新文献

{"title":"An activatable unimolecular phototheranostic agent for synergistic chemo-photodynamic therapy.","authors":"Jinliang Han, Kang Li, Mingwang Yang, Jiangli Fan, Xiaojun Peng","doi":"10.1039/d5sc02877a","DOIUrl":"10.1039/d5sc02877a","url":null,"abstract":"<p><p>Precise control over spatiotemporal release of cancer therapeutics remains a significant challenge in developing effective combination therapies. Herein, we report a hydrogen peroxide (H₂O₂)-activatable unimolecular platform (ICy-Cb) that integrates cancer imaging and synchronized dual-modal therapy. An iodized hemicyanine photosensitizer and chlorambucil are integrated into a single molecular structure that selectively reacts to the high concentration of H₂O₂ present in the tumor microenvironment. ICy-Cb initially exhibits no fluorescence and is therapeutically inert due to the suppression of its intramolecular charge transfer (ICT) effect. Upon exposure to tumor-associated H₂O₂, ICy-Cb simultaneously releases both therapeutic components, demonstrating exceptional tumor selectivity (5 to 8 folds higher activation in cancer cells), deep penetration in 3D tumor models (180 μm), and persistent tumor accumulation <i>in vivo</i>. Most importantly, this synchronized chemo-photodynamic agent achieves superior tumor growth inhibition (92%) compared to either monotherapy. This theranostic agent represents a significant advancement for precision cancer treatment by enabling spatiotemporally controlled combination therapy within the tumor microenvironment.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12152736/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144282696","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the chemistry of higher acenes: from synthesis to applications.","authors":"Hironobu Hayashi, Hiroko Yamada","doi":"10.1039/d5sc02422f","DOIUrl":"10.1039/d5sc02422f","url":null,"abstract":"<p><p>This review explores the advancements in the chemistry of higher acenes and their derivatives, with a focus on their synthesis, characterization, and potential applications. Historically, higher acenes have presented challenges to study due to their inherent instability and reactivity under ambient conditions. However, innovative synthetic strategies, including on-surface synthesis and the precursor approach, have significantly contributed to the ability to synthesize higher acenes even at preparative scales while evaluating their magnetic and semiconducting properties. Furthermore, ethynylene-bridged acene oligomers and polymers, known for their extended π-conjugated systems, have shown promise not only as semiconducting materials but also as topological materials. As synthetic methods continue to evolve and characterization techniques become more sophisticated, higher acenes offer exciting opportunities for progress in the fields of organic chemistry and materials science, paving the way for advanced applications in organic electronics.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12135676/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144233352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Concise Total Synthesis of the Cage-Like Sesquiterpenoid (+)-Daphnepapytone A","authors":"Elijah C. Gonzalez, Isabel de la Torre Roehl, Brian M. Stoltz","doi":"10.1039/d5sc02952j","DOIUrl":"https://doi.org/10.1039/d5sc02952j","url":null,"abstract":"We report a non-biomimetic total synthesis of (+)-daphnepapytone A, an unprecedented member of the guaiane-derived sesquiterpenoids that displays moderate inhibitory activity against -glycosidase (IC50 = 159 ± 2.1 M) and possesses a highly strained bridging cyclobutane motif. Our de novo approach provided expedient access to the tetracyclic core of (+)-daphnepapytone A through an intramolecular allenyl thermal [2+2] cycloaddition and a Pauson–Khand reaction with a labile cyclobutane. Finally, a late-stage oxidation/reduction sequence delivered (+)-daphnepapytone A with striking chemoselectivity and excellent diastereoselectivity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"56 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211468","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":"BaSbBS₄: a record-high-performance birefringent crystal identified by a target-driven closed-loop strategy.","authors":"Ming-Zhi Zhang, Yue Zhao, Chun-Li Hu, Jiang-Gao Mao","doi":"10.1039/d5sc01983d","DOIUrl":"10.1039/d5sc01983d","url":null,"abstract":"<p><p>Exploring infrared (IR) birefringent materials with both large birefringence (Δ<i>n</i>) and wide band gaps (<i>E</i> _g) is urgently demanded for high-power optoelectronic applications and has long been a tough challenge due to the intrinsic contradictory relationship between the two metrics. Herein, we developed a target-driven closed-loop framework in coupling with functional motif and crystal structure screening, deep learning assisted high-throughput optical property computation, targeted experiment and mechanism investigation, enabling efficient discovery of potential birefringent materials. Utilizing it, a batch of superior IR birefringent crystals containing planar [BS₃]^3- and/or stereochemically active lone pair (SCALP) groups ([SbS₃]^3-, [SnS₃]^4-, <i>etc.</i>) were identified: six with huge birefringence (Δ<i>n</i> > 1.0) and three with both large birefringence (Δ<i>n</i> > 0.5) and wide band gaps (<i>E</i> _g > 3.5 eV). Remarkably, benefiting from a maximal synergy of [BS₃]^3- and [SbS₃]^3- motifs achieved by an optimal assembly of 1D [SbBS₄]_∞ chains, BaSbBS₄ was highlighted and then validated experimentally as the most promising IR birefringent crystal, unlocking a record high birefringence in the wide-band-gap range (Δ<i>n</i> = 0.95 & 2.70 eV). This work not only discovers new high-performance birefringent crystals but also offers a universal avenue for precise and efficient evaluation of optical functional materials.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12153103/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144282697","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the switching mechanism of robust tetrazine-based memristive nociceptors via a spectroelectrochemical approach","authors":"Ji-Yu Zhao, Kun Liu, Wei Zeng, Zhuo Chen, Yifan Zheng, Zherui Zhao, Wen-Min Zhong, Su-Ting Han, Guang-Long Ding, Ye Zhou, Xiaojun Peng","doi":"10.1039/d5sc02710a","DOIUrl":"https://doi.org/10.1039/d5sc02710a","url":null,"abstract":"Threshold switching memristors exhibit significant potential for developing artificial nociceptors as their working principles and electrical characteristics closely mimic biological nociceptors. However, the development of high-performance artificial nociceptors is hindered by the randomness of conductive filament (CF) formation/rupture, caused by low-quality resistive switching (RS) films and complex, and uncontrollable RS mechanisms. Organic small-molecule materials are favored in electronic devices for their designability, low cost, easy synthesis, and high stability. In this study, we meticulously designed two D-π-A-π-D structured molecules, designated as TZ-1 and TZ-2, to serve as the RS layer in artificial nociceptors. By precisely modulating the electron-donating ability of the donor groups in these molecules, some key electrical properties of the memristor, such as the low SET voltage (0.42 V) and variation (0.055), high current ON/OFF ratio (˜10<small>^-6</small>) and nanosecond level switching time (60 ns), can be successfully optimized. Moreover, a spectroelectrochemistry strategy was first employed to investigate the RS mechanism at the molecular level, elucidating the critical role of molecular design in modulating the device's working principles and electrical characteristics. The optimized memristor is capable of accurately emulating the four key behaviors of nociceptors. This achievement not only advances the application of organic materials in neuromorphic devices but also opens new possibilities for the specialized customization of nociceptors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"61 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201754","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":"Ppm level palladium catalyzed regioselective remote arylation of alkenyl alcohols.","authors":"Chong Liu, Ling Wang, Haibo Ge","doi":"10.1039/d5sc02745d","DOIUrl":"10.1039/d5sc02745d","url":null,"abstract":"<p><p>Recent studies highlight the importance and application of parts per million (ppm) palladium concentration in catalytic reactions. Lowering catalyst loading minimizes costs, simplifies purification, and reduces metal contamination, making it highly attractive for pharmaceutical and fine chemical manufacturing. Here, we report a ppm level Pd-catalyzed remote arylation reaction of alkenols, achieving high efficiency, regioselectivity, and flexible carbonyl scaffold construction. Notably, this strategy exhibits excellent compatibility with styrene-derived substrates and has been successfully achieved on a gram scale, providing a solid foundation for potential large-scale applications.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12147037/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144265383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxidant-assisted methane pyrolysis","authors":"Marco Gigantino, Henry Moise, Vasudev Haribal, Andrew Tong, Jian-Ping Shen, Dimitri Saad, Jacob Fishman, Alexander J.H. Nelson, Harry Voorhis, Eddie Sun, Adam Robert Brandt, Raghubir Gupta, Arun Majumdar, Matteo Cargnello","doi":"10.1039/d5sc00768b","DOIUrl":"https://doi.org/10.1039/d5sc00768b","url":null,"abstract":"Methane pyrolysis has been proposed as a cost-competitive route to produce low-CO2-emissions hydrogen that can utilize today’s infrastructure to supply feedstock and manage waste, and thereby be rapidly scalable. However, this process faces challenges such as catalyst deactivation and carbon build-up that hinder its large-scale implementation. Pyrolysis is usually conducted in the absence of oxidizers to avoid combustion products such as CO2. Here, we demonstrate that the addition of small concentrations of an oxidant to a methane pyrolysis reaction on Fe-based catalysts prevented catalyst deactivation and increased the net production of carbon and hydrogen. Methane pyrolysis in the presence of a small amount of CO2 demonstrated a twofold increase in carbon yield and a 7.5-fold increase in hydrogen concentration in the effluent compared to that of a pure methane feed during 1 h operation in a fluidized bed reactor at 750 °C. A similar beneficial effect was observed by adding small amounts of H2O in the feed. We provide evidence that the cyclic formation and decomposition of an iron carbide catalyst phase allowed for increased methane decomposition and significant carbon removal from the catalyst surface, thus increasing carbon and hydrogen yields. A similar result was obtained for Ni- and Co-based catalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201751","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":"Photoaffinity SAM analogues for the identification of SAM-binding proteins.","authors":"Xiangyu Wu, Min Dong","doi":"10.1039/d5sc03424h","DOIUrl":"10.1039/d5sc03424h","url":null,"abstract":"<p><p><i>S</i>-Adenosylmethionine (SAM) serves as an important substrate in a variety of biochemical reactions, and it is important to identify unknown SAM-binding proteins to fully understand the biological functions of SAM. Previous studies on SAM-binding proteins used <i>S</i>-Adenosylhomocystein (SAH)-analogues, which mainly identified SAM dependent methyltransferases. Here, we developed and validated three SAM photoaffinity probes to label and enrich SAM-binding proteins. These probes efficiently labeled the known SAM-binding protein Dph2 involved in diphthamide biosynthesis from cell lysates. Using these probes, we enriched SAM-binding proteins from the cell lysates of <i>Burkholderia gladioli</i> and <i>Saccharomyces cerevisiae</i>. In addition, we validated five SAM binders and revealed the SAM cleavage activities of three of them, including the radical SAM enzyme ArsL, which cleaves SAM to generate methylthioadenosine (MTA), and AcnA and EDD84_07545, which generate <i>S</i>-adenosyl-l-homocysteine (SAH). Therefore, our SAM-based photoaffinity probes are promising tools for the identification of SAM-binding proteins.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12134932/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144233354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Collective motions in the primary coordination sphere: a critical functional framework for catalytic activity of the oxygen-evolving complex of photosystem II.","authors":"Hiroshi Isobe, Takayoshi Suzuki, Michihiro Suga, Jian-Ren Shen, Kizashi Yamaguchi","doi":"10.1039/d5sc02386f","DOIUrl":"10.1039/d5sc02386f","url":null,"abstract":"<p><p>Photosynthetic water oxidation, vital for dioxygen production and light energy conversion, is catalyzed by the oxygen-evolving complex of photosystem II, where the inorganic Mn₄CaO₅ cluster acts as the catalytic core. In this study, we investigate the functional significance of collective motions of amino acid side chains within the primary coordination sphere of the Mn cluster, focusing on their role in modulating the energetic demands for catalytic transformations in the S₃ state. We applied regularized canonical correlation analysis to quantitatively correlate the three-dimensional arrangement of coordinating atoms with catalytic driving forces computed <i>via</i> density functional theory. Our analysis reveals that distinct collective side chain motions profoundly influence the energetic requirements for structural reconfigurations of the Mn cluster, achieved through expansion and contraction of the ligand cavity while fine-tuning its geometry to stabilize key intermediates. Complementary predictions from a neural network-based machine learning model indicate that the coordination sphere exerts a variable energetic impact on the catalytic transformations of the Mn cluster, depending on the S-state environment. Integrated computational analyses suggest that the extended lifetime of the S₃Y_Z˙ state, consistently observed after three flash illuminations, may result from slow, progressive protein dynamics that continuously reshape the energy landscape, thereby shifting the equilibrium positions of rapid, reversible chemical processes over time. Overall, our findings demonstrate that collective motions in the primary coordination sphere constitute an active, dynamic framework essential for the efficient execution of multi-electron catalysis under ambient conditions, while simultaneously achieving a high selectivity with irreversible nature required for effective ³O₂ evolution.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12132551/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144224445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cefiderocol under siege? Understanding the rise of NDM-mediated resistance","authors":"Alejandro J. Vila, Brenda Agustina Warecki, Pablo Emiliano Tomatis, Maria-Fernanda Mojica, Christopher R Bethel, Magdalena Rodriguez Saravia, Salvador Drusin, Daisuke Ono, Guillermo Bahr, Krisztina Papp-Wallace, Pranita Tamma, Diego Martín Moreno, Graciela Mahler, Robert Bonomo","doi":"10.1039/d5sc02122g","DOIUrl":"https://doi.org/10.1039/d5sc02122g","url":null,"abstract":"The global spread of antimicrobial resistance (AMR) underscores the critical need for the rapid development of new drugs. Particularly alarming are the surge in metallo-β-lactamases (MBLs) - broad spectrum enzymes able to inactivate penicillins, cephalosporins, and carbapenems. Cefiderocol (FDC), a siderophore-containing cephalosporin, was initially reported as resistant to MBL hydrolysis. Indeed, FDC has been designated as the preferred treatment for Gram-negative pathogens producing MBLs – with the most common MBLs of clinical concern belonging to the NDM, VIM, or IMP families. Regrettably, increasing reports of FDC resistance are emerging. Many of these events are linked to overexpression of NDM, sometimes coupled to alterations in iron transporters, challenging the notion of FDC being invulnerable to MBL hydrolysis. Herein, we demonstrate that NDM-1 and -5 are able to inactivate FDC efficiently, while VIM-2 and IMP-1 show impaired catalytic efficiency against this substrate. All these MBL enzymes form a reversible enzyme-product adduct with FDC, whose lifetime varies considerably among MBLs. In IMP-1 and VIM-2, this results in efficient enzyme inhibition. In contrast, NDM variants are poorly inhibited, eliciting efficient turnover rates. As a result, we propose a mechanistic explanation for FDC action that aligns with clinical findings suggesting NDMs as responsible for FDC resistance. Based on these conclusions, we suggest caution when using this potent cephalosporin against NDM-producers. FDC paired with an NDM-inhibitor may be a strategy to preserve this important antibiotic.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201756","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}