Chemical Science最新文献

{"title":"A Photo- and Cobalt-Catalyzed Highly Selective and Divergent Hydrofunctionalization of 1,3-Dienes with Phenols","authors":"Yue Wang, Junhao Miao, Honglin Dong, Dongliang Zhang, Bei Chen, Meihui Guan, Ge Zhang, Qian Zhang","doi":"10.1039/d5sc00438a","DOIUrl":"https://doi.org/10.1039/d5sc00438a","url":null,"abstract":"An applicable cobalt-hydride mediated selective, divergent hydroetherification and sequential hydroetherification/hydroarylation of dienes with simple phenol feedstocks under photoredox and cobalt catalytic system was developed. A variety of allyl aryl ethers and value-added chroman derivatives can be obtained in good to excellent yields and stereoselectivity. This method not only obviates the need for extra hydrosilanes and stoichiometric oxidants thereby offering an exceedingly mild condition for alkene hydroetherification but also represents the first case of CoH-HAT catalyzed sequential double hydrofunctionalization of alkenes with sole nucleophile. The continuous and selective bond-forming catalytic system expands the applications of cobalt-hydride MHAT reaction and provides a novel approach for the design and synthesis of heterocyclic molecules.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"81 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444003","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":"An argument for abandoning the “allowed” and “forbidden” classification of electrocyclic reactions","authors":"Barry K. Carpenter","doi":"10.1039/d4sc08748h","DOIUrl":"https://doi.org/10.1039/d4sc08748h","url":null,"abstract":"The division of electrocyclic reactions into “allowed” and “forbidden” classes carries the implication that reactions of the latter class are so energetically penalised that they will occur only if their “allowed” alternatives are rendered effectively impossible. The present work tests that assumption, using NEVPT2 and DFT calculations on a variety of cyclobutene ring openings and (<em>Z</em>)-1,3,5-hexatriene ring closures, and their benzannelated congeners. The results show the assumption to be incorrect. The potential energy differences between “forbidden” and “allowed” transition states are found to cover a wide range of values, with the smallest being less than half the classical barrier to internal rotation of ethane. It follows that planning a total synthesis on the presumption that electrocyclic reactions will always follow the “allowed” stereochemical course is an unreliable strategy because other commonly occurring factors, such as routine steric and electronic substituent effects, can easily outweigh the electronic penalty for following the nominally forbidden mechansim. A particular case involving a proposed synthetic route to a class of anticancer compounds is highlighted as an example.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"49 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443956","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":"Logic-gated approach for targeted delivery and site-selective activation of photothermal agents in precision cancer treatment","authors":"Chang Jiang, Zhengxiang Zhao, Amanda K. East, Suritra Bandyopadhyay, Ziyi Jiang, Jefferson Chan","doi":"10.1039/d4sc08228a","DOIUrl":"https://doi.org/10.1039/d4sc08228a","url":null,"abstract":"Logic-gated strategies represent a promising approach to achieving highly selective cancer therapies. In this work, we present LG-AB (Logic-Gated Aza-BODIPY), an OFF–ON photothermal therapy (PTT) agent designed to selectively target cancer cells. LG-AB undergoes a red-shift in its maximum absorbance wavelength when activated in the tumor microenvironment, enabling the molecule to precisely generate heat in the cancerous tissue upon light irradiation. Unlike conventional activatable agents that rely on a single biomarker, LG-AB employs an AND logic-gated design, where glucose transporter 1 (GLUT1) overexpression facilitates targeted cellular uptake in cancer cells, followed by activation through elevated glutathione (GSH) levels. Beyond demonstrating photothermal efficacy in human lung cancer and murine breast cancer cells, we show that LG-AB effectively attenuates cancer progression through heat-induced apoptosis, with minimal off-target effects to surrounding tissues. The versatility of this strategy is further demonstrated through the development and application of LG-CPT (Logic-Gated Camptothecin), which utilizes the same logic-gated design. Our results show that enhancing specificity and limiting collateral damage can be broadly applied across different therapeutic agents.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"33 3 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443960","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":"Photocatalytic 1,3-Difluoroalkylcarboxylation of Alkenes by Triple Kinetic-Controlled Radical Self-Ordering","authors":"Hong Fu, Zuo-Shuai Wang, Si-Jia Li, Lin-Yuan Zhu, Xiao-Jian Wang, Hong-Chen Wang, Bing Han","doi":"10.1039/d4sc08607d","DOIUrl":"https://doi.org/10.1039/d4sc08607d","url":null,"abstract":"A transition metal-free protocol for the unsymmetrical radical 1,3-difunctionalization of alkenes has been established for the first time in the form of 1,3-difluoroalkylcarboxylation by a photocatalytic radical three-component reaction of allyl formates, trifluoroacetanilides, and cesium formate. This reaction employs formate as the carboxylating reagent and trifluoroacetanilide as the difluoroalkylating reagent via C-F bond activation. As a result, a series of previously inaccessible unsymmetrical difluorinated adipic acid derivatives can be easily and efficient prepared. Mechanism studies reveal that a triple-kinetic controlled radical self-ordering is the key core for this unique reaction. This radical sorting involves fast initiation of CO2 radical anion and its chemoselective addition and reduction, followed by the slow generation of fluoroalkyl radical and its chemo-/regioselective addition. Notably, this strategy is also suitable for the 1,3-difluoroalkylcarboxylation of unsymmetrical and cyclic alkenes by diastereoselectively constructing two or three consecutive stereocenters.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443977","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":"A Switch-On Luminescent Europium(III) Probe for Selective and Time-Resolved Detection of Adenosine Diphosphate (ADP)","authors":"Samantha E Bodman, Patrycja Stachelek, Umatur Rehman, Felix Plasser, Robert Pal, Stephen Jonathan Butler","doi":"10.1039/d4sc07188c","DOIUrl":"https://doi.org/10.1039/d4sc07188c","url":null,"abstract":"Adenosine diphosphate (ADP) is a key product of two essential classes of biological reactions, catalysed by ATPases and kinases. This makes ADP a highly appealing target for supramolecular detection. However, doing so selectively is exceedingly difficult due to ADP‘s lower overall charge and similar structure to ATP and the need for compatibility with biological media. Overcoming this challenge, here we present a water-soluble, ADP-selective, luminescent europium(III) probe suitable for use in vitro and in cellular microscopy. This negatively charged Eu(III) complex binds ADP reversibly and responds by switching on its luminescence, whilst showing minimal interference from ATP, pyrophosphate and a wide range of biological anions. The probe is equipped with two -conjugated quinolyl-phenoxyacetate antennae, facilitating excitation at 355 nm in fluorescence microscopy. The ancillary carboxylate groups ensure high water solubility and supress non-specific binding to albumin protein. Our novel probe demonstrates a level of sensing selectivity for ADP that is unrivaled, producing a linear emission response across the physiologically relevant concentration range (10–400 μM), even in the presence of excess millimolar ATP. We demonstrate that this amphiphilic Eu(III) probe permeates mammalian cells and localises within the mitochondria and lysosomes. The low background emission of the probe combined with its excellent ADP selectivity and long-lived luminescence makes it a promising tool for visualising ADP levels in living cells.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"46 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443955","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":"Heterogeneously Catalyzed Supramolecular Polymerization: Essential Roles of Nucleation and Fragmentation-Induced Autocatalysis in Chiral Transfer","authors":"Peichen Shi, Ganyu Chen, Qiang Chen, Huiting Wu, Suixu Li, Xiaoyu Cao, Liulin Yang, Zhong-qun Tian","doi":"10.1039/d4sc07894b","DOIUrl":"https://doi.org/10.1039/d4sc07894b","url":null,"abstract":"The complexity of multi-component molecular assembly demands precise control strategies to enhance both efficiency and selectivity. Heterogeneous nucleation and autocatalytic secondary nucleation, as key regulatory strategies, have attracted widespread attention for their crucial roles in crystal growth and amyloid protein aggregation. Here, we apply a heterogeneous nucleation strategy to supramolecular polymer systems and report the first direct observation of surface-enrichment-induced primary nucleation and a spontaneous fragmentation-driven autocatalytic secondary process. Heterogeneous nucleating agent promotes primary nucleation, facilitating supramolecular chiral induction. The resulting chiral polymers undergo a catalytic cycle of fragmentation and re-growth at their termini, with the fragments also acting as seeds for secondary nucleation and growth. These pathways play a crucial role in the polymerization process and are essential for chiral transfer and amplification, enabling the achievement of maximum enantioselectivity with as little as 0.5% molar equivalent of the heterogeneous nucleating agent. Furthermore, we reveal the existence of an optimal equivalent in their catalytic kinetics, arising from a surface assembly mechanism. In this mechanism, monomers adsorbed on the surface of the heterogeneous nucleating agent assemble with those in solution, rather than through surface diffusion and assembly. This process resembles the surface-catalyzed Eley-Rideal mechanism. Our study highlights the potential of heterogeneous nucleation as an effective strategy for controlling supramolecular polymerization and offers new insights into its underlying mechanism.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435429","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":"Operando evidence on the chirality-enhanced oxygen evolution reaction in intrinsically chiral electrocatalysts†","authors":"Felipe Garcés-Pineda, Jiahao Yu, Camilo A. Mesa, Sergi Plana-Ruiz, Daniel Ruano, Yunchang Liang, Magalí Lingenfelder, Sixto Giménez Juliá, Jose Galan-Mascaros","doi":"10.1039/d4sc07927b","DOIUrl":"https://doi.org/10.1039/d4sc07927b","url":null,"abstract":"Electrolytic hydrogen is identified as a crucial component in the desired decarbonisation of the chem- ical industry, utilizing renewable energy to split water into hydrogen and oxygen. Water electrolysis still requires important scientific advances to improve its performance and lower its costs. One of the bottlenecks in this direction relates to the sluggish anodic oxygen evolution reaction (OER). Produc- ing anodes with competitive performance remains challenging due to the high energy loses and the harsh working conditions typically imposed by this complex oxidation process. Recent advancements point to spin polarization as an opportunity to enhance the kinetics of this spin-restricted reaction, yielding the paramagnetic O2 molecule. One powerful strategy deals with the generation of chiral catalytic surfaces, typically by surface functionalisation with chiral organic molecules, to promote chiral-induced spin selectivity (CISS) effect during electron transfer. However, the relationship be- tween chirality and enhanced electrocatalysis has been established only from indirect experimental evidences. In this work, we have exploited operando electrochemical and spectroscopic tools to con- firm the direct relationship between the faster OER kinetics and the optical activity of enantiopure Fe-Ni metal oxides when compared with their achiral catalysts in alkaline conditions. Our results show the participation of chiral species as reactive intermediates during the electrocatalytic reaction, supporting the appearance of a mechanistic CISS enhancement. Furthermore, these intrinsically chi- ral transition-metal oxides maintain their enhanced activity in full cell electrolyser architectures at industrially relevant current densities.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435414","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":"Helix-Induced Full-color Circularly Polarized Luminescence Films with Multiple Information Encryption and Multi-stimuli Responsiveness","authors":"Shi-Yi Li, Yang Zong, Bing-Hao Liu, Na Liu, Zong-Quan Wu","doi":"10.1039/d5sc00019j","DOIUrl":"https://doi.org/10.1039/d5sc00019j","url":null,"abstract":"The development of full-color circularly polarized luminescence (CPL) materials is of great significance in the field of luminescent materials; however, it is difficult due to the limitations in the synthesis and preparation methods. Helical polymers, with their high optical activity and easy processability, offer a promising solution for the construction of high-performance CPL materials. In this study, we successfully prepared full-color CPL composite films using precisely synthesized polyisocyanide (PI) as chiral source, poly(methyl methacrylate) as the matrix, and commercially available fluorescein as fluorescence source. The introduction of PI not only improves the mechanical properties and fluorescence lifetime of the composite films but also facilitates recyclability through centrifugation after dissolving the composite films with the poor solvent of PI. Moreover, the use of spiropyran as a red fluorescein allows for dynamic responsiveness to light, heat, and acid-base stimuli, broadening the functionality of the CPL materials and constructs a multiple information encryption system. This work presents a low-cost, easily processable, and multi-stimuli responsive strategy for full-color fabrication of CPL materials based on helical PI.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435416","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":"A focus on copper depletion-induced cuproptosis for cancer therapy","authors":"Hongjie Zhang","doi":"10.1039/d5sc90034d","DOIUrl":"https://doi.org/10.1039/d5sc90034d","url":null,"abstract":"Copper has emerged as a promising target for cancer therapy, with extensive studies on copper accumulation-induced cuproptosis. However, the potential of copper depletion-induced cuproptosis remains largely unexplored. Recently, Zhou <em>et al.</em> (M. Zhou, F. Muhammad, Y. Zhang, T. Li, J. Feng, J. Zhao and H. Wei, <em>Chem. Sci.</em>, 2025, https://doi.org/10.1039/D4SC04712E) reported an innovative strategy for copper depletion-based cuproptosis. Notably, this approach leverages the solubility product principle, a mechanism not previously addressed in studies, to achieve effective tumor therapy through the disruption of copper homeostasis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"49 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435413","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":"Stereochemical expression of Bi 6s2 lone pairs mediates fluoride-ion (De)insertion in tunnel-structured Bi2PdO4 and Bi1.6Pb0.4PtO4","authors":"George Agbeworvi, Anindya Pakhira, Shruti Hariyani, Wasif Zaheer, Alice Giem, Jaime R. Ayala, John D. Ponis, Saul Perez-Beltran, Cherno Jaye, Conan Weiland, Daniel A. Fischer, Hassan S. Bazzi, Mohammed Al-Hashimi, Sarbajit Banerjee","doi":"10.1039/d4sc08111k","DOIUrl":"https://doi.org/10.1039/d4sc08111k","url":null,"abstract":"Fluoride-ion batteries are a promising alternative to lithium-ion batteries by dint of the greater crustal abundance of fluorine and the potential to alleviate the need for metal electrodeposition. However, conventional metal fluoride cathodes typically rely on conversion-type reactions that require propagation of a reaction—diffusion front, thereby limiting cycling performance and rate capability. In contrast, the topochemical insertion of fluoride-ions in periodic solids remains a relatively unexplored approach. Here, we explore the mechanisms of fluoridation of Bi<small>₂</small>PdO<small>₄</small> and Bi<small>_1.6</small>Pb<small>_0.4</small>PtO<small>₄</small> insertion hosts that possess capacious tunnels that can accommodate fluoride-ions with a particular emphasis on elucidating the role of stereochemical expression of bismuth 6s<small>²</small> lone pairs in mediating anion diffusion. We reveal that the topochemical solution-phase insertion and deinsertion of fluoride-ions at room temperature is mediated by redox reactions at platinum and palladium centers but involves multi-center synergies between d- and p-block atoms across the one-dimensional (1D) tunnel structure. While Pt and Pd centers mediate redox reactions, the stereochemically active lone pair electrons of Bi<small>³⁺</small> play a pivotal role in facilitating reversible fluoride-ion diffusion. Consequently, Bi<small>_1.6</small>Pb<small>_0.4</small>PtO<small>₄</small> and Bi<small>₂</small>PdO<small>₄</small> can be reversibly fluoridated with full recovery of the crystal lattice and with minimal alteration of the unit cell volume. The results reveal a key principle that the stereochemical activity of p-block electron lone pairs can be harnessed to modulate anion–lattice interactions and mediate facile anion diffusion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"129 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435412","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}