Chemical Science最新文献

{"title":"Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines","authors":"Huan Meng, Jun-Song Jia, Peng-Fei Yang, Yu-Long Li, Qiong Yu, Wei Shu","doi":"10.1039/d4sc07728h","DOIUrl":"https://doi.org/10.1039/d4sc07728h","url":null,"abstract":"Catalytic methods allow for regioselective and site-divergent transformations for rapid construction of different complex architectures from identical and readily-available starting materials by switching the least parameters are among the most ideal catalytic protocols. However, the associated challenge to precisely control both regioselectivity and site-diversity renders this strategy appealing yet challenging. Herein, a Ni-catalyzed cross-electrophile regioselective and site-divergent 1,2- and 1,3-arylalkylations of allylic amines have been developed. This Ni-catalyzed reductive three-component protocol enables 1,2-arylalkylation and 1,3-arylalkylations of allylic amines with aryl halides and alkyl halides with excellent chemo-, regio- and site-selectivity, representing the first example of controlled migratory difunctionalization of alkenes under reductive conditions. A wide range of sterically and electronically differentiated terminal and internal unactivated allylic amines, aryl halides and alkyl precursors were tolerated, providing a straightforward and efficient access to diverse C(sp3)-rich branched aliphatic amines from identical starting materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020806","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":"Uncovering the potent antimicrobial activity of squaramide based anionophores – chloride transport and membrane disruption","authors":"Robert B. P. Elmes, Luke Edward Brennan, Xuanyang Luo, Farhad Ali Mohammed, Kevin Kavanagh","doi":"10.1039/d4sc01693a","DOIUrl":"https://doi.org/10.1039/d4sc01693a","url":null,"abstract":"Antimicrobial resistance (AMR) - often referred to as a silent pandemic, is at present the most serious threat to medicine, and with constantly emerging resistance to novel drugs, combined with the paucity of their development, is likely to worsen. To circumvent this, supramolecular chemists have proposed the applicability of synthetic anion transporters in the fight against AMR. In this article we discuss the synthesis, supramolecular characterisation and biological profiling of six structurally simple squaramide anion transporters. Through a combination of spectroscopic techniques, and cellular assays we have deduced the mode of action of these antimicrobial agents to be as a result of both anion transport and membrane disruption. Furthermore, through the synthesis of two fluorescent analogues we verified this membrane-localised activity using Super-Resolution nanoscopy methods. These compounds represent particularly active antimicrobial anionophores and compliment similar reports showing the applicability of agents such as these in the fight against AMR.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020343","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 Mesityl-Functionalized Double-Boron-Nitrogen-Oxygen-Embedded Multi-Resonance Framework Achieves Anti-Quenching Narrowband Deep-Blue Electroluminescence with EQE over 30% and CIEy of 0.046","authors":"Zhuixing Xue, Zhengqi Xiao, Yang Zou, Zhanxiang Chen, Jiahui Liu, Zhongyan Huang, Chuluo Yang","doi":"10.1039/d4sc07503j","DOIUrl":"https://doi.org/10.1039/d4sc07503j","url":null,"abstract":"Developing highly efficient deep-blue multi-resonance thermal activated delayed fluorescence (MR-TADF) materials for ultra-high-definition organic light-emitting diodes (OLEDs) displays that meet the stringent BT.2020 standard remains a significant challenge. In this study, we present a strategy to achieve high-performance deep-blue MR-TADF emitters by integrating a large π-conjugated double-boron-embedded MR skeleton with strategically positioned peripheral steric hinderance groups. The developed molecule, DMBNO, exhibits a narrow full-width at half maximum (FWHM) of 19 nm, with a deep-blue emission peak at 444 nm in diluted toluene solutions. Additionally, it achieves high photoluminescence quantum yield (PLQY) and a horizontal ratios of emitting dipole orientation (Θ//) exceeding 90% in doped films. Notably, DMBNO demonstrates anti-quenching properties and effectively suppresses spectrum broadening. Consequently, OLEDs based on DMBNO achieve a high maximum external quantum efficiency (EQEmax) of 32.3%, with an impressive Commission Internationale de l'Eclairage (CIE) y-coordinate of 0.046, fully satisfying the BT.2020 blue gamut at a high doping concentration of 10 wt%. These findings offer valuable insights into molecular design tactics for deep-blue MR-TADF emitters featuring high efficiency, ultra-pure color, and anti-quenching characteristics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020355","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":"Initiating photocatalytic degradation of organic pollutants under ultra-low light intensity via oxygen-centered organic radicals","authors":"Yingge He, Yuyan Huang, Yuxin Ye, Yanchun Deng, Xin Yang, Gangfeng Ouyang","doi":"10.1039/d4sc06339b","DOIUrl":"https://doi.org/10.1039/d4sc06339b","url":null,"abstract":"Photocatalysis, as a promising method for in-situ water pollution remediation but faces challenges due to the limited natural light intensity. Herein, we achieve highly-efficient photocatalytic removal of organic pollutants even under ultra-low light intensities of only 0.1 mW·cm⁻². This was accomplished by developing and effectively stabilizing a novel reactive species - oxygen-centered organic radicals (OCORs), which has an impressive half-life of up to seven minutes in water. With lifetimes 8 to 11 orders of magnitude longer than traditional transient radicals, OCORs can effectively wait for pollutants to diffuse, enabling them to remove organic pollutants through polymerization and degradation pathways. The mechanism behind the stability of OCORs lies in the enhanced electron-withdrawing ability of the electron acceptor and the extended conjugation of the catalyst, which effectively prevent back electron transfer. This study provides a theoretical foundation for practical applications of photochemistry in pollution remediation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020356","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":"Exploiting the inherent promiscuity of the acyl transferase of the stambomycin polyketide synthase for the mutasynthesis of analogues","authors":"Li SU, Yaouba Souaibou, Laurence Hôtel, Christophe Jacob, Peter Grün, Yan-Ni Shi, Alicia Chateau, Sophie Pinel, Helge Bode, Bertrand Aigle, Kira Weissman","doi":"10.1039/d4sc06976e","DOIUrl":"https://doi.org/10.1039/d4sc06976e","url":null,"abstract":"The polyketide specialized metabolites of bacteria are attractive targets for generating analogues, with the goal of improving their pharmaceutical properties. Here, we aimed to produce C-26 derivatives of the giant anti-cancer stambomycin macrolides using a mutasynthesis approach, as this position has been shown previously to directly impact bioactivity. For this, we leveraged the intrinsically broad specificity of the acyl transferase domain (AT12) of the modular polyketide synthase (PKS), which is responsible for the alkyl branching functionality at this position. Feeding of a panel of synthetic and commercially available dicarboxylic acid ‘mutasynthons’ to an engineered strain of Streptomyces ambofaciens (Sa) deficient in synthesis of the native α-carboxyacyl-CoA extender units, resulted in six new series of stambomycin derivatives as judged by LC-HRMS and NMR. Notably, the highest product yields were observed for substrates which were only poorly accepted when AT12 was transplanted into a different PKS module, suggesting a critical role for domain context in the overall functioning of PKS proteins. We also demonstrate the superiority of this mutasynthesis approach − both in terms of absolute titers and yields relative to the parental compounds − in comparison to the alternative precursor-directed strategy in which monoacid building blocks are supplied to the wild type strain. We further identify a malonyl-CoA synthetase, MatB_Sa, with specificity distinct from previously identified promiscuous enzymes, making it a useful addition to a mutasynthesis toolbox for generating atypical, CoA activated extender units. Finally, we show that two of the obtained (deoxy)-butyl-stambomycins exhibit antibacterial and antiproliferative activities similar to the parental stambomycins, while an unexpected butyl-demethyl congener is less potent. Overall, this works confirms the interest of biosynthetic pathways which combine a dedicated route to extender unit synthesis and a broad specificity AT domain for producing bioactive derivatives of fully-elaborated complex polyketides.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020351","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":"Low Temperature Thermal RAFT Depolymerization: The Effect of Z-group Substituents on Molecular Weight Control and Yield","authors":"Nethmi De Alwis Watuthanthrige, Anastasiia Moskalenko, Asja A. Kroeger, Michelle Coote, Nghia Truong Phuoc, Athina Anastasaki","doi":"10.1039/d4sc07518h","DOIUrl":"https://doi.org/10.1039/d4sc07518h","url":null,"abstract":"The labile end-groups inherent to many controlled radical polymerization methodologies, including atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization, can trigger the efficient chemical recycling of polymethacrylates yielding high percentages of pristine monomer. Yet, current thermal solution ATRP and RAFT depolymerization strategies require relatively high temperatures (i.e. 120-170 °C) to proceed, with slower depolymerization rates, and moderate yields often reported under milder reaction conditions (i.e. lower temperatures). In this work, we seek to promote the low temperature RAFT depolymerization of polymethacrylates via regulating the Z-group substitution of dithiobenzoate. While electron-withdrawing meta and para substituents, including trifluoromethyl (CF<small>₃</small>) and trifluoromethoxy (OCF<small>₃</small>), compromised the percentage of monomer recovery at 90 °C (e.g. 18% of conversion), instead the incorporation of electron-donating groups in the benzene ring, such as methoxy (OMe) and tertiary butoxy (OtBu), had a remarkable effect leading to up to four times higher conversions (e.g. 75%). Notably, electron-withdrawing Z-groups imposed control over depolymerization, reflected in the gradual decrease of the molecular weight during the reaction, as opposed to electron-donating groups which underwent a more uncontrolled depolymerization pathway. Density Functional Theory (DFT) calculations revealed accelerated bond fragmentation for electron-donating Z-groups, further supporting our findings. Taken altogether, this work highlights the importance of RAFT agent selection to either lower the reaction’s temperature while maintaining high conversions, or induce control over the depolymerization.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"84 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020354","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":"Exploiting spatial isomerism to modulate the assembled phase and rheological response of compositionally identical sugar-based surfactants","authors":"Jia-Fei Poon, Alfonso Cabezon, Alessandro Gulotta, Najet Mahmoudi, Stefan Ulvenlund, Rebeca Garcia Fandino, Adrian Sanchez-Fernandez","doi":"10.1039/d4sc08242g","DOIUrl":"https://doi.org/10.1039/d4sc08242g","url":null,"abstract":"For decades, extensive surfactant libraries have been developed to meet the requirements of downstream applications. However, achieving functional diversity has traditionally demanded a vast array of chemical motifs and synthetic pathways. Herein, a new approach for surfactant design based on structural isomerism is utilised to access a wide spectrum of functionalities. A library of C18-aliphatic maltosides was prepared through Koenigs–Knorr glycosylation, of which their properties were tuned through anomerism, stereoisomerism, regioisomerism, and degree of tail unsaturation. Self-assembly of the amphiphiles give rise to various morphologies, ranged from small micelles to large one-dimensional semiflexible assemblies, which were ultimately defined by the directionality of the supramolecular interactions imposed by the angular restraints of the isomeric centres. Remarkably, the microscopic phase determines the rheological behaviour of the system, which access Newtonian solutions, viscoelastic fluids, and gels with customised mechanical properties. The approach outlined in this study serves as a blueprint for the design of novel bioderived surfactants with diverse behaviour without altering the chemical composition of the surfactants, where the understanding of molecular interactions can potentially be used to predict and design the assembly and function of isomerically varied amphiphiles.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"75 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020386","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":"CO2 Hydrosilylation Catalyzed by an N-Heterocyclic Carbene (NHC)-Stabilized Stannyliumylidene","authors":"Dechuang Niu, Arseni Kostenko, John A. Kelly, Debotra Sarkar, Huihui Xu, Shigeyoshi Inoue","doi":"10.1039/d4sc07116f","DOIUrl":"https://doi.org/10.1039/d4sc07116f","url":null,"abstract":"The bis-N-heterocyclic carbene (NHC) stabilized stannyliumylidene, [<small>^Mes</small>TerSn(IMe<small>₄</small>)<small>₂</small>][BArF], (<small>^Mes</small>Ter = 2,6-Mes<small>₂</small>C<small>₆</small>H<small>₃</small>, Mes = 2,4,6-Me<small>₃</small>-C<small>₆</small>H<small>₂</small>, IMe<small>₄</small> = 1,3,4,5-tetramethylimidazol-2-ylidene, BArF = (3,5-(CF<small>₃</small>)<small>₂</small>-C<small>₆</small>H<small>₅</small>)<small>₄</small>B), was isolated in the reaction of (<small>^Mes</small>Ter)SnCl with two equivalents of IMe<small>₄</small>, followed by one equivalent of NaBArF. This stannyliumylidene acts as a precatalyst for the homogeneous hydrosilylation of CO<small>₂</small>. Experimental mechanistic studies and quantum chemical calculations have been conducted to elucidate the catalytically active species and the mechanism of the catalytic reaction, revealing the stannyliumylidene [<small>^Mes</small>TerSn(CO<small>₂</small>IMe<small>₄</small>)<small>₂</small>][BArF], which is formed in the presence of CO<small>₂</small> as the catalytically active species.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020350","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":"Tunable structural rearrangement in Cu cluster assemblies through linker and solvent alterations","authors":"Saikat Das, Jin Sakai, Riki Nakatani, Ayumu Kondo, Rina Tomioka, Subhabrata Das, Shuntaro Takahashi, Tokuhisa Kawawaki, Sourav Biswas, Yuichi Negishi","doi":"10.1039/d4sc07730j","DOIUrl":"https://doi.org/10.1039/d4sc07730j","url":null,"abstract":"The scarcity of approaches to assembling copper nanoclusters (Cu NCs) has restricted advancements in Cu NCs research, largely due to stability challenges of the individual NCs. By utilizing the structural adaptability of Cu NCs, we systematically investigate how variations in organic linkers and solvents affect the cluster node size, shape, and their assembling dimensionality. Here, we introduce a facile, one-pot synthesis method for obtaining a range of crystalline Cu cluster-assembled materials (CAMs) through a liquid-liquid interfacial crystallization technique. Our approach demonstrates that the electronic environment of linker molecules plays a crucial role in constructing the geometry of cluster nodes and the overall dimensionality of the framework. Solvent effects further influence the electronic environment of linkers, leading to tunable rearrangements in cluster node size and geometry. Additionally, coordination sites of the linker molecules and architectural properties significantly affect the overall dimensionality of the frameworks. Furthermore, correlations between solid-state photophysical properties and structural architecture expand the scope of this study, introducing the potential for tunable optical properties. We anticipate that this work will not only open avenues for designing novel Cu CAMs but also guide future research toward Cu-based materials with customizable optical features.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020387","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":"Lanthanide-Tetrazine Probes for Bio-Imaging and Click Chemistry","authors":"Benjamin Woolley, Yue Wu, Xiong Li, Ho-Fai Chau, Junhui Zhang, Ga-Lai Law, Ka Leung Wong, Nicholas J Long","doi":"10.1039/d4sc02335h","DOIUrl":"https://doi.org/10.1039/d4sc02335h","url":null,"abstract":"The blood-brain-barrier stops many imaging agents and therapeutics from being delivered to the brain that could fight central nervous system diseases such as Alzheimer’s Disease and strokes. However, techniques such as the use of stapled peptides or peptide shuttles may allow payloads through, with bioconjugation achieved <em>via</em> bio-orthogonal tetrazine/norbornene click chemistry. A series of lanthanide-tetrazine probes have been synthesised herein which could be utilised in bio-orthogonal click chemistry with peptide-based delivery systems to deliver MRI agents through the blood-brain-barrier. The Gd complexes show higher relaxivities than the clinical standard of Gd(DOTA) at 1.4 T and phosphorescence is observed from the Eu and Tb complexes<em> via</em> tetrazine sensitization. A bio-orthogonal click reaction between a Gd-tetrazine complex and a cyclic-RGD-norbornene conjugate was successful and the resulting clicked probe demonstrated enhanced relaxivity and could potentially act as a peptide shuttle for the Gd MRI agent.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"136 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020388","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}