Chemical Science最新文献

{"title":"Synergistic action of two radical SAM enzymes in the biosynthesis of thuricin CD, a two-component sactibiotic","authors":"Yifei Jia, Yuanjun Han, Xuxue Liu, Qi Zhang","doi":"10.1039/d5sc01546d","DOIUrl":"https://doi.org/10.1039/d5sc01546d","url":null,"abstract":"Thuricin CD, comprised of two ribosomally derived peptides trnα and trnβ, is a distinct two component sactipeptide antibiotic known for its potent narrow spectrum antibacterial activity against several strains including Clostridioides difficile. Despite its early discovery, how the characteristic thioether crosslinks are installed on thuricin CD remained largely elusive. In this report, we demonstrate that neither of the two radical S-adenosylmethionine (rSAM) enzymes, TrnC and TrnD, can effectively modify the precursors individually. Instead, TrnC and TrnD form a tight complex and collaboratively catalyze thioether crosslinking on the two precursor peptides TrnA and TrnB. Although both TrnC and TrnD are active rSAM enzymes, only the rSAM activity of TrnC is strictly essential for thioether crosslink, demonstrating a unique enzyme synergy in the biosynthesis of two component antibiotics. We also generate an active thuricin CD variant by a procedure involving coexpression followed by in vitro proteolysis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920237","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":"Merging directed sp3 and nondirected sp2 C–H functionalization for Pd-catalyzed polydeuteration of (hetero)arenes","authors":"Soo Eun Park, Sungjun Choi, Chaewon Lim, Sang Hak Lee, Siyeon Jeong, Jung Min Joo","doi":"10.1039/d5sc01407g","DOIUrl":"https://doi.org/10.1039/d5sc01407g","url":null,"abstract":"Polydeuteration has emerged as a key strategy in the development of pharmaceuticals and functional organic materials, advancing beyond monodeuteration and trideuteromethylation. We have developed methods for the polydeuteration of a wide range of organic compounds through Pd-catalyzed directed sp<small>³</small> C–H activation and nondirected sp<small>²</small> C–H activation, using readily available deuterium source, AcOH-<em>d</em><small>₄</small>. This approach addresses the challenge of facilitating both directed and nondirected C–H functionalization of electronically and sterically diverse (hetero)aromatic compounds through the use of a versatile [2,2′-bipyridin]-6(1<em>H</em>)-one (<strong>BpyOH</strong>) ligand. This method demonstrates high functional group compatibility, readily applicable in the presence of directing functional groups such as carboxylic acids, amides, and azoles, as well as nondirecting electron-withdrawing groups such as nitro, sulfonamide, and ester groups. DFT calculations reveal that ligands influence intermediates and transition states by providing bidentate chelation, internal base, and hydrogen bonding. The Pd(<strong>BpyOH</strong>) complex exhibits well-balanced reactivity for C–H cleavage while readily forming complexes with substrates, which is relevant to other Pd-catalyzed C–H functionalization reactions. Our approach significantly broadens the scope of deuterated building blocks and late-stage deuteration, thereby facilitating evaluation of the deuterium effect in various applications across medicinal chemistry, materials science, and beyond.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"63 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920292","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":"Harnessing C–H acetoxylation: a gateway to oxygen-enriched organic frameworks","authors":"Jagrit Grover, Bishal Dutta, Devika Ghosh, Prakash Kumar Shee, Siddhartha Maiti, Daniel B. Werz, Debabrata Maiti","doi":"10.1039/d5sc00449g","DOIUrl":"https://doi.org/10.1039/d5sc00449g","url":null,"abstract":"Transition metal catalyzed C-H functionalization has emerged as a robust tool in organic synthesis, as it utilizes the most abundant functional group of an organic compound i.e. C-H bonds, omitting the need for pre-functionalization. Selectively functionalizing a particular C-H bond out of numerous C-H bonds present in the molecular skeleton is a fascinating and difficult task to perform. To differentiate between almost identical CH bonds, various strategies have evolved. Directing group (DG) assistance, non-directed functionalizations, and non-covalent interactions have significantly contributed to address the challalenge of regioselectivity in taregting distinct C-H bonds. However, further advancements are still required. Among various C-H functionalizations, C-H acetoxylation is a pivotal organic transformation which enables direct functionalization of otherwise inert C-H bonds into versatile acetoxy groups. In this review, various strategies for C-H acetoxylation, i.e. directed and non-directed C-H acetoxylation, electrochemical C-H acetoxylation, photo-induced C-H acetoxylation, are covered. A comprehensive coverage provided by this review will be extremely useful to chemists in both academia and industry, who are striving to incorporate oxygen into organic molecular skeletons.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915865","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":"Light-induced twisting, untwisting, and retwisting of aromatic polyamides: an interplay between the induced chirality and the co-facial π-stacking interactions","authors":"Subhendu Samanta, Raj Kumar Roy","doi":"10.1039/d4sc08795j","DOIUrl":"https://doi.org/10.1039/d4sc08795j","url":null,"abstract":"The ability of proteins to undergo conformational changes in response to varying environmental conditions has inspired chemists to devise smart materials that can achieve comparable functions. Oligopeptides, which are simplified versions of proteins, have demonstrated the ability to undergo conformational changes in response to stimuli, transitioning between two ordered structures: helix and sheet. In contrast, such conformational transitions in non-peptidic synthetic polymers are generally limited to order-disorder transitions, specifically shifting between helix and coil states. This report presents a novel approach in which we designed a periodically functionalized aromatic polyamide that exhibits the conformational dynamicity between two order structures (helix ↔ pleated-sheet ↔ helix). The enantiopure pendants of this aromatic polyamide induce a helical structure into the achiral polyamide backbones. At the same time, incorporating the guest molecule enhances the co-facial π-stacking and mediates a conformational transition from a helix to a pleated sheet-like structure. Subsequently, we employed photoresponsive merocyanine as the planar guest molecule, which served as a reversible conformational switch for this aromatic polyamide. The planer merocyanine induces the host–guest complex with this polymer and transforms the helical structure of polyamides into a pleated sheet-like structure. When exposed to visible light, the planar merocyanine changes into a non-planar spyropyran, which breaks apart the host–guest complex and effectively restores the helical structure of aromatic polyamides. Therefore, we present an intriguing demonstration of the twisting, untwisting, and retwisting of aromatic polyamides by balancing two key interactions, such as co-facial π-stacking along the aromatic polyamide backbone and the helical induction from the grafted enantiopure residues.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"47 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915863","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":"In situ transmission electron microscopy characterization and manipulation of the morphology, composition and phase evolution of nanomaterials under microenvironment conditions","authors":"Na Li, Tian Wang, Bo Wen, Zicheng Yin, Xinyang Li, Jie Feng, Shujiang Ding, Shengchun Yang, Guorui Yang, Yawei Yang","doi":"10.1039/d5sc01214g","DOIUrl":"https://doi.org/10.1039/d5sc01214g","url":null,"abstract":"Nanomaterials possess a broad range of applications in areas such as catalysis, energy, and biomedicine because of their unique properties. However, from the perspective of materials synthesis, there are numerous challenges in the controllable preparation of nanomaterials. These include the control of their size, morphology, crystal structure, and surface properties, which are essential for their performance in specific applications. The fundamental cause of these issues is the limitation in the real-time observation of the growth process of nanomaterials. In situ transmission electron microscopy (TEM), on the other hand, overcomes the limitations of traditional in situ testing techniques. It enables the real-time observation and analysis of the dynamic structural evolution during the growth of nanomaterials at the atomic scale. This contributes to a profound understanding of the nucleation and growth mechanisms of nanomaterials and facilitates the controlled preparation of nanomaterials. This review centers on the utilization of in situ TEM to observe and study the complex dynamic processes of zero-, one-, and two-dimensional nanomaterial growth and evolution in different environments (liquid, gas, and solid phases) from the atomic scale. This is of great significance for the design and preparation of nanomaterials with specific properties. The proposed future development of in situ TEM, in combination with advanced data analysis and integration with other techniques, holds great potential for the further advancement of nanotechnology and its applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"43 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915868","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":"Two-dimensional Infrared Spectroscopy as a Tool to Reveal the Vibrational and Molecular Structure of [FeFe] Hydrogenases","authors":"Cornelius Constantin Maria Bernitzky, yvonne rippers, Denise Poire, Mathesh Vaithiyanathan, Solomon Lewis David Wrathall, Barbara Procacci, Igor V. Sazanovich, Gregory M Greetham, Patricia Rodriguez Macia, Neil Hunt, James A. Birrell, Marius Horch","doi":"10.1039/d5sc01811k","DOIUrl":"https://doi.org/10.1039/d5sc01811k","url":null,"abstract":"[FeFe] hydrogenases are Nature’s most efficient catalysts for the cleavage and evolution of molecular hydrogen. Despite decades of research, key aspects of the catalytic cycle and the underlying geometrical and electronic properties of the active-site cofactor, called the H-cluster, are not fully understood. Spectroscopic techniques have played a central role in establishing the current state of knowledge on [FeFe] hydrogenases, and further advances in the field depend critically on novel techniques that yield so-far inaccessible insights into structural and mechanistic aspects. Infrared (IR) absorption spectroscopy represents a well-established and versatile technique that can identify and characterize all active and inactive states of the H-cluster by means of structurally sensitive and spectrally isolated CO and CN stretching vibrations. However, the amount of information that can be extracted from these linear experiments is inherently limited. Here we introduce experimental and computational two-dimensional (2D-)IR spectroscopy for the characterization of [FeFe] hydrogenases. Utilizing the H<small>_inact</small> state of the H-cluster as a model system, we demonstrate that this nonlinear technique yields direct information about the nature and interactions of the CO and CN stretching vibrations. These insights allow, for the first time, to quantitatively describe the character of these widely used reporter vibrations, their spatial localization, and the way they change upon structural variation of the H-cluster. The strength of this approach is demonstrated by correctly identifying the proposed structure of the H<small>_inact</small> state, in solution and at ambient temperature. In conclusion, the introduced combination of experimental and computational 2D-IR spectroscopy represents a powerful approach for studying [FeFe] hydrogenases and other complex organometallic targets.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915864","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":"Binding assays enable discovery of Tet(X) inhibitors that combat tetracycline destructase resistance","authors":"Matthew J. Beech, Edmond C. Toma, Helen G. Smith, Maria M. Trush, Jit H. J. Ang, Mei Y. Wong, Chung H. J. Wong, Hafiz S. Ali, Zakia Butt, Viha Goel, Fernanda Duarte, Alistair J. M. Farley, Timothy R. Walsh, Christopher J. Schofield","doi":"10.1039/d5sc00964b","DOIUrl":"https://doi.org/10.1039/d5sc00964b","url":null,"abstract":"The Tet(X) flavin-dependent monooxygenases enable tetracycline antibiotic resistance by catalysing inactivating hydroxylation, so preventing inhibition of bacterial ribosomes. Tet(X) resistance is growing rapidly, threatening the efficacy of important last-resort tetracyclines such as tigecycline. Tet(X) inhibitors have potential to protect tetracyclines in combination therapies, but their discovery has been hampered by lack of high-throughput assays. We report the development of an efficient fluorescence polarisation Tet(X) binding assay employing a tetramethylrhodamine-glycyl-minocycline conjugate that enables inhibitor discovery. The assay was applied to tetracycline substrates and reported inhibitors, providing insight into their binding modes. Screening of a bioactive molecule library identified novel Tet(X) inhibitors, including psychoactive phenothiazine derivatives and the 5-HT<small>₄</small> agonist tegaserod, the activities of which were validated by turnover assays. Crystallographic studies of Tet(X4)-inhibitor complexes reveal two new inhibitor binding modes, importantly providing evidence for active site binding of Tet(X) inhibitors that do not share structural similarity with tetracycline substrates. In some cases, potentiation of tigecycline activity was observed in bacteria expressing Tet(X4). The combined results provide non-tetracycline scaffolds for development of potent Tet(X) inhibitors and highlight the need to evaluate the impact of non-antibiotics on antimicrobial resistance.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"62 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915872","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":"Correction: A comprehensive approach for elucidating the interplay between 4fn+1 and 4fn5d1 configurations in Ln2+ complexes","authors":"Maria J. Beltran-Leiva, William N. G. Moore, Tener F. Jenkins, William J. Evans, Thomas E. Albrecht, Cristian Celis-Barros","doi":"10.1039/d5sc90097b","DOIUrl":"https://doi.org/10.1039/d5sc90097b","url":null,"abstract":"Correction for ‘A comprehensive approach for elucidating the interplay between 4f<small>^<em>n</em>+1</small> and 4f<small>^<em>n</em></small>5d<small>¹</small> configurations in Ln<small>²⁺</small> complexes’ by Maria J. Beltran-Leiva <em>et al.</em>, <em>Chem. Sci</em>., 2025, <strong>16</strong>, 2024–2033, https://doi.org/10.1039/d4sc05438e.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915867","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":"Multiple stimulus modulated organic crystal polymorphs with tunable luminescence behavior","authors":"Qian Zhou, Mingxia Feng, Caihong Shi, Mengqiu Qian, Xiurong Ma, Runying He, Xian Meng, Yonggang Shi, Qiue Cao, Liyan Zheng","doi":"10.1039/d5sc01503k","DOIUrl":"https://doi.org/10.1039/d5sc01503k","url":null,"abstract":"Polymorphism is defined as the ability of a substance to exist in two or more crystalline forms, which provide a unique platform for revealing the relationship between its spatial structure and properties. However, organic crystal polymorphism can be commonly obtained by growing crystals in different solvents or at different temperatures. This study reports a compound named <em>p</em>-An-Br containing carbazole and anthracene chromophores with three multiple stimulus modulated crystal polymorphs with green, yellow and red fluorescence, respectively. Interestingly, switching of <em>p</em>-An-Br between crystal G, crystal Y and crystal R can be achieved through the uptake and release of methanol using different stimuli, which shows dynamically adjustable luminescent colors. Significantly, structure–property investigations <em>via</em> the in-depth analysis of molecular conformations and frameworks of the polymorphic crystals demonstrate that the diverse conformations and abundant noncovalent interactions have a predominant impact on emission behavior. Consequently, the crystals R can be used for the highly sensitive and specific sensing of methanol with a detection limit of 39.35 ppm. This study not only provides a new strategy for crystal polymorphism, but also develops an effective method for the detection of methanol.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910196","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":"Exciton and charge transfer processes within singlet fission micelles","authors":"Daniel Malinowski, Guiying He, Bernardo Salcido-Santacruz, Kanad Majumder, Junho Kwon, Matthew Y. Sfeir, Luis M. Campos","doi":"10.1039/d5sc01479d","DOIUrl":"https://doi.org/10.1039/d5sc01479d","url":null,"abstract":"Multiexciton (ME) mechanisms hold great promise for enhancing energy conversion efficiency in optoelectronic and photochemical systems. In singlet fission (SF), the generation of two triplet excitons from a single photon provides a route to circumvent thermal energy losses and organic systems offer opportunities to modulate ME dynamics. However, the practical implementation of SF-based materials is hindered by poor triplet exciton mobility, interfacial recombination losses, and complex dynamics at heterogeneous interfaces. While studies of interfacial SF dynamics have demonstrated the potential for efficient charge and exciton transfer, experimental conditions and design of interfaces vary widely. To address this, we explore polymer-based self-assembled architectures as a tunable platform for studying mesoscale SF interfacial dynamics of (multi)exciton transfer, as well as electron and hole transfer. Specifically, we design amphiphilic block copolymers (BCPs) incorporating pendent tetracene moieties that self-assemble into micellar nanoparticles, placing the tetracenes in the amorphous core. These micelles provide a controlled environment to systematically introduce “dopants” to investigate interfacial dynamics. Importantly, the use of solvents within the micelle core can be also applied to impart polymer chain mobility.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"139 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910378","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}