Nature chemistry最新文献

High-performance recyclable polymers enabled by stereo- and sequence-controlled polymerization 立体和顺序控制聚合使高性能可回收聚合物成为可能

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-16 DOI: 10.1038/s41557-025-01828-6

Meng-Yuan Wang, Yi-Min Tu, Qing-Qian Zeng, Kun Li, Wei Xiong, Zhongzheng Cai, Jian-Bo Zhu

{"title":"High-performance recyclable polymers enabled by stereo- and sequence-controlled polymerization","authors":"Meng-Yuan Wang, Yi-Min Tu, Qing-Qian Zeng, Kun Li, Wei Xiong, Zhongzheng Cai, Jian-Bo Zhu","doi":"10.1038/s41557-025-01828-6","DOIUrl":"https://doi.org/10.1038/s41557-025-01828-6","url":null,"abstract":"Monomer design strategy has become a powerful tool to access chemically recyclable polymers with desired and diverse properties. The presence of two or multiple stereogenic centres in one monomer offers a new dimension to fine-tune the polymer performance. However, it is still a formidable challenge in synthetic polymer chemistry to achieve precise stereocontrol and sequence control over the polymer microstructure. Here we report a stereo- and sequence-controlled polymerization of 5H-1,4-benzodioxepin-3(2H)-one-based monomers with two stereogenic centres (M) to furnish a series of isoenriched AB diblock polymers P(cis-M)-b-P(trans-M) and ABA triblock polymers P(trans-M)-b-P(cis-M)-b-P(trans-M). Notably, P(cis-M2)900-b-P(trans-M2)38 delivered impressive toughness and ductility, comparable to the commodity plastic isotactic polypropylene; the ABA triblock P(trans-M2)26-b-P(cis-M2)900-b-P(trans-M2)26 appeared to be softer and resembled low-density polyethylene. These various materials could fully convert to the monomer M. The establishment of stereo- and sequence-controlled polymerization not only provides an effective and robust strategy to tailor polymer properties on the molecular level, but also delivers various chemically recyclable materials that can be converted back to monomers.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066084","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}

引用次数: 0

Structural insights into two thiamine diphosphate-dependent enzymes and their synthetic applications in carbon-carbon linkage reactions. 两种硫胺素二磷酸依赖酶的结构见解及其在碳-碳连锁反应中的合成应用。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-05-14 DOI: 10.1038/s41557-025-01822-y

Tan Liu, Guiyang Wang, Jiahui Yu, Mengyuan Li, Tianbo Peng, Jie Wang, Houhua Li, Xiao-Dong Su, Changtao Jiang, Min Ye, Donghui Yang, Ming Ma

{"title":"Structural insights into two thiamine diphosphate-dependent enzymes and their synthetic applications in carbon-carbon linkage reactions.","authors":"Tan Liu, Guiyang Wang, Jiahui Yu, Mengyuan Li, Tianbo Peng, Jie Wang, Houhua Li, Xiao-Dong Su, Changtao Jiang, Min Ye, Donghui Yang, Ming Ma","doi":"10.1038/s41557-025-01822-y","DOIUrl":"https://doi.org/10.1038/s41557-025-01822-y","url":null,"abstract":"The α-hydroxy-β-keto acid synthases are thiamine diphosphate-dependent enzymes catalysing carbon-carbon linkage reactions in the biosynthesis of primary metabolites and various secondary metabolites. However, the substrate selectivity and catalytic stereoselectivity of α-hydroxy-β-keto acid synthases are poorly understood, greatly hindering their synthetic application in generating diverse carbon frameworks. We here report the discovery of two new α-hydroxy-β-keto acid synthases CsmA and BbmA, which show different substrate selectivities in catalysing carbon-carbon coupling reactions between two β-keto acids. Four crystal structures of CsmA or BbmA complexed with thiamine diphosphate and their substrates were determined, clearly revealing their structural bases of substrate selectivity and catalytic stereoselectivity. Substrate scope expansion enables us to generate 120 α-hydroxy-β-keto acids together with 240 NaBH4-reduction products. Furthermore, we applied CsmA and BbmA into enzymatic total synthesis, generating 36 γ-butyrolactone-containing furanolides. These results provide new structural insights into the catalyses of α-hydroxy-β-keto acid synthases and highlight their great potential in carboligation catalysis and synthetic applications.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":19.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144079247","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}

引用次数: 0

Controlled anionic polymerization mediated by carbon dioxide 二氧化碳介导的可控阴离子聚合

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-13 DOI: 10.1038/s41557-025-01819-7

Paige E. Jacky, Alexandra D. Easley, Brett P. Fors

{"title":"Controlled anionic polymerization mediated by carbon dioxide","authors":"Paige E. Jacky, Alexandra D. Easley, Brett P. Fors","doi":"10.1038/s41557-025-01819-7","DOIUrl":"https://doi.org/10.1038/s41557-025-01819-7","url":null,"abstract":"Anionic polymerizations of vinyl monomers are powerful synthetic platforms for making well-defined materials. However, these reactions are extremely sensitive to moisture and oxygen, require the use of highly purified reagents, must be run at low temperatures, and use hazardous and difficult-to-handle alkyl lithium initiators. Together, these drawbacks limit the practicality of these polymerizations and impede their widespread usage. On this basis, the development of a user-friendly anionic polymerization process for methacrylates is a grand challenge. Here we report an anionic polymerization of methacrylates mediated by CO2 that can be run at elevated temperatures and uses an easy-to-handle solid initiator. The reversible addition of CO2 to the enolate chain end efficiently tempers the reactivity of the anion, giving polymers with narrow molar mass distributions and excellent molecular weight targeting at elevated temperatures. Our scalable and more user-friendly CO2-mediated method improves the accessibility and safety of anionic polymerizations and facilitates the production of a variety of polymeric materials.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"44 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940676","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}

引用次数: 0

Connecting the dots in a pH-dependent oxygen evolution reaction 连接ph依赖性析氧反应中的点

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-13 DOI: 10.1038/s41557-025-01826-8

Thomas Götsch, Travis E. Jones, Detre Teschner

引用次数: 0

Exo-templating via pseudorotaxane formation reduces pathway complexity in the multicomponent self-assembly of M12L24 nanospheres 通过假紫杉烷形成的外模板降低了M12L24纳米球多组分自组装的路径复杂性

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-12 DOI: 10.1038/s41557-025-01808-w

T. Bouwens, E. O. Bobylev, L. S. D. Antony, D. A. Poole, E. Alarcón-Lladó, S. Mathew, J. N. H. Reek

{"title":"Exo-templating via pseudorotaxane formation reduces pathway complexity in the multicomponent self-assembly of M12L24 nanospheres","authors":"T. Bouwens, E. O. Bobylev, L. S. D. Antony, D. A. Poole, E. Alarcón-Lladó, S. Mathew, J. N. H. Reek","doi":"10.1038/s41557-025-01808-w","DOIUrl":"https://doi.org/10.1038/s41557-025-01808-w","url":null,"abstract":"Selective formation of multicomponent structures via the self-assembly of numerous building blocks is ubiquitous in biological systems but challenging to emulate synthetically. More components introduce additional possibilities for kinetic intermediates with trap-state ability, hampering access to desired products. In covalent chemistry, templates, reagents and catalysts are applied to create alternative pathways for desired product formation. Analogously, we enlist exo-templating to mould the formation of large, multicomponent supramolecular structures. Specifically, a charged ring docks at 1,5-dioxynaphthalene stations within exo-functionalized building blocks to promote formation of cuboctahedral Pd12L24 nanospheres via exoskeletal templating. With the exo-templating ring present, nanosphere formation occurs via small Pdx–Ly oligomers, while in the absence of the ring a Pdx–Ly polymer resting state rapidly evolves, from which nanosphere formation occurs slowly. We demonstrate a form of kinetic templating—via intermediate destabilization—resembling properties observed in catalysis. Importantly, unlike typically employed endo-templates, we demonstrate that exo-templating is particularly suited for larger, complex, self-assembled structures.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"5 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933438","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}

引用次数: 0

Carnot batteries for dispatchable renewables 可调度可再生能源的卡诺电池

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-07 DOI: 10.1038/s41557-025-01813-z

Bruce C. Gibb

引用次数: 0

Shining light on flavin mononucleotide 照亮黄素单核苷酸

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-07 DOI: 10.1038/s41557-025-01809-9

Qinglong Shi, Juntao Ye

引用次数: 0

Efficient and selective energy transfer photoenzymes powered by visible light 由可见光驱动的高效和选择性能量转移光酶

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-06 DOI: 10.1038/s41557-025-01820-0

Rebecca Crawshaw, Ross Smithson, Johannes Hofer, Florence J. Hardy, George W. Roberts, Jonathan S. Trimble, Anna R. Kohn, Colin W. Levy, Deborah A. Drost, Christian Merten, Derren J. Heyes, Richard Obexer, Thorsten Bach, Anthony P. Green

{"title":"Efficient and selective energy transfer photoenzymes powered by visible light","authors":"Rebecca Crawshaw, Ross Smithson, Johannes Hofer, Florence J. Hardy, George W. Roberts, Jonathan S. Trimble, Anna R. Kohn, Colin W. Levy, Deborah A. Drost, Christian Merten, Derren J. Heyes, Richard Obexer, Thorsten Bach, Anthony P. Green","doi":"10.1038/s41557-025-01820-0","DOIUrl":"https://doi.org/10.1038/s41557-025-01820-0","url":null,"abstract":"The development of [2 + 2] cyclases containing benzophenone triplet sensitizers highlights the potential of engineered enzymes as a platform for stereocontrolled energy transfer photocatalysis. However, the suboptimal photophysical features of benzophenone necessitates the use of ultraviolet light, limits photochemical efficiency and restricts the range of chemistries accessible. Here we engineer an orthogonal Methanococcus jannaschii tyrosyl-tRNA synthetase/tRNA pair for encoding thioxanthone triplet sensitizers into proteins, which can efficiently harness visible light to drive photochemical conversions. Initially, we developed an enantioselective [2 + 2] cyclase that is orders of magnitude more efficient than our previously developed photoenzymes (kcat = 13 s−1, >1,300 turnovers). To demonstrate that thioxanthone-containing enzymes can enable more challenging photochemical conversions, we developed a second oxygen-tolerant enzyme that can steer selective C–H insertions of excited quinolone substrates to afford spirocyclic β-lactams with high selectivity (99% e.e., 22:1 d.r.). This photoenzyme also suppresses a competing substrate decomposition pathway observed with small-molecule sensitizers, underscoring the ability of engineered enzymes to control the fate of excited-state intermediates.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"35 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910380","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}

引用次数: 0

Sharpening the lens of NMR spectroscopy to study large proteins 锐化核磁共振光谱的透镜来研究大的蛋白质

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-05 DOI: 10.1038/s41557-025-01817-9

Yun Huang, David Eliezer

引用次数: 0

Leveraging relaxation-optimized 1H–13CF correlations in 4-19F-phenylalanine as atomic beacons for probing structure and dynamics of large proteins 利用弛豫优化的4- 19f -苯丙氨酸中的1H-13CF相关性作为探测大蛋白质结构和动力学的原子信标

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-05 DOI: 10.1038/s41557-025-01818-8

Andras Boeszoermenyi, Denitsa L. Radeva, Sebastian Schindler, Veronica Valadares, Krishna M. Padmanabha Das, Abhinav Dubey, Thibault Viennet, Max Schmitt, Peter Kast, Vladimir M. Gelev, Nikolay Stoyanov, Nikola Burdzhiev, Ognyan Petrov, Scott Ficarro, Jarred Marto, Ezekiel A. Geffken, Sirano Dhe-Paganon, Hyuk-Soo Seo, Nathan D. Alexander, Richard B. Cooley, Ryan A. Mehl, Helena Kovacs, Clemens Anklin, Wolfgang Bermel, Ilya Kuprov, Koh Takeuchi, Haribabu Arthanari

{"title":"Leveraging relaxation-optimized 1H–13CF correlations in 4-19F-phenylalanine as atomic beacons for probing structure and dynamics of large proteins","authors":"Andras Boeszoermenyi, Denitsa L. Radeva, Sebastian Schindler, Veronica Valadares, Krishna M. Padmanabha Das, Abhinav Dubey, Thibault Viennet, Max Schmitt, Peter Kast, Vladimir M. Gelev, Nikolay Stoyanov, Nikola Burdzhiev, Ognyan Petrov, Scott Ficarro, Jarred Marto, Ezekiel A. Geffken, Sirano Dhe-Paganon, Hyuk-Soo Seo, Nathan D. Alexander, Richard B. Cooley, Ryan A. Mehl, Helena Kovacs, Clemens Anklin, Wolfgang Bermel, Ilya Kuprov, Koh Takeuchi, Haribabu Arthanari","doi":"10.1038/s41557-025-01818-8","DOIUrl":"https://doi.org/10.1038/s41557-025-01818-8","url":null,"abstract":"NMR spectroscopy of biomolecules provides atomic level information into their structure, dynamics and interactions with their binding partners. However, signal attenuation from line broadening caused by fast relaxation and signal overlap often limits the application of NMR to large macromolecular systems. Here we leverage the slow relaxation properties of 13C nuclei attached to 19F in aromatic 19F–13C spin pairs as well as the spin–spin coupling between the fluorinated 13C nucleus and the hydrogen atom at the meta-position to record two-dimensional 1H–13CF correlation spectra with transverse relaxation-optimized spectroscopy selection on 13CF. To accomplish this, we synthesized [4-19F13Cζ; 3,5-2H2ε] Phe, engineered for optimal relaxation properties, and adapted a residue-specific route to incorporate this residue globally into proteins and a site-specific 4-19F Phe encoding strategy. This approach resulted in narrow linewidths for proteins ranging from 30 kDa to 180 kDa, enabling interaction studies with small-molecule ligands without requiring specialized 19F-compatible probes.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"113 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143905685","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}

引用次数: 0