Nature chemistry最新文献_第2页

4f-orbital covalency enables a single-crystal-to-single-crystal ring-opening isomerization in a Ce^IV-cyclopropenyl complex. 在ceiv -环丙烯配合物中，4f轨道共价使单晶到单晶开环异构化。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-06-01 Epub Date: 2025-04-23 DOI: 10.1038/s41557-025-01791-2

Brett D Vincenzini, Xiaojuan Yu, Sébastien Paloc, Patrick W Smith, Himanshu Gupta, Pragati Pandey, Greggory T Kent, Osvaldo Ordonez, Taylor Keller, Michael R Gau, Alexandra M Bacon, Stefan G Minasian, Trevor W Hayton, Jochen Autschbach, Eric J Schelter

{"title":"4f-orbital covalency enables a single-crystal-to-single-crystal ring-opening isomerization in a CeIV-cyclopropenyl complex.","authors":"Brett D Vincenzini, Xiaojuan Yu, Sébastien Paloc, Patrick W Smith, Himanshu Gupta, Pragati Pandey, Greggory T Kent, Osvaldo Ordonez, Taylor Keller, Michael R Gau, Alexandra M Bacon, Stefan G Minasian, Trevor W Hayton, Jochen Autschbach, Eric J Schelter","doi":"10.1038/s41557-025-01791-2","DOIUrl":"10.1038/s41557-025-01791-2","url":null,"abstract":"Metal-ligand bonding interactions for f-element compounds are typically highly polarized with only minor covalent character. Whereas the 5d/6d orbitals are known to be chemically accessible for dative bonding, recent quantum chemical and spectroscopic analyses have indicated appreciable 4f/5f-orbital involvement in certain metal-ligand bonds. However, 4f-orbital covalency has not been compellingly linked to distinctive modes of chemical reactivity via rigorous comparative study and mechanistic investigation. Here a series of MIV-cyclopropenyl complexes (M = Ti, Zr, Ce, Hf, Th) are described, wherein the cerium congener exhibits a 4f-covalent Ce=Cα interaction, causing a ring-opening isomerization reaction through a single-crystal-to-single-crystal transformation. The results provide evidence for 4f-orbital covalency by demonstrating its expression in the reactivity of an f-element complex within an isostructural series of tetravalent d- and f-block metal complexes. They also provide new directions for the study of orbital covalency effects of molecular compounds in solid-state chemical transformations.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":"961-967"},"PeriodicalIF":19.2,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143981694","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

Macrocyclic β-arch peptides that mimic the structure and function of disease-associated tau folds. 模拟疾病相关tau折叠结构和功能的大环β-弓肽。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-06-01 Epub Date: 2025-04-30 DOI: 10.1038/s41557-025-01805-z

Isaac J Angera, Xueyong Xu, Benjamin H Rajewski, Grace I Hallinan, Xiaoqi Zhang, Bernardino Ghetti, Ruben Vidal, Wen Jiang, Juan R Del Valle

{"title":"Macrocyclic β-arch peptides that mimic the structure and function of disease-associated tau folds.","authors":"Isaac J Angera, Xueyong Xu, Benjamin H Rajewski, Grace I Hallinan, Xiaoqi Zhang, Bernardino Ghetti, Ruben Vidal, Wen Jiang, Juan R Del Valle","doi":"10.1038/s41557-025-01805-z","DOIUrl":"10.1038/s41557-025-01805-z","url":null,"abstract":"Tauopathies are a class of neurodegenerative disorders that feature tau protein aggregates in the brain. Misfolded tau has the capacity to seed the fibrillization of soluble tau, leading to the prion-like spread of aggregates. Within these filaments, tau protomers always exhibit a cross-β amyloid structure. However, distinct cross-β amyloid folds correlate with specific diseases. An understanding of how these conformations impact seeding activity remains elusive. Identifying the minimal epitopes required for transcellular propagation of tau aggregates represents a key step towards more relevant models of disease progression. Here we implement a diversity-oriented peptide macrocyclization approach towards miniature tau, or 'mini-tau', proteomimetics that can seed the aggregation of tau in engineered cells and primary neurons. Structural elucidation of one such seed-competent macrocycle reveals remarkable conformational congruence with core folds from patient-derived extracts of tau. The ability to impart β-arch form and function through peptide stapling has broad-ranging implications for the minimization and mimicry of pathological tau and other amyloid proteins that drive neurodegeneration.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":"865-874"},"PeriodicalIF":19.2,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143993951","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

A glycan foldamer that uses carbohydrate-aromatic interactions to perform catalysis. 一种利用碳水化合物-芳香相互作用进行催化作用的聚糖折叠物。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-06-01 Epub Date: 2025-02-26 DOI: 10.1038/s41557-025-01763-6

Kaimeng Liu, Martina Delbianco

{"title":"A glycan foldamer that uses carbohydrate-aromatic interactions to perform catalysis.","authors":"Kaimeng Liu, Martina Delbianco","doi":"10.1038/s41557-025-01763-6","DOIUrl":"10.1038/s41557-025-01763-6","url":null,"abstract":"In nature, the ability to catalyse reactions is primarily associated with proteins and ribozymes. Inspired by these systems, peptide-based catalysts have been designed to accelerate chemical reactions and/or ensure regio- and stereoselective transformations. We wondered whether other biomolecules (such as glycans) could be designed to perform catalytic functions, expanding the portfolio of synthetic functional oligomers. Here we report a glycan foldamer inspired by the natural Sialyl Lewis X antigen that acts as catalyst in a chemical reaction. This glycan-based catalyst benefits from structural rigidity and modular adaptability, incorporating a substrate-recognition motif alongside a catalytic active site. Leveraging the inherent ability of carbohydrates to engage in CH-π interactions with aromatic substrates, we demonstrate the recruitment and functionalization of a tryptophan via a Pictet-Spengler transformation. Our modular glycan catalyst accelerates the reaction kinetics, enabling the modification of tryptophan-containing peptides in aqueous environments. Our findings pave the way for the development of glycan-based catalysts and suggest the possibility of catalytic capabilities of glycans in biological contexts.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":"883-889"},"PeriodicalIF":19.2,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12141037/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143516250","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}

引用次数: 0

Non-enzymatic methylcyclization of alkenes. 烯烃的非酶甲基环化。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-06-01 Epub Date: 2025-03-07 DOI: 10.1038/s41557-025-01774-3

Immanuel Plangger, Elias Schmidhammer, Sebastian Schaar, Klaus Wurst, Maren Podewitz, Thomas Magauer

{"title":"Non-enzymatic methylcyclization of alkenes.","authors":"Immanuel Plangger, Elias Schmidhammer, Sebastian Schaar, Klaus Wurst, Maren Podewitz, Thomas Magauer","doi":"10.1038/s41557-025-01774-3","DOIUrl":"10.1038/s41557-025-01774-3","url":null,"abstract":"Methyltransferases are a broad class of enzymes that catalyse the transfer of methyl groups onto a wide variety of substrates and functionalities. In their most striking variant, bifunctional methyltransferase-cyclases both transfer a methyl group onto alkenes and induce cyclization (methylcyclization). Although recent years have seen substantial advances in the methylation of alkenes, especially hydromethylation, the reactivity demonstrated by bifunctional methyltransferase-cyclases in nature has yet to be developed into a synthetically viable method. Here we report a silver(I)-mediated electrophilic methylcyclization that rivals selectivities found in enzymes while not being limited by their inherent substrate specificity. Our method benefits from the use of commercial reagents, is applicable to a wide range of substrates, including heterocycles, and affords unique structures that are difficult to access via conventional synthetic methods. Furthermore, computational studies have been utilized to unravel the underlying mechanism and ultimately support a stepwise cationic reaction pathway with a rate-limiting methyltransfer.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":"904-910"},"PeriodicalIF":19.2,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7617478/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143586327","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}

引用次数: 0

Stereospecific molecular rearrangement via nucleophilic substitution at quaternary stereocentres in acyclic systems. 在非环体系中通过亲核取代在四元立体中心进行立体定向分子重排。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-06-01 Epub Date: 2025-03-19 DOI: 10.1038/s41557-025-01783-2

Kaushalendra Patel, Ilan Marek

{"title":"Stereospecific molecular rearrangement via nucleophilic substitution at quaternary stereocentres in acyclic systems.","authors":"Kaushalendra Patel, Ilan Marek","doi":"10.1038/s41557-025-01783-2","DOIUrl":"10.1038/s41557-025-01783-2","url":null,"abstract":"Nucleophilic substitution at tetravalent (sp3) carbon is a fundamental transformation in organic synthesis, essential for creating carbon-carbon and carbon-heteroatom bonds. While the mechanism of the SN2 reaction is well understood, achieving stereochemical control in SN1-type reactions remains extremely challenging due to the complexity of successive carbocation intermediates. Here we present a strategy for preparing complex molecular skeletons via stereospecific SN1 at a quaternary stereocentre in acyclic systems. By leveraging neighbouring group participation, we facilitate the selective formation of a unique cyclopropylcarbinyl cation intermediate that undergoes selective nucleophilic substitution with high diastereoselectivity and complete inversion of configuration at a distant position from the original carbocation via molecular rearrangement. This methodology has been applied to generate homoallylic tertiary fluorides, bromides, chlorides, ethers, thiocyanates and azides, demonstrating its applicability in accessing diverse functional groups with exceptional diastereoselectivities. This transformation opens new avenues for constructing complex molecular architectures through precise stereocontrol of C-C bond cleavage at a quaternary stereocentre in acyclic systems.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":"933-940"},"PeriodicalIF":19.2,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143663929","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

Gold redox catalysis with hydrogen peroxide 过氧化氢催化金氧化还原

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-29 DOI: 10.1038/s41557-025-01838-4

Sandip A. Bhadange, Nitin T. Patil

引用次数: 0

Bidentate N-ligand-assisted gold redox catalysis with hydrogen peroxide 双齿n配体辅助过氧化氢催化金氧化还原

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-29 DOI: 10.1038/s41557-025-01835-7

Hongwei Shi, Matthias Rudolph, Jun Li, Yu Tian, Martin C. Dietl, Hadil Alshurafa, Yaowen Liu, Tao Wang, Henrik Habeck, Philipp M. Stein, Petra Krämer, Frank Rominger, Thomas Oeser, Ning Jiao, A. Stephen K. Hashmi

{"title":"Bidentate N-ligand-assisted gold redox catalysis with hydrogen peroxide","authors":"Hongwei Shi, Matthias Rudolph, Jun Li, Yu Tian, Martin C. Dietl, Hadil Alshurafa, Yaowen Liu, Tao Wang, Henrik Habeck, Philipp M. Stein, Petra Krämer, Frank Rominger, Thomas Oeser, Ning Jiao, A. Stephen K. Hashmi","doi":"10.1038/s41557-025-01835-7","DOIUrl":"https://doi.org/10.1038/s41557-025-01835-7","url":null,"abstract":"Gold redox catalysis, which exploits the ability of strong π-acid activation in combination with redox reactions, has emerged as an attractive synthetic method with unique reactivities compared to other transition metals. However, gold redox chemistry bears the challenge to overcome the high redox potential of Au(I)/Au(III) (1.41 V). The classical strategy of gold redox catalysis applies strong external chemical oxidants which inevitably results in low atom economy and substrate limitations due to incompatibility with functional groups. Here we report a bidentate N-ligand (for example, Phen, Bpy) assisted gold redox catalysis using H2O2 as oxidant, which proved to be generally applicable for many forms of coupling reactions. In addition, C(sp2)–C(sp2) bicyclization coupling (cross-coupling of two cyclized substrates) is accessible under our conditions. Mechanistic studies reveal a redox elimination process in which a bidentate N-ligand is crucial for the catalytic cycle. The formation of alkynyl-AuIII–OH and vinyl-AuIII–OH species is the key process for the synergistic π-bond activation and AuI oxidation.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"134 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165536","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

Photoinduced bulk polymerization strategy in melt state for recyclable polydiene derivatives 可回收聚二烯衍生物熔融态光诱导本体聚合策略

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-28 DOI: 10.1038/s41557-025-01821-z

Pengfei Wu, Qixuan Hu, Andrew V. Marquardt, Lawal A. Ogunfowora, Jeong Hui Kim, Yuanhao Tang, Chenjian Lin, Brett M. Savoie, Letian Dou

{"title":"Photoinduced bulk polymerization strategy in melt state for recyclable polydiene derivatives","authors":"Pengfei Wu, Qixuan Hu, Andrew V. Marquardt, Lawal A. Ogunfowora, Jeong Hui Kim, Yuanhao Tang, Chenjian Lin, Brett M. Savoie, Letian Dou","doi":"10.1038/s41557-025-01821-z","DOIUrl":"https://doi.org/10.1038/s41557-025-01821-z","url":null,"abstract":"Polydienes, particularly 1,3-butadiene derivatives, are integral to the chemical industry due to their widespread applications. However, current commercial production methods depend largely on gas- or solution-phase processes involving sophisticated initiators, catalysts and additives that require additional purification and cost. Here we introduce an ultraclean photo-melt-bulk polymerization strategy that enables the precise synthesis of high-molecular-weight polydienes without the need for solvents, catalysts or initiators. Using UV irradiation, we can generate long-lived biradicals in muconate derivatives that facilitate controlled chain propagation with minimal termination. This approach also simplifies the synthesis of ABA triblock co-polymers and allows for efficient random co-polymerization, yielding a plastic with excellent mechanical properties and processability. Furthermore, the inherently weaker carbon–carbon bonds in these polymers allow for facile depolymerization into monomers with high yields, providing an efficient pathway for chemical recycling. This work highlights a simple, yet effective polymerization method that aligns with the principles of green chemistry and advances the development of recyclable polymeric materials.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"10 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153316","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

Trinucleotide substrates under pH–freeze–thaw cycles enable open-ended exponential RNA replication by a polymerase ribozyme 在ph -冻融循环下的三核苷酸底物可以通过聚合酶核酶进行开放式指数RNA复制

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-28 DOI: 10.1038/s41557-025-01830-y

James Attwater, Teresa L. Augustin, Joseph F. Curran, Samantha L. Y. Kwok, Luis Ohlendorf, Edoardo Gianni, Philipp Holliger

{"title":"Trinucleotide substrates under pH–freeze–thaw cycles enable open-ended exponential RNA replication by a polymerase ribozyme","authors":"James Attwater, Teresa L. Augustin, Joseph F. Curran, Samantha L. Y. Kwok, Luis Ohlendorf, Edoardo Gianni, Philipp Holliger","doi":"10.1038/s41557-025-01830-y","DOIUrl":"https://doi.org/10.1038/s41557-025-01830-y","url":null,"abstract":"RNA replication is considered a key process in the origins of life. However, both enzymatic and non-enzymatic RNA replication cycles are impeded by the ‘strand separation problem’, a form of product inhibition arising from the extraordinary stability of RNA duplexes and their rapid reannealing kinetics. Here we show that RNA trinucleotide triphosphates can overcome this problem by binding to and kinetically trapping dissociated RNA strands in a single-stranded form, while simultaneously serving as substrates for replication by an RNA polymerase ribozyme. When combined with coupled pH and freeze–thaw cycles, this enabled exponential replication of both (+) and (−) strands of double-stranded RNAs, including a fragment of the ribozyme itself. Subjecting random RNA sequence pools to open-ended replication yielded either defined replicating RNA sequences or the gradual emergence of diverse sequence pools. The latter derived from partial ribozyme self-replication alongside generation of new RNA sequences, and their composition drifted towards hypothesized primordial codons. These results unlock broader opportunities to model primordial RNA replication.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"83 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153332","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

Structure-informed design of an ultrabright RNA-activated fluorophore 一种超亮rna激活荧光团的结构设计

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-05-28 DOI: 10.1038/s41557-025-01832-w

Mo Yang, Peri R. Prestwood, Luiz F. M. Passalacqua, Sumirtha Balaratnam, Christopher R. Fullenkamp, J. Winston Arney, Kevin M. Weeks, Adrian Ferre-D’Amare, John S. Schneekloth

{"title":"Structure-informed design of an ultrabright RNA-activated fluorophore","authors":"Mo Yang, Peri R. Prestwood, Luiz F. M. Passalacqua, Sumirtha Balaratnam, Christopher R. Fullenkamp, J. Winston Arney, Kevin M. Weeks, Adrian Ferre-D’Amare, John S. Schneekloth","doi":"10.1038/s41557-025-01832-w","DOIUrl":"https://doi.org/10.1038/s41557-025-01832-w","url":null,"abstract":"RNA-based fluorogenic aptamers, such as Mango, are uniquely powerful tools for imaging RNA that activate the fluorescence of a weakly or non-fluorescent small molecule when bound. A central challenge has been to develop brighter, more specific and high-affinity aptamer–ligand systems for cellular imaging. Here we report an ultrabright fluorophore for the Mango II system discovered using a structure-informed, fragment-based small-molecule microarray approach. This dye—termed SALAD1 (structure-informed, array-enabled LigAnD 1)—exhibits subnanomolar aptamer affinity and 3.5-fold brighter fluorescence than Mango II-TO1–biotin pair, a widely used fluorogenic system. Performance was improved by modulating RNA-dye molecular recognition without altering the fluorophore’s π-system. High-resolution X-ray structures reveal the binding mode for SALAD1, which exhibits improved pocket occupancy, a more defined binding pose and a unique bonding interaction with potassium. SALAD1 is cell-permeable and facilitates improved in-cell confocal RNA imaging. This work introduces an additional RNA-activated fluorophore demonstrating how fragment-based ligand discovery can be used to create high-performance ligands for RNA targets.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"42 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144153331","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