Nature chemistry最新文献_第10页

Phosphorus-mediated hydrogenation catalysis 磷介导的氢化催化。

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-24 DOI: 10.1038/s41557-024-01588-9

Josh Abbenseth

引用次数: 0

Light strikes gold to purify water 光打金，净化水。

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-24 DOI: 10.1038/s41557-024-01581-2

Zhipeng Yu, Lifeng Liu

引用次数: 0

A template for artificial life 人工生命的模板

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-23 DOI: 10.1038/s41557-024-01589-8

Rahul Dev Mukhopadhyay

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Protein semisynthesis reveals plasticity in HECT E3 ubiquitin ligase mechanisms 蛋白质半合成揭示了 HECT E3 泛素连接酶机制的可塑性

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-19 DOI: 10.1038/s41557-024-01576-z

Hanjie Jiang, Bryant D. Miller, Thibault Viennet, Hyojeon Kim, Kwangwoon Lee, Haribabu Arthanari, Philip A. Cole

{"title":"Protein semisynthesis reveals plasticity in HECT E3 ubiquitin ligase mechanisms","authors":"Hanjie Jiang, Bryant D. Miller, Thibault Viennet, Hyojeon Kim, Kwangwoon Lee, Haribabu Arthanari, Philip A. Cole","doi":"10.1038/s41557-024-01576-z","DOIUrl":"10.1038/s41557-024-01576-z","url":null,"abstract":"Lys ubiquitination is catalysed by E3 ubiquitin ligases and is central to the regulation of protein stability and cell signalling in normal and disease states. There are gaps in our understanding of E3 mechanisms, and here we use protein semisynthesis, chemical rescue, microscale thermophoresis and other biochemical approaches to dissect the role of catalytic base/acid function and conformational interconversion in HECT-domain E3 catalysis. We demonstrate that there is plasticity in the use of the terminal side chain or backbone carboxylate for proton transfer in HECT E3 ubiquitin ligase reactions, with yeast Rsp5 orthologues appearing to be possible evolutionary intermediates. We also show that the HECT-domain ubiquitin covalent intermediate appears to eject the E2 conjugating enzyme, promoting catalytic turnover. These findings provide key mechanistic insights into how protein ubiquitination occurs and provide a framework for understanding E3 functions and regulation. Lysine ubiquitination, catalysed by E3 ubiquitin ligases, is pivotal for regulating protein stability and cell signalling. Using protein semisynthesis, the roles of the C-terminal carboxylate and conformational interconversion in HECT-domain E3 catalysis are now characterized, revealing evolutionary plasticity in side chain versus backbone utilization.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1894-1905"},"PeriodicalIF":19.2,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141725935","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

An evolved artificial radical cyclase enables the construction of bicyclic terpenoid scaffolds via an H-atom transfer pathway 进化的人工自由基环化酶可通过 H 原子转移途径构建双环萜类支架

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-19 DOI: 10.1038/s41557-024-01562-5

Dongping Chen, Xiang Zhang, Anastassia Andreevna Vorobieva, Ryo Tachibana, Alina Stein, Roman P. Jakob, Zhi Zou, Damian Alexander Graf, Ang Li, Timm Maier, Bruno E. Correia, Thomas R. Ward

{"title":"An evolved artificial radical cyclase enables the construction of bicyclic terpenoid scaffolds via an H-atom transfer pathway","authors":"Dongping Chen, Xiang Zhang, Anastassia Andreevna Vorobieva, Ryo Tachibana, Alina Stein, Roman P. Jakob, Zhi Zou, Damian Alexander Graf, Ang Li, Timm Maier, Bruno E. Correia, Thomas R. Ward","doi":"10.1038/s41557-024-01562-5","DOIUrl":"10.1038/s41557-024-01562-5","url":null,"abstract":"While natural terpenoid cyclases generate complex terpenoid structures via cationic mechanisms, alternative radical cyclization pathways are underexplored. The metal-catalysed H-atom transfer reaction (M-HAT) offers an attractive means for hydrofunctionalizing olefins, providing access to terpenoid-like structures. Artificial metalloenzymes offer a promising strategy for introducing M-HAT reactivity into a protein scaffold. Here we report our efforts towards engineering an artificial radical cyclase (ARCase), resulting from anchoring a biotinylated [Co(Schiff-base)] cofactor within an engineered chimeric streptavidin. After two rounds of directed evolution, a double mutant catalyses a radical cyclization to afford bicyclic products with a cis-5-6-fused ring structure and up to 97% enantiomeric excess. The involvement of a histidine ligation to the Co cofactor is confirmed by crystallography. A time course experiment reveals a cascade reaction catalysed by the ARCase, combining a radical cyclization with a conjugate reduction. The ARCase exhibits tolerance towards variations in the dienone substrate, highlighting its potential to access terpenoid scaffolds. Although natural terpenoid cyclases generate polycyclic structures through cationic intermediates, alternative radical cyclization pathways are underexplored. Now an artificial radical cyclase has been prepared by anchoring a biotinylated cobalt Schiff-base complex within a chimeric streptavidin scaffold. Chemogenetic optimization of the catalytic performance affords enantioenriched terpenoids via a metal-catalysed H-atom transfer mechanism.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1656-1664"},"PeriodicalIF":19.2,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141725782","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

Collisional alignment and molecular rotation control the chemi-ionization of individual conformers of hydroquinone with metastable neon 碰撞排列和分子旋转控制着对苯二酚单个构象与可迁移氖的化学电离

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-19 DOI: 10.1038/s41557-024-01590-1

L. Ploenes, P. Straňák, A. Mishra, X. Liu, J. Pérez-Ríos, S. Willitsch

{"title":"Collisional alignment and molecular rotation control the chemi-ionization of individual conformers of hydroquinone with metastable neon","authors":"L. Ploenes, P. Straňák, A. Mishra, X. Liu, J. Pérez-Ríos, S. Willitsch","doi":"10.1038/s41557-024-01590-1","DOIUrl":"10.1038/s41557-024-01590-1","url":null,"abstract":"The relationship between the shape of a molecule and its chemical reactivity is a central tenet in chemistry. However, the influence of the molecular geometry on reactivity can be subtle and result from several opposing effects. Here, using a crossed-molecular-beam experiment in which individual rotational quantum states of specific conformers of a molecule are separated, we study the chemi-ionization reaction of hydroquinone with metastable neon atoms. We show that collision-induced alignment of the reaction partners caused by geometry-dependent long-range forces influences reaction pathways, which is, however, countered by molecular rotation. The present work provides insights into the conformation-specific stereodynamics of complex polyatomic systems and illustrates the capability of advanced molecule-control techniques to unravel these effects. Molecular geometry can influence chemical reactivity through several opposing effects. By selecting individual conformers of hydroquinone in the chemi-ionization reaction with metastable neon, it is now shown that reaction pathways can be governed by molecular alignment due to geometry-dependent forces that are, however, countered by molecular rotation.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1876-1881"},"PeriodicalIF":19.2,"publicationDate":"2024-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141725934","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

Single crystals of purely organic free-standing two-dimensional woven polymer networks 纯有机独立二维编织聚合物网络单晶体。

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-18 DOI: 10.1038/s41557-024-01580-3

Ding Xiao, Zhitong Jin, Guan Sheng, Liya Chen, Xuedong Xiao, Tianyu Shan, Jiao Wang, Rahul Navik, Jianping Xu, Lin Zhou, Qing-Hui Guo, Guangfeng Li, Yihan Zhu, J. Fraser Stoddart, Feihe Huang

{"title":"Single crystals of purely organic free-standing two-dimensional woven polymer networks","authors":"Ding Xiao, Zhitong Jin, Guan Sheng, Liya Chen, Xuedong Xiao, Tianyu Shan, Jiao Wang, Rahul Navik, Jianping Xu, Lin Zhou, Qing-Hui Guo, Guangfeng Li, Yihan Zhu, J. Fraser Stoddart, Feihe Huang","doi":"10.1038/s41557-024-01580-3","DOIUrl":"10.1038/s41557-024-01580-3","url":null,"abstract":"The aesthetic and practicality of macroscopic fabrics continue to encourage chemists to weave molecules into interlaced patterns with the aim of providing emergent physical and chemical properties when compared with their starting materials. Weaving purely organic molecular threads into flawless two-dimensional patterns remains a formidable challenge, even though its feasibility has been proposed on several occasions. Herein we describe the synthesis of a flawless, purely organic, free-standing two-dimensional woven polymer network driven by dative B−N bonds. Single crystals of this woven polymer network were obtained and its well-defined woven topology was revealed by X-ray diffraction analysis. Free-standing two-dimensional monolayer nanosheets of the woven polymer network were exfoliated from the layered crystals using Scotch Magic Tape. The surface features of the nanosheets were investigated by integrated low-dose and cryogenic electron microscopy imaging techniques. These findings demonstrate the precise construction of purely organic woven polymer networks and highlight the unique opportunities for the application of woven topologies in two-dimensional organic materials. Weaving purely organic molecular threads into two-dimensional patterns remains a formidable challenge. Now, driven by the formation of dative B–N bonds, a purely organic, two-dimensional and flawless woven polymer network has been prepared. In addition, free-standing monolayers of woven polymer nanosheets have been obtained through mechanical exfoliation.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1906-1914"},"PeriodicalIF":19.2,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11527790/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141724010","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

Template-based copying in chemically fuelled dynamic combinatorial libraries 基于模板的化学动态组合库复制

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-16 DOI: 10.1038/s41557-024-01570-5

Christine M. E. Kriebisch, Ludwig Burger, Oleksii Zozulia, Michele Stasi, Alexander Floroni, Dieter Braun, Ulrich Gerland, Job Boekhoven

{"title":"Template-based copying in chemically fuelled dynamic combinatorial libraries","authors":"Christine M. E. Kriebisch, Ludwig Burger, Oleksii Zozulia, Michele Stasi, Alexander Floroni, Dieter Braun, Ulrich Gerland, Job Boekhoven","doi":"10.1038/s41557-024-01570-5","DOIUrl":"10.1038/s41557-024-01570-5","url":null,"abstract":"One of science’s greatest challenges is determining how life can spontaneously emerge from a mixture of molecules. A complicating factor is that life and its molecules are inherently unstable—RNA and proteins are prone to hydrolysis and denaturation. For the de novo synthesis of life or to better understand its emergence at its origin, selection mechanisms are needed for unstable molecules. Here we present a chemically fuelled dynamic combinatorial library to model RNA oligomerization and deoligomerization and shine new light on selection and purification mechanisms under kinetic control. In the experiments, oligomers can only be sustained by continuous production. Hybridization is a powerful tool for selecting unstable molecules, offering feedback on oligomerization and deoligomerization rates. Moreover, we find that templation can be used to purify libraries of oligomers. In addition, template-assisted formation of oligomers within coacervate-based protocells changes its compartment’s physical properties, such as their ability to fuse. Such reciprocal coupling between oligomer production and physical properties is a key step towards synthetic life. Selection mechanisms were critical at the emergence of life and will also be important for the synthesis of life. Now, it has been shown that template-based copying controls the selection of unstable molecules in a chemically fuelled dynamic combinatorial library. Moreover, when encapsulated inside coacervate droplets, these mechanisms change the coacervate’s physical properties.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 8","pages":"1240-1249"},"PeriodicalIF":19.2,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41557-024-01570-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141624693","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

Heterotrimeric collagen helix with high specificity of assembly results in a rapid rate of folding 具有高度装配特异性的异三聚胶原蛋白螺旋可实现快速折叠

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-15 DOI: 10.1038/s41557-024-01573-2

Carson C. Cole, Douglas R. Walker, Sarah A. H. Hulgan, Brett H. Pogostin, Joseph W. R. Swain, Mitchell D. Miller, Weijun Xu, Ryan Duella, Mikita Misiura, Xu Wang, Anatoly B. Kolomeisky, George N. Philips Jr, Jeffrey D. Hartgerink

{"title":"Heterotrimeric collagen helix with high specificity of assembly results in a rapid rate of folding","authors":"Carson C. Cole, Douglas R. Walker, Sarah A. H. Hulgan, Brett H. Pogostin, Joseph W. R. Swain, Mitchell D. Miller, Weijun Xu, Ryan Duella, Mikita Misiura, Xu Wang, Anatoly B. Kolomeisky, George N. Philips Jr, Jeffrey D. Hartgerink","doi":"10.1038/s41557-024-01573-2","DOIUrl":"10.1038/s41557-024-01573-2","url":null,"abstract":"The most abundant natural collagens form heterotrimeric triple helices. Synthetic mimics of collagen heterotrimers have been found to fold slowly, even compared to the already slow rates of homotrimeric helices. These prolonged folding rates are not understood. Here we compare the stabilities, specificities and folding rates of three heterotrimeric collagen mimics designed through a computationally assisted approach. The crystal structure of one ABC-type heterotrimer verified a well-controlled composition and register and elucidated the geometry of pairwise cation–π and axial and lateral salt bridges in the assembly. This collagen heterotrimer folds much faster (hours versus days) than comparable, well-designed systems. Circular dichroism and NMR data suggest the folding is frustrated by unproductive, competing heterotrimer species and these species must unwind before refolding into the thermodynamically favoured assembly. The heterotrimeric collagen folding rate is inhibited by the introduction of preformed competing triple-helical assemblies, which suggests that slow heterotrimer folding kinetics are dominated by the frustration of the energy landscape caused by competing triple helices. The mechanism of collagen heterotrimer folding is difficult to recapitulate synthetically. Now an ABC collagen mimetic heterotrimer has been designed that employs pairwise amino acid interactions, validated by X-ray crystallography, to promote composition- and register-specific assembly. The high specificity of its assembly leads to an increased rate of folding compared with similar collagen heterotrimers.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1698-1704"},"PeriodicalIF":19.2,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141618383","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

Isolation and characterization of a two-coordinate phosphinidene oxide 双配位氧化膦的分离与表征

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-07-15 DOI: 10.1038/s41557-024-01586-x

Chenyang Hu, Nicolas H. Rees, Maren Pink, Jose M. Goicoechea

{"title":"Isolation and characterization of a two-coordinate phosphinidene oxide","authors":"Chenyang Hu, Nicolas H. Rees, Maren Pink, Jose M. Goicoechea","doi":"10.1038/s41557-024-01586-x","DOIUrl":"10.1038/s41557-024-01586-x","url":null,"abstract":"Nitroso compounds, R–N=O, are common intermediates in organic synthesis, and are typically amenable to storage and manipulation at ambient temperature under aerobic conditions. By contrast, phosphorus-containing analogues, such as R–P=O (R = OH, CH3, OCH3, Ph), are extremely reactive and need to be studied in inert gas matrices at ultralow temperatures (3–15 K). These species are believed to be key intermediates in the degradation/combustion of organic phosphorus compounds, a class of chemicals that includes chemical warfare agents and flame retardants. Here we describe the isolation of a two-coordinate phosphorus(III) oxide under ambient conditions, enabled by the use of an extremely bulky amine ligand. Reactivity studies reveal that the phosphorus centre can be readily oxidized, and that in doing so, the P–O bond remains intact, an observation that is of interest to the proposed reactivity of transient phosphorus(III) oxides. Phosphinidene oxides are intermediates in the combustion of organic phosphorus compounds; however, they are highly unstable and their observation requires ultralow temperatures. Now it has been shown that a combination of steric bulk and electronic stabilization enables the isolation and manipulation of a two-coordinate phosphorus(III) oxide compound at room temperature.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1855-1860"},"PeriodicalIF":19.2,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141618385","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