Pub Date : 2024-07-24DOI: 10.1038/s41557-024-01581-2
Zhipeng Yu, Lifeng Liu
Hydroxyl radicals (·OH) are important reactive oxygen species in environmental chemistry. The most efficient way to generate them is through a single-electron water-oxidation step, but this light-driven process is inefficient over inorganic semiconductor materials. Now, a judiciously designed polymeric carbon nitride has demonstrated high photocatalytic efficiency.
{"title":"Light strikes gold to purify water","authors":"Zhipeng Yu, Lifeng Liu","doi":"10.1038/s41557-024-01581-2","DOIUrl":"10.1038/s41557-024-01581-2","url":null,"abstract":"Hydroxyl radicals (·OH) are important reactive oxygen species in environmental chemistry. The most efficient way to generate them is through a single-electron water-oxidation step, but this light-driven process is inefficient over inorganic semiconductor materials. Now, a judiciously designed polymeric carbon nitride has demonstrated high photocatalytic efficiency.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 8","pages":"1217-1218"},"PeriodicalIF":19.2,"publicationDate":"2024-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141759882","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}
Pub Date : 2024-07-23DOI: 10.1038/s41557-024-01589-8
Rahul Dev Mukhopadhyay
Selection rules play an important role in Darwinian evolution. Now, it has been shown that selective templation enables the purification of oligomer libraries in a coacervate model, and that the oligomer library can reversibly affect the coacervates’ fusion behaviour.
{"title":"A template for artificial life","authors":"Rahul Dev Mukhopadhyay","doi":"10.1038/s41557-024-01589-8","DOIUrl":"10.1038/s41557-024-01589-8","url":null,"abstract":"Selection rules play an important role in Darwinian evolution. Now, it has been shown that selective templation enables the purification of oligomer libraries in a coacervate model, and that the oligomer library can reversibly affect the coacervates’ fusion behaviour.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 8","pages":"1214-1216"},"PeriodicalIF":19.2,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141750249","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}
Pub Date : 2024-07-19DOI: 10.1038/s41557-024-01576-z
Hanjie Jiang, Bryant D. Miller, Thibault Viennet, Hyojeon Kim, Kwangwoon Lee, Haribabu Arthanari, Philip A. Cole
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.
{"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}
Pub Date : 2024-07-19DOI: 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
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.
天然萜类环化酶通过阳离子机制生成复杂的萜类结构，但对其他自由基环化途径的探索还不够。金属催化的 H 原子转移反应（M-HAT）为烯烃的氢官能化提供了一种极具吸引力的方法，从而提供了获得类萜结构的途径。人工金属酶为将 M-HAT 反应性引入蛋白质支架提供了一种前景广阔的策略。在此，我们报告了通过将生物素化的[Co（希夫碱）]辅助因子锚定在工程化的嵌合链霉亲和素中，我们在工程化人工自由基环化酶（ARCase）方面所做的努力。经过两轮定向进化后，一个双突变体催化了自由基环化，产生了具有顺式-5-6-融合环结构的双环产物，对映体过量率高达 97%。晶体学研究证实了组氨酸与 Co 辅助因子的连接。时程实验揭示了 ARCase 催化的级联反应，它将自由基环化与共轭还原结合在一起。ARCase 对二烯酮底物的变化表现出耐受性，突显了其获取萜类支架的潜力。
{"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}
Pub Date : 2024-07-19DOI: 10.1038/s41557-024-01590-1
L. Ploenes, P. Straňák, A. Mishra, X. Liu, J. Pérez-Ríos, S. Willitsch
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.
{"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}
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.
宏观织物的美观性和实用性不断鼓励化学家将分子编织成交错的图案，目的是提供与其初始材料相比新出现的物理和化学特性。将纯有机分子线编织成完美无瑕的二维图案仍然是一项艰巨的挑战，尽管其可行性已被多次提出。在此，我们介绍了一种由双向 B-N 键驱动的无缺陷、纯有机、独立的二维编织聚合物网络的合成。我们获得了这种编织聚合物网络的单晶体，并通过 X 射线衍射分析揭示了其清晰的编织拓扑结构。使用 Scotch Magic Tape 从层状晶体中剥离出编织聚合物网络的独立二维单层纳米片。通过综合低剂量和低温电子显微镜成像技术研究了纳米片的表面特征。这些研究结果表明了纯有机编织聚合物网络的精确构造，并强调了在二维有机材料中应用编织拓扑结构的独特机遇。
{"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}
Pub Date : 2024-07-16DOI: 10.1038/s41557-024-01570-5
Christine M. E. Kriebisch, Ludwig Burger, Oleksii Zozulia, Michele Stasi, Alexander Floroni, Dieter Braun, Ulrich Gerland, Job Boekhoven
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.
{"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}
Pub Date : 2024-07-15DOI: 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
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.
{"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}
Pub Date : 2024-07-15DOI: 10.1038/s41557-024-01586-x
Chenyang Hu, Nicolas H. Rees, Maren Pink, Jose M. Goicoechea
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.
{"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}
Pub Date : 2024-07-15DOI: 10.1038/s41557-024-01585-y
Baochen Ma, Haikuo Zhang, Ruhong Li, Shuoqing Zhang, Long Chen, Tao Zhou, Jinze Wang, Ruixin Zhang, Shouhong Ding, Xuezhang Xiao, Tao Deng, Lixin Chen, Xiulin Fan
Ideal rechargeable lithium battery electrolytes should promote the Faradaic reaction near the electrode surface while mitigating undesired side reactions. Yet, conventional electrolytes usually show sluggish kinetics and severe degradation due to their high desolvation energy and poor compatibility. Here we propose an electrolyte design strategy that overcomes the limitations associated with Li salt dissociation in non-coordinating solvents to enable fast, stable Li chemistries. The non-coordinating solvents are activated through favourable hydrogen bond interactions, specifically Fδ−–Hδ+ or Hδ+–Oδ−, when blended with fluorinated benzenes or halide alkane compounds. These intermolecular interactions enable a dynamic Li+–solvent coordination process, thereby promoting the fast Li+ reaction kinetics and suppressing electrode side reactions. Utilizing this molecular-docking electrolyte design strategy, we have developed 25 electrolytes that demonstrate high Li plating/stripping Coulombic efficiencies and promising capacity retentions in both full cells and pouch cells. This work supports the use of the molecular-docking solvation mechanism for designing electrolytes with fast Li+ kinetics for high-voltage Li batteries. Conventional Li-ion battery electrolytes often show sluggish kinetics and severe degradation due to high Li+ desolvation energies and poor compatibility. Now, a molecular-docking strategy between solvents and inducers has been shown to enable dynamic Li+ coordination that promotes fast, stable and high-voltage lithium battery chemistries.
{"title":"Molecular-docking electrolytes enable high-voltage lithium battery chemistries","authors":"Baochen Ma, Haikuo Zhang, Ruhong Li, Shuoqing Zhang, Long Chen, Tao Zhou, Jinze Wang, Ruixin Zhang, Shouhong Ding, Xuezhang Xiao, Tao Deng, Lixin Chen, Xiulin Fan","doi":"10.1038/s41557-024-01585-y","DOIUrl":"10.1038/s41557-024-01585-y","url":null,"abstract":"Ideal rechargeable lithium battery electrolytes should promote the Faradaic reaction near the electrode surface while mitigating undesired side reactions. Yet, conventional electrolytes usually show sluggish kinetics and severe degradation due to their high desolvation energy and poor compatibility. Here we propose an electrolyte design strategy that overcomes the limitations associated with Li salt dissociation in non-coordinating solvents to enable fast, stable Li chemistries. The non-coordinating solvents are activated through favourable hydrogen bond interactions, specifically Fδ−–Hδ+ or Hδ+–Oδ−, when blended with fluorinated benzenes or halide alkane compounds. These intermolecular interactions enable a dynamic Li+–solvent coordination process, thereby promoting the fast Li+ reaction kinetics and suppressing electrode side reactions. Utilizing this molecular-docking electrolyte design strategy, we have developed 25 electrolytes that demonstrate high Li plating/stripping Coulombic efficiencies and promising capacity retentions in both full cells and pouch cells. This work supports the use of the molecular-docking solvation mechanism for designing electrolytes with fast Li+ kinetics for high-voltage Li batteries. Conventional Li-ion battery electrolytes often show sluggish kinetics and severe degradation due to high Li+ desolvation energies and poor compatibility. Now, a molecular-docking strategy between solvents and inducers has been shown to enable dynamic Li+ coordination that promotes fast, stable and high-voltage lithium battery chemistries.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 9","pages":"1427-1435"},"PeriodicalIF":19.2,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141618382","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}
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