{"title":"丝氨酸八聚体簇控制微水滴中形成的肽的手性。","authors":"Brison A Shira, R Graham Cooks","doi":"10.1021/acs.jpca.5c00473","DOIUrl":null,"url":null,"abstract":"<p><p>The chemistry underlying biological homochirality remains challenging. We propose that noncovalent clusters may have served as the means by which an enantiomeric excess of one amino acid could direct other racemic amino acids toward homochiral biochemistry. Serine has long been known to exhibit a chiral preference when clustering to form the octamer; here, we extend this finding by reporting the effects of a nonzero e.e. serine on the formation of noncovalent clusters with other amino acids as well as on the formation of peptides, their covalent condensation products. We show that (i) enantiopure serine directs racemic leucine and proline to enantioselective dipeptide formation in water microdroplets and (ii) likely intermediates are seen as the proline and leucine substituted serine octamer clusters. This work indicates the relevance of microdroplet sprays, <i>e.g.</i>, natural aerosols, to molecular clustering and to homochirality.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4535-4542"},"PeriodicalIF":2.8000,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12105033/pdf/","citationCount":"0","resultStr":"{\"title\":\"Serine Octamer Clusters Direct the Chirality of Peptides Formed in Water Microdroplets.\",\"authors\":\"Brison A Shira, R Graham Cooks\",\"doi\":\"10.1021/acs.jpca.5c00473\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The chemistry underlying biological homochirality remains challenging. We propose that noncovalent clusters may have served as the means by which an enantiomeric excess of one amino acid could direct other racemic amino acids toward homochiral biochemistry. Serine has long been known to exhibit a chiral preference when clustering to form the octamer; here, we extend this finding by reporting the effects of a nonzero e.e. serine on the formation of noncovalent clusters with other amino acids as well as on the formation of peptides, their covalent condensation products. We show that (i) enantiopure serine directs racemic leucine and proline to enantioselective dipeptide formation in water microdroplets and (ii) likely intermediates are seen as the proline and leucine substituted serine octamer clusters. This work indicates the relevance of microdroplet sprays, <i>e.g.</i>, natural aerosols, to molecular clustering and to homochirality.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":\" \",\"pages\":\"4535-4542\"},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2025-05-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12105033/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.jpca.5c00473\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/5/8 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.5c00473","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/5/8 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
生物同手性的化学基础仍然具有挑战性。我们提出,非共价团簇可能是一种手段,通过对映体过量的氨基酸可以指导其他外消旋氨基酸进行同手性生物化学。人们早就知道丝氨酸在聚类形成八聚体时表现出手性偏好;在这里,我们通过报道非零e - e -丝氨酸对与其他氨基酸形成非共价簇的影响以及对肽及其共价缩合产物的形成的影响来扩展这一发现。我们发现(i)对映不纯丝氨酸引导外消旋亮氨酸和脯氨酸在水微滴中形成对映选择性二肽;(ii)可能的中间体被视为脯氨酸和亮氨酸取代的丝氨酸八聚体簇。这项工作表明了微滴喷雾,例如天然气溶胶,与分子聚类和同手性的相关性。
Serine Octamer Clusters Direct the Chirality of Peptides Formed in Water Microdroplets.
The chemistry underlying biological homochirality remains challenging. We propose that noncovalent clusters may have served as the means by which an enantiomeric excess of one amino acid could direct other racemic amino acids toward homochiral biochemistry. Serine has long been known to exhibit a chiral preference when clustering to form the octamer; here, we extend this finding by reporting the effects of a nonzero e.e. serine on the formation of noncovalent clusters with other amino acids as well as on the formation of peptides, their covalent condensation products. We show that (i) enantiopure serine directs racemic leucine and proline to enantioselective dipeptide formation in water microdroplets and (ii) likely intermediates are seen as the proline and leucine substituted serine octamer clusters. This work indicates the relevance of microdroplet sprays, e.g., natural aerosols, to molecular clustering and to homochirality.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.