{"title":"自发镜像对称破缺使外消旋物失稳：一条通向同手性和逆转化学选择性的途径。","authors":"Josep M Ribó, Jean-Claude Micheau, Thomas Buhse","doi":"10.1002/cphc.202500384","DOIUrl":null,"url":null,"abstract":"<p><p>Several models and experiments yielding to spontaneous mirror-symmetry breaking (SMSB) have been revisited. It is concluded that all show first-order autocatalytic dynamics for the emergence of an enantiomeric excesses (ee). However, first-order autocatalysis is by itself unable to lead to SMSB. Therefore, the emergence of scalemic nonequilibrium stationary state (NESS) is due to racemate destabilization through the coupling of autocatalysis with other enantioselective reactions. In contrast with the nonlinear effects and kinetic control in asymmetric synthesis SMSB appears as the signature of a bifurcation scenario leading to scalemic NESSs. Stoichiometric network analysis points to the potential interest of these autocatalytic networks to interpret the changes in the chemical selectivity between nonenantiomeric competitive replicators in far-from-equilibrium conditions.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500384"},"PeriodicalIF":2.2000,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Spontaneous Mirror-Symmetry Breaking Destabilizes Racemates: A Route to Homochirality and Reversed Chemical Selectivity.\",\"authors\":\"Josep M Ribó, Jean-Claude Micheau, Thomas Buhse\",\"doi\":\"10.1002/cphc.202500384\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Several models and experiments yielding to spontaneous mirror-symmetry breaking (SMSB) have been revisited. It is concluded that all show first-order autocatalytic dynamics for the emergence of an enantiomeric excesses (ee). However, first-order autocatalysis is by itself unable to lead to SMSB. Therefore, the emergence of scalemic nonequilibrium stationary state (NESS) is due to racemate destabilization through the coupling of autocatalysis with other enantioselective reactions. In contrast with the nonlinear effects and kinetic control in asymmetric synthesis SMSB appears as the signature of a bifurcation scenario leading to scalemic NESSs. Stoichiometric network analysis points to the potential interest of these autocatalytic networks to interpret the changes in the chemical selectivity between nonenantiomeric competitive replicators in far-from-equilibrium conditions.</p>\",\"PeriodicalId\":9819,\"journal\":{\"name\":\"Chemphyschem\",\"volume\":\" \",\"pages\":\"e202500384\"},\"PeriodicalIF\":2.2000,\"publicationDate\":\"2025-10-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemphyschem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/cphc.202500384\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemphyschem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cphc.202500384","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Spontaneous Mirror-Symmetry Breaking Destabilizes Racemates: A Route to Homochirality and Reversed Chemical Selectivity.
Several models and experiments yielding to spontaneous mirror-symmetry breaking (SMSB) have been revisited. It is concluded that all show first-order autocatalytic dynamics for the emergence of an enantiomeric excesses (ee). However, first-order autocatalysis is by itself unable to lead to SMSB. Therefore, the emergence of scalemic nonequilibrium stationary state (NESS) is due to racemate destabilization through the coupling of autocatalysis with other enantioselective reactions. In contrast with the nonlinear effects and kinetic control in asymmetric synthesis SMSB appears as the signature of a bifurcation scenario leading to scalemic NESSs. Stoichiometric network analysis points to the potential interest of these autocatalytic networks to interpret the changes in the chemical selectivity between nonenantiomeric competitive replicators in far-from-equilibrium conditions.
期刊介绍：
ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.
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