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Realization of Chiral Symmetry Breaking Transition as a Dissipative Structure in Chemical Reaction System

化学反应体系中手性对称破缺跃迁作为耗散结构的实现

基本信息

批准号：
17540361
负责人：
ASAKURA Kouichi
金额：
$ 2.46万
依托单位：
Keio University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2007
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-17540361/
关键词：
Chiral Symmetry Breaking Dissipative Structure Chiral Autocatalytic Reaction Asymmetric Amplification ReactionC Crystal Growth Non-linear Dynamic Model International Information Exchange U. S. A.開放化学系

项目摘要

Attempts were made to realize chiral symmetry breaking as a dissipative structure in chemical reaction system. Following subjects have been studied.Subject 1 : Analysis of the mechanism of chirally autocatalytic reactionSubject 2 : Analysis of the mechanism of asymmetric amplificationSubject 3: Analysis of the behavior of the spatially inhomogeneous chirally autocatalytic crystal growth modelIn subject 1, behaviors of the reaction of diisopropylzinc with pyrimidine aldehyde were analyzed. The reaction is called Soai reaction, and it is known to exhibit chirally autocatalytic behavior. We found that precipitation proceeded during the reaction, and this process influenced on the reaction behavior such as time evolution of enantiomeric excess and rate of reaction during the reaction. The reaction is one of the candidates to realize chiral symmetry breaking in chemical reaction system.In subject 2, behaviors of the asymmetric amplification reaction of diethylzinc with benzaldehyde were ana … More lyzed. In asymmetric amplification, enantiomeric excess of a product is higher than that of chiral catalyst or chiral auxiliary for catalyst, and the compounds used for this reaction is similar to the ones used in Sods reaction. Formation of heterochiral inactive precipitate and its dissolution was found to be influence on the behaviors of the reaction.In subject 3, a discrete three-dimensional model of conglomerate crystallization based on the crystallization of 1, 1'-binaphthyl was proposed. The growth of the crystal phase in the model was the repetition of the surface nucleation, and the position and environment of every elementary growth unit was taken into account for the simulation. The model was succeeded in reproducing not only the average but also the variation of enantiomeric excess of the crystal phase of 1, 1'-binaphthyl obtained by the crystallization experiments.The results gave us important information for analyzing the mechanism of Soai's reaction to realize chiral symmetry breaking transition. Less

将手征对称性破缺作为一种耗散结构在化学反应体系中进行了尝试。本论文主要研究了以下几个方面的内容：课题1：手性自催化反应机理的分析课题2：不对称放大机理的分析课题3：空间非均匀手性自催化晶体生长模型的行为分析课题1：分析了二异丙基锌与嘧啶醛的反应行为。该反应被称为Soai反应，并且已知其表现出手性自催化行为。我们发现在反应过程中会发生沉淀，沉淀过程对反应过程中的对映体过量随时间的变化和反应速率等反应行为产生影响。该反应是化学反应体系中实现手性对称性破缺的候选反应之一，课题2研究了二乙基锌与苯甲醛的不对称放大反应的行为， ...更多信息溶解的。在不对称放大反应中，产物的对映体过量高于手性催化剂或催化剂的手性助剂的对映体过量，并且用于该反应的化合物与Sods反应中所用的化合物相似。在课题3中，以1，1 '-联萘的结晶为基础，提出了一个离散的三维聚集结晶模型。模型中晶相的生长是表面形核的重复，模拟中考虑了每个基元生长基元的位置和环境。该模型不仅成功地再现了1，1 '-联萘结晶实验所得晶相对映体过量的平均值，而且再现了其变化规律，为分析Soai反应实现手性对称性破缺跃迁的机理提供了重要信息。少