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

在化学反应体系中，手性对称性破缺是一种耗散结构。主题1：手性自催化反应机理分析主题2：不对称放大机理分析主题3：空间非均匀手性自催化晶体生长模型的行为分析在主题1中，分析了二异丙基锌与嘧啶醛的反应行为。这个反应被称为Soai反应，它表现出手性自催化行为。研究发现，在反应过程中发生了沉淀过程，这一过程影响了反应过程中对映体过量的时间演化和反应速率。该反应是在化学反应体系中实现手性对称性破缺的候选反应之一。在对象2中，二乙基锌与苯甲醛的不对称放大反应的行为是Ana…更具抒情性。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，用于该反应的化合物与用于SODS反应的化合物相似。异手性非活性沉淀物的形成及其溶解对反应行为有影响。在课题3中，提出了一个基于1，1‘-联萘结晶的三维离散模型。模型中晶相的生长是表面形核的重复，模拟时考虑了每个元素生长单元的位置和环境。该模型不仅成功地再现了结晶实验得到的1，1‘-联萘的晶相对映体过量的平均值，而且还再现了晶相对映体过量的变化，为分析Soai反应实现手性对称性破缺转变的机理提供了重要的信息。较少

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