Probability distributions of enantiomeric excess in unstirred and stirred crystallization of 1,1'-binaphthyl melt
Probability distributions of enantiomeric excess in unstirred and stirred crystallization of 1,1'-binaphthyl melt
复制标题
DOI：
10.1002/chir.10046
复制
发表时间：
2002-01-01
期刊：
影响因子：
2
通讯作者：
Kondepudi, DK
中科院分区：
文献类型：
--
作者：
Asakura, K;Soga, T;Kondepudi, DK
1,1′-联萘基熔体的结晶可以自发地产生光学活性。由于结晶是一个随机过程，每次结晶中产生的对映体过量（ee）是随机变化的。研究了砾岩结晶发生在150℃和152℃两种温度下结晶ee的概率分布的定性特征。在两种温度下均未形成透明的晶体，表明熔体中形成的固态为多晶。在不同的运行过程中，ee随机波动，在152℃和150℃结晶时，ee的平均波动率分别为26.9%和2.7%。概率分布的扩展也有很大的不同。研究了不同转速下ee在搅拌结晶中的概率分布。结果表明：在对称破断过渡中，随着搅拌转速-非典型行为的增加，概率分布逐渐展宽并演化为双峰分布；这些结果揭示了二次成核和晶体生长中对映体选择性的本质。(C) 2002 Wiley-Liss, Inc。
Crystallization of 1,1'-binaphthyl from its melt can generate optical activity spontaneously. Since crystallization is a stochastic process, the enantiomeric excess (ee) generated in each crystallization varies randomly. We investigated the qualitative features of probability distribution of the ee for crystallization at two temperatures, 150 degreesC and 152 degreesC, at which conglomerate crystallization occurs. No clear transparent crystals were produced at either temperature, indicating that the solid states formed in the melt were polycrystalline. The ee randomly fluctuated from run to run, with an average of 26.9% and 2.7% when the crystallization was carried out at 152 degreesC, and 150 degreesC, respectively. The spread of the probability distribution is also substantially different. We also studied the probability distribution of ee in stirred crystallization at different stirring RPM. The results show probability distribution's broadening and evolution to a bimodality with increasing stirring RPM-atypical behavior in symmetry-breaking transitions. These results shed light on the nature of enantioselectivity in secondary nucleation and crystal growth. (C) 2002 Wiley-Liss, Inc.