首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Random Chiral Asymmetry Generation by Chiral Autocatalysis in a Far-from-Equilibrium Reaction System
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Random Chiral Asymmetry Generation by Chiral Autocatalysis in a Far-from-Equilibrium Reaction System

机译:在远离平衡的反应系统中通过手性自催化产生随机手性不对称

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If the growth in a local concentration due to an autocatalytic process overcomes diffusion a concentration fluctuation in a small volume will grow. In a chirally autocatalytic system, this phenomenon could produce a large variation in the enantiomeric excess (ee). Here we report kinetic studies that show such stochastic behavior in the synthesis of an autocatalytic chiral cobalt complex. The established values of the kinetic parameters indicate that temperature inhomogeneities in the form of local hot spots can have a significant effect on the progress of the reaction as well as the ee of the final product. Stochastic kinetics of this type are in stark contrast to deterministic kinetics that are usually encountered in chemistry; in these systems random fluctuations play an important role in determining the product distribution. In the present case we find large random fluctuations in the ee.
机译:如果由于自动催化过程而引起的局部浓度的增长克服了扩散,则小体积的浓度波动将增大。在手性手催化系统中,这种现象可能会导致对映体过量(ee)发生较大变化。在这里我们报告动力学研究,表明在自动催化手性钴配合物的合成中这种随机行为。动力学参数的确定值表明,局部热点形式的温度不均匀性可能对反应进程以及最终产物的ee产生重大影响。这种随机动力学与化学中通常遇到的确定性动力学形成鲜明对比。在这些系统中,随机波动在确定产品分布方面起着重要作用。在当前情况下,我们发现ee中存在较大的随机波动。

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