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在有限的对映选择性模型中手性的自发出现:由外部试剂驱动的自催化循环。

Spontaneous emergence of chirality in the limited enantioselectivity model: autocatalytic cycle driven by an external reagent.

机构信息

Centro de Astrobiología (CSIC-INTA), 28850 Torrejon de Ardoz, Madrid, Spain.

出版信息

Chemphyschem. 2013 Aug 5;14(11):2432-40. doi: 10.1002/cphc.201300350. Epub 2013 Jul 2.

Abstract

The model of limited enantioselectivity (LES) in closed systems, and under experimental conditions able to achieve chemical equilibrium, can give rise to neither spontaneous mirror symmetry breaking (SMSB) nor kinetic chiral amplifications. However, it has been recently shown that it is able to lead to SMSB, as a stationary final state, in thermodynamic scenarios involving nonuniform temperature distributions and for compartmentalized separation between the two autocatalytic reactions. Herein, it is demonstrated how SMSB may occur in LES in a cyclic network with uniform temperature distribution if the reverse reaction of the nonenantioselective autocatalysis, which gives limited inhibition on the racemic mixture, is driven by an external reagent, that is, in conditions that keep the system out of chemical equilibrium. The exact stability analysis of the racemic and chiral final outcomes and the study of the reaction parameters leading to SMSB are resolved analytically. Numerical simulations, using chemical kinetics equations, show that SMSB may occur for chemically reasonable parameters. Numerical simulations on SMSB are also presented for speculative, but reasonable, scenarios implying reactions common in amino acid chemistry.

摘要

在封闭系统中,模型的对映选择性有限(LES),并在能够达到化学平衡的实验条件下,既不能自发地打破镜像对称性(SMSB),也不能进行动力学手性放大。然而,最近有人表明,在涉及非均匀温度分布和两个自催化反应之间的分隔式分离的热力学情况下,它能够导致 SMSB 作为稳定的最终状态。本文证明了,如果对映选择性自催化的逆反应受到外部试剂的驱动,即系统保持在化学平衡之外的条件下,那么在具有均匀温度分布的循环网络中,LES 中可能会发生 SMSB。通过解析方法解决了关于手性和外消旋最终产物的精确稳定性分析,以及导致 SMSB 的反应参数的研究。使用化学动力学方程的数值模拟表明,对于化学上合理的参数,SMSB 可能会发生。还针对氨基酸化学中常见的反应提出了关于 SMSB 的推测性但合理的场景的数值模拟。

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