Centro de Astrobiología (CSIC-INTA), Ctra. Ajalvir Km. 4, 28850 Torrejón de Ardoz, Madrid, Spain.
Phys Chem Chem Phys. 2012 Feb 21;14(7):2301-11. doi: 10.1039/c2cp22813k. Epub 2012 Jan 12.
We present a differential rate equation model of chiral polymerization based on a simple copolymerization scheme in which the enantiomers are added to, or removed from, the homochiral or heterochiral chains (reversible stepwise isodesmic growth or dissociation). The model is set up for closed systems and takes into account the corresponding thermodynamic constraints implied by the reversible monomer attachments, while obeying a constant mass constraint. In its simplest form, the model depends on a single variable rate constant, the maximum chain length N, and the initial concentrations. We have fit the model to the experimental data from the Rehovot group on lattice-controlled chiral amplification of oligopeptides. We find in all the chemical systems employed, except for one, that the model fits the measured relative abundances of the oligopeptides with higher degrees of correlation than from a purely random polymerization process.
我们提出了一个基于简单共聚方案的手性聚合的差分速率方程模型,其中对映异构体被添加到同手性或异手性链中(可逆逐步等规生长或解离)。该模型是为封闭系统建立的,并考虑了可逆单体连接所隐含的相应热力学约束,同时遵守恒定质量约束。在其最简单的形式中,该模型取决于一个单一的变量速率常数、最大链长 N 和初始浓度。我们已经将模型拟合到来自雷霍沃特小组的实验数据,该实验研究了寡肽的格子控制手性扩增。我们发现,在所使用的所有化学系统中,除了一个系统之外,模型拟合测量到的寡肽的相对丰度的相关性都高于纯粹的随机聚合过程。