Homochiral oligopeptides by chiral amplification: Interpretation of experimental data with a copolymerization model

TL;DR

This paper introduces a copolymerization model for chiral oligopeptides that accurately fits experimental data, revealing insights into chiral amplification mechanisms in closed systems.

Contribution

The paper develops a differential rate equation model incorporating thermodynamic constraints to interpret chiral polymerization data, advancing understanding of homochiral oligopeptide formation.

Findings

Model fits experimental data with high correlation in most systems.

Reversible stepwise isodesmic growth explains chiral amplification.

Model outperforms purely random polymerization assumptions.

Abstract

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 oligopetides with higher degrees of correlation than from a purely random polymerization process.