Shape-free theory for the self-assembly kinetics in macromolecular systems

Departamento de Física, Universidade Federal de Viçosa (UFV) - Av. P. H. Rolfs s/n, 36570-900, Viçosa, Brazil

^(a) lerizzi@ufv.br (corresponding author)

Received: 13 October 2021
Accepted: 25 February 2022

Abstract

Although temperature-dependent self-assembly kinetics is usually described by approaches which assume that the macromolecular aggregates have a definite shape, sometimes that assumption might be inappropriate, as in the case of several colloidal and biopolymeric systems. Here we consider a simple model for particle aggregation which displays a first-order phase transition in order to illustrate a rate theory based on microcanonical thermostatistics that allows one to obtain a shape-free description of its thermally induced self-assembly kinetics. Stochastic simulations are performed to validate our approach and demonstrate how the equilibrium thermostatistics properties of the system can be related to the temperature-dependent rate constants. As a model-independent kinetic approach, it may provide experimentalists with a reliable method to extract information about free-energy profiles and microcanonical entropies from kinetic data.