Reversible Gel Formation of Triblock Copolymers Studied by Molecular Dynamics Simulation

TL;DR

This study uses molecular dynamics simulations to investigate the reversible gel formation of amphiphilic triblock copolymers in water, revealing structural and dynamical changes associated with gelation and network formation.

Contribution

It provides a detailed simulation-based analysis of the structural and dynamical properties of triblock copolymer gels, mimicking experimental hydrogel systems.

Findings

Network structures form at lower temperatures with increased ordering.

Micelle formation correlates with changes in diffusion and viscosity.

System exhibits glass-like dynamical behavior and solid-like response upon gelation.

Abstract

Molecular dynamics simulations have been employed to study the formation of a physical (thermoreversible) gel by amphiphilic A-B-A triblock copolymers in aqueous solution. In order to mimic the structure of hydrogel-forming polypeptides employed in experiments [W.A. Petka et al., Science 281, 389 (1998)], the endblocks of the polymer chains are modeled as hydrophobic rods representing the alpha-helical part of the polypeptides whereas the central B-block is hydrophilic and semi-flexible. We have determined structural properties, such as the hydrophobic cluster-size distribution function, the geometric percolation point and pair correlation functions, and related these to the dynamical properties of the system. Upon decrease of the temperature, a network structure is formed in which bundles of endblocks act as network junctions. Both at short and medium distances an increased ordering is observed, as characterized by the pair correlation function. Micelle formation and the corresponding onset of geometric percolation induce a strong change in dynamical quantities, e.g., in the diffusion constant and the viscosity, and causes the system to deviate from the Stokes-Einstein relation. The dynamical properties show a temperature dependence that is strongly reminiscent of the behavior of glass-forming liquids. The appearance of a plateau in the stress autocorrelation function suggests that the system starts to exhibit a solid-like response to applied stress once the network structure has been formed, although the actual sol-gel transition occurs only at a considerably lower temperature.