Self-assembly of spherical interpolyelectrolyte complexes from oppositely charged polymers

TL;DR

This paper investigates the self-assembly process of spherical interpolyelectrolyte complexes formed from oppositely charged polymers, analyzing their structure, formation conditions, and specific size distributions using theoretical models.

Contribution

It introduces a theoretical framework for predicting the structure and size distribution of interpolyelectrolyte complexes based on free energy minimization and Poisson-Boltzmann theory.

Findings

Complexes have a charged core with a dilute corona.

The aggregation number is determined by free energy minimization.

Complexation can be highly specific with localized size distributions.

Abstract

The formation of inter-polyelectrolyte complexes from the association of oppositely charged polymers in an electrolyte is studied. The charged polymers are linear oppositely charged polyelectrolytes, with possibly a neutral block. This leads to complexes with a charged core, and a more dilute corona of dangling chains, or of loops (flower-like structure). The equilibrium aggregation number of the complexes (number of polycations m+ and polyanions m-) is determined by minimizing the relevant free energy functional, the Coulombic contribution of which is worked out within Poisson-Boltzmann theory. The complexes can be viewed as colloids that are permeable to micro-ionic species, including salt. We find that the complexation process can be highly specific, giving rise to very localized size distribution in composition space (m+,m-).