Interfacial properties of polymeric complex coacervates from simulation and theory

Polymeric complex coacervation occurs when two oppositely charged polyelectrolytes undergo an associative phase separation in aqueous salt solution, resulting in a polymer-dense coacervate phase and a polymer-dilute supernatant phase. This phase separation process represents a powerful way to tune polymer solutions using electrostatic attraction and is sensitive to environmental conditions such as salt concentration and valency. One area of particular research interest is using this to create nanoscale polymer assemblies, via (for example) block copolymers with coacervate-forming blocks. The key to understanding coacervate-driven assembly is the formation of the interface between the coacervate and supernatant phases and its corresponding thermodynamics. In this work, we use recent advances in coacervate simulation and theory to probe the nature of the coacervate-supernatant interface. First, we show that self-consistent field theory informed by either Monte-Carlo simulations or transfer matrix theories is capable of reproducing interfacial features present in large-scale molecular dynamics simulations. The quantitative agreement between all three methods gives us a way to efficiently explore interfacial thermodynamics. We show how salt affects the interface, and we find qualitative agreement with literature measurements of interfacial tension. We also explore the influence of neutral polymers, which we predict to drastically influence the phase behavior of coacervates. These neutral polymers can significantly alter the interfacial tension in coacervates; this has a profound effect on the design and understanding of coacervate-driven self-assembly, where the equilibrium structure is tied to interfacial properties. Published by AIP Publishing.