(142c) Thermodynamics and Molecular Engineering of Complex Coacervates

Complex coacervation is an associative liquid-liquid phase separation phenomenon resulting from the complexation of oppositely charged macro-ions. The driving force for coacervation comes from the electrostatic attraction between oppositely charged polyelectrolytes, coupled with entropic gains associated with the release of bound counterions and the restructuring of water. We have explored a range of different polymer systems to develop a molecular-level understanding of polyelectrolyte complexation. In particular, we take advantage of well-controlled model systems of synthetic polymers and/or sequence-controlled polypeptides to study how molecular level features, as well as the identity of both small molecule salt ions and the chemistry of our polyelectrolytes affects the driving force and subsequent phase behavior of coacervate forming systems. Ultimately, our goal is to establish a thermodynamically-informed, molecular-level set of design rules to facilitate the tailored creation of materials based on complex coacervation that can both illuminate self-assembly phenomena found in nature, and find utility across a wide range of real-world applications.