(59i) Charge Sequence and Assembly in Polyelectrolyte Complex Coacervates

Oppositely-charged polyelectrolytes can undergo an associative phase separation to form a polymer-dense 'complex coacervate' phase. This charge-driven phase separation is used in applications ranging from food science to self-assembled materials. A fundamental understanding of these materials is necessary for materials design, however a comprehensive physical picture of complex coacervation is still emerging. Our work has led to the development of a new theoretical framework for coacervation, that is informed by coarse-grained molecular simulation and compared with experiment. We show how this approach is capable of capturing the thermodynamic effect of charge monomer sequences in two limits; local monomer-to-monomer sequence variations can be used to tune the strength of electrostatic interactions, while contour-wide variations in charge 'blockiness' can be used to induce molecular self-assembly. We explore the continuum between these two limits, and show how charge monomer sequence can be used to design the molecular interactions of polymers via precision polymer sequences.