(397g) Sequence Effects in Coacervate-Driven Self-Assembly

Oppositely-charged polyelectrolytes in aqueous solution can undergo associative phase separation in a process known as 'complex coacervation'. Originally discovered in biopolymers, and used in a variety of food and personal care products, the underlying physical process is now being harnessed for soft material self-assembly. We have used a combination of simulation and theory to demonstrate that structural features at the molecular level have a profound effect on coacervation. Motivated by this observation, we have developed a new hybrid simulation method that couples molecular Monte Carlo and Single Chain in Mean Field simulations to provide the multi-scale picture necessary to study coacervation-driven self-assembly. We demonstrate that this provides predictions that deviate significantly from prior theoretical results, and show that the sequence of charges along the backbone is a useful way to tune and design the self-assembly properties of charged block copolymers. Our investigaion has important implications for how monomer sequence may be used to design the next generation of self-assembled soft materials.