(59l) A Materials Genome Approach to Unravel the Formation, Growth, and Demise of Complex Coacervate Assemblies

The route by which polyelectrolyte complex assemblies undergo phase separation and structural evolution remains unclear because of the enormous number of nonlinearly coupled variables at play from electrostatic correlations, hydrophobic effects, and other chemical contributions. To elucidate structure-function relationships in charge driven assemblies and diversify custom-built materials infrastructures for end-use technologies, we have pursued multiple synthesis–screening campaigns using aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization. Families of RAFT polycations and polyanions were systematically constructed into datasets, varying macromolecular size, chemical microstructure, and chain architecture. With select pairings of these tunable materials, we investigated several platforms to provide direct insight on the kinetic assembly (and disassembly) pathways for viscoelastic liquid coacervates, self-assembled micelles, and DNA nanocarriers. Vignettes that illustrate the breadth of complex behavior and spatiotemporal dynamics captured from these designer materials as a function of polymer and salt concentrations will be presented, centered on time-resolved dynamic light scattering, small angle X-ray/neutron scattering, rheology, and cryo imaging characterization. Collectively, this concerted endeavor reveals how to better predict and strategically design specialized polyelectrolytes with enhanced performance and elevated reliability for applications in 3D nanocompartmentalization, multiresponsive materials fabrication, and genome editing formulation.