Structure and Dynamics of Hybrid Colloid–Polyelectrolyte Coacervates

[Image: see text] We develop a scaling theory for the structure and dynamics of “hybrid” complex coacervates formed from linear polyelectrolytes (PEs) and oppositely charged spherical colloids, such as globular proteins, solid nanoparticles, or spherical micelles of ionic surfactants. At low concentrations, in stoichiometric solutions, PEs adsorb at the colloids to form electrically neutral finite-size complexes. These clusters attract each other through bridging between the adsorbed PE layers. Above a threshold concentration, macroscopic phase separation sets in. The coacervate internal structure is defined by (i) the adsorption strength and (ii) the ratio of the resulting shell thickness to the colloid radius, H/R. A scaling diagram of different coacervate regimes is constructed in terms of the colloid charge and its radius for Θ and athermal solvents. For high charges of the colloids, the shell is thick, H ≫ R, and most of the volume of the coacervate is occupied by PEs, which determine its osmotic and rheological properties. The average density of hybrid coacervates exceeds that of their PE–PE counterparts and increases with nanoparticle charge, Q. At the same time, their osmotic moduli remain equal, and the surface tension of hybrid coacervates is lower, which is a consequence of the shell’s inhomogeneous density decreasing with the distance from the colloid surface. When charge correlations are weak, hybrid coacervates remain liquid and follow Rouse/reptation dynamics with a Q-dependent viscosity, η(Rouse) ∼ Q(4/5) and η(rep) ∼ Q(28/15) for a Θ solvent. For an athermal solvent, these exponents are equal to 0.89 and 2.68, respectively. The diffusion coefficients of colloids are predicted to be strongly decreasing functions of their radius and charge. Our results on how Q affects the threshold coacervation concentration and colloidal dynamics in condensed phases are consistent with experimental observations for in vitro and in vivo studies of coacervation between supercationic green fluorescent proteins (GFPs) and RNA.