Dynamics of Liquid Coacervates Part II: Higher Charged Density Polyelectrolyte Is in Entangled Semiflexible Regime

Solutions made from oppositely charged polyelectrolytes can phase separate to form a polymer rich coacervate phase, important in biology and technological applications. In coacervates made from polyelectrolytes of high enough molecular weights, topological constraints known as entanglements alter the dynamic properties and can be due to either the polyanion, the polycation or both. In charge density asymmetric coacervates the high charge density and low charge density polymers have qualitatively different conformations. We developed a scaling theory to predict the dynamics of entangled liquid coacervates with both bare and electrostatic persistence lengths smaller than the diameter of their confining tube. Here, we consider the case in which the electrostatic persistence length of the high charge density polymer can be larger than the diameter of a confining tube made of low charge density polymers. We develop a scaling theory that predicts that the high charge density polyelectrolyte behaves in this case similar to entangled semiflexible polymers. The effect of these “semiflexible” dynamics on rheological properties as well as polymer diffusion will be discussed.