Hydrodynamic Effects on the Collapse Kinetics of Flexible Polyelectrolytes.

Abstract

Understanding the collapse kinetics of polyelectrolytes (PEs) is crucial for comprehending various biological and industrial phenomena. Despite occurring in an aqueous environment, previous computational studies have overlooked the influence of hydrodynamic interactions (HIs) facilitated by fluid motion. Here, we directly compute the Navier-Stokes equation to investigate the collapse kinetics of a highly charged flexible PE. Our findings reveal that HI accelerates PE collapse induced by hydrophobicity and multivalent salt. In the case of hydrophobicity, HI induces long-range collective motion of monomers, accelerating the coarsening of local clusters through either Brownian-coagulation-like or evaporation-condensation-like processes, depending on the strength of hydrophobicity with respect to electrostatic interaction. Regarding multivalent salt, HI does not affect the condensation dynamics of multivalent ions but facilitates quicker movement of local dipolar clusters along the PE, thereby expediting the collapse process. These results provide valuable insights into the underlying mechanisms of HI in PE collapse kinetics.