Extreme dependence of dynamics on concentration in highly crowded polyelectrolyte solutions

Charge-carrying species, such as polyelectrolytes, are vital to natural and synthetic processes that rely on their dynamic behavior. Through single-particle tracking techniques, the diffusivity of individual polyelectrolyte chains and overall system viscosity are determined for concentrated polylysine solutions. These studies show scaling dependences of D ~ c^-6.1 and η ~ c^7.2, much stronger than theoretical predictions, drawing the applicability of power law fits into question. Similar trends are observed in concentrated solutions prepared at various pH and counterion conditions. These hindered system dynamics appear universal to polyelectrolyte systems and are attributed to the large effective excluded volumes of polyelectrolyte chains inducing glassy dynamics. The framework of the Vrentas-Duda free-volume theory is used to compare polyelectrolyte and neutral systems. Supported by this theory, excluding counterion mass from total polymer mass results in all environmental conditions collapsing onto a common trendline. These results are applicable to crowded biological systems, such as intracellular environments where protein mobility is strongly inhibited.