Water's effect on the glass transition and dynamic mechanical properties of polyelectrolyte complexes*

Charged assemblies bearing opposite or complementary charges span natural (proteins, enzymes, DNA) to synthetic materials (surfactants, synthetic polyelectrolytes). Assembly is facilitated by electrostatic attraction and entropic release of counterions, and most often occurs in aqueous media. Notably decades ago, Michaels described synthetic polyelectrolyte complexes as brittle when dry but “leathery or rubberlike” when wet, which points to the strong effect of water on the mobility of a charged assembly. Here, the molecular origin of the glass transition is quantified for several charged macromolecular systems is investigated using calorimetry and molecular modeling as a function of water content. A general relationship is revealed as it holds for two completely different types of charged systems (pH- and salt-sensitive) and for both polyelectrolyte complexes and polyelectrolyte multilayers, which are made by different paths. This suggests that water facilitates the relaxation of charged assemblies by reducing attractions between oppositely charged intrinsic ion pairs. We further demonstrate the dual role of water and temperature in the dynamics of polyelectrolyte complexes by showing time-temperature and time-water superpositioning in a single polyelectrolyte complex system. This is accomplished by changing the relative humidity to adjust the water content in the complex during testing. Results indicate the existince of a water-based shift factor (a_w) that bears a log-linear relationship.