Local Confinement Controls Diffusive Nanoparticle Dynamics in Semidilute Polyelectrolyte Solutions

We investigate the mobility of polystyrene particles ranging from 100 to 790 nm in diameter in dilute and semidilute sodium polystyrene sulfonate (NaPSS) solutions using fluorescence microscopy. We tune the polymer conformations by varying the ionic strength of the solution. The nanoparticle mean-squared displacements evolve linearly with time at all time scales, indicating Fickian diffusive dynamics. In solutions of high ionic strength, chains adopt a random walk conformation and particle dynamics couple to the bulk zero-shear rate viscosity, according to the Stokes–Einstein picture. In solutions of low ionic strength, however, particle dynamics nonmonotonically deviate from bulk predictions as polymer concentration increases and are not accurately predicted by the available models. These nonmonotonic dynamics directly correlate with the non-Gaussianity in distributions of particle displacements, suggesting the emergence of a local confining length scale as polyelectrolyte concentration increases.