How polymer surface diffusion depends on surface coverage

Measurements are presented of how surface diffusion of flexible polymers at the solid-liquid interface is controlled by surface coverage. Surface coverage is varied over the full range from dilute to saturated surface coverage. The method of measurement is fluorescence correlation spectroscopy (FCS), and the systems are polyethylene oxide) (PEG) and dextran adsorbed onto methyl-terminated self-assembled monolayers in buffered aqueous solution. A detailed study of PEG (M_w = 10 800 g mol^-1) shows nonmonotonic behavior. The translational diffusion coefficient (D) at first increases with increasing surface concentration, presumably because the number of adsorption sites per molecule decreases as chains switch from pancake to loop-train-tail conformation. Excellent fits to behavior characteristic of a single diffusion process argue against aggregation or crystallization in the adsorbed state. In-situ ellipsometry measurements appear to rule out conformation changes to a hypothetical helical structure, as this would introduce birefringence to the adsorbed polymer layer causing deviations from the observed linear growth of apparent layer thickness with increasing surface coverage. For all three samples studied (PEG of M_w = 10 800 and 20 000 g mol^-1 and also dextran with M_w = 10 000 g mol ^-1), D at surface coverages larger than the estimated surface overlap concentration slow by 1 order of magnitude, presumably reflecting crowding and entanglement with neighboring chains.