Single-molecule tracking
was used to characterize the mobility
of poly(ethylene glycol) chains at a solid–liquid interface
over a wide range of surface coverage. Trajectories exhibited intermittent
motion consistent with a generalized continuous time random walk (CTRW)
model, where strongly confined “waiting times” alternated
with rapid flights. The presence of three characteristic regimes emerged
as a function of surface coverage, based on an analysis of effective
short-time diffusion coefficients, mean-squared displacement, and
CTRW distributions. The dilute “site-blocking” regime
exhibited increasing short-time diffusion, less confined behavior,
and shorter waiting times with higher surface coverage, as anomalously
strong adsorption sites were increasingly passivated. At intermediate
values of surface coverage, the “crowding” regime was
distinguished by the exact opposite trends (slower, more confined
mobility), presumably due to increasing intermolecular interactions.
The trends reversed yet again in the “brush” regime,
where adsorbing molecules interacted weakly with a layer of extended
overlapping chains.