Nanoscale topography influences polymer surface diffusion.

Using high-throughput single-molecule tracking, we studied the diffusion of poly(ethylene glycol) chains at the interface between water and a hydrophobic surface patterned with an array of hexagonally arranged nanopillars. Polymer molecules displayed anomalous diffusion; in particular, they exhibited intermittent motion (i.e., immobilization and "hopping") suggestive of continuous-time random walk (CTRW) behavior associated with desorption-mediated surface diffusion. The statistics of the molecular trajectories changed systematically on surfaces with pillars of increasing height, exhibiting motion that was increasingly subdiffusive and with longer waiting times between diffusive steps. The trajectories were well-described by kinetic Monte Carlo simulations of CTRW motion in the presence of randomly distributed permeable obstacles, where the permeability (the main undetermined parameter) was conceptually related to the obstacle height. These findings provide new insights into the mechanisms of interfacial transport in the presence of obstacles and on nanotopographically patterned surfaces.