Tuning the Flight Length of Molecules Diffusing on a Hydrophobic Surface

Transport at solid–liquid interfaces is critical to self-assembly, biosensing, and heterogeneous catalysis, but surface diffusion remains difficult to characterize and rationally manipulate, due to the inherent heterogeneity of adsorption on solid surfaces. Using single-molecule tracking, we characterized the diffusion of a fluorescent long-chain surfactant on a hydrophobic surface, which involved periods of confinement alternating with bulk-mediated “flights”. The concentration of methanol in solution was varied to tune the strength of the hydrophobic surface-molecule interaction. The frequency of confinement had a nonmonotonic dependence on methanol concentration that reflected the relative influence of anomalously strong adsorption sites. By carefully accounting for the effect of this surface heterogeneity, we demonstrated that flight lengths increased monotonically as the hydrophobic attraction decreased, in agreement with theoretical predictions for bulk-mediated surface diffusion. The theory provided an accurate description of surface diffusion, despite the system being heterogeneous, and can be leveraged to optimize molecular search and assembly processes.