Effects of Hydrodynamic Interactions on the Near-Surface Diffusion of Spheroidal Molecules

We investigated diffusion of spheroidal molecules near a planar surface, accounting for spatially dependent translational and rotational mobilities of molecules resulting from their hydrodynamic interactions with the plane. Rigid-body Brownian dynamics simulations of prolate ellipsoids of revolution of an axial ratio in the range of 1.5 to 3.0, suspended in a viscous fluid, with a no-slip flat boundary confining the suspension were employed. Mobility tensor matrices of molecules were evaluated as functions of spheroids' distance and orientation with respect to the plane. Hydrodynamic interactions with the surface lead to substantial changes of spheroids' translational diffusion coefficients both in the direction perpendicular and parallel to the plane when compared with the values characterizing the bulk diffusion. Moreover, the short-time translational diffusion of molecules, measured in the laboratory frame, both in an unbounded fluid and under the confinement, is non-Gaussian, with much larger deviations from Gaussianity observed in the latter case. In an unbounded fluid, distributions of translational displacements of molecules deviate from those expected for a simple Brownian motion as a result of shape anisotropy. In the presence of the plane, spheroids experience an additional anisotropic drag, and consequently, their mobilities depend on their positions and orientations. Therefore, anomalies in the short-time dynamics observed under confinement can be explained in terms of the so-called diffusing-diffusivity mechanism. Our findings have implications for understanding of a wide range of biological and technological processes that involve diffusion of anisotropic molecules near surfaces of natural and model cell membranes, biosensors and nanosensors, and electrodes.