Shape induced segregation and anomalous particle transport under spherical confinement

Abstract

Colloid or nanoparticle mobility under confinement is of central importance to a wide range of physical and biological processes. Here, we introduce a minimal model of particles in a hydrodynamic continuum to examine how particle shape and concentration affect the transport of particles in spherical confinement. Specifically, an immersed boundary-General geometry Ewald-like approach is adopted to simulate the dynamics of spheres and cylinders under the influence of short-and long-range fluctuating hydrodynamic interactions with appropriate non-slip conditions at the confining walls. An efficient O(N) parallel finite element algorithm is used, thereby allowing simulations at high concentrations, while a Chebyshev polynomial approximation is implemented in order to satisfy the fluctuation-dissipation theorem. A concentration-dependent anomalous diffusion is observed for suspended particles. It is found that introducing cylinders in a background of spheres, i.e. particles with a simple degree of anisotropy, has a pronounced influence on the structure and dynamics of the particles. First, increasing the fraction of cylinders induces a particle segregation effect, where spheres are pushed towards the wall and cylinders remain near the center of the cavity. This segregation leads to a lower mobility for the spheres relative to that encountered in a system of pure spheres at the same volume fraction. Second, the diffusive-to-anomalous transition and the degree of anomaly -quantified by the power law exponent in the mean square displacement vs. time relation -both increase as the fraction of cylinders becomes larger. These findings are of relevance for studies of diffusion in the cytoplasm, where proteins exhibit a distribution of size and shapes that could lead to some of the effects identified in the simulations reported here.