Diffusion and rheology in crowded, 3D-confined suspensions: A model for intracellular transport

Deparment of Chemical & Biomolecular Engineering

Cornell University

Crowded, watery compartments filled with complex fluids are ubiquitous in natural and engineered systems, ranging from consumer products such as cosmetic products to living systems such as biofilms and the interior of cells. They are set apart from simple fluids by the presence of microscopic constituents embedded within the fluid that give it structure, i.e. a microstructure. Distortion of this microstructure by externally imposed forces or fields gives rise to non-Newtonian rheological behavior such as shear thinning, shear thickening, and time-dependent (memory) effects. A primary goal in the study of complex fluids is the development of theoretical and computational models that relate microstructural evolution to macroscopic material and flow properties. An important element in the construction of such models is the accurate representation of the physical forces between the microstructural constituents, and the influence exerted by system boundaries on such interactions. Particle-particle and particle-boundary interactions can include electrostatic, entropic and hydrodynamic forces, among others. While numerous models, both analytical and computational, successfully describe microstructural evolution and its connection to macroscopic flow for unbound suspensions, the study of suspensions enclosed by a finite boundary is an emergent area of research. In these micro-confined systems particle-scale structure and dynamics are influenced not only by interactions between particles themselves, but also between particles and nearby boundaries. A primary challenge in the development of such models is the accurate and efficient representation of many-body hydrodynamic interactions and the influence exerted on such interactions by boundaries. Such studies include systems confined by a channel to particles confined in a droplet, but scant attention has been paid to fully three-dimensional confinement, where flow recirculation and entropic restrictions are expected to play a special role.

In this work, we study the short- and long-time self-diffusion of hydrodynamically interacting colloids enclosed within a spherical cavity, as a model for intracellular and other confined biophysical transport. Prior models of such behavior began with a single enclosed particle; attempts to enlarge such models to many particles have seen limited success owing to the challenges of accurately modeling many- body far-field and singular near-field hydrodynamic interactions. To overcome these difficulties we have developed a new set of hydrodynamic mobility functions to couple particle motion with hydrodynamic force moments which, when inverted and combined with near-field resistance functions form a complete coupling tensor that accurately captures full many-body interactions, for an arbitrary number of particles enclosed by a spherical cavity of arbitrary relative size. The mobility functions are implemented in a Stokesian dynamics framework, and particle motion obtained via dynamic simulation, for suspensions from dilute to near jamming. We present results for a range of volume fractions from dilute to concentrated, and a range of particle-to-cavity size ratios, where interplay between entropic restriction and hydrodynamic entrainment gives rise to novel diffusive behavior. Results are compared to experiments with excellent agreement. In some prior studies, attempts have been made to circumvent the challenges of modeling many-body and lubrication hydrodynamics by modeling all particle interactions as pairwise additive, and accounting only for leading-order far-field interactions (neglecting near-field lubrication interactions entirely). A discussion of the regimes in which such approximations may be valid is given.