Direct measurements & simplified models of colloidal interactions & diffusion with adsorbed macromolecules

Abstract

We report total internal reflection microscopy measurements of 3D trajectories of ensembles of micron sized colloidal particles near interfaces with and without adsorbed macromolecules. Evanescent wave scattering reveals nanometer scale motion normal to planar surfaces and sub-diffraction limit lateral motion is resolved via image analysis. Equilibrium and non-equilibrium analyses of particle trajectories reveal self-consistent position dependent energies (energy landscapes) and position dependent diffusivities (diffusivity landscapes) both perpendicular and parallel to interfaces. For bare colloids and surfaces, electrostatic and hydrodynamic interactions are accurately quantified with established analytical theories. For colloids and surfaces with adsorbed macromolecules, conservative forces are accurately quantified with models for interactions between brush layers, whereas directly measured position dependent diffusivities require novel models of spatially varying permeability within adsorbed layers. Agreement between spatially resolved interactions and diffusivities and rigorous simplified models provide a basis to consistently interpret, predict, and design colloidal transport in the presence of adsorbed macromolecules for diverse applications.