Dynamic heterogeneity controls diffusion and viscosity near biological interfaces

Abstract

At a nanometer scale, the behavior of biological fluids is largely governed by interfacial physical chemistry. This may manifest as slowed or anomalous diffusion. Here we describe how measures developed for studying glassy systems allow quantitative measurement of interfacial effects on water dynamics, showing that correlated motions of particles near a surface result in a viscosity greater than anticipated from individual particle motions. This effect arises as a fundamental consequence of spatial heterogeneity on nanometer length scales and applies to any fluid near any surface. Increased interfacial viscosity also causes the classic finding that large solutes such as proteins diffuse much more slowly than predicted in bulk water. This has previously been treated via an empirical correction to the solute size: the hydrodynamic radius. Using measurements of quantities from theories of glass dynamics, we can now calculate diffusion constants from molecular details alone, eliminating the empirical correction factor.