Activation Energy for Mobility of Dyes and Proteins in Polymer Solutions: From Diffusion of Single Particles to Macroscale Flow

Abstract

We measure the activation energy Ea for the diffusion of molecular probes (dyes and proteins of radii from 0.52 to 6.9 nm) and for macroscopic flow in a model complex liquid-aqueous solutions of polyethylene glycol. We cover a broad range of polymer molecular weights, concentrations, and temperatures. Fluorescence correlation spectroscopy and rheometry experiments reveal a relationship between the excess of the activation energy in polymer solutions over the one in pure solvent ΔEa and simple parameters describing the structure of the system: probe radius, polymer hydrodynamic radius, and correlation length. ΔEa varies by more than an order of magnitude in the investigated systems (in the range of ca. 1-15 kJ/mol) and for probes significantly larger than the polymer hydrodynamic radius approaches the value measured for macroscopic flow. We develop an explicit formula describing the smooth transition of ΔEa from the diffusion of molecular probes to macroscopic flow. This formula is a reference for the quantitative analysis of specific interactions of moving nano-objects with their environment as well as active transport. For instance, the power developed by a molecular motor moving at constant velocity u is proportional to u2exp(Ea/RT).