Polymer Dynamics in Glycerol–Water Mixtures

Abstract

Velocity correlation spectra (VAS) in binary mixtures of water and glycerol (G/W), obtained by measurements using the modulated gradient spin echo (MGSE) NMR method, were explained by the interactions of water molecules with clusters formed around the hydrophilic glycerol molecule, which drastically change the molecular dynamics and rheology of the mixture. It indicates a thickening of the shear viscosity, which could affect the dynamics of submerged macromolecules. The calculation of the polymer dynamics with the Langevin equations according to the Rouse model, where the friction was replaced by the memory function of the retarded friction, gave the dependence of the dynamics of the polymer on the rate of shear viscous properties of the solvent. The obtained formula was used to calculate the segmental VAS of the polymer when immersed in pure water and in a G/W mixture with 33 vol% glycerol content, taking into account the inverse proportionality between the solvent VAS and friction. The spectrum shows that in the G/W mixture, the fast movements of the polymer segments are strongly inhibited, which creates the conditions for slow processes caused by the internal interaction between the polymer segments, such as interactions that cause disordered polypeptides to spontaneously fold into biologically active protein molecules when immersed in such a solvent.