| Abstract: | The dynamic viscosity η′ of a dilute solution of poly(L-glutamic acid) (DP = 1370) in a mixed solvent made up of aqueous 0.2M NaCl and dioxane (2:1 by volume) is measured over the pH range 4.2–10 and in the frequency range 2–500 kHz. The frequency dependence of η′ in the helix region (low pH) is interpreted in terms of a model molecule consisting of n rigid helical segments connected by universal joints. The steady-flow viscosity, relaxation time, and high-frequency limiting viscosity at pH 4.75 (helical content 80%) are well explained by this model with n = 5. This value of n is consistent with that estimated from the nucleation parameter σ = 1.4 × 10?3 obtained from the relation between reduced steady-flow viscosity and helical content. The high-frequency values of η′ in the coil region (high pH) are fitted by Peterlin's theory. The internal viscosity seems to arise in part from the polyelectrolytic character of the molecule. An additional relaxation at low frequencies in the coil region is ascribed to rotation of molecules elongated by the electrostatic interaction. The lower value of reduced steady-flow viscosity in the coil region in the mixed solvent compared with that in water is interpreted in terms of the lower degree of effective ionization and the selective solvation of water by the polypeptide. No anomaly is observed in the helix–coil transition region, indicating that the relaxation time for helix–coil equilibrium is less than 10?6sec. |
