Hydrodynamic properties and unperturbed dimensions of poly(gamma-hydroxy-L-proline) in aqueous solution

Intrinsic viscosities and sedimentation coefficients have been measured as a function of molecular weight for poly(gamma-hydroxy-L-proline) in water. The molecular weight range covered is 9,000-35,000. High molecular weight poly(gamma-hydroxy-L-proline) in water has the hydrodynamic behavior of a random coil immersed in a good solvent, as judged by d ln [eta]/d ln M, d ln so/d ln M, dbeta/dM, and the size of beta[= nu rho (-1)]/1/3etaM-2/3(1 - nurho)-1]. The characteristic ratio, ((r2)o/nplp2) infinity, is found to be 15.9 +/- 1.6, which is not significantly different from the result of 13.7 +/- 0.9 obtained for poly(L-proline) by Mattice and Mandelkern under the same conditions. This observation casts doubt on the importance of intrachain hydrogen bonded bridges from the hydroxyl group to a carbonyl oxygen via a water molecule. The characteristic ratios and the effects of calcium chloride on the hydroynamic properties suggest that poly(L-proline) and poly(gamma-hydroxy-L-proline) possess a similar source of flexibility which is often overlooked. Two possibilities for this flexibility are a second energy minimum about the Calpha-C' bond and cis-trans isomerization about the peptide bond.