13C Nuclear Magnetic Relaxation Study of Segmental Dynamics of the Heteropolysaccharide Pullulan in Dilute Solutions

13C spin−lattice relaxation times (T 1) and nuclear Overhauser enhancements (NOE) were measured as a function of temperature and magnetic field strength for the heteropolysaccharide pullulan in two solvents, water and dimethyl sulfoxide. The relaxation data of the endocyclic ring carbons were successfully interpreted in terms of chain segmental motions by using the bimodal time−correlation function of Dejean de la Batie, Laupretre, and Monnerie. On the basis of the calculated correlation times for segmental motion, the flexibilities of the pullulan chain at a repeat-unit level have been studied and compared with the segmental mobility of the homopolysaccharides amylose and dextran in the same solvents. The internal rotation of the free hydroxymethyl groups about the exocyclic C-5−C-6 bonds superimposed on segmental motion has been described as a diffusion process of restricted amplitude. The rate and amplitude of the internal rotation of the free hydroxymethyl groups were not affected by the local geometry of the pullulan chain.