Anisotropy of local relaxation properties of macromolecules. Spin-lattice relaxation of 13C nuclei, the nuclear overhauser effect and the estimation of parameters of an equivalent ellipsoid for kinetic segments of polymer chains

Abstract

The expressions for the functions of spectral density at different orientations of the components of the internuclear vector with respect to the chain backbone, the frequency dependences of the spin-lattice relaxation time of 13C nuclei (T1C) and the values of the nuclear Overhauser effect (NOE) were obtained for the tetrahedral lattice model of a polymer chain with three-unit kinetic elements. It was shown that peculiar features of the behavior of T1C and NOE reflect the characteristic properties of the spectra of relaxation (correlation) times for “longitudinal” and “transverse” components of the internuclear vector. It was established that in the range of relatively short times of the relaxation spectrum the dynamics of an anisotropic kinetic segment of the chain may be described with the aid of a simple model of an elongated ellipsoid of rotation with an axial ratio of about 10. It is shown that the equivalent-ellipsoid model leads to significant differences from a more specific model of chain dynamics when a broad frequency range is considered.