Journal of Physical Chemistry A, Vol.122, No.45, 8938-8947, 2018
Quasi-Equilibria and Polarization Transfer Between Adjacent and Remote Spins: H-1-C-13 CP MAS Kinetics in Glycine
The H-1-C-13 CP MAS kinetic curves were measured in glycine powder sample at the MAS rates of 7, 10, and 12 kHz. Each experimental curve contained up to 1000 equidistant points over the whole contact time range of 10 mu s - 10 ms. The CP kinetic data for CH(2 )group, i.e., for the system containing adjacent H-1-C-13 spin pairs with a definite dominant dipolar coupling can be described in the frame of the isotropic spin-diffusion approach. The local order parameter (S) approximate to 1.0, determined as the ratio of the measured dipolar H-1-C-13 coupling constant and the calculated static dipolar coupling constant, is very close to the values deduced in series of other amino acids. The strong narrow peaks observed in the spin coupling spectrum at multiples of the MAS frequency can be considered as the confirmation that the periodic quasi-equilibrium state can appear also in the powder samples. The anisotropic spin-diffusion approach improved by the introducing of the thermal equilibration in the proton bath is the most proper model to describe the CP kinetics in the system containing remote spins. Very realistic values of the spin-cluster size (N) have been obtained without any constraint on the flow of the nonlinear curve fitting. The finite values of N <= 4 means that CP transfer is located within one glycine molecule.