NMR studies of 1H NOEs in glycogen.

We have examined the cross-relaxation behavior among the protons of oyster glycogen using nuclear Overhauser enhancement (NOE). Steady-state and transient NOEs were generated using low-power CW irradiation and frequency-selective inversions. In D2O, saturation of glycogen H2 and H4' at 3.64 ppm gave a strong negative NOE (eta = -0.74) at H1. The NOE was similar to the value predicted by the correlation time (tau c) calculated from the T1 and T2 of glycogen H1 in D2O assuming an isotropic rigid motor dipole-dipole model. Selective inversion of H2 and H4' gave a transient NOE at H1. In D2O, selective inversion of H1 also led to negative transient NOEs in the H2 + H4', H3, and H5 resonances. The magnitude and rates of appearance of the NOEs in H3 and H5 were too large to arise from direct H1-H3 and H1-H5 dipolar interactions, but were consistent with very efficient cross-relaxation leading to large second-order NOEs. The glycogen H1 NOE in H2O was also studied. Replacement of D2O with H2O as solvent significantly reduced the steady-state NOE at H1 following saturation of H2 + H4'. Saturation of the water resonance caused a large negative NOE at H1 (eta = -0.55) consistent with our earlier study which indicated that there was no direct dipolar interaction between H1 and free H2O.