An optimal strategy for recovering the deuterium (2H) quadrupolar interaction under magic-angle spinning NMR.
By exploiting the homology in the form of the truncated high-field homonuclear dipole-dipole and quadrupole coupling Hamiltonians, we have previously demonstrated that a simple adaptation of a rotor-synchronized pulse sequence (DRAMA) used for the recovery of dipole-dipole couplings can also be used to resurrect quadrupole couplings (QUADRAMA). In the canonical implementation of these recovery pulse sequences, the couplings are not significantly scaled down from their static sample values. While such minimal scaling is of course desirable in the recovery of typical homonuclear dipolar couplings (< or =2 kHz) and small quadrupole couplings, it is clearly not ideal for the recovery of the much larger quadrupole couplings (20-200 kHz) often encountered in solid-state 2H NMR. In such a case, some prior knowledge of the order of magnitude of the coupling is required to optimize the experimental conditions for QUADRAMA. In order to overcome this drawback, in this study, we have developed a general and optimized strategy for implementing the QUADRAMA technique which does not require any knowledge of the size of the coupling vQ. Experimental tests of the optimized protocol demonstrate that by judicious choices of a combination of scaling factors and recoupling times, 2H quadrupole couplings ranging over an order of magnitude from 3 to 42 kHz can be measured. Since this optimized protocol can reliably be used to recover couplings over a broad range, it expands the range of systems accessible to study by 2H NMR into a realm where static sample NMR and simple MAS NMR may fail.
Jarrell
H C
HC
Institute for Biological Sciences, National Research Council of Canada, Ottawa, Ontario.
Siminovitch
D J
DJ