A method for detection of spectral spin diffusion from minor peaks, and its application to 19F MAS NMR of antimony(III)-doped fluorapatite.
A new technique for detecting spectral spin diffusion in solids under MAS NMR conditions that is particularly well suited for accurately measuring cross-relaxation from minor spectral components is presented. The pulse sequence, SINK (Saturation Inter-Nuclear Kinetics), selectively saturates the magnetization of a minor spectral component with a series of rotor-synchronized DANTE pulse trains and monitors spin diffusion to other peaks with a non-selective 90 degrees pulse. We have used SINK with 19F MAS NMR on samples of calcium fluorapatite doped with Sb3+ to measure spin diffusion between a weak peak at 68.6 ppm due to fluoride ions associated with Sb3+ and other peaks in the spectrum. The SINK experiment clearly demonstrates that spin diffusion from the former peak to the main resonance of fluorapatite at 64.0 ppm is faster than spin diffusion to a second antimony-related peak at 65.6 ppm. These results strengthen our previous conclusion that antimony(III) occupies a phosphate site in the apatite lattice, with an SbO3(3-) group replacing a PO4(3-) group. The SINK experiment also enables the detection of a "hidden" peak at approximately 62.9 ppm that is otherwise obscured by the intense main peak at 64.0 ppm.
Moran
L B
LB
Department of Chemistry, Michigan State University, East Lansing 48824-1322.
Berkowitz
J K
JK
Yesinowski
J P
JP
D000965:Antimony / Q000737:chemistry; D001031:Apatites / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008956:Models, Chemical; D015394:Molecular Structure
D001031:Apatites; D005461:Fluorine; D000965:Antimony; C025105:fluorapatite