The mechanistic action of fluoride on inhibition of enamel demineralization was investigated using 19F magic angle spinning nuclear magnetic resonance (MAS-NMR). The aim of this study was to monitor the fluoride-mineral phase formed on the enamel as a function of the concentration of fluoride ions [F-] in the demineralizing medium. The secondary aim was to investigate fluorapatite formation on enamel in the mechanism of fluoride anti-caries efficacy. Enamel blocks were immersed into demineralization solutions of 0.1 M acetic acid (pH 4) with increasing concentrations of fluoride up to 2,262 ppm. At and below 45 ppm [F-] in the solution, 19F MAS-NMR showed fluoride-substituted apatite formation, and above 45 ppm, calcium fluoride (CaF2) formed in increasing proportions. Further increases in [F-] caused no further reduction in demineralization, but increased the proportion of CaF2 formed. Additionally, the combined effect of strontium and fluoride on enamel demineralization was also investigated using 19F MAS-NMR. The presence of 43 ppm [Sr2+] in addition to 45 ppm [F-] increases the fraction of fluoride-substituted apatite, but delays formation of CaF2 when compared to the demineralization of enamel in fluoride-only solution.

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