Effect of fluoride on crystal growth of calcium apatites in the presence of a salivary inhibitor.

The effect of fluoride on the kinetics of crystal growth of calcium apatites was studied using seed crystals of hydroxyapatite coated with PRP-3, a proline-rich phosphoprotein salivary inhibitor of crystal growth. Initial precipitation rates in the presence of PRP-3, under conditions of partial inhibition, were enhanced by fluoride, effectively counteracting the inhibitory activity of the macromolecule. This rate enhancement is related to an increase in the precipitation driving force, i.e., the degree of supersaturation with respect to the precipitating phase; in this case a fluoridated hydroxyapatite. The growth of this phase takes place at the uncovered crystal growth sites which have been previously shown to be the same sites as the adsorption sites for the protein inhibitors. Explanations based on fluoride activation of secondary crystal growth sites and on the displacement of adsorbed inhibitor by fluoride are not substantiated by the present results. It has been demonstrated that under conditions of maximum coverage of available crystal growth sites by PRP-3, resulting in no apparent crystal growth, measurable crystal growth is observed upon the addition of fluoride (1 ppm). This phenomenon is best explained by the fact that at maximum PRP-3 coverage, a small number (16%) of crystal growth sites remain uncovered, which support an unmeasurable rate of crystal growth. Upon the addition of fluoride, this rate is significantly enhanced. It is suggested that the fraction of uncovered growth sites is related to steric interactions of the PRP-3 molecule in the adsorbed state. Overall, the results presented suggest that fluoride can accelerate crystal growth in an environment such as the enamel surface where the acquired pellicle is formed.