Fluoride participates in many aspects of calcium phosphate formation i
n vivo and has enormous effects on the process and on the nature and p
roperties of formed mineral. The most well-documented effect of fluori
de is that this ion substitutes for a column hydroxyl in the apatite s
tructure, giving rise to a reduction of crystal volume and a concomita
nt increase in structural stability. In the process of enamel minerali
zation during amelogenesis (a unique model for the cell-mediated forma
tion of well-crystallized carbonatoapatite), free fluoride ions in the
fluid phase are supposed to accelerate the hydrolysis of acidic precu
rsor(s) and increase the driving force for the growth of apatitic mine
ral, Once fluoride is incorporated into the enamel mineral, the ion li
kely affects the subsequent mineralization process by reducing the sol
ubility of the mineral and thereby modulating the ionic composition in
the fluid surrounding the mineral, and enhancing the matrix protein-m
ineral interaction, But excess fluoride leads to anomalous enamel form
ation by retarding tissue maturation. It is worth noting that enameloi
d/enamel minerals found in vertebrate teeth have a wide range of CO3 a
nd fluoride substitutions. In the evolutionary process from elasmobran
ch through teleost enameloid to mammalian enamel, the biosystems appea
r to develop regulatory functions for limiting the fluoridation of the
formed mineral, but this development is accompanied by an increase of
carbonate substitution or defects in the mineral. In research on the
cariostatic effect of fluoride, considerable emphasis is placed on the
roles of free fluoride ions (i.e., preventing the dissolution and acc
elerating the kinetics of remineralization) in the oral fluid bathing
tooth mineral. Fluoride also has been used for the treatment of osteop
orosis, but much still remains to be learned about maximizing the bene
fit and minimizing the risk of fluoride when used as a public health m
easure.