Hydroxyapatite fluoride interaction with

The various findings about fluoride and its interaction with the hydroxyapatite at the molecular level show that the relationship is complicated and multifaceted. The broad conclusion from the enormous volume of work that has led to our current understanding of the role of fluoride is that it is overwhelmingly beneficial. It promotes numerous desirable properties in tooth mineral, reducing solubility through action in both the saliva and in the mineral phase, it shifts the demineralisation/remineralisation equilibrium in favour of remineralisation, and through its actions in the solid state, ensures that the kinetically favoured OCP is transformed into the more thermodynamically stable hydroxyapatite. Research continues, and there is no doubt that there is still more to learn about the complexities of the interaction of fluoride with hydroxypatite under physiological conditions. 

More recently, it was demonstrated that the thermistor approach could be used to monitor specific interactions of fluoride ions with silica-packed columns in the flow injection mode. A thermometric method for detection of fluoride [56] was developed that relies on the specific interaction of fluoride with hydroxyapatite. The detection principle is based on the measurement of the enthalpy change upon adsorption of fluoride onto ceramic hydroxyapatite, by temperature monitoring with a thermistor-based flow injection calorimeter. The detection limit for fluoride was 0.1 ppm, which is in the same range as that of a commercial ion-selective electrode. The method could be applied to fluoride in aqueous solution as well as in cosmetic preparations. The system yielded highly reproducible results over at least 6 months, without the need of replacing or regenerating the ceramic hydroxyapatite column. The ease of operation of thermal sensing and the ability to couple the system to flow injection analysis provided a versatile, low-cost, and rapid detection method for fluoride. 

The first and primary protective effect of fluoride is due to its strong, spontaneous reaction with metal ions. Biologically, the most important of these ions is the calcium ion, large amounts of which interact with phosphate to form bones and teeth. Studies show that fluoride reduces apatite solubility in acids by an isomorphic replacement of hydroxide ions with fluoride ions to form fluoro-hydroxyapatite and difluoro-apatite (Fig. 16.6a). 

There are a certain number of options to control and reduce dental caries, the biggest problem in tooth care. The use of fluoride salts is one of the most effective methods to prevent or slow down demineralization that causes tooth decay [16,17]. The action of fluoride can be explained by its antimicrobial action, its interaction with enamel to form a fluorinated hydroxyapatite compound (hydroxyfluorapa-tite or fluorapatite Ca5(P04)3F) by substitution of an hydroxyl ion in hydroxyapatite Ca5(P04)3(0H), which is more resistant to add than enamel on its own, and its repairing effect by formation of calcium and phosphate, which ranineralize the tiny lesions in which caries begin. 

Studies of the interaction of hydroxyapatite with the acid washings from glass-ionomer cements show that fluoride is taken up readily by the mineral phase, despite the initial state of fluoride as a complex ion or covalent species [106]. There was no concomitant uptake of aluminium by the hydroxyapatite, suggesting that any complexes formed are dissociated by the mineral phase, allowing only fluoride to be taken up. 

S.M. Lewis, B. Czamecka, N.J. Coleman, J.W. Nicholson, Interaction of aluminium fluoride complexes derived from glass-ionomer eements with hydroxyapatite, Ceram. Silikaty 57 (2013) 196-200. 

Schafer et al. used several spectroscopic techniques to characterize the surface species on phosphate-modified zirconia particles. Their results show that phosphate merely adsorbs on the surface of zirconia under the mildest phosphate concentration, i.e., neutral pH, room temperature, and short contact times. However, at acidic pH and higher temperarnres, esterification of the phosphate with surface hydroxyls takes place as the kinetic barriers are overcome. The solid NMR studies clearly show the presence of covalently bound phosphate. This phosphate modification effectively blocks the sites responsible for the strong interaction of certain Lewis bases with the zirconia surface, resulting in a more biocompatible stationary phase. Unlike fluoride-modified zirconia, phosphate-modified zirconia behaves as a classic cation exchanger and not as a mixed-mode medium analogous to hydroxyapatite, despite spectroscopic evidence of zirconium phosphate formation on the surface. This limits the applicability of the supports, as most proteins and enzymes are anionic at neutral pH. Nevertheless, its ability to separate proteins with high p/ values still deserves much attention. The preparative-scale separation of murine IgGs from a fermentation broth demonstrates the utiUty of the supports for solutes that are retained. 

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