The surface chemistry of bone mineral and related calcium phosphates

A review of the surface chemistry of bone mineral, hydroxyapatite and amorphous calcium phosphate is presented. Small-angle x-ray scattering and low-temperature nitrogen adsorption measurements show the magnitude of bone mineral surface to range from 100-200 m-2/g; the synthetic hydroxyapatite surface can vary from 25-200 m-2/g, while synthetic amorphous calcium phosphate ranges in surface from 20-60 m-2/g, according to the respective preparation conditions. The magnitude of heats of adsorption of certain small molecules (CO, Ar, N2, H2O, CH3OH) on bone mineral and hydroxyapatite show that these are polarizing surfaces that form strong bonds with polar or polarizable molecules; water is hydrogen-bonded to these surfaces with energies ranging from 23 kcal/mole for low coverage to 11 kcal/mole after two full monolayers; concomitantly, methanol ranges from 24 kcal/mole to 9 kcal/mole after the adsorption of one and a half monolayers. Stearic acid will close-pack perpendicularly on bone apatite surfaces when adsorbed from cyclohexane solution in a way reminiscent of the adsorption of this long, straight-chain molecule on water surface. It is believed that these molecules are hydrogen-bonded to electronegative ions on the apatite surface. Synthetic hydroxyapatite has long been used in chromatographic adsorption columns because of the specific bonding capacity the surfaces have for certain proteins and polynucleotides. The metabolic interrelationship of bone mineral and the body fluids is in great part dependent upon the nature and magnitude of mineral surface. From the surface studies described herein it was suggested that a chemical linkage could exist in bone between the mineral surface and certain free polar groups of collagen.