Preparation of amorphous calcium-magnesium phosphates at pH 7 and characterization by x-ray absorption and fourier transform infrared spectroscopy

Abstract

Amorphous calcium-magnesium phosphates were prepared by precipitation from moderately supersaturated aqueous solutions at pH 7. Chemical analysis of the samples by ion chromatography showed that up to about 50% of the phosphate ions were protonated, the proportion increasing with the magnesium to calcium ion activity ratio in the solution. When left it contact with the supernatant, the amorphous precipitates matured to form the crystalline calcium phosphate brushite (CaHPO4·2H2O). The amorphous phases were characterized by X-ray absorption spectroscopy and by Fourier transform infrared spectroscopy and their properties compared with those of a basic amorphous tricalcium phosphate precipitated at pH 10. The X-ray absorption spectra near the K edge of calcium were very similar for all samples but there were differences in the infrared spectra between the basic and the more acidic salts. In the phosphate stretching region, the main band of the more acidic materials occured at higher wavenumber and was broader. Also there was a broad band of medium intensity at about 890 cm-1 whereas there was virtually no absorption band in this region in the spectrum of the amorphous tricalcium phosphate. The acidic amorphous calcium phosphates may be useful as model compounds in describing some complex biological calcium phosphates that form near neutral pH.