Model Studies on the Interaction of Amino Acids with Biominerals: The Effect of [formula omitted]-Serine at the Hydroxyapatite–Water Interface

Abstract

The effect of L-serine in supersaturated solutions of calcium phosphate was investigated under plethostatic conditions. The rates of crystal growth measured in the presence of L-serine at relatively high concentrations and in the range between 2×10−3 and 1×10−2 mol dm−3 were appreciably reduced. The inhibitory effect of L-serine was found to be due to blocking of a portion of the active growth sites by adsorption. Kinetics measurements in the presence of L-serine as well as adsorption isotherm analysis suggested Langmuir-type adsorption of L-serine on the surface of hydroxyapatite (HAP) with a relatively low affinity for the substrate. Adsorption experiments showed that at pH 7.4 considerable adsorption of L-serine onto HAP takes place, whereas at pH 10.0 the adsorption was negligible, suggesting that electrostatic interactions are dominant. Attraction between the positively charged protonated amino group of the L-serine molecule and the negatively charged HAP surface contributed largely to the adsorption. This was corroborated by the fact that, in the presence of L-serine in the solution, a significant shift of ζ-potential of the HAP particles to less negative values was found at pH values close to 7.4. At pH values higher than 10.0 essentially no shift of ζ-potential takes place. On the basis of the experimental results, a model was proposed according to which L-serine absorbs on the surface of HAP through electrostatic attractions exerted between one negative site of the HAP surface, i.e., phosphate or hydroxyl ion, and the positively charged protonated amino group of one L-serine molecule, forming a surface ion pair.