Nuclear Magnetic Resonance Spin-Spin Relaxation of the Crystals of Bone, Dental Enamel, and Synthetic Hydroxyapatites

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Abstract
Studies of the apatitic crystals of bone and enamel by a variety of spectroscopic techniques have established clearly that their chemical composition, short‐range order, and physical chemical reactivity are distinctly different from those of pure hydroxyapatite. Moreover, these characteristics change with aging and maturation of the bone and enamel crystals. Phosphorus‐31 solid state nuclear magnetic resonance (NMR) spin‐spin relaxation studies were carried out on bovine bone and dental enamel crystals of different ages and the data were compared with those obtained from pure and carbonated hydroxyapatites. By measuring the31P Hahn spin echo amplitude as a function of echo time, Van Vleck second moments (expansion coefficients describing the homonuclear dipolar line shape) were obtained and analyzed in terms of the number density of phosphorus nuclei.31P magnetization prepared by a 90° pulse or by proton‐phosphorus cross‐polarization (CP) yielded different second moments and experienced different degrees of proton spin‐spin coupling, suggesting that these two preparation methods sample different regions, possibly the interior and the surface, respectively, of bone mineral crystals. Distinct differences were found between the biological apatites and the synthetic hydroxyapatites and as a function of the age and maturity of the biological apatites. The data provide evidence that a significant fraction of the protonated phosphates (HPO4−2) are located on the surfaces of the biological crystals, and the concentration of unprotonated phosphates (PO4−3) within the apatitic lattice is elevated with respect to the surface. The total concentration of the surface HPO4−2 groups is higher in the younger, less mature biological crystals.