Effect of borate, fluoride and strontium ions on biomimetic nucleation of calcium phosphate studied using solid-state nuclear magnetic resonance and X-ray diffraction

Abstract

ObjectivesApatite minerals can have various anions and cations in their crystal structure in addition to phosphate ion (PO₄³⁻) and calcium ion (Ca2+). The aim of this study is to investigate effects of the borate, fluoride and strontium ions on biomimetic nucleation of calcium phosphate. MethodsNano-crystalline hydroxyapatite (H-Ap) was obtained from a supersaturated buffered solution containing 4.12 mM HPO42- and 5.88 mM Ca2+ (H-Ap). Four additives were used in solid solution methods: (i) 0.588 mM F- (F-Ap), (ii) 5.88 mM Sr2+ (Sr-Ap), (iii) 4.12 mM BO33- (BO3-Ap), and (iv) a surface pre-reacted glass ionomer (S-PRG) filler eluate that contained 0.17 mM Sr2+, 0.588 mM F-, 11.1 mM BO33-- (SPRG-Ap). Apatite crystallization was investigated using a solid-state magic-angle spinning NMR spectroscopy and X-ray diffraction (XRD) with the Rietveld analysis. ResultsA 2D 1H–31P heteronuclear-correlation NMR showed F- ion incorporation in the apatite structure of the F-Ap and SPRG-Ap. The peaks on the 31P axis of the F-Ap, Sr-Ap, and BO3-Ap were different from that of the H-Ap, and the full width at half maximum increased in the following order: H-Ap∼F-Ap∼BO3-Ap< SPRG-Ap< Sr-Ap, suggesting the incorporation of the F-, Sr2+ and BO33-. The incorporation of F and BO3 was further confirmed by 19F and 11B NMR. The XRD revealed that Sr2+ was preferentially incorporated into the CaII site. SignificanceThe F-, Sr2+ and BO33-ions might be involved in modifying the crystallization of apatite precipitation, producing a variety of apatite. S-PRG filler that release these ions may have an effect on remineralization, i.e., the reformation of apatite lost due to caries.