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Bioactive glass–ceramics containing fluorapatite, xonotlite, cuspidine and wollastonite form apatite faster than their corresponding glasses
Crystallisation of bioactive glasses has been claimed to negatively affect the ion release from bioactive glasses. Here, we compare ion release and mineralisation in Tris–HCl buffer solution for a series of glass–ceramics and their parent glasses in the system SiO2–CaO–P2O5–CaF2. Time-resolved X-ray diffraction analysis of glass–ceramic degradation, including quantification of crystal fractions by full pattern refinement, show that the glass–ceramics precipitated apatite faster than the corresponding glasses, in agreement with faster ion release from the glass–ceramics. Imaging by transmission electron microscopy and X-ray nano-computed tomography suggest that this accelerated degradation may be caused by the presence of nano-sized channels along the internal crystal/glassy matrix interfaces. In addition, the presence of crystalline fluorapatite in the glass–ceramics facilitated apatite nucleation and crystallisation during immersion. These results suggest that the popular view of bioactive glass crystallisation being a disadvantage for degradation, apatite formation and, subsequently, bioactivity may depend on the actual system study and, thus, has to be reconsidered.
An NMR Study of Biomimetic Fluorapatite - Gelatine Mesocrystals
The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers and with experimental observations of an amorphous cover layer in biominerals.