Chitosan/apatite composite beads prepared by in situ generation of apatite or Si-apatite nanocrystals.

The objective of this work was to develop nanocrystalline apatite (Ap) dispersed in a chitosan (CHI) matrix as a material for applications in bone tissue engineering. CHI/Ap composites of different weight ratios (20/80, 50/50 and 80/20) and with CHI of different molecular weights were prepared by a biomimetic stepwise route. Firstly, CaHPO(4).2H(2)O (DCPD) crystals were precipitated from Ca(CH(3)COO)(2) and NaHPO(4) in the bulk CHI solution, followed by the formation of CHI/DCPD beads by coacervation. The beads were treated with Na(3)PO(4)/Na(5)P(3)O(10) solution (pH 12-13) to crosslink the CHI and to hydrolyse the DCPD to nanocrystalline Ap. This new experimental procedure ensured that complete conversion of DCPD into sodium-substituted apatite was achieved without appreciable increases in its crystallinity and particle size. In addition, composites with silicon-doped Ap were prepared by substituting Na(3)PO(4) by Na(2)SiO(3) in the crosslinking/hydrolysis step. Characterization of the resultant composites by scanning electron microscopy, X-ray powder diffraction (XRD), thermal analysis and Fourier transform infrared spectroscopy confirmed the formation, within the CHI matrix, of nanoparticles of sodium- and carbonate-substituted hydroxyapatite [Ca(10-x)Na(x)(PO(4))(6-x)(CO(3))(x)(OH)(2)] with diameters less than 20nm. Relatively good correspondence was shown between the experimentally determined inorganic content and that expected theoretically. Structural data obtained from its XRD patterns revealed a decrease in both crystal domain size and cell parameters of Ap formed in situ with increasing CHI content. It was found that the molecular weight of CHI and silicate doping both affected the nucleation and growth of apatite nanocrystallites. These effects are discussed in detail.