Robert M. Moss

Bioactive glass sol-gel foam scaffolds: Evolution of nanoporosity during processing and in situ monitoring of apatite layer formation using small- and wide-angle X-ray scattering

Recent work has highlighted the potential of sol-gel-derived calcium silicate glasses for the regeneration or replacement of damaged bone tissue. The work presented herein provides new insight into the processing of bioactive calcia-silica sol-gel foams, and the reaction mechanisms associated with them when immersed in vitro in a simulated body fluid (SBF). Small-angle X-ray scattering and wide-angle X-ray scattering (diffraction) have been used to study the stabilization of these foams via heat treatment, with analogous in situ time-resolved data being gathered for a foam immersed in SBF. During thermal processing, pore sizes have been identified in the range of 16.5-62.0 nm and are only present once foams have been heated to 400 degrees C and above. Calcium nitrate crystallites were present until foams were heated to 600 degrees C; the crystallite size varied from 75 to 145 nm and increased in size with heat treatment up to 300 degrees C, then decreased in size down to 95 nm at 400 degrees C. The in situ time-resolved data show that the average pore diameter decreases as a function of immersion time in SBF, as calcium phosphates grow on the glass surfaces. Over the same time, Bragg peaks indicative of tricalcium phosphate were evident after only 1-h immersion time, and later, hydroxycarbonate apatite was also seen. The hydroxycarbonate apatite appears to have preferred orientation in the (h,k,0) direction.

Structural characterization by x-ray methods of novel antimicrobial gallium-doped phosphate-based glasses

Antimicrobial gallium-doped phosphate-based glasses of general composition (P(2)O(5))(0.45)(CaO)(0.16)(Na(2)O)(0.39-x)(Ga(2)O(3))(x) (where x=0, 0.01, 0.03, and 0.05) have been studied using the advanced synchrotron-based techniques of Ga K-edge x-ray absorption spectroscopy and high-energy x-ray diffraction to provide a structural insight into their unique properties. The results show that the Ga(3+) ions are octahedrally coordinated. Furthermore, substitution of Na(2)O by Ga(2)O(3) strengthens the phosphate network structure because the presence of GaO(6) octahedra inhibits the migration of the remaining Na(+) ions. The results are discussed in terms of the use of Na(2)O-CaO-P(2)O(5) glasses as controlled-delivery devices for antimicrobial Ga(3+) ions in biomedical applications. We are thereby able to relate the atomic-scale environment of the Ga(3+) ions beneficially to the glass dissolution, and thus to their ability to disrupt bacterial cell activity by usurping the role of iron.

Structural characterization of titanium-doped Bioglass using isotopic substitution neutron diffraction

Melt quenched silicate glasses containing calcium, phosphorus and alkali metals have the ability to promote bone regeneration and to fuse to living bone. Of these glasses 45S5 Bioglass® is the most widely used being sold in over 35 countries as a bone graft product for medical and dental applications; particulate 45S5 is also incorporated into toothpastes to help remineralize the surface of teeth. Recently it has been suggested that adding titanium dioxide can increase the bioactivity of these materials. This work investigates the structural consequences of incorporating 4 mol% TiO(2) into Bioglass® using isotopic substitution (of the Ti) applied to neutron diffraction and X-ray Absorption Near Edge Structure (XANES). We present the first isotopic substitution data applied to melt quench derived Bioglass or its derivatives. Results show that titanium is on average surrounded by 5.2(1) nearest neighbor oxygen atoms. This implies an upper limit of 40% four-fold coordinated titanium and shows that the network connectivity is reduced from 2.11 to 1.97 for small quantities of titanium. Titanium XANES micro-fluorescence confirms the titanium environment is homogenous on the micron length scale within these glasses. Solid state magic angle spinning (MAS) NMR confirms the network connectivity model proposed. Furthermore, the results show the intermediate range order containing Na-O, Ca-O, O-P-O and O-Si-O correlations are unaffected by the addition of small quantities of TiO(2) into these systems.