Papers by Author: Iain R. Gibson

Abstract: The properties of hydroxyapatite can be improved by substitution of biologically relevant ions, such as magnesium (Mg) and strontium (Sr), into its structure. Previous work in the literature has not reached agreement as to site preferences in these substitutions, and there are suggestions that these may change with differing levels of substitution. The current work adopted a quantum mechanical approach based on density functional theory using the CRYSTAL09 code to investigate the structural changes relating to, and site preferences of, magnesium and strontium substitution (to 10 mol%) in hydroxyapatites and also to predict the corresponding vibrational spectra in the harmonic approximation. The structures underwent full geometrical optimisation within the P6₃ space group, indicating an energetic site preference for the Ca (2) site in the case of Mg substitution, and the Ca (1) site in the case of Sr. Shrinkage of the unit cell was observed in the case of Mg substitution, and expansion in the case of Sr substitution, in agreement with the corresponding ionic radii. Thermodynamic properties of the structures obtained from the harmonic vibrational frequency calculations confirmed that the structures were minima on the potential energy surface. Isotopic substitutions indicated that the main contribution of Sr and Mg to vibrational modes is at frequencies < 400 cm^-1.

Abstract: The addition of silicon ions to hydroxyapatite (HA) provides a more inorganic bone-like chemical composition compared to stoichiometric HA. It is known to aid the bioactivity of the material and to improve the rates of osseointegration, osteoconduction and bone mineralisation. The literature, however, lacks detailed information regarding each step of the aqueous precipitation procedure to produce silicon-substituted HA (Si-HA). The current work utilised Raman spectroscopy at each stage of the aqueous precipitation method to determine how the silicate is incorporated into the HA structure when producing Si-HA. Raman spectra indicated that at the initial stages of the reaction the disilicate ion (Si₂O₇^6-) formed with the orthosilicate (SiO₄^4-) ion becoming more dominant after sintering. The results demonstrated that the form of silicate in the Si-HA aqueous precipitation method can be tracked using Raman spectroscopy.

Abstract: Magnesium and strontium both play important roles in the growth of bone and so are desirable ions for substitution into hydroxyapatite (HA) intended for use as bioinstructive bone substitutes. A range of compositions were prepared by a solid state method based on the nominal composition of HA (Ca₁₀(PO₄)₆(OH)₂), with various levels of strontium and/or magnesium substitution: strontium-substituted HA (Ca₈Sr₂(PO₄)₆(OH)₂), magnesium-substituted HA (Ca_9.8Mg_0.2(PO₄)₆(OH)₂ and Ca₉Mg (PO₄)₆(OH)₂), and strontium and magnesium co-substituted HA (Ca_7.8Sr₂Mg_0.2(PO₄)₆(OH)₂ and Ca₇Sr₂Mg (PO₄)₆(OH)₂). Materials were characterised by powder X-ray diffraction, Fourier-transform infrared spectroscopy and Raman spectroscopy. These analyses indicated that the co-substituted materials were composed of mixtures of strontium-substituted hydroxyapatite and magnesium and strontium co-substituted β-tricalcium phosphate. In the magnesium-substituted materials, increased magnesium content was related to increased proportion of β-tricalcium phosphate phase, both with and without strontium co-substitution. The unsubstituted and strontium mono-substituted materials, however, were pure apatite phase, suggesting that magnesium was the destabilising factor in the phase compositions of the magnesium mono-substituted and magnesium and strontium co-substituted materials.

Abstract: Novel hybrid gels in the system gelatin-GPTMS-TEOS were prepared via a sol-gel route, and their ability to release Si(IV) was examined using MG63 osteoblast-like cell culture. The amount of Si released and the release rate were controllable by changing the mixing ratio of GPTMS and TEOS. In addition, the hybrids had biocompatible surfaces. It is expected that the hybrids will be utilized for the investigation of the effect of Si on cell differentiation and tissue regeneration.

Abstract: A systematic study of the stability of potassium/carbonate co-substituted hydroxyapatite has been carried out, with samples synthesized by aqueous precipitation according to the chargebalanced mechanism: Ca10-xKx(PO4)6-x(CO3)x(OH)2 Samples up to x=1.0 were prepared and their stability determined by heating at a range of temperatures in both air and CO2 environments. Results showed that whilst samples up to x=1.0 can be prepared phase-pure, the stability of these materials is strongly dependent on sintering temperature with the full range of compositions only being stable at 600°C in CO2. The c unit cell parameter increases linearly with x, and, for a fixed composition, decreases linearly with temperature indicating loss of carbonate from the A-site. FTIR showed that samples contained carbonate at both A- and B-sites, and that carbonate content increased with x.

Abstract: Silicate-substituted calcium phosphates have been shown to result in enhanced biological performance compared to the corresponding, silicate-free, calcium phosphates. We have produced a range of silicate-substituted alpha-TCP compositions using two different synthesis methods and two different substitution mechanisms. Single phase compositions were only observed for a silicate substitution of 1.3 wt% by both solid state synthesis and aqueous precipitation synthesis, although the latter was the result of a design composition with a higher silicate substitution (3 wt%). The silicate substitution resulted in small changes in the unit cell parameters of the alpha-TCP. More importantly, this small level of silicate substitution had a strong effect on the thermal stability of the alpha-TCP phase, with the silicate substitution stabilising the alpha-polymorph to lower temperatures. This has an immediate advantage in that the quenching conditions are not as critical for the production of silicate-substituted alpha-TCP compositions compared to silicate-free alpha- TCP.

Abstract: Silicon-substituted hydroxyapatite (SiHA) bioceramics are widely used as bone replacement materials. There are various synthesis methods used to produce SiHA samples using different sources of silicon. This study aims to investigate the role of tetraethyl orthosilicate (TEOS) as the silicon source in the precipitation reaction synthesis of silicate-substituted HA. Four different synthesis methods were studied by changing the order of addition of the TEOS solution during the precipitation reaction. XRD and QXRD were used to determine the phase purity of the prepared samples. FTIR and SSNMR were used to assess silicon/silicate substitution in the prepared materials. Of the initial four methods used, only one resulted in a sample that was phase pure. The other three syntheses, which produced biphasic compositions, were modified and a further single phase sample was prepared. Results showed that the final composition is strongly dependant on how and when the TEOS was added during the precipitation reaction.

Abstract: Silicate substituted hydroxyapatite bioceramics have been shown to enhance bone repair in vivo compared to hydroxyapatite (HA), although the amount of silicate ions that can be substituted alone into the hydroxyapatite structure is limited to approximately 5.2 wt%, or 1.6 wt% Si. This study describes the substitution of greater levels of silicate ions via co-substitution of silicate ions with trivalent yttrium ions, without resulting in the formation of any secondary phases. This substitution mechanism involves a coupled substitution of yttrium and silicate ions for calcium and phosphate ions, respectively, and enables a level of silicate substitution up to approximately 9 wt%. Two different substitution mechanisms result in subtle differences in the crystal structure. When the mechanism xY3+ + xSiO4 4- was used, a small decrease in the a-axis, but no change in the c-axis, of the unit cell compared to HA was observed. In contrast, when the mechanism x/2Y3+ + xSiO4 4- was used, a significant increase in the c-axis of the unit cell was observed, compared to HA. XRF analysis and FTIR spectroscopy supported the proposed substitution mechanisms. These novel substitution mechanisms not only enable greater levels of silicate-substitution in HA to be prepared, but also allow the production of compositions with the same level of silicate substitution, and with subtle differences in chemical structure.

Abstract: Carbonate hydroxyapatite (CHA) bioceramics can be synthesised to contain sodium ions as a co-substituted ion, or as sodium-free compositions. It is unclear, however, which composition would produce the optimum biological response. The aim of this study was to find a reliable method to produce sodium co-substituted and sodium-free CHA compositions that would have the same level of carbonate substitution, and to characterise the effects of the two different substitutions on the structure of the CHA samples. After sintering at 900oC in a CO2 atmosphere, all samples contained approximately equal amounts of carbonate groups on the A- and B-sites, as observed by FTIR. The sample produced with NaHCO3 and the sodium-free sample (CHA1) have comparable carbonate contents, whereas the sample produced with Na2CO3 contains significantly more carbonate, probably due to the excess sodium ions allowing more carbonate co-substitution. The sodium-free CHA sample, however, has significantly smaller unit cell parameters compared to both sodium co-substituted CHA samples, and also to HA. This characterisation of the samples shows that the sodium-free CHA sample (CHA1) and the sample produced with NaHCO3 would provide CHA compositions for biological testing with similar carbonate contents and distributions, but with structural differences due to the sodium substitution.