Uptake of Sr2+ and Co2+ into biogenic hydroxyapatite: implications for biomineral ion exchange synthesis.

Biomineral hydroxyapatite (Bio-HAp) produced by Serratia sp. has the potential to be a suitable material for the remediation of metal contaminated waters and as a radionuclide waste storage material. Varying the Bio-HAp manufacturing method was found to influence hydroxyapatite (HAp) properties and consequently the uptake of Sr(2+) and Co(2+). All the Bio-HAp tested in this study were more efficient than the commercially available hydroxyapatite (Com-HAp) for Sr(2+) and Co(2+) uptake. For Bio-HAp the uptake for Sr(2+) and Co(2+) ranged from 24 to 39 and 29 to 78 mmol per 100 g, respectively. Whereas, the uptake of Sr(2+) and Co(2+) by Com-HAp ranged from 3 to 11 and 4 to 18 mmol per 100 g, respectively. Properties that increased metal uptake were smaller crystallite size (<40 nm) and higher surface area (>70 m(2) g(-1)). Organic content which influences the structure (e.g., crystallite arrangement, size and surface area) and composition of Bio-HAp was also found to be important in Sr(2+) and Co(2+) uptake. Overall, Bio-HAp shows promise for the remediation of aqueous metal waste especially since Bio-HAp can be synthesized for optimal metal uptake properties.

Effect of plasma surface modification on the biocompatibility of UHMWPE.

In this paper active screen plasma nitriding (ASPN) is used to chemically modify the surface of UHMWPE. This is an unexplored and new area of research. ASPN allows the homogeneous treatment of any shape or surface at low temperature; therefore, it was thought that ASPN would be an effective technique to modify organic polymer surfaces. ASPN experiments were carried out at 120 °C using a dc plasma nitriding unit with a 25% N(2) and 75% H(2) atmosphere at 2.5 mbar of pressure. UHMWPE samples treated for different time periods were characterized by nanoindentation, FTIR, XPS, interferometry and SEM. A 3T3 fibroblast cell line was used for in vitro cell culture experiments. Nanoindentation of UHMWPE showed that hardness and elastic modulus increased with ASPN treatment compared to the untreated material. FTIR spectra did not show significant differences between the untreated and treated samples; however, some changes were observed at 30 min of treatment in the range of 1500-1700 cm(-1) associated mainly with the presence of N-H groups. XPS studies showed that nitrogen was present on the surface and its amount increased with treatment time. Interferometry showed that no significant changes were observed on the surfaces after the treatment. Finally, cell culture experiments and SEM showed that fibroblasts attached and proliferated to a greater extent on the plasma-treated surfaces leading to the conclusion that ASPN surface treatment can potentially significantly improve the biocompatibility behaviour of polymeric materials.

MAS-NMR spectroscopy studies in the setting reaction of glass ionomer cements.

OBJECTIVES: The main objective is the characterisation of the setting reaction in glass ionomer cements based on experimental ionomer glasses with different fluorine content and a commercial glass ionomer cement liquid by using 13C CP/MAS-NMR, 29Si, 27Al and 31P MAS-NMR spectroscopy in order to receive information specifically about the cross-linking process. METHODS: Different fluorine containing glass compositions based on 4.5SiO2-3Al2O3-1.5P2O5-(5-z)CaO-zCaF(2) where z=0-3, were mixed with a commercially available polymer liquid to form glass ionomer cements. The cements were subjected to 27Al, 13C CP/MAS, 29Si, and 31P MAS-NMR analysis. RESULTS: The 27Al spectra showed clearly the formation of six-fold coordinate Al(VI), that may crosslink the carboxyl groups in the poly-acid molecules. A shift towards to more positive values of the carboxyl peak in the 13C CP/MAS-NMR spectra showed clearly the proton dissociation of the carboxyl groups. A shift towards more negative values was observed in the 29Si MAS-NMR spectra, suggesting formation of hydrated silica gel and consequently formation of additional Si-O-Si bonds. 31P MAS-NMR spectra also reflected changes in the coordination state around a PO4(3-) tetrahedron. Increasing the fluorine content of the glasses resulted generally in increased reactivity during setting, due to promoting cross-linking and repolymerisation of the silicate phase, followed by clear changes in the MAS-NMR spectra. CONCLUSIONS: The cross-linking process during the setting reaction of glass ionomer cements can be followed by MAS-NMR spectroscopy observing the conversion of Al(IV) to Al(VI). The acid base setting reaction is completed in 1 day and no further significant changes in the MAS-NMR spectra can be observed. Further study is required in order to understand the role of phosphorus.

Characterisation of fluorine containing glasses by 19F, 27Al, 29Si and 31P MAS-NMR spectroscopy.

OBJECTIVE: The aim of this study is to characterise a range of model and commercially available glasses used to form glass (ionomer) polyalkenoate cements. METHODS: A range of model fluoro-alumino-silicate glasses that form the basis of glass (ionomer) polyalkenoate cements and five commercial glasses have been characterised by 29Si, 27Al, 31P and 19F Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR). RESULTS: The 29Si spectra indicate a predominantly Q33Al and Q44Al structure where the Q33Al species represents a silicon with one non-bridging oxygen and three Si-O-Al linkages and the Q44Al species a silicon with four Si-O-Al bonds. Aluminium was found in predominantly four coordinate sites, but glasses with high fluorine contents showed an increasing proportion of five and six coordinate aluminium. In phosphate containing glasses the phosphorus was present as Al-O-PO3(2-) type species indicating local charge compensation of Al3+ and P5+ in the glass structure. 19F MAS-NMR indicated the presence of F-Ca(n), Al-F-Ca(n), F-Sr(n), Al-F-Sr(n) and Al-F-Na(n) species where F-M(n) indicates a fluorine surrounded by n next nearest neighbour cations and Al-F-M(n) represents a fluorine bonded to aluminium with the metal, M in close proximity charge balancing the tetrahedral AlO3F species. The proportion of Al-F-M(n) species increased with increasing fluorine content of the glass and lower non-bridging oxygen contents. There was no evidence of Si-F bonds in any of the glasses. CONCLUSIONS: The local structure of the phosphate containing glasses with regard to fluorine, calcium, strontium and phosphate is similar to that of fluorapatite the mineral phase of tooth. This may explain the ease with which these glasses crystallize to fluorapatites and the recently observed mineralization of glass polyalkenoate cements found in vivo.

Mechanical properties of biodegradable polymer sutures coated with bioactive glass.

Combining commercially available Polyglactin 910 (Vicryl) sutures with bioactive glass powder offers new possibilities for application of composite materials in tissue engineering. Commercial bioactive glass (45S5 Bioglass) powder was used to coat Vicryl sutures and the tensile strength of the sutures was tested before and after immersion in simulated body fluid (SBF) as a means to assess the effect of the bioactive glass coating on suture degradation. Different gauge lengths (126.6 and 111.6 mm) and strain rates (2.54, 11.4 and 25.4 mm/min) were tested. The tensile strength of composite sutures was slightly lower than that of as-received Vicryl sutures (404 MPa versus 463 MPa). However after 28 days immersion in SBF the residual tensile strength of the coated sutures was significantly higher, indicating a protective function of the Bioglass coating. The tensile strength results were similar for the different gauge lengths and strain rates investigated. A qualitative explanation for the effect of bioactive glass coating on polymer degradation is offered.