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In this study, for a series phosphate-based glasses ((P2O5)0.45(CaO)0.3(Na2O)0.25−x(TiO2)x, 0 ≤ x ≤ 0.15), their degradation, ion release, surface and thermal properties have been determined. The results show that adding TiO2 was associated with a significant increase in density and glass transition temperature, but a decrease in degradation rate and ion release. 31P solid-state magic-angle-spinning nuclear magnetic resonance (MAS-NMR) showed that the local structure of the glasses changes with increasing TiO2 content. As TiO2 is incorporated into the glass, the phosphate connectivity increases as Q1 units transform to Q2, confirming that an increase in the nominal TiO2 content correlates unequivocally with an increase in glass stability. As reported for titania–silica gels, Ti4+ is clearly adopting a network former role in these phosphate-based glasses. 23Na MAS-NMR results corroborate this phenomenon with a marked upfield trend of the 23Na isotropic chemical shift suggesting that the local Na–O bond distances are decreasing within a more condensed glass network upon increased incorporation of TiO2.

To significantly improve the biocompatibility of titanium doped phosphate based glasses, codoping with zinc has been attempted. This study investigated the effect of doping a quaternary 15Na2O:30CaO:5TiO2:50P2O5 glass with zinc oxide (1, 3, and 5 mol %) on bulk, structural, surface, and biological properties; the results were compared with glasses free from ZnO and/or TiO2. ZnO as adjunct to TiO2 was effective in changing density, interchain bond forces, degradation behavior, and ions released from the degrading glasses. Incorporation of both TiO2 and ZnO in T5Z1, T5Z3, and T5Z5 glasses reduced the level of Zn2+ release by two to three orders of magnitude compared with glasses containing ZnO only (Z5). 31P NMR results for T5Z1, T5Z3, and T5Z5 glasses showed the presence of Q3 species suggesting that the TiO2 is acting as a network former, and the phosphate network becomes slightly more connected with increasing ZnO incorporation. Regardless of their relative lower hydrophilicity and surface reactivity compared with the control glass free from TiO2 and ZnO (T0Z0), these glasses have significantly higher surface reactivity compared with Thermanox®. This has been also reflected in the maintenance of >98% viable Osteoblasts, proliferation rate, and expression level of osteoblastic marker genes in a comparable manner to Thermanox® and T5 glasses, particularly T5Z1 and T5Z3 glasses. However, T0Z0 and Z5 glasses showed significantly reduced viability compared to Thermanox®. Therefore, it can be concluded that ZnO doped titanium phosphate glasses, T5Z1 and T5Z3 in particular, can be promising substrates for bone tissue engineering applications.

This study investigates the effect of doping a high calcium oxide containing metaphosphate glass series (CaO)(40)(Na2O)(10)(P2O5)(50) with TiO2 (1, 3, and 5 mol. TiO2 incorporation increased the density and glass transition temperature while reduced the degradation rate (5 mol% in particular) by twofold compared with (CaO)30 system reported previously. This has been confirmed by ion release and the minimal pH changes. TiP2O7, NaCa(PO3)(3) and CaP2O6 phases were detected for all TiO2-containing ceramics. XPS showed that the surface is composed of Ca, h, and Ti. Ti was recognized mainly as TiO2, but its total amount was lower than theoretical values. P-31 magic angle spinning (MAS) NMR showed a downfield shift of the P-31 lineshape with increasing TiO2, interpreted as an effect of the titanium cation rather than an increase in the phosphate network connectivity. FTIR showed that incorporation of TiO2 increased the strength of the phosphate chains, and the O/P ratio while introducing more Q(1) units into the structure at the expense of the Q(2) units. There were no differences, however, in surface topography roughness and free energies between these glasses. These results suggested that TiO2 and CaO were acting synergistically in producing glasses with controllable bulk and structural properties.

P-31 and Na-23 one-dimensional MAS NMR, as well as two-dimensional P-31 refocused INADEQUATE and Na-23 multiple quantum (MQ) MAS, experiments have been used in combination with powder XRD to identify various phases present in three metal-containing sodium calcium phosphate ceramics of interest as potential biomaterials. Each sample is shown to consist of multiple phases (at least seven in the case of the Zn-containing sample), several of which were identified by NMR, but not by XRD. Solid-state NMR is thus demonstrated to be an important characterisation tool in studying multi-phase phosphate ceramics, especially those containing a mixture of crystalline and amorphous components. (C) 2008 Elsevier B.V. All rights reserved.

Owing to similarity in both ionic size and polarity, strontium (Sr2+) is known to behave in a comparable way to calcium (Ca2+), and its role in bone metabolism has been well documented as both anti-resorptive and bone forming. In this study, novel quaternary strontium-doped phosphate-based glasses, containing 1, 3 and 5 mol% SrO, were synthesized and characterized. P-31 magic angle spinning (MAS) nuclear magnetic resonance results showed that, as the Sr2+ content is increased in the glasses, there is a slight increase in disproportionation of Q(2) phosphorus environments into Q(1) and Q(3) environments. Moreover, shortening and strengthening of the phosphorus to bridging oxygen distance occurred as obtained from FTIR. The general broadening of the spectral features with Sr2+ content is most probably due to the increased variation of the phosphate cation bonding interactions caused by the introduction of the third cation. This increased disorder may be the cause of the increased degradation of the Sr-containing glasses relative to the Sr-free glass. As confirmed from elemental analysis, all Sr-containing glasses showed higher Na2O than expected and this also could be accounted for by the higher degradation of these glasses compared with Sr-free glasses. Measurements of surface free energy (SFE) showed that incorporation of strontium had no effect on SFE, and samples had relatively higher fractional polarity, which is not expected to promote high cell activity. From viability studies, however, the incorporation of Sr2+ showed better cellular response than Sr2+-free glasses, but still lower than the positive control. This unfavourable cellular response could be due to the high degradation nature of these glasses and not due to the presence of Sr2+.

Novel quaternary gallium-doped phosphate-based glasses (1, 3, and 5 mol % Ga2O3) were synthesized using a conventional melt quenching technique. The bactericidal activities of the glasses were tested against both Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, and Clostridium difficile) bacteria. Results of the solubility and ion release studies showed that these glass systems are unique for controlled delivery of Ga3+.Ga-71 NMR measurements showed that the gallium is mostly octahedrally coordinated by oxygen atoms, whilst FTIR spectroscopy provided evidence for the presence of a small proportion of tetrahedral gallium in the samples with the highest gallium content. FTIR and Raman spectra also afford an insight into the correlation between the structure and the observed dissolution behavior via an understanding of the atomic-scale network bonding characteristics. The results confirmed that the net bactericidal effect was due to Ga3+, and a concentration as low as 1 mol % Ga2O3 was sufficient to mount a potent antibacterial effect. The dearth of new antibiotics in development makes Ga3+ a potentially promising new therapeutic agent for pathogenic bacteria including MRSA and C. difficile.

A P-31 refocused INADEQUATE pulse sequence has been used in combination with XRD to identify and quantify the crystalline phases present in a ternary sodium calcium phosphate ceramic of composition (CaO)(0.4)(Na2O)(0.1)(P2O5)(0.5). Both the NMR and XRD identified the two main phases present as NaCa(PO3)(3) and beta-Ca(PO3)(2). A third unidentified calcium phosphate phase was also observed by MAS NMR, featuring a chain of six crystallographically distinct PO4 units, the P-31 MAS NMR chemical shifts of which have been identified in the correct sequence along the chain. (C) 2008 Elsevier B.V. All rights reserved.

Bulk and structural properties of zinc oxide (0 up to 20 mol%) containing phosphate glasses, developed for biomedical applications, were investigated throughout this study using differential thermal analysis (DTA), differential scanning calorimetry, X-ray powder diffraction and P-31 and Na-23 MAS NMR. Surface wettability and MG63 viability were also considered for surface characterisation of these glasses. The results indicated that incorporation of zinc oxide as a dopant into phosphate glasses produced a significant increase in density; however, the thermal properties presented in glass transition, and melting temperatures were reduced. NaZn(PO3)(3) was detected in the X-Ray Powder Diffraction Analysis (XRD) trace of zinc containing glasses, and the proportion of this phase increased with increasing zinc oxide content. NaCa(PO3)(3) as a second main phase and CaP2O6 in minor amounts were also detected. The P-31 and Na-23 MAS NMR results suggested that the relative abundances of the Q(1) and Q(2) phosphorus sites, and the local sodium environment were unaffected as CaO was replaced by ZnO in this system. The replacement of CaO with ZnO did seem to have the effect of increasing the local disorder of the Q(2) metaphosphate chains, but less so for the Q(1) chain-terminating sites which were already relatively disordered due to the proximity of modifying cations. Glasses with zinc oxide less than 5 mol% showed higher surface wettability, while those with 5 up to 20 mol% showed comparable wettability as zinc oxide free glasses. Regardless of the high hydrophilicity and surface reactivity of these zinc oxide containing glasses, they had lower biocompatibility, in particular 10-20 mol% ZnO, compared to both zinc free glasses and Thermanox (R). This may be associated with the release of significant amount of Zn2+ enough to be toxic to MG63.

Ti K-edge XANES (X-ray absorption near edge structure) spectroscopy has been used to study the local coordination of titanium in biocompatible and bioresorbable TiO2-CaO-Na2O-P2O5 glasses. Both conventional melt-quenched glasses of composition (TiO2) (x)(CaO)(0.30)(Na2O)((0.20-x))(P2O5)(0.50), where x = 0.01, 0.03 and 0.05, and sol-gel derived (TiO2)(0.25)(CaO)(0.25)(P2O5)(0.50) glass have been studied. The results show that in all the materials studied, titanium is surrounded by an octahedron of oxygen atoms. Further analysis reveals that the TiO6 site in the amorphous samples is not heavily distorted relative to that in rutile, anatase or CaSiTiO5. The spectra from the (TiO2)(0.25)(CaO)(0.25)(P2O5)(0.50) sol-gel samples reveal greater distortion in the TiO6 site in the dried gel compared to the heat-treated sol-gel glass. The XANES spectra from melt-quenched glass samples soaked in distilled water for various times do not shown any evidence of degradation of the titanium site over periods of up to 14 days.

Glasses in the system 40(P2O5)-x(B2O3)-(60-x)(Na2O) (10 <= x <= 30 mol%) have been prepared by the melt-quenching technique. Thermal properties were studied using differential thermal analysis and the relationship between composition and thermal stability was obtained. Structural characterization was achieved by a combination of experimental data (infrared and Raman spectroscopy, B-11 and P-31 solid state NMR). In particular, variations in the phosphate network structure upon addition of B2O3 and Na2O were investigated. Analysis of the data indicates that with increasing B2O3 content and decreasing Na2O, the glass network shows increasing levels of cross-linking between phosphate and borate units. Evidence of direct B-O-P bonds was observed. In the compositional range investigated, borate groups contain boron almost exclusively in four-fold coordination. (C) 2008 Elsevier B.V. All rights reserved.