Many commercial bone grafts cannot regenerate healthy bone in place of diseased bone. Bioactive glasses have received much attention in this regard due to the ability of their ionic dissolution products to promote cell proliferation, cell differentiation and activate gene expression. Through the incorporation of certain ions, bioactive glasses can become therapeutic for specific pathological situations. Calcium-strontium-sodium-zinc-silicate glass bone grafts have been shown to release therapeutic levels of zinc and strontium, however the in vitro compatibility of these materials is yet to be reported. In this study, the in vitro cytocompatibility of three different calcium-strontium-sodium-zinc-silicate glasses was examined as a function of their ion release profiles, using Novabone® bioglass as a commercial comparison. Experimental compositions were shown to release Si(4+) ranging from 1 to 81 ppm over 30 days; comparable or enhanced release in comparison to Novabone. The maximum Ca(2+) release detected for experimental compositions was 9.1 ppm, below that reported to stimulate osteoblasts. Sr(2+) release was within known therapeutic ranges, and Zn(2+) release ranged from 0.5 to 1.4 ppm, below reported cytotoxic levels. All examined glass compositions show equivalent or enhanced in vitro compatibility in comparison to Novabone. Cells exposed to BT112 ionic products showed enhanced cell viabilities indicating cell proliferation was induced. The ion release profiles suggest this effect was due to a synergistic interaction between certain combinations and concentrations of ions. Overall, results indicate that the calcium-strontium-sodium-zinc-silicate glass compositions show equivalent or even enhanced in vitro compatibility compared to Novabone®.
The suitability of Glass Polyalkenoate Cements (GPCs) for use in orthopaedics is retarded by the presence in the glass phase of aluminium, a neurotoxin. Unfortunately, the aluminium ion plays an integral role in the setting process of GPCs and its absence is likely to hinder cement formation. However, the authors have previously shown that aluminium free GPCs may be formulated based on calcium zinc silicate glasses and these novel materials exhibit significant potential as hard tissue biomaterials. To further improve their potential, and given that Strontium (Sr) based drugs have had success in the treatment of osteoporosis, the authors have substituted Calcium (Ca) with Sr in the glass phase of a series of aluminium free GPCs. However to date little data exists on the effect SrO has on the structure and reactivity of SrO-CaO-ZnO-SiO(2) glasses. The objective of this work was to characterise the effect of the Ca/Sr substitution on the structure of such glasses, and evaluate the subsequent reactivity of these glasses with an aqueous solution of Polyacrylic acid (PAA). To this end (29)Si MAS-NMR, differential scanning calorimetry (DSC), X-ray diffraction, and network connectivity calculations, were used to characterize the structure of four strontium calcium zinc silicate glasses. Following glass characterization, GPCs were produced from each glass using a 40 wt% solution of PAA (powder:liquid = 2:1.5). The working times and setting times of the GPCs were recorded as per International standard ISO9917. The results acquired as part of this research indicate that the substitution of Ca for Sr in the glasses examined did not appear to significantly affect the structure of the glasses investigated. However it was noted that increasing the amount of Ca substituted for Sr did result in a concomitant increase in setting times, a feature that may be attributable to the higher basicity of SrO over CaO.
A gallium (Ga) glass series (0.48SiO(2)-0.40ZnO-0.12CaO, with 0.08 mol% substitution for ZnO) was developed to formulate a Ga-containing Glass Polyalkenoate Cement (GPC) series. Network connectivity (NC) and X-ray Photoelectron Spectroscopy (XPS) was employed to investigate the role of Ga(3+) in the glass, where it is assumed to act as a network modifier. Ga-GPC series was formulated with E9 and E11 polyacrylic acid (PAA) at 50, 55 and 60 wt% additions. E11 working times (T(w)) ranged from 68 to 96 s (Lcon.) and 106 s for the Ga-GPCs (LGa-1 and LGa-2). Setting times (T(s)) ranged from 104 to 226 s (Lcon.) and 211 s for LGa-1 and LGa-2. Compression (σc) and biaxial flexural (σf) testing were conducted where Lcon. increased from 62 to 68 MPa, LGa-1 from 14 to 42 MPa and LGa-2 from 20 to 47 MPa in σc over 1-30 days. σf testing revealed that Lcon. increased from 29 to 42 MPa, LGa-1 from 7 to 32 MPa and LGa-2 from 12 to 36 MPa over 1-30 days.
The suitability of zinc-based glass polyalkenoate cements (GPCs) for use in orthopaedics can be improved by the substitution of strontium into the glass phase which should impart improved radiopacity and bone forming properties to the cements without retarding strength. The purpose of this research was to produce novel GPCs based on calcium-strontium-zinc-silicate glasses and to evaluate their mechanical properties and biocompatibility with the ultimate objective of developing a new range of cements for skeletal applications. Three glass compositions, based on incremental substitutions of strontium for calcium, were synthesized; BT100 (0.16CaO, 0.36ZnO, 0.48SiO2), BT101 (0.04SrO, 0.12CaO, 0.36ZnO, 0.48SiO2) and BT102 (0.08SrO 0.08CaO, 0.36ZnO, 0.48SiO2). Each glass was then mixed with varying concentrations and molecular weights of polyacrylic acids in order to determine the working times, setting times, compressive strengths and biaxial flexural strengths of the novel cements. The maximum working time and setting time achieved was 29 and 110 s respectively; which, at present is inadequate for current clinical procedures. However, the optimum compressive and biaxial flexural strengths were up to 75 and 34 MPa respectively indicating that these formulations have potential in load bearing applications. Importantly, the substitution of Ca with Sr in the glasses did not have a deleterious effect on strengths or working times. Finally, the bioactivity of the best performing cements was determined in vitro using simulated body fluid. It was found that all cements facilitate the formation of an amorphous calcium phosphate at their surface which increases in density and coverage with time, indicating that these cement will bond directly to bone in vivo.
Conventional polymethylmethacrylate (PMMA) cements and more recently Bisphenol-a-glycidyl dimethacrylate (BIS-GMA) composite cements are employed in procedures such as vertebroplasty. Unfortunately, such materials have inherent drawbacks including, a high curing exotherm, the incorporation of toxic components in their formulations, and critically, exhibit a modulus mismatch between cement and bone. The literature suggests that aluminium free, zinc based glass polyalkenoate cements (Zn-GPC) may be suitable alternative materials for consideration in such applications as vertebroplasty. This paper, examines one formulation of Zn-GPC and compares its strengths, modulus, and biocompatibility with three commercially available bone cements, Spineplex, Simplex P and Cortoss. The setting times indicate that the current formulation of Zn-GPC sets in a time unsuitable for clinical deployment. However during setting, the peak exotherm was recorded to be 33 degrees C, the lowest of all cements examined, and well below the threshold level for tissue necrosis to occur. The data obtained from mechanical testing shows the Zn-GPC has strengths of 63 MPa in compression and 30 MPa in biaxial flexure. Importantly these strengths remain stable with maturation; similar long term stability was exhibited by both Spineplex and Simplex P. Conversely, the strengths of Cortoss were observed to rapidly diminish with time, a cause for clinical concern. In addition to strengths, the modulus of each material was determined. Only the Zn-GPC exhibited a modulus similar to vertebral trabecular bone, with all commercial materials exhibiting excessively high moduli. Such data indicates that the use of Zn-GPC may reduce adjacent fractures. The final investigation used the well established simulated body fluid (SBF) method to examine the ability of each material to bond with bone. The results indicate that the Zn-GPC is capable of producing a bone like apatite layer at its surface within 24 h which increased in coverage and density up to 7 days. Conversely, Spineplex, and Simplex P exhibit no apatite layer formation, while Cortoss exhibits only minimal formation of an apatite layer after 7 days incubation in SBF. This paper shows that Zn-GPC, with optimised setting times, are suitable candidate materials for further development as bone cements.
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