Declan J. Curran

A Novel Glass Polyalkenoate Cement for Fixation and Stabilisation of the Ribcage, Post Sternotomy Surgery: An ex-Vivo Study

This study investigates the use of gallium (Ga) based glass polyalkenoate cements (GPCs) as a possible alternative adhesive in sternal fixation, post sternotomy surgery. The glass series consists of a Control (CaO–ZnO–SiO2), and LGa-1 and LGa-2 which contain Ga at the expense of zinc (Zn) in 0.08 mol% increments. The additions of Ga resulted in increased working time (75 s to 137 s) and setting time (113 to 254 s). Fourier Transform Infrared (FTIR) analysis indicated that this was a direct result of increased unreacted poly(acrylic acid) (PAA) and the reduction of crosslink formation during cement maturation. LGa samples (0.16 wt % Ga) resulted in an altered ion release profile, particularly for 30 days analysis, with maximum Ca2+, Zn2+, Si4+ and Ga3+ ions released into the distilled water. The additions of Ga resulted in increased roughness and decreased contact angles during cement maturation. The presence of Ga has a positive effect on the compressive strength of the samples with strengths increasing over 10 MPa at 7 days analysis compared to the 1 day results. The additions of Ga had relatively no effect on the flexural strength. Tensile testing of bovine sterna proved that the LGa samples (0.16 wt % Ga) are comparable to the Control samples.

Comparison of the Weibull characteristics of hydroxyapatite and strontium doped hydroxyapatite.

The effects of two strontium (Sr) additions, 5% and 10% of the total calcium (Ca) content, on the phase assemblage and Weibull statistics of hydroxyapatite (HA) are investigated and compared to those of undoped HA. Sintering was carried out in the range of 900-1200 °C in steps of 1000 °C in a conventional furnace. Sr content had little effect on the mean particulate size. Decomposition of the HA phase occurred with Sr incorporation, while β-TCP stabilization was shown to occur with 10% Sr additions. Porosity in both sets of doped samples was at a comparable level to porosity in the undoped HA samples, however the 5% Sr-HA samples displayed the greatest reduction in porosity with increasing temperature while the porosity of the 10% Sr-HA samples remain relatively constant over the full sintering temperature range. The undoped HA samples displayed the greatest Weibull strengths and the porosity was determined to be the major controlling factor. However, with the introduction of decompositional phases in the Sr-HA samples, the dependence of strength on porosity is reduced and the phase assemblage becomes the more dominant factor for Weibull strength. The Weibull modulus is relatively independent of the porosity in the undoped HA samples. The 5% Sr-HA samples experience a slight increase in Weibull modulus with porosity, indicating a possible relationship between the parameters. However the 10% Sr-HA samples show the highest Weibull modulus with a value of approximately 15 across all sintering temperatures. It is postulated that this is due to the increased amount of surface and lattice diffusion that these samples undergo, which effectively smooths out flaws in the microstructure, due to a saturation of Sr content occurring in grain boundary movement.

Glass Polyalkenoate Cements Designed for Cranioplasty Applications: An Evaluation of Their Physical and Mechanical Properties

Glass polyalkenoate cements (GPCs) have potential for skeletal cementation. Unfortunately, commercial GPCs all contain, and subsequently release, aluminum ions, which have been implicated in degenerative brain disease. The purpose of this research was to create a series of aluminum-free GPCs constructed from silicate (SiO2), calcium (CaO), zinc (ZnO) and sodium (Na2O)-containing glasses mixed with poly-acrylic acid (PAA) and to evaluate the potential of these cements for cranioplasty applications. Three glasses were formulated based on the SiO2-CaO-ZnO-Na2O parent glass (KBT01) with 0.03 mol % (KBT02) and 0.06 mol % (KBT03) germanium (GeO2) substituted for ZnO. Each glass was then mixed with 50 wt % of a patented SiO2-CaO-ZnO-strontium (SrO) glass composition and the resultant mixtures were subsequently reacted with aqueous PAA (50 wt % addition) to produce three GPCs. The incorporation of Ge in the glass phase was found to result in decreased working (142 s to 112 s) and setting (807 s to 448 s) times for the cements manufactured from them, likely due to the increase in crosslink formation between the Ge-containing glasses and the PAA. Compressive (σc) and biaxial flexural (σf) strengths of the cements were examined at 1, 7 and 30 days post mixing and were found to increase with both maturation and Ge content. The bonding strength of a titanium cylinder (Ti) attached to bone by the cements increased from 0.2 MPa, when placed, to 0.6 MPa, after 14 days maturation. The results of this research indicate that Germano-Silicate based GPCs have suitable handling and mechanical properties for cranioplasty fixation.

The role of poly(acrylic acid) in conventional glass polyalkenoate cements

Abstract Glass polyalkenoate cements (GPCs) have been used in dentistry for over 40 years. These novel bioactive materials are the result of a reaction between a finely ground glass (base) and a polymer (acid), usually poly(acrylic acid) (PAA), in the presence of water. This article reviews the types of PAA used as reagents (including how they vary by molar mass, molecular weight, concentration, polydispersity and content) and the way that they control the properties of the conventional GPCs (CGPCs) formulated from them. The article also considers the effect of PAA on the clinical performance of CGPCs, including biocompatibility, rheological and mechanical properties, adhesion, ion release, acid erosion and clinical durability. The review has critically evaluated the literature and clarified the role that the polyacid component of CGPCs plays in setting and maturation. This review will lead to an improved understanding of the chemistry and properties of the PAA phase which will lead to further innovation in the glass-based cements field.

Investigating the addition of SiO2–CaO–ZnO–Na2O–TiO2 bioactive glass to hydroxyapatite: Characterization, mechanical properties and bioactivity

Hydroxyapatite (Ca10(PO4)6(OH)2) is widely investigated as an implantable material for hard tissue restoration due to its osteoconductive properties. However, hydroxyapatite in bulk form is limited as its mechanical properties are insufficient for load-bearing orthopedic applications. Attempts have been made to improve the mechanical properties of hydroxyapatite, by incorporating ceramic fillers, but the resultant composite materials require high sintering temperatures to facilitate densification, leading to the decomposition of hydroxyapatite into tricalcium phosphate, tetra-calcium phosphate and CaO phases. One method of improving the properties of hydroxyapatite is to incorporate bioactive glass particles as a second phase. These typically have lower softening points which could possibly facilitate sintering at lower temperatures. In this work, a bioactive glass (SiO2–CaO–ZnO–Na2O–TiO2) is incorporated (10, 20 and 30 wt%) into hydroxyapatite as a reinforcing phase. X-ray diffraction confirmed that no additional phases (other than hydroxyapatite) were formed at a sintering temperature of 560 ℃ with up to 30 wt% glass addition. The addition of the glass phase increased the % crystallinity and the relative density of the composites. The biaxial flexural strength increased to 36 MPa with glass addition, and there was no significant change in hardness as a function of maturation. The pH of the incubation media increased to pH 10 or 11 through glass addition, and ion release profiles determined that Si, Na and P were released from the composites. Calcium phosphate precipitation was encouraged in simulated body fluid with the incorporation of the bioactive glass phase, and cell culture testing in MC-3T3 osteoblasts determined that the composite materials did not significantly reduce cell viability.

A multi-study cost-effectiveness comparison of the QFracture and FRAX fracture risk algorithms

BACKGROUND: The FRAX and QFracture risk calculators have previously been validated but their relative performance with respect to cost-effectiveness has yet to be evaluated. METHODS: The relative costs of implementing these two fracture risk calculators were assessed in two scenarios, firstly in a case-control group of 584 post-menopausal women using the National Osteoporosis Guideline Group (NOGG) guidelines, and then using the QResearch database, which contains over 8 million patient-years of prospective data. RESULTS: QFracture was more cost-effective in the first scenario while the underlying cost drivers were different for each algorithm; however, the cost per fracture prevented could not be estimated. The incremental cost-effectiveness ratio of FRAX was £516.22 per hip fracture saved compared with QFracture in the second scenario. LIMITATIONS: The comparison yielded virtually identical false negative rates for both calculators. In cases where these rates are significantly different, an all-encompassing cost comparison would be a challenge. CONCLUSIONS: FRAX was more cost-effective per fracture prevented when the same risk assessment cost was used for the two algorithms; a key factor in assessing the relative cost-effectiveness of these algorithms is the cost of the risk assessment process. QFracture considers more risk factors than FRAX and has been developed to incorporate additional risk factors in the future. This makes QFracture costly, however, this calculator may benefit from automated systems to reduce its cost of implementation.

Comparative study of Weibull characteristic strength and mean strength of GPCs to confirm the minimum number of samples needed for confident strength reporting.

This short communication determines the strength of two glass polyalkenoate cements that differ from each other through the composition of their glass phase. Sample sets of n=5, 10, 20 and 30 were formulated and tested in biaxial flexure. The derived mean for each sample set was compared against the Weibull characteristic strength. The mean and corresponding characteristic strength show a maximum percentage difference 10.1%, and the 95% confidence intervals calculated from the mean data encompass the corresponding characteristic strength down to a sample set of n=5. This suggests that, for brittle materials such as glass polyalkenoate cements, it is acceptable to test only five samples of each material in biaxial flexure and the resultant 95% confidence intervals will encompass the corresponding Weibull characteristic strength of the material.

Raman Spectroscopy Applied to the Noninvasive Detection of Monosodium Urate Crystal Deposits

An off-the-shelf Raman Spectrometer (RS) was used to noninvasively determine the presence of monosodium urate (MSU) crystals on the metatarsophalangeal joint (MTPJ) of a single gout sufferer. The spectrum sourced from the clinically diagnosed gout sufferer was compared to that sourced from an age-matched healthy subject scanned using the same protocol. Minimal signal processing was conducted on both spectra. Peaks characteristic of MSU crystals were evident on the spectrum sourced from the gout sufferer and not on the spectrum from the healthy control.