D Boyd

Dalhousie University, Halifax, Nova Scotia, Canada

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Publications (60)120.72 Total impact

  • Lauren Kiri, Daniel Boyd
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    ABSTRACT: Adjusting powder-liquid ratio (P/L) and polyacrylic acid concentration (AC) has been documented as a means of tailoring the handling and mechanical properties of glass ionomer cements (GICs). This work implemented a novel approach in which the interactive effects of these two factors on three key GIC properties (working time, setting time, and compressive strength) were investigated using a central composite design of experiments. Using nonlinear regression analysis, formulation-property relationships were derived for each property, which enabled prediction of an optimal formulation (P/L and AC) through application of the desirability approach. A novel aluminum free GIC was investigated, as this material may present the first clinically viable GIC for use in injectable spinal applications, such as vertebroplasty. Ultimately, this study presents the first series of predictive regression models that explain the formulation-dependence of a GIC, and the first statistical method for optimizing both P/L and AC depending on user-defined inputs.
    Journal of the Mechanical Behavior of Biomedical Materials 02/2015; DOI:10.1016/j.jmbbm.2015.02.007 · 3.05 Impact Factor
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    ABSTRACT: The purpose of this study was to synthesize and optimize intrinsically radiopaque composite embolic microspheres for sustained release of doxorubicin in drug-eluting bead transarterial chemoembolization. Using a design of experiments approach, 12 radiopaque composites composed of polylactic-co-glycolic acid and a radiopaque glass (ORP5) were screened over a range of compositions and examined for radiopacity (computed tomography) and density. In vitro cell viability was determined using an extract assay derived from each composition against the human hepatocellular carcinoma cell line, HepG2. Mathematical models based on a D-Optimal response surface methodology were used to determine the preferred radiopaque composite. The resulting radiopaque composite was validated and subsequently loaded with doxorubicin between 0 and 1.4% (wt% of polylactic-co-glycolic acid) to yield radiopaque composite drug-eluting beads. Thereafter, the radiopaque composite drug-eluting beads were subjected to an elution study (up to 168 h) to determine doxorubicin release profiles (UV-Vis spectroscopy) and in vitro cell viability. Radiopaque composites evaluated for screening purposes had densities between 1.28 and 1.67 g.cm(-3), radiopacity ranged between 211 and 1450HU and cell viabilities between 91 and 106% were observed. The optimized radiopaque composite comprised 23 wt% polylactic-co-glycolic acid and 60 wt% ORP5 with a corresponding density of 1.63 ± 0.001 g.cm(-3), radiopacity at 1930 ± 44HU and cell viability of 89 ± 7.6%. Radiopaque composite drug-eluting beads provided sustained doxorubicin release over 168 h. In conclusion, the mathematical models allowed for the identification and synthesis of a unique radiopaque composite. The optimized radiopaque composite had similar density and cell viability to commercially available embolic microspheres. It was possible to preload doxorubicin into radiopaque composite drug-eluting beads, such that sustained release was possible under simulated physiological conditions. © The Author(s) 2015 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.
    Journal of Biomaterials Applications 02/2015; DOI:10.1177/0885328215572196 · 2.76 Impact Factor
  • Journal of Vascular and Interventional Radiology 02/2015; 26(2):S80. DOI:10.1016/j.jvir.2014.12.222 · 2.15 Impact Factor
  • S. Kehoe, R. Abraham, D. Boyd
    Journal of Vascular and Interventional Radiology 02/2015; 26(2):S79-S80. DOI:10.1016/j.jvir.2014.12.221 · 2.15 Impact Factor
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    ABSTRACT: 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. Copyright © 2014 Elsevier Ltd. All rights reserved.
    Journal of the Mechanical Behavior of Biomedical Materials 12/2014; 43C:53-58. DOI:10.1016/j.jmbbm.2014.12.008 · 3.05 Impact Factor
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    ABSTRACT: Non-classical ionomer glasses like those based on zinc-boron-germanium glasses are of special interest in a variety of medical applications owning to their unique combination of properties and potential therapeutic efficacy. These features may be of particular benefit with respect to the utilization of glass ionomer cements for minimally invasive dental applications such as the atruamatic restorative treatment, but also for expanded clinical applications in orthopedics and oral-maxillofacial surgery. A unique system of zinc-boron-germanium-based glasses (10 compositions in total) has been designed using a Design of Mixtures methodology. In the first instance, ionomer glasses were examined via differential thermal analysis, X-ray diffraction, and (11)B MAS NMR spectroscopy to establish fundamental composition - structure-property relationships for the unique system. Secondly, cements were synthesized based on each glass and handling characteristics (working time, Wt, and setting time, St) and compression strength were quantified to facilitate the development of both experimental and mathematical composition-structure-property relationships for the new ionomer cements. The novel glass ionomer cements were found to provide Wt, St, and compression strength in the range of 48-132 s, 206-602 s, and 16-36 MPa, respectively, depending on the ZnO/GeO2 mol fraction of the glass phase. A lower ZnO mol fraction in the glass phase provides higher glass transition temperature, higher N4 rate, and in combination with careful modulation of GeO2 mol fraction in the glass phase provides a unique approach to extending the Wt and St of glass ionomer cement without compromising (in fact enhancing) compression strength. The data presented in this work provide valuable information for the formulation of alternative glass ionomer cements for applications within and beyond the dental clinic, especially where conventional approaches to modulating working time and strength exhibit co-dependencies (i.e. the enhancement of one property comes at the expense of the other) and therefore limit development strategies.
    Journal of Biomaterials Applications 11/2014; DOI:10.1177/0885328214557906 · 2.76 Impact Factor
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    ABSTRACT: We have synthesized TiO2 doped strontium borate glasses, 70B2O3-(30-x)SrO-xTiO2 and 70B2O3-20SrO(10-x)Na2O-xTiO2. The composition dependence of glass structure, density, thermal properties, durability and cytotoxicity of degradation products was studied. Digesting the glass in mineral acid and detecting the concentrations of various ions using an ICP provided the actual compositions that were 5-8% deviated from the theoretical values. The structure was investigated by means of 11B magic angle spinning (MAS) NMR spectroscopy. DSC analyses provided the thermal properties and the degradation rates were measured by measuring the weight loss of glass disc-samples in phosphate buffered saline at 37 C in-vitro. Finally the MTT assay was used to analyse the cytotoxicity of the degradation products. The structural analysis revealed that replacing TiO2 for SrO or Na2O increased the BO3/BO4 ratio suggesting the network-forming role of TiO2. Thermal properties, density and degradation rates also followed the structural changes. Varying SrO content predominantly controlled the degradation rates, which in turn controlled the ion release kinetics. A reasonable control (2-25% mass loss in 21 days) over mass loss was achieved in current study. Even though very high concentrations (up to 5500ppm B, and 1200ppm Sr) of ions were released from the ternary glass compositions, that saturated the degradation media in 7 days, the degradation products from ternary glass system was found non-cytotoxic. However, quaternary glasses demonstrated negative affect on cell viability due to very high (7000ppm) Na ion concentration. All the glasses investigated in current study are deemed fast degrading with further control over degradation rates, release kinetics desirable.
    Journal of Biomedical Materials Research Part A 11/2014; DOI:10.1002/jbm.a.35361 · 2.83 Impact Factor
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    ABSTRACT: Si–Ca–Zn–La–Ti–Mg–Sr–Na glasses have demonstrated excellent biocompatibility both in vitro using the MTT/LDH assays (with L929 mouse fibroblast cells and human blood platelets), and in vivo using New Zealand White rabbits. However, the biological evaluation of the materials was performed on as-manufactured glass granules that were autoclaved, rather than aged or γ-irradiated glass microspheres; the sterilization procedure required prior to implantation of these materials in its final form inside the human body. Given the fact that when a glass is subjected to aging either accelerated or natural changes in its physical properties can take place, it is imperative to determine whether the structure of such glasses will be altered over time in order to substantiate shelf-life claims. The structure of such glasses may also be altered as a result of exposure to the typical amounts of γ-irradiation required to sterilize such materials prior to implantation. This paper therefore examines the structure of Si–Ca–Zn–La–Ti–Mg–Sr–Na glasses using XRD, DSC, pycnometry, 29Si MAS-NMR and ICP–OES to evaluate both the effect of accelerated aging and multiple cycles of 30 kGy γ-irradiation on their structure and subsequent radiopacity. The 29Si MAS-NMR results indicate that the peak maxima for each glass remain between − 83 ppm and − 86 ppm; a chemical shift for 29Si associated with Q2 to Q3 units in silicate glasses, and that the local environment around the 29Si isotope remains unaltered as a result of aging or exposure. Additional analysis (XRD, DSC, pycnometry, ICP–OES and radiopacity) showed that the glass transition temperature, Tg (676 ± 4 °C) typically remains unchanged, as a result of exposure to both accelerated aging and ionizing radiation, as do the density (3.63 ± 0.02 g/cm3) radiopacity (7049 ± 847HU), chemical composition and XRD diffractograms for each glass. Therefore it can be concluded that the accelerated aging conditions tested herein or use of 30 kGy γ-irradiation dose or subsequent effects does not affect the local environment of the 29Si isotope in the glasses, nor does it significantly alter the XRD diffraction patterns, chemical composition, Tg, density or the radiopacity values for the glass composition (0.562Si–0.035Ca–0.188Zn–0.068La–0.042Ti–0.035 Mg–0.035Sr–0.035Na) described in this work.
    Journal of Non-Crystalline Solids 10/2014; 402:84–90. DOI:10.1016/j.jnoncrysol.2014.05.016 · 1.72 Impact Factor
  • M. S. Hasan, S Kehoe, D Boyd
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    ABSTRACT: Embolization of vascular tumors is an important tool in minimally invasive surgical intervention. Radiopaque, non-degradable, and non-deformable spherical zinc–silicate glass particles were produced in a range of 45–500 μm. Three size ranges (45–150, 150–300, and 300–500 μm) were used in the current study. The glass microspheres were eluted in polar (saline solution) and non-polar (dimethyl sulfoxide) medium, and ion release profiles were recorded using inductively coupled plasma atomic emission spectroscopy. Approximately 80% of Gaussian distribution was achieved by simple sieving. The ions released from the microspheres were dependent upon surface area to volume ratio as well as the nature of elution media. Greater ions were released from smaller particles (45–150 μm) having largest surface area in polar medium. For the genotoxicity bacterial mutation Ames assay, the concentrations of all the ions were well below their therapeutic concentration reported in the literature. No mutagenic effect was observed in the bacterial mutation Ames test. Hence, it can be concluded that the glass microspheres produced herein are non-mutagenic further supporting the materials potential as a suitable embolic agent.
    Journal of Biomaterials Applications 09/2014; 29(4). DOI:10.1177/0885328214537694 · 2.76 Impact Factor
  • Lauren Kiri, Daniel Boyd
    European Society of Biomaterials Annual Meeting, Liverpool, United Kingdom; 08/2014
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    ABSTRACT: This study investigates the effect of gallium (Ga) additions, substituting for zinc (Zn), on the physio-chemical surface properties of aluminium-free glass polyalkenoate cements (GPCs). Substituting Zn with Ga resulted in a significant increase in hydrophilicity and thusly wettability, as shown by a decrease in water contact angle. Increasing Ga resulted in increased Zn release, irrespective of decreasing Zn content of the starting glass. This resulted in increased antibacterial efficiency, against Escherichia coli, but not Staphylococcus epidermidis. Ga was shown to have no effect on antibacterial efficiency.
    Materials Chemistry and Physics 07/2014; 147(3):1-5. DOI:10.1016/j.matchemphys.2014.06.020 · 2.13 Impact Factor
  • Lauren Kiri, Brett DIckey, Daniel Boyd
    Canadian Biomaterials Society Annual Meeting, Halifax, Nova Scotia; 06/2014
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    ABSTRACT: Polylactic acid (PLA) fibers were produced with an average diameter of 11.2 (±0.9) μm via a melt-drawing process. The surface of the PLA fibers was coated with blends of cellulose nanowhiskers (CNWs) (65 to 95 wt %) and polyvinyl acetate (PVAc). The CNWs bound to the smooth PLA fiber surface imparted roughness, with the degree of roughness depending on the coating blend used. The fiber tensile modulus increased 45% to 7 GPa after coating with 75 wt % CNWs compared with the uncoated PLA fibers, and a significant increase in the fiber moisture absorption properties at different humidity levels was also determined. Cytocompatibility studies using NIH-3T3 mouse fibroblast cells cultured onto CNWs-coated PLA surface revealed improved cell adhesion compared with the PLA control, making this CNW surface treatment applicable for biomedical and tissue engineering applications. Initial studies also showed complete cell coverage within 2 days.
    Biomacromolecules 04/2014; 15(4):1498-506. DOI:10.1021/bm5001444 · 5.79 Impact Factor
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    ABSTRACT: 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.
    11/2013; 4:329-357. DOI:10.3390/jfb4040329
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    ABSTRACT: Due to the deficiencies of current commercially available biological bone grafts, alternative bone graft substitutes have come to the forefront of tissue engineering in recent times. The main challenge for scientists in manufacturing bone graft substitutes is to obtain a scaffold that has sufficient mechanical strength and bioactive properties to promote formation of new tissue. The ability to synthesise hydrogel based composite scaffolds using photopolymerisation has been demonstrated in this study. The prepared hydrogel based composites were characterised using techniques including Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), Energy-dispersive X-ray spectrometry (EDX), rheological studies and compression testing. In addition, gel fraction, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), porosity and swelling studies of the composites were carried out. It was found that these novel hydrogel bioglass composite formulations did not display the inherent brittleness that is typically associated with bioactive glass based bone graft materials and exhibited enhanced biomechanical properties compared to the polyethylene glycol hydrogel scaffolds along. Together, the combination of enhanced mechanical properties and the deposition of apatite on the surface of these hydrogel based composites make them an ideal candidate as bone graft substitutes in cancellous bone defects or low load bearing applications.
    10/2013; 33(7):4203-12. DOI:10.1016/j.msec.2013.06.013
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    ABSTRACT: Embolization with micron-sized particulates is widely applied to treat uterine fibroids. The objective of this work was to develop mixture designs to predict materials composition–structure–property relationships for the SiO2–CaO–ZnO–La2O3–TiO2–MgO–SrO–Na2O glass system and compare its fundamental materials properties (density and cytocompatibility), against a state-of-the-art embolic agent (contour polyvinyl alcohol) to assess the potential of these materials for embolization therapies. The glass structures were evaluated using 29Si MAS NMR to identify chemical shift and line width; the particulate densities were determined using helium pycnometry and the cell viabilities were assessed via MTT assay. 29Si MAS NMR results indicated peak maxima for each glass in the range of −82.3 ppm to −89.9 ppm; associated with Q2 to Q3 units in silicate glasses. All experimental embolic compositions showed enhanced in vitro compatibility in comparison to Contour PVA with the exceptions of ORP9 and ORP11 (containing no TiO2). In this study, optimal compositions for cell viability were obtained for the following compositional ranges: 0.095–0.188 mole fraction ZnO; 0.068–0.159 mole fraction La2O3; 0.545–0.562 mole fraction SiO2 and 0.042–0.050 mole fraction TiO2. To ensure ease of producibility in obtaining good melts, a maximum loading of 0.068 mole fraction La2O3 is required. This is confirmed by the desirability approach, for which the only experimental composition (ORP5) of the materials evaluated was presented as an optimum composition; combining high cell viability with ease of production (0.188 mole fraction ZnO; 0.068 mole fraction La2O3; 0.562 mole fraction SiO2 and 0.042 mole fraction TiO2).
    Journal of Biomaterials Applications 09/2013; 28(3):416-433. DOI:10.1177/0885328212455834 · 2.76 Impact Factor
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    ABSTRACT: Experimental embolic particles based on a novel zinc-silicate glass system have been biologically evaluated for potential consideration in transcatheter arterial embolization procedures. In addition to controlling the cytotoxicity and haemocompatibility for such embolic particles, its glass structure may mediate specific responses via dissolution in the physiological environment. In a 120 h in-vitro dissolution study, ion release levels for silicon (Si4+), sodium (Na+), calcium (Ca2+), zinc (Zn2+), titanium (Ti4+), lanthanum (La3+), strontium (Sr2+), and magnesium (Mg2+), were found to range from 0.04 to 5.41 ppm, 0.27-2.28 ppm, 2.32-8.47 ppm, 0.16-0.20 ppm, 0.12-2.15 ppm, 0.16-0.49 ppm and 0.01-0.12 ppm, respectively for the series of glass compositions evaluated. Initial release of Zn2+ (1.93-10.40 ppm) was only evident after 120 h. All compositions showed levels of cell viabilities ranging from 61.31 ± 4.33% to 153.7 ± 1.25% at 25%-100% serial extract dilutions. The conformational state of fibrinogen, known to induce thrombi, indicated that no changes were induced with respect of the materials dissolution by-products. Furthermore, the best-in-class experimental composition showed equivalency to contour PVA in terms of inducing platelet adhesion. The data generated here provides requisite evidence to continue to in-vivo pre-clinical evaluation using the best-in-class experimental composition evaluated.
    09/2013; 4(3):89-113. DOI:10.3390/jfb4030089
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    Materials Science and Engineering C 06/2013; · 2.74 Impact Factor
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    ABSTRACT: The structural role of Gallium (Ga) is investigated when substituted for Zinc (Zn) in a 0.42SiO(2)-0.40-xZnO-0.10Na(2)O-0.08CaO glass series, (where x = 0.08). Each starting material was amorphous, and the network connectivity (NC) was calculated assuming Ga acts as both a network modifier (1.23), and also as a network former. Assuming a network forming role for Ga the NC increased with increasing Ga concentration throughout the glass series (Control 1.23, TGa-1 2.32 and TGa-2 3.00). X-ray photoelectron spectroscopy confirmed both composition and correlated NC predictions. Raman spectroscopy was employed to investigate Q-structure and found that a shift in wavenumbers occurred as the Ga concentration increased through the glass series, from 933, 951 to 960 cm(-1). Magic angle spinning nuclear magnetic resonance determined a chemical shift from -73, -75 to -77 ppm as the Ga concentration increased, supporting Raman data. These results suggest that Ga acts predominantly as a network former in this particular Zn-silicate system.
    Journal of Materials Science 06/2013; 48(11):3999-4007. DOI:10.1007/s10853-013-7211-2 · 2.31 Impact Factor
  • B T Dickey, S Kehoe, D Boyd
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    ABSTRACT: Aluminum-free glass polyalkenoate cements (GPC) have been hindered for use as injectable bone cements by their inability to balance handling characteristics with mechanical integrity. Currently, zinc-based, aluminum-free GPCs demonstrate compression strengths in excess of 60MPa, but set in c. 1-2min. Previous efforts to extend the setting reaction have remained clinically insufficient and are typically accompanied by a significant drop in strength. This work synthesized novel glasses based on a zinc silicate composition with the inclusion of GeO2, ZrO2, and Na2O, and evaluated the setting reaction and mechanical properties of the resultant GPCs. Germanium based GPCs were found to have working times between 5 and 10min, setting times between 14 and 36min, and compression strengths in excess of 30MPa for the first 30 days. The results of this investigation have shown that the inclusion of GeO2, ZrO2, and Na2O into the glass network have produced, for the first time, an aluminum-free GPC that is clinically viable as injectable bone cements with regards to handling characteristics and mechanical properties.
    04/2013; 23C:8-21. DOI:10.1016/j.jmbbm.2013.03.012

Publication Stats

517 Citations
120.72 Total Impact Points


  • 2010–2015
    • Dalhousie University
      • • School of Biomedical Engineering
      • • Faculty of Dentistry
      Halifax, Nova Scotia, Canada
  • 2014
    • Halifax Biomedical Inc.
      Halifax, Nova Scotia, Canada
  • 2009
    • Cork Institute of Technology
      • Department of Biological Sciences
      Corcaigh, Munster, Ireland
  • 2004–2009
    • University of Limerick
      • Materials and Surface Science Institute (MSSI)
      Luimneach, Munster, Ireland