Lana M. Placek

Silver Nanoparticle Coated Bioactive Glasses – Composites with Dex/CMC Hydrogels: Characterization, Solubility, and In Vitro Biological Studies

Silver (Ag) coated bioactive glass particles (Ag-BG) were formulated and compared to uncoated controls (BG) in relation to glass characterization, solubility and microbiology. X-ray diffraction (XRD) confirmed a crystalline AgNP surface coating while ion release studies determined low Ag release (<2 mg/L). Cell culture studies presented increased cell viability (127 and 102%) with lower liquid extract (50 and 100 ml/ml) concentrations. Antibacterial testing of Ag-BG in E. coli, S. epidermidis and S. aureus significantly reduced bacterial cell viability by 60-90%. Composites of Ag-BG/CMC-Dex Hydrogels were formulated and characterized. Agar diffusion testing was conducted where Ag-BG/hydrogel composites produced the largest inhibition zones of 7 mm (E. coli), 5 mm (S. aureus) and 4 mm (S. epidermidis).

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.

Investigating the effect of TiO2 on the structure and biocompatibility of bioactive glass

Titanium (Ti4+ ) containing materials have been widely used in medical applications due to its associated bioactivity in vivo. This study investigates the replacement of Si4+ with Ti4+ within the system SiO2 -Na2 O-CaO-P2 O5 to determine its influence on glass structure. This strategy was conducted in order to control the glass solubility to further improve the cellular response. Ti4+ incorporation was found to have little influence on the glass transition temperature (Tg  = 520 ± 8°C) and magic angle spinning-nuclear magnetic resonance (MAS-NMR) shifts (-80 ppm) up to additions of 18 wt %. However, at 30 wt % the Tg increased to 600°C and MAS-NMR spectra shifted to -88 ppm. There was also an associated reduction in glass solubility as a function of Ti4+ incorporation as determined by inductively coupled plasma optical emission spectroscopy where Si4+ (1649-44 mg/L) and Na+ (892-36 mg/L) levels greatly reduced while Ca2+ (3-5 mg/L) and PO43- (2-7 mg/L) levels remained relatively unchanged. MC3T3 osteoblasts were used for cell culture testing and it was determined that the Ti4+ glasses increased cell viability and also facilitated greater osteoblast adhesion and proliferation to the glass surface compared to the control glass.

Bioactivity of Y2O3 and CeO2 doped SiO2-SrO-Na2O glass-ceramics

The bioactivity of yttrium and cerium are investigated when substituted for Sodium (Na) in a 0.52SiO2-0.24SrO-0.24-xNa2O-xMO glass-ceramics (where x = 0.08 and MO = Y2O3 or CeO2). Bioactivity is monitored through pH and inductively coupled plasma-optical emission spectrometry where pH of simulated body fluid ranged from 7.5 to 7.6 and increased between 8.2 and 10.0 after 14-day incubation with the glass-ceramic disks. Calcium (Ca) and phosphorus (P) levels in simulated body fluid after incubation with yttrium and cerium containing disks show a continual decline over the 14-day period. In contrast, Con disks (not containing yttrium or cerium) caused the elimination of Ca in solution after 1 day and throughout the incubation period, and initially showed a decline in P levels followed by an increase at 14 days. Scanning electron microscopy and energy dispersive spectroscopy confirmed the presence of Ca and P on the surface of the simulated body fluid-incubated disks and showed precipitates on Con and HCe (8 mol% cerium) samples. Cell viability of MC3T3 osteoblasts was not significantly affected at a 9% extract concentration. Optical microscopy after 24 h cell incubation with disks showed that Con samples do not support osteoblast or Schwann cell growth, while all yttrium and cerium containing disks have direct contact with osteoblasts spread across the wells. Schwann cells attached in all wells, but only showed spreading with the HY-S (8 mol% yttrium, heated to sintering temperature) and YCe (4 mol% yttrium and cerium) disks. Scanning electron microscopy of the compatible disks shows osteoblast and sNF96.2 Schwann cells attachment and spreading directly on the disk surfaces.

Investigating the effect of silver coating on the solubility, antibacterial properties, and cytocompatibility of glass microspheres

Silver (Ag) coatings have been incorporated into many medical materials due to its ability to eradicate harmful microbes. In this study, glass microspheres (SiO2–Na2O–CaO–Al2O3) were synthesized and employed as substrates to investigate the effect Ag coating has on glass solubility and the subsequent biological effects. Initially, glasses were amorphous with a glass transition point (Tg) of 605℃ and microspheres were spherical with a mean particle diameter of 120 µm (±27). The Ag coating was determined to be crystalline in nature and its presence was confirmed using scanning electron microscopy and X-ray photoelectron spectroscopy. Ion release determined that Ag-coated (Ag-S) microspheres increased the Na+ release rate but slightly reduced the Ca2+ and Si4+ release compared to an uncoated control (UC-S). Additionally, the Ag-S reduced the pH to just above neutral (7.3–8.5) compared to the UC-S (7.7–9.1). Antibacterial testing determined significant reductions in planktonic Escherichia coli (p = 0.000), Staphylococcus epidermidis (p = 0.000) and Staphylococcus aureus (p = 0.000) growth as a function of the presence of Ag and with respect to maturation (1, 7, and 30 days). Testing for toxicity levels using L929 Fibroblasts determined higher cell viability for the Ag-S at lower concentrations (5 µg/ml); in addition, no significant reduction in cell viability was observed with higher concentrations (15, 30 µg/ml).

Synthesis, characterization, and in vitro cytocompatibility of Ga-bioactive glass/polymer hydrogel composites:

A bioactive glass series (0.42SiO2-0.10Na2O-0.08CaO-(0.40–x)ZnO-(x)Ga2O3) was incorporated in carboxymethyl cellulose–dextran hydrogels at three different loadings (0.05, 0.10, and 0.25 m2), and the resulting composites were characterized using scanning electron microscopy, physical swelling characteristics, and inductively coupled plasma optical emission spectroscopy. In vitro cytocompatibility was also evaluated for composite extracts in contact with L-929 mouse fibroblasts and MC3T3-E1 human osteoblasts. Scanning electron microscopy confirmed that glass particles were distributed throughout the hydrogels, and swelling studies showed that glass presence can increase the amount of fluid that can be absorbed by the hydrogels after seven days of immersion in phosphate-buffered saline by up to 180%. Several trends were observed in the inductively coupled plasma optical emission spectroscopy data, with the most important being the release of Ga3+ from both Ga-containing glasses at all three loadings, with a maximum of 4.7 mg/L released after 30 days of incubation in phosphate-buffered saline. Cell viability analysis suggested that most composite extracts did not decrease neither fibroblast nor osteoblast viability. These results indicate that it is possible to embed bioactive glass particles into carboxymethyl cellulose–dextran hydrogels, and upon submersion in aqueous media, release ions from the glass particles that may elicit therapeutic effects.

Structural characterization and anti-cancerous potential of gallium bioactive glass/hydrogel composites

A bioactive glass series (0.42SiO2-0.10Na2O-0.08CaO-(0.40-X)ZnO-(X)Ga2O3) was incorporated into carboxymethyl cellulose (CMC)/dextran (Dex) hydrogels in three different amounts (0.05, 0.10, and 0.25m(2)), and the resulting composites were characterized using transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and (13)C Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CP MAS-NMR). Composite extracts were also evaluated in vitro against MG-63 osteosarcoma cells. TEM confirmed glass distribution throughout the composites, although some particle agglomeration was observed. DSC revealed that glass composition and content did have small effects on both Tg and Tm. MAS-NMR revealed that both CMC and Dex were successfully functionalized, that cross-linking occurred, and that glass addition did slightly alter bonding environments. Cell viability analysis suggested that extracts of the glass and composites with the largest Ga-content significantly decreased MG-63 osteosarcoma viability after 30days. This study successfully characterized this composite series, and demonstrated their potential for anti-cancerous applications.

Characterization of Y 2 O 3 and CeO 2 doped SiO 2 -SrO-Na 2 O glasses

Abstract The structural effects of yttrium (Y) and cerium (Ce) are investigated when substituted for sodium (Na) in a 0.52SiO2–0.24SrO–(0.24−x)Na2O–xMO (where x = 0.08; MO = Y2O3 and CeO2) glass series. Network connectivity (NC) was calculated assuming both Y and Ce can act as a network modifier (NC = 2.2) or as a network former (NC up to 2.9). Thermal analysis showed an increase in glass transition temperature (Tg) with increasing Y and Ce content, Y causing the greater increase from the control (Con) at 493∘C to 8 mol% Y (HY) at 660∘C. Vickers hardness (HV) was not significantly different between glasses. 29Si Magic Angle Spinning-Nuclear Magnetic Resonance (MAS-NMR) did not show peak shift with addition of Y, however Ce produced peak broadening and a negative shift in ppm. The addition of 4 mol% Ce in the YCe and LCe glasses shifted the peak from Con at −81.3 ppm to −82.8 ppm and −82.7 ppm respectively; while the HCe glass produced a much broader peak and a shift to −84.8 ppm. High resolution X-ray Photoelectron Spectroscopy for the O 1s spectral line showed the ratio of bridging (BO) to non-bridging oxygens (NBO), BO:NBO,was altered,where Con had a ratio of 0.7, HY decreased to 0.4 and HCe to 0.5.

Characterization and solubility of Y 2 O 3 and CeO 2 containing bioactive glasses to aid spinal cord recovery

SiO2-SrO-Na2O glasses containing incremental amounts of yttrium (Y) and/or cerium (Ce), were developed and characterized. Magic angle spinning-nuclear magnetic resonance (MAS-NMR) revealed a primarily Q2/Q3 network for each glass. Additionally, silicon (Si), strontium (Sr), sodium (Na), Y, and Ce ion release studies were completed. The maximum release was found in the control glass (LP-NC) for Si (up to 16210 ppm), Sr (up to 780 ppm), and Na (up to 8016 ppm). No release of Y or Ce was detected in any of the glasses.

Characteristics of glass ionomer cements composed of glass powders in CaO–SrO–ZnO–SiO2 system prepared by two different synthetic routes

AbstractGlass ionomer cements (GICs) are composed of an acid degradable glass, polyacrylic acid and water. Sol–gel processing to prepare the glass phase has certain advantages, such as the ability to employ lower synthesis temperatures than melt quenching and glasses that are reported to have higher purity. A previous study reported the effects of glass synthesis route on GIC fabrication. However, in that study, the sol–gel derived glass exhibited a reduced concentration of cations. This study investigates increasing the cation content of a sol–gel derived glass, 12CaO·4SrO·36ZnO·48SiO2 (molar ratio) by heating before aging to reduce dissolution of cations. This glass was prepared by both sol–gel and melt-quenched routes. GICs were subsequently prepared using both glasses. The resultant cement based on the sol–gel derived glass had a shorter working time than the cement based on the melt-quenched one. Contrary to this, setting time was considerably longer for the cement based on the sol–gel derived glass than for the cement based on the melt-quenched one. The cements based on the sol–gel derived glass were stronger in both compression and biaxial flexure than the cements prepared from the melt-quenched glass. The differences in setting and mechanical properties were associated with both cation content in the glass phase and the different surface area of the resultant cements.