Lambrini Papadopoulou

Development of micro- and nano-porous composite materials by processing cellulose with ionic liquids and supercritical CO2

Three lines of green chemistry were combined in this study, in order to produce porous materials with pore size distributions in the micro- and nano-scales. These lines are: (i) the renewable and biodegradable sources (cellulose), (ii) ionic liquids, and (iii) supercritical fluids. By dissolving cellulose in a room temperature ionic liquid and regenerating with water or methanol we obtained cellulose hydrogels and methanogels. The liquid mixtures were separated by vacuum distillation with high yield of recovery. The obtained gels were processed by supercritical carbon dioxide to give porous materials. A novel foaming procedure was applied to hydrogels in order to obtain microporous structures of cellulose and cellulose composites, while in alcogels the supercritical point drying method resulted in nanoporous aerogels. For elucidating physicochemical aspects involved in the two processes and for characterization of the produced materials, X-ray diffraction, sorption measurements (by a modified mass loss analysis and the BET method) and scanning electron microscopy were used. The role of various process parameters on the final porous structure was investigated.

Hydroxy Carbonate Apatite Formation on Particulate Bioglass In Vitro as a Function of Time

The mechanism of bonding of bioactive glasses with living tissues has been reported to be associated with the development of a layer consisting of carbonate-containing hydroxyapatite similar to that of bone on the surface of the materials. This layer is also formed in vitro, in solutions with ion concentrations similar to those of human blood plasma, like SBF (Simulated Body Fluid). The development of HCAp (Hydroxy carbonate apatite) layer on the surface of a commercially available Bioglass® Synthetic Bone Graft Particulate (Perioglas®) after immersion in SBF solution using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) with associated Energy Dispersive Spectroscopy (EDS). PerioGlas® powder with particle size 20-63μm, pressed in a vacuum press in order to produce pellets. The pellets were soaked in SBF for 12, 18, 24 and 48 hours at 37°C. Results revealed the formation of an amorphous CaO-P 2 O 5 - rich layer on the surface of the specimens after 12 hours in the solution and a well crystalline HCAp layer after 24 hours immersion time.

Study of road dust magnetic phases as the main carrier of potentially harmful trace elements

Mineralogical and morphological characteristics and heavy metal content of different fractions (bulk, non-magnetic fraction-NMF and magnetic fraction-MF) of road dusts from the city of Thessaloniki (Northern Greece) were investigated. Main emphasis was given on the magnetic phases extracted from these dusts. High magnetic susceptibility values were presented, whereas the MFs content of road dust samples ranged in 2.2-14.7 wt.%. Thermomagnetic analyses indicated that the dominating magnetic carrier in all road dust samples was magnetite, while the presence of hematite and iron sulphides in the investigated samples cannot be excluded. SEM/EDX analyses identified two groups of ferrimagnetic particles: spherules with various surface morphologies and textures and angular/aggregate particles with elevated heavy metal contents, especially Cr. The road dusts (bulk samples) were dominated by calcium, while the mean concentrations of trace elements decreased in the order Zn > Mn > Cu > Pb > Cr > Ni > V > Sn > As > Sb > Co > Mo > W > Cd. MFs exhibited significantly higher concentrations of trace elements compared to NMFs indicating that these potentially harmful elements (PHEs) are preferentially enriched in the MFs and highly associated with the ferrimagnetic particles. Hazard Index (HI) obtained for both adults and children through exposure to bulk dust samples were lower or close to the safe level (=1). On the contrary, the HIs for the magnetic phases indicated that both children and adults are experiencing potential health risk since HI for Cr was significantly higher than safe level. Cancer risk due to road dust exposure is low.

Effect of heat treatment and in vitro aging on the microstructure and mechanical properties of cold isostatic-pressed zirconia ceramics for dental restorations

OBJECTIVES The temperature variations during the veneering firing cycles of a zirconia dental ceramic can negatively affect its mechanical properties. A possible synergistic effect of both heat-treatment and aging while exposed to the oral environment could result to catastrophic failure. The aim of the present study was to investigate the effect of heat treatment followed during veneering and in vitro aging on the mechanical and microstructural properties of zirconia dental ceramics. METHODS Three specimens from each of two zirconia blocks (Ivoclar IPS e.max ZirCAD (IV) and Wieland ZENO Zr (WI)) were cut by CAD/CAM technology, fully sintered and polished. Each one was cut in four equal parts. One part was used as control (C), one was heat-treated (H), one was aged (A) (134°C, 2bar, 10h) and one was heat-treated and subsequently aged (HA). The mechanical properties (nano-hardness (H) and elastic modulus (E*)) were investigated by nano-indentation tests while the surface characterization was carried out with XRD, FTIR and SEM. RESULTS Different treatments on IV and WI samples resulted in a reduction of both H and E* values, however the differences were not statistically significant (p>0.05). The combination of treatments imposes an overall effect (p<0.001), enhancing the influence on both H and E* values. This reduction in mechanical properties was followed by an increase of monoclinic content. Greater variations in both H and E* values were recorded for WI samples. SIGNIFICANCE The clinical performance of zirconia dental ceramics may be affected during firing and aging resulting in increased probability of failure.

Sol-Gel Derived Mg-Based Ceramic Scaffolds Doped with Zinc or Copper Ions: Preliminary Results on Their Synthesis, Characterization, and Biocompatibility

Glass-ceramic scaffolds containing Mg have shown recently the potential to enhance the proliferation, differentiation, and biomineralization of stem cells in vitro, property that makes them promising candidates for dental tissue regeneration. An additional property of a scaffold aimed at dental tissue regeneration is to protect the regeneration process against oral bacteria penetration. In this respect, novel bioactive scaffolds containing Mg2+ and Cu2+ or Zn2+, ions known for their antimicrobial properties, were synthesized by the foam replica technique and tested regarding their bioactive response in SBF, mechanical properties, degradation, and porosity. Finally their ability to support the attachment and long-term proliferation of Dental Pulp Stem Cells (DPSCs) was also evaluated. The results showed that conversely to their bioactive response in SBF solution, Zn-doped scaffolds proved to respond adequately regarding their mechanical strength and to be efficient regarding their biological response, in comparison to Cu-doped scaffolds, which makes them promising candidates for targeted dental stem cell odontogenic differentiation and calcified dental tissue engineering.

Study of the Bioactive Behavior of Thermally Treated Modified 58S Bioactive Glass

Thermal treatment of bioactive glasses can affect their microstructure and thus their bioactivity. The aim of this study was the characterization of the thermally treated sol-gel-derived bioactive glass 58S at characteristic temperatures and the dependence of its bioactive behavior on the specific thermal treatment. The thermal behavior of the bioactive glass was studied by thermal analysis (TG/DTA). Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Diffractometry (XRD) were used for the characterization of the bioactive glass. The bioactive behavior in Simulated Body Fluid (SBF) was examined by Scanning Electron Microscopy (SEM-EDS) and FTIR. The major crystal phases after thermal treatment were Calcium Silicates, Wollastonite and Pseudowollastonite, while all thermally treated samples developed apatite after 48 hours in SBF. A slight enhancement of bioactivity was observed for the samples heated at the temperature range 910-970oC.

A Bioactive Glass/Dental Porcelain System by the Sol Gel Route: Fabrication and Characterization

Melt derived bioactive glass- porcelain system is reported to be bioactive but with a slow rate of bioactivity. The aim of this work is to fabricate and characterize bioactive glass/dental porcelain composites produced by the sol-gel method. Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and X-ray Diffractometry (XRD) were used to characterize the fabricated materials. The FTIR spectra and the XRD patterns confirm the presence of both constituents in the mixtures, while the dominant crystal phases in bioactive glass/dental porcelain specimens are leucite and wollastonite.

Reinforcement of a PMMA resin for interim fixed prostheses with silica nanoparticles

PURPOSE Fractures in long span provisional/interim restorations are a common complication. Adequate fracture toughness is necessary to resist occlusal forces and crack propagation, so these restorations should be constructed with materials of improved mechanical properties. The aim of this study was to investigate the possible reinforcement of neat silica nanoparticles and trietoxyvinylsilane-modified silica nanoparticles in a PMMA resin for fixed interim restorations. MATERIALS AND METHODS Composite PMMA-Silica nanoparticles powders were mixed with PMMA liquid and compact bar shaped specimens were fabricated according to the British standard BS EN ISO 127337:2005. The single-edge notched method was used to evaluate fracture toughness (three-point bending test), while the dynamic thermomechanical properties (Storage Modulus, Loss Modulus, tanδ) of a series of nanocomposites with different amounts of nanoparticles (0.25%, 0.50%, 0.75%, 1% w.t.) were evaluated. Statistical analysis was performed and the statistically significant level was set to p<0.05. RESULTS The fracture toughness of all experimental composites was remarkably higher compared to control. There was a tendency to decrease of fracture toughness, by increasing the concentration of the filler. No statistically significant differences were detected among the modified/unmodified silica nanoparticles. Dynamic mechanical properties were also affected. By increasing the silica nanoparticles content an increase in Storage Modulus was recorded, while Glass Transition Temperature was shifted at higher temperatures. CONCLUSIONS Under the limitations of this in-vitro study, it can be suggested that both neat silica nanoparticles and trietoxyvinylsilane-modified silica nanoparticles, especially at low concentrations, may enhance the overall performance of fixed interim prostheses, as can effectively increase the fracture toughness, the elastic modulus and the Glass Transition Temperature of PMMA resins used in fixed provisional restorations.

Study of fossil bones by synchrotron radiation micro-spectroscopic techniques and scanning electron microscopy

Earlymost Villafranchian fossil bones of an artiodactyl and a perissodactyl from the Milia excavation site in Grevena, Greece, were studied in order to evaluate diagenetic effects. Optical microscopy revealed the different bone types (fibro-lamellar and Haversian, respectively) of the two fragments and their good preservation state. The spatial distribution of bone apatite and soil-originating elements was studied using micro-X-ray fluorescence (µ-XRF) mapping and scanning electron microscopy. The approximate value of the Ca/P ratio was 2.2, as determined from scanning electron microscopy measurements. Bacterial boring was detected close to the periosteal region and Fe bearing oxides were found to fill bone cavities, e.g. Haversian canals and osteocyte lacunae. In the perissodactyl bone considerable amounts of Mn were detected close to cracks (the Mn/Fe weight ratio takes values up to 3.5). Goethite and pyrite were detected in both samples by means of metallographic microscopy. The local Ca/P ratio determined with µ-XRF varied significantly in metal-poor spots indicating spatial inhomogeneities in the ionic substitutions. XRF line scans that span the bone cross sections revealed that Fe and Mn contaminate the bones from both the periosteum and medullar cavity and aggregate around local maxima. The formation of goethite, irrespective of the local Fe concentration, was verified by the Fe K-edge X-ray absorption fine structure (XAFS) spectra. Finally, Sr K-edge extended XAFS (EXAFS) revealed that Sr substitutes for Ca in bone apatite without obvious preference to the Ca1 or Ca2 unit-cell site occupation.

The effect of high tempered firing cycle on the bioactive behavior of sol–gel derived dental porcelain modified by bioactive glass

The purpose of the present study was to investigate the influence of end-temperature over the structural properties, chemical composition and bioactivity of dental porcelain modified by bioactive glass. In particular, sol–gel derived specimens of bioactive glass dental porcelain underwent firing at two increased end-temperatures. All specimens were characterized using Scanning Electron Microscopy, Fourier Transform Infrared and Raman Spectroscopy, X-ray diffraction and N2-porosimetry. In vitro bioactivity test was performed too. SEM analysis of both specimens revealed smooth morphology of particles, which were sintered together. Spherical and closed porei were evident. N2- adsorption isotherms of specimens represented non nano-/meso-porous materials. FTIR and Raman spectroscopy revealed the predominance of b-wollastonite as well as the appearance of a-cristobalite. XRD confirmed the results. In vitro tests evidenced the bioactivity of the specimens regardless of temperature. However, the increased temperature caused delayed apatite precipitation. In conclusion, increased temperature favored the sintering process initiation, along with the surface crystallization, which in turn delayed bioactivity.