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Study of devitrification of Dicor glass.

The nucleation and crystallization of tetrasilicic fluormica crystals in the Dicor group of glass ceramics is not as well understood as the crystallization sequence of trisilicic mica in the Macor group of glass ceramics. The main aim of this investigation was to obtain kinetic data of crystallization and to examine the devitrification process at different stages of heat treatment during non-isothermal heating. The kinetic parameters, such as the activation energy, Ec, the reaction order, n, and the frequency factor, v, for the devitrification reaction were computed using the Johnson-Mehl-Avrami (JMA) equation and the data from differential thermal analysis (DTA). The crystallization at different stages of devitrification was evaluated by scanning electron microscopy (SEM) observations, and Fourier transform infrared (FTIR) spectroscopy with KBr-reflectance technique. All DTA curves at different heating rates showed a single exothermic crystallization peak, just above the glass transition temperature in the temperature range of 745-850 degrees C. Linear relationships between the logarithm of heating rate and the reciprocal of temperature, and the logarithm of temperature rise and the reciprocal of temperature were observed. The computation of kinetic parameters gave the values for activation energy, Ec = 203 kJ mol-1, the reaction order n = 3.4 +/- 0.20 and the frequency factor v = 2.88 x 10(11) s-1. SEM observation showed precipitation of crystals in the DTA run which were considerably finer (approximately 0.1 micron) than the block shaped mica plates (approximately 4 microns) observed in the sample subjected to recommended non-isothermal-isothermal heating cycle. The FTIR spectra of beyond the exothermic peak DTA run samples, and the completely cerammed samples showed two additional peaks at wave numbers of 705 and 671 cm-1 compared with the ascast glass and the samples heated before the onset of the exothermic peak. Similar peaks in FTIR spectra also appeared from MgF2- powder at the same wave numbers. Based upon these results, it is proposed that during non-isothermal heating a spinodal decomposition of glass matrix occurs, which is followed by the exothermal precipitation of round tetrasilicic fluormica crystals by a cellular precipitation mechanism.

Chemical Phenomena↗

Immobilization of ultra-thin layer of monoclonal antibody on glass surface.

When preparing an affinity column and a biosensor, it is desirable to immobilize a unimolecular layer of pure protein on a matrix. In this work, we tried to immobilize a monoclonal antibody on a surface of a glass test-tube as a model, to confirm the stability of this ultra-thin layer by an enzyme immunoassay, and to estimate the thickness of the layer on a slide glass by Fourier transform infrared reflection spectrometry. A new test-tube was washed and dried. The tube was filled with 5% 3-aminopropyltriethoxysilane. The 3-aminopropylsilylated surface was treated with glutaraldehyde and 5.6.10(-2) mg/ml solution of a normal mouse monoclonal antibody. The Schiff base between glutaraldehyde and the antibody was further reduced with 7.9.10(-3)% NaBH4. The tube was washed with 0.05% Tween 20 to block non-specific binding. The antibody immobilized on the surface was measured by an enzyme immunoassay based on a reaction of anti-mouse immunoglobulin G labelled with alkaline phosphatase, with which p-nitrophenol was produced from p-nitrophenylphosphate as a substrate. Meanwhile, various amounts of the antibody were immobilized on slide glasses in the same manner. The antibody on each surface was measured by Fourier transform infrared reflection spectrometry. The antibody immobilized under the final conditions was detectable by the enzyme immunoassay, and stable at 4 degrees C for ten days. The antibody on the slide glass was a unimolecular layer, as judged from the Fourier transform infrared spectra referred to -CONH- band semiquantitatively. Thus, we found the optimal conditions for immobilizing an ultra-thin layer of the monoclonal antibody on the glass surface.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

Micropatterning of biomolecules on glass surfaces modified with various functional groups using photoactivatable biotin.

Biomolecule patterning by photolithographic methods has considerable advantages because a large number of different biomolecules can be assembled on a spatial area by a combinatorial method and complex biomolecule patterning can be created in situ in closed environments such as microfluidic channels. Here, a photobiotin was used as the photoactivatable reagent to create patterned arrays of biomolecules. The variability of photobiotin deposition on glass substrates modified with a variety of materials having carboxyl, lysine, aldehyde, amine groups, and BSA (bovine serum albumin) was characterized by subsequent derivatization with Cy3-labeled streptavidin. The fluorescence images of the photobiotin patterned glass surfaces showed that the BSA/aldehyde-coated glass could be considered as the most appropriate substrate to immobilize photobiotin, in view of the homogeneous immobilization of biomolecules with high density in defined regions and the reduction of nonspecific binding to the surface. In streptavidin equilibrium adsorption assays, the maximum amount of streptavidin-Cy3 bound to the BSA/aldehyde-coated glass surface continued to rise with increasing streptavidin-Cy3 concentration until 12.0 microg/mL was reached and the surface then became saturated. Also, a line array of biotin-labeled single-strand probe DNAs was created on the BSA/aldehyde-coated glass by photolysis of photobiotin through a slit-type mask and biotin/streptavidin/biotin chemistry, extended to a quantitative measurement of the concentrations of target DNA. The results of target DNA analysis showed linearity over a wide range from 0.5 ng/mL to 5 microg/mL and were reproducible.

Aldehydes↗

Effect of iron on the surface, degradation and ion release properties of phosphate-based glass fibres.

Phosphate-based glass fibres (PGF) have the unique characteristic of being completely soluble in an aqueous environment, releasing bioactive and biocompatible ions. They have been proposed as tissue engineering scaffolds for craniofacial skeletal muscle regeneration, where myoblasts are seeded directly onto the fibres. Studies have shown that these cells have a preference in their initial attachment to fibres of certain composition and size, which in turn control the rate of degradation. This study investigated the relationship between the surface properties, degradation properties and ion release (cationic and anionic species) by altering the chemical composition of the PGF. Iron oxide (Fe2O3) was incorporated into glasses containing P2O5 (50 mol%), CaO (30 mol%) and Na2O (20 mol%). Six glass compositions with Fe2O3 ranging from 0 to 5 mol% by replacing the equivalent Na2O mol% were investigated. Contact angle measurements showed that polar interactions occurring on the glass surfaces diminished with increasing Fe2O3 content. This behaviour was reflected in the estimated surface energies of the glasses, where the overall surface energy decreased with increasing Fe2O3 content due to the decrease in polar or acid/base component. The incorporation of up to 5 mol% Fe2O3 into PGF resulted in a significant reduction in the degradation rate (by two orders of magnitude), which can be related to the formation of more hydration resistant P-O-Fe bonds. However, the degradation rate increased with decreasing fibre diameter (comparing average diameters of 31.6 +/- 6.5 microm versus 13.1 +/- 1.3 microm) for a given mass of fibre, and this is related to the surface area to volume ratio. Taken together the results suggest that fibres with the larger diameters and containing 3-5 mol% Fe2O3 could initially be a more durable scaffold than ones with 1 or 2 mol% Fe2O3 for initial cell attachment.

Absorbable Implants↗

Development of glass-ceramic scaffolds for bone tissue engineering: characterisation, proliferation of human osteoblasts and nodule formation.

Glass-ceramic macroporous scaffolds for tissue engineering have been developed using a polyurethane sponge template and bioactive glass powders. The starting glass (CEL2) belongs to the system SiO(2)-P(2)O(5)-CaO-MgO-Na(2)O-K(2)O and has been synthesised by a conventional melting-quenching route. A slurry of CEL2 powder, polyvinyl alcohol and water has been prepared in order to coat, by impregnation, the polymeric template. An optimised thermal treatment was then use to remove the sponge and to sinter the glass powders, leading to a glass-ceramic replica of the template. Morphological observations, image analyses, mechanical tests and in vitro tests showed that the obtained devices are good candidates as scaffolds for bone-tissue engineering, in terms of pore-size distribution, pore interconnection, surface roughness, and both bioactivity and biocompatibility. In particular, a human osteoblast cell line (MG-63) seeded onto the scaffold after a standardised preconditioning route in simulated body fluid showed a high degree of cell proliferation and a good ability to produce calcium nodules. The obtained results were enhanced by the addition of bone morphogenetic proteins after cell seeding.

Biocompatible Materials↗

Nodule formation and mineralisation of human primary osteoblasts cultured on a porous bioactive glass scaffold.

The aim of this study was to analyse human osteoblast responses to a porous bioactive glass scaffold. It was hypothesised that osteoblasts would attach, proliferate and form mineralised nodules in response to culture on the bioactive glass. As dissolution products are a key feature of bioactive glasses, this was measured by inductively coupled plasma optical emission spectroscopy to determine effects of both the glass surface and ion release. Osteoblasts attached and proliferated on the foams as demonstrated by scanning electron microscopy. Nodule formation was also observed in the pores of the glass and also in conditioned medium containing dissolution products at certain concentrations and these nodules were shown to be mineralised by alizarin red staining. Undiluted dissolution products from the foams however caused significant apoptosis suggesting an ion concentration dependent response.

Apoptosis↗

Processing, characterisation and biocompatibility of iron-phosphate glass fibres for tissue engineering.

Iron-phosphate glass fibres based on the CaO-Na2O-Fe2O3-P2O5 system have been processed and characterised via thermal, XRPD, dissolution rates, diameter and biocompatibility studies. The compositions investigated were fixed at 50mol% P2O5, and the CaO content was varied between 30, 35 and 40mol%. The Fe2O3 was added in low amounts from 1-5mol%, substituting it for the Na2O mol%. The number of Tc (crystallisation temperature) peaks detected from the thermal analysis traces only showed correlation with XRPD analysis, for five out of the 15 compositions investigated. It has been suggested that either the crystalline phases had very similar Tc temperatures or that the other phase(s) were present in very small quantities. There was a good match seen with number of Tm (melting temperature) peaks picked up from the DTA traces, with the number of phases identified from XRPD analysis. The main phases identified from XRPD were NaCa(PO3)3, CaP2O6 and NaFeP2O7. Using network connectivity (NC), predictions on Qn species present within the compositions investigated were made. The predicted species (metaphosphates) matched with phases identified from XRPD analysis. A decrease in dissolution rates for the bulk glass and glass fibres was seen with an increase in CaO mol%, along with an increase in Fe2O3 mol%. An increase in fibre dissolution rates was seen with a decrease in diameter size. The biocompatibility studies were conducted using a conditionally immortal muscle precursor cell line derived from the H-2Kb-tsA58 immortomouse. It was found that iron-phosphate glass fibres containing 4-5mol% Fe2O3 was sufficient for cell attachment and differentiation. It was seen that myotubes formed along the axis of the fibres (which was indicative of differentiation). The biocompatibility of these compositions was attributed to the enhanced chemical durability of the glass fibres.

Animals↗

The effect of the topical administration of bioactive glass on inflammatory markers of human experimental gingivitis.

Recent studies demonstrated that bioactive glass attenuated inflammatory reactions and bacterial growth in vitro. The aim of the present clinical study was to evaluate the effects of local bioactive glass-administration in vivo in subjects with experimental gingivitis. In each individual, contralateral teeth served as test and control over a 21-day non-hygiene (preventive phase) and a 7-day therapeutic phase. A 45S5 bioactive glass (10% solution) was applied daily (2 x 1 h) on the test teeth during the preventive and therapeutic phase of the study. Inflammation assessment was based on the plaque index record (PI), on the bleeding frequency (BOP) and the gingival crevicular fluid volume (GCF). Interleukin-1beta levels (IL-1beta) in the GCF were measured by ELISA. Bacterial deposits on teeth increased during the 21-days non-brushing period, with no difference in plaque accumulation between test and control sides. BOP levels were significantly reduced during the therapeutic phase by the application of bioactive glass. GCF-values showed a significant reduction on the test compared to control side during the preventive and therapeutic phase. IL-1beta counts decreased during the last 7 days of the study on the test side, but no significance was given. The topical application of 45S5 bioactive glass in humans with experimental gingivitis attenuated the clinical signs of inflammation, although the bacterial accumulation was not inhibited in this clinical trial.

Administration, Topical↗

A new heterobifunctional reagent for immobilization of biomolecules on glass surface.

Synthesis of a new heterobifunctional reagent, [N-(2-trifluoroethanesulfonatoethyl)-N-(methyl)-triethoxysilylpropyl-3-amine] (NTMTA) is described for the immobilization of a variety of biomolecules on glass surface. Its triethoxysilyl group reacts with glass surface and trifluoroethanesulfonate ester structure reacts selectively with aminoalkyl/mercaptoalkyl function in biomolecules. The immobilization can be achieved by two ways involving two steps. The first route involves the reaction of NTMTA with glass beads followed by attachment of aminoalkyl- or mercaptoalkylated biomolecules. The second one involves the reaction of biomolecules, viz., oligonucleotides, proteins, etc., with NTMTA via their aminoalkyl or mercaptoalkyl functions to form a biomolecule conjugate, which is then reacted with glass beads (unmodified) to complete immobilization process. This has been demonstrated by successful immobilization of 5'-mercaptoalkyl- or aminoalkylated oligonucleotides and some commonly used enzymes on glass beads using NTMTA reagent.

Glass↗

Selectivity and dynamic behavior of glass electrodes.

Two types of models are presently used to describe the potential of a glass electrode: the ion exchange type, which is based on the equilibrium binding ratio of the glass surface, and the permeability type, based on the permeability ratio of the ions within the glass matrix. It is shown that the permeability type models can be derived from first physical principles while the exchange type models are questionable from the physical point of view. The derivation of the potential-concentration behavior shows that the steady-state characteristic of the electrode potential is determined by the selectivity properties of the dry glass layer. The rapidity of the potential response of the glass electrode can be traced back to the fact that, under certain constraints regarding the diffusion coefficients, the potential difference across this layer only depends on the boundary concentrations. The potential drift, in contrast, is determined by ion transport in the hydrated surface layers of the electrode. The theoretical predictions of single- and multi-layer permeability models are compared with experimental data for a sodium selective electrode.

Electrochemistry↗

The impact of ultraviolet light on bacterial adhesion to glass and metal oxide-coated surface.

Biofouling of glass and quartz surfaces can be reduced when the surface is coated with photocatalytically active metal oxides, such as TiO2 (anatase form) or SnO2. We measured the attachment of eight strains of bacteria to these two metal oxides (TiO2 and SnO2), and to an uncoated glass (control; designated Si-m) before and after exposure to UV light at wavelengths of 254 nm (UVC) or 340 nm UV (UVA). TiO2-coated surfaces were photocatalytically active at both 254 and 340 nm as evidenced by a decrease in the water contact angle of the surface from 59 degrees +/-2 to <5 degrees. The water contact angle of the SnO2 surface was reduced only at 254 nm, while contact angle of the Si-m glass surface was not altered by light of either wavelength. Bacterial adhesion decreased by 10-50% to photocatalyzed glass surfaces. In all cases, bacteria exposed to the UV light were completely killed due to a combination of exposure to UV light and the photocatalytic activity of the glass surfaces. These results show that UV light irradiation of TiO2-coated surfaces can be an effective method of reducing bacterial adhesion.

Bacillus subtilis↗

Ion processes in glass ionomer cements.

Ion processes are involved in many aspects of glass-ionomer cements. The ions released from the glass take part in the formation of the cement matrix. Although this process has been investigated, particularly using model cement systems, no study provides a complete matrix composition. Combining results from different studies enables an approximate composition to be derived. The importance of Phosphorous in controlling ion release from the glass surface has been identified in a number of studies. The release of ions from the set cement into water (and other aqueous liquids) has been much reported, particularly for fluoride. Over most of the release periods studied (i.e. from >7 days up to 3 years), release of F ion is related to t1/2 indicating a diffusion-controlled process. Other ions, except possibly Na+ also show this relationship. The amount of cumulative F release whilst maintaining this relationship indicates that more F than is in the matrix is involved. Ion chromatography would probably elucidate the precise form of the ionic species released. Glass-ionomer cements take up ions from solutions in which they are immersed. The levels are much higher than required to produce as internal/external equilibrium. Studies using dynamic SIMS and XPS give some information on ion location and elemental association. It is suggested that ToF SIMS would elucidate these further. Re-release of uptaken ions can vary considerably for different cements and ion species. Surface disruption of glass ionomers is caused by both F ion and monofluorophosphate ion and occurs much more readily in F containing cements than in F free ones. The mechanism of this process has not been elucidated. Analysis of the ions released from the cement as disruption occurs should provide an indication of the site of attack.

Aluminum Silicates↗

Spectral properties of Er3+/Yb3+ codoped tungsten-tellurite glasses.

The spectral properties of Er3+/Yb3+ codoped tungsten-tellurite (WT) glasses have been investigated. The measured absorption spectra are analyzed by Judd-Ofelt theory. The compositional change of intensity parameter omega2 is attributed to the change in the covalency between the Er3+ and oxygen ions, the asymmetry in the local structures around the Er3+ ions can be neglected. The lifetimes of 4I(13/2) level of Er3+ in WT glasses are measured and comparable with other TeO2-based glasses. The stimulated emission cross-section is calculated based on McCumber theory. The fluorescence full width at half maximum (FWHM) and the emission cross-section (sigma(peak)) of the 4I(13/2) --> 4I(15/2) transition of Er3+ in different glass hosts have been compared. The suitability of such WT glasses as host materials for 1.5 microm broadband amplification is discussed.

Cations↗

Fe(3+) ions in alkali lead tetraborate glasses--an electron paramagnetic resonance and optical study.

Glass systems of composition 90R(2)B(4)O(7)+9PbO+1Fe(2)O(3) (R=Li, Na and K) and 90Li(2)B(4)O(7)+(10-x)PbO+xFe(2)O(3) (x=0.5, 1, 3, 4, 5, 7 and 9 mol %) have been investigated by means of electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra exhibit three resonance signals at g approximately 6.0, 4.2 and 2.0. The resonances at g approximately 6.0 and 4.2 are attributed to Fe(3+) ions in rhombic and axial symmetry sites, respectively. The g approximately 2.0 resonance signal is due to two or more Fe(3+) ions coupled together with dipolar interaction. The EPR spectra of 1 mol % of Fe(2)O(3) doped in lithium lead tetraborate glass samples have been studied at different temperatures (123-433 K). The intensity of g approximately 4.2 resonance signal decreases and the intensity of g approximately 2.0 resonance signal increases with the increase of temperature. The line widths are found to be independent of temperature. The EPR spectra exhibit a marked concentration dependence on iron content. A decrease in intensity for the resonance signal at g approximately 4.2 with increase in iron content for more than 4 mol % has been observed in lithium lead tetraborate glass samples and this has been attributed to the formation of Fe(3+) ion clusters in the glass samples. The paramagnetic susceptibility (chi) is calculated from the EPR data at various temperatures and the Curie constant (C) has been evaluated from 1/chi versus T graph. The optical absorption spectrum of Fe(3+) ions in lithium lead tetraborate glasses exhibits three bands characteristic of Fe(3+) ions in an octahedral symmetry. The crystal field parameter D(q) and the Racah interelectronic repulsion parameters B and C have also been evaluated. The value of interelectronic repulsion parameter B (825 cm(-1)) obtained in the present work suggests that the bonding is moderately covalent.

Borates↗

EPR and optical investigations of manganese ions in alkali lead tetraborate glasses.

Electron paramagnetic resonance (EPR) and optical absorption spectra of Mn2+ ions in different alkali lead tetraborate glasses 90R2B4O7+9.25PbO+0.75MnSO4 (R=Li, Na and K) and 90Li2B4O7+(10-x)PbO+xMnSO4 (x=0.1, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5 and 2 mol%) have been studied. The EPR spectrum of all the glass samples exhibit three resonance signals at g=2.0, 3.3 and 4.3. The resonance signal at g=2.0 is attributed to the Mn2+ ions in an environment close to an octahedral symmetry. The resonance signals at g=3.3 and 4.3 have been attributed to the rhombic symmetry of the Mn2+ ions. The effect of temperature (123-433 K) and the composition dependence of EPR signals have been studied for Mn2+ ions in lithium lead tetraborate glasses. It is interesting to observe that the variation of paramagnetic susceptibility (chi) with temperature obeys Curie-Weiss law. From the slope of 1/chi versus T graph, the Curie constant (C) has been evaluated. The zero-field splitting (zfs) parameter D has been calculated for different alkali lead tetraborate glasses from the intensities of the allowed hyperfine lines. The optical absorption spectrum exhibits three bands. An intense and broad band at lower energy side has been assigned to the spin-allowed (5Eg-->5T2g) transition of Mn3+ ions in an octahedral symmetry. The intense and sharp band and a broad band at higher energy side have been assigned to charge transfer bands. A red shift is observed with increase of alkali ion size. The optical band gap energy (Eopt) decreases, whereas the Urbach energies (DeltaE) increases with increase of Mn content. The theoretical values of optical basicity (Lambdath) of the glasses have also been evaluated.

Alkalies↗

EPR investigation of the gamma radiation response of different types of glasses.

Several types of laboratory glasses such as: "Jena", "Rasotherm", "Thüring" as well as window and windscreen glasses were studied by the method of EPR spectroscopy as possible emergency radiation dosimeters for gamma-ray irradiation. The most appropriate values of modulation amplitude and microwave power were found to obtain best sensitivity for the measured signals. Dose measurements have shown a linear dependence between the EPR signal intensity of radiation created defects in glasses and applied dose in the dose range 50-500 Gy. "Thüring" glass was found to be the most sensitive sample to radiation. The magnitude of window glass absorbed dose was evaluated as the difference between the intensity of its EPR signal recorded after irradiation and the background signal, obtained after thermal relaxation of the former.

Dose-Response Relationship, Radiation↗

Preparation and characterization of Nd3+ doped sodium leadbismuthate glass.

Nd(3+) doped unconventional sodium leadbismuthate glass is prepared through the melt quenching method. The amorphous nature of the glass is confirmed through the X-ray diffraction study. The differential thermal study was performed to identify the glass transition and approximate glass thermal stability measurements. To identify the local structure of the glass, Fourier transform infrared spectral analysis was also carried out. By performing the Judd-Ofelt theory, the theoretical and experimental oscillator strengths were calculated.

Absorption↗

Effect of B2O3 on luminescence of erbium doped tellurite glasses.

The B2O3 was introduced into the Er3+ doped TeO2-ZnO-Na2O glass to increase the phonon energy of the host. The effect of B2O3 on the non-radiative rate of the 4I11/2-->4I13/2 transition of Er3+, the lifetime of the 4I11/2 and 4I13/2 levels, the green and red upconversion emissions intensity, and the 4I13/2-->4I15/2 emission intensity was discussed. The results show that the phonon energy of boro-tellurite glass is close to that of germanate glass and is quite smaller than that of borate glass. The lifetime of 4I11/2 level and the upconversion emissions decrease with increasing B2O3 concentration. The higher OH group concentration presented in the boro-tellurite glass may shorten the lifetime of 4I13/2 level and also reduce the quantum efficiency of 4I13/2-->4I15/2 emission. The future dehydrating procedures are suggested to enhance the efficiency of amplification at 1.5 microm band.

Boron Compounds↗