SEM analysis and push-out bond strength of fiberglass posts luted with different cements of glass-ionomer in humid environment: pilot test

The objective of this study was to evaluate the push-out bond strength of fiberglass resin reinforced bonded with five ionomer cements. Also, the interface between cement and dentin was inspected by means of SEM. Fifty human canines were chose after rigorous scrutiny process, endodontically treated and divided randomly into five groups (n = 3) according to cement tested: Group I – Ionoseal (VOCO), Group II – Fugi I (GC), Group III – Fugi II Improved (GC), Group IV – Rely X Luting 2 (3M ESPE), Group V – Ketac Cem (3M ESPE). The post-space was prepared to receive a fiberglass post, which was tried before cementation process. No dentin or post surface pretreatment was carried out. After post bonding, all roots were cross-sectioned to acquire 3 thin-slices (1 mm) from three specific regions of tooth (cervical, medium and apical). A Universal test machine was used to carry out the push-out test with cross-head speed set to 0.5mm/mim. All failed specimens were observed under optical microscope to identify the failure mode. Representative specimens from each group was inspected under SEM. The data were analyzed by Kolmogorov-Smirnov and Levene’s tests and by two-way ANOVA, and Tukey’s port hoc test at a significance level of 5%. It was compared the images obtained for determination of types of failures more occurred in different levels. SEM inspection displayed that all cements filled the space between post and dentin, however, some imperfections such bubles and voids were noticed in all groups in some degree of extension. The push-out bond strength showed that cement Ketac Cem presented significant higher results when compared to the Ionoseal (P = 0.02). There were no statistical significant differences among other cements.

Push-out bond strengths of different dental cements used to cement glass fiber posts

Statement of problem: Since the introduction of glass fiber posts, irreversible vertical root fractures have become a rare occurrence; however, adhesive failure has become the primary failure mode. Purpose: The purpose of this study was to evaluate the push-out bond strength of glass fiber posts cemented with different luting agents on 3 segments of the root. Material and methods: Eighty human maxillary canines with similar root lengths were randomly divided into 8 groups (n=10) according to the cement assessed (Rely X luting, Luting and Lining, Ketac Cem, Rely X ARC, Biscem, Duo-link, Rely X U100, and Variolink II). After standardized post space preparation, the root dentin was pretreated for dualpolymerizing resin cements and untreated for the other cements. The mixed luting cement paste was inserted into post spaces with a spiral file and applied to the post surface that was seated into the canal. After 7 days, the teeth were sectioned perpendicular to their long axis into 1-mm-thick sections. The push-out test was performed at a speed of 0.5 mm/min until extrusion of the post occurred. The results were evaluated by 2-way ANOVA and the all pairwise multiple comparison procedures (Tukey test) (?=.05). Results: ANOVA showed that the type of interaction between cement and root location significantly influenced the push-out strength (P<.05). The highest push-out strength results with root location were obtained with Luting and Lining (S3) (19.5 ±4.9 MPa), Ketac Cem (S2) (18.6 ±5.5 MPa), and Luting and Lining (S1) (18.0 ±7.6 MPa). The lowest mean values were recorded with Variolink II (S1) (4.6 ±4.0 MPa), Variolink II (S2) (1.6 ±1.5 MPa), and Rely X ARC (S3) (0.9 ±1.1 MPa). Conclusions: Self-adhesive cements and glass ionomer cements showed significantly higher values compared to dual-polymerizing resin cements. In all root segments, dual-polymerizing resin cements provided significantly lower bond strength. Significant differences among root segments were found only for Duo-link cement.

Effect of 2% chlorhexidine digluconate on bond strength of a glass-fibre post to root dentine

Aim: To assess the immediate influence of dentine bonding systems (DBS) associated with 2% chlorhexidine digluconate (CHX) on glass-fibre post-bond strength to root dentine, in terms of coronal, middle and apical thirds. Methodology: Sixty bovine roots were root filled and randomly assigned to 1 of 6 groups (n = 10): SBMP (3-step etch-and-rinse system, Scotchbond Multi-Purpose), SB (2-step etch-and-rinse system, Single Bond 2), SE (2-step self-etching system, Clearfil SE Bond) and SBMP-CHX, SB-CHX and SE-CHX, respectively, associated with CHX. For all groups, a glassfibre post was luted with a dual-cure resin cement, RelyX ARC. After 7-day storage, specimens were subjected to the push-out test. Failure modes were analysed under optical microscopy (40x). Bond strength values were statistically analysed by two-way ANOVA and Bonferroni tests (P < 0.05). Results: The effect of DBS was significant (P < 0.05), and SE reached higher bond strength in comparison with the other DBS tested. CHX association did not show improvement with any DBS (P > 0.05); rather, it negatively affected SE, which was detected for all thirds. There was no difference between thirds (P > 0.05), except for the SE-CHX, which presented lower values for the apical third (P < 0.05). Adhesive cement/dentine adhesive failure was predominant for all groups. CHX did not influence the failure mode for any DBS (P > 0.05). Conclusions: The performance of the dentine bonding systems was material dependent. CHX did not improve immediate bond strength; however, CHX negatively affected the bond strength of the self-etching system, especially in the third apical

Selection of compositions with high glass forming ability in the Ni-Nb-B alloy system

A combination of an extension of the topological instability "λ criterion" and the "average electronegativity" has been recently reported in the literature to predict compositions with high glass-forming ability (GFA). In the present work, both criteria have been applied to select the Ni61.0Nb36.0B3 alloy with a high glass-forming ability. Ingots were prepared by arc-melting and were used to produce ribbons processed by the melt-spinning technique further characterized by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Ni61.0Nb36.0B3 alloy revealed a complete amorphization and supercooled liquid region ΔTx = 68 K. In addition, wedge-shaped samples were prepared using copper mold casting in order to determine the critical thickness for amorphous formation. Scanning electron microscopy (SEM) revealed that fully amorphous samples could be obtained, reaching up to ~800 µm in thickness.

In vitro fracture resistance of glass-fiber and cast metal posts with different designs

PURPOSE: To evaluate the in vitro fracture resistance of roots with glass-fiber and metal dowels with different designs. METHODS: Fifty-endodontically treated maxillary central incisors were embedded in acrylic resin. Ten of them received only the coronary preparation, and the remaining forty were embedded (except for 4mm of the cervical area) after removing the clinical crowns. Specimens were divided into five groups (n=10): control (teeth with only coronary preparation), cylindrical cast dowel, conical cast dowel, cylindrical glass-fiber dowel and conical glass-fiber dowel. Specimens were subjected to an increasing compressive load (N) until fracture. RESULTS: ANOVA indicated significant difference (P<.05) among the groups, and the Tukey-Kramer´s test identified these differences. The control group (867±243 N) presented the highest values and was statistically similar to cylindrical glass-fiber dowel group (711±180 N). There is no significant difference among the metal dowel cylindrical (435±245 N) or conical (585±164 N) group and conical glass-fiber dowel (453±112 N). Cylindrical glass-fiber dowel (711±180 N) and conical cast dowel and core (585±164 N) groups had intermediate values and did not differ from each other. CONCLUSIONS: Cylindrical glass fiber dowels represent a viable alternative to the cast-metal dowel cylindrical or conical. Cylindrical glass fiber dowels also increase endodontically treated incisors' resistance to fracture.

Luminescence quantum efficiency at 1.5 µm of Er3+- doped tellurite glass determined by thermal lens spectroscopy

Erbium doped tellurite glasses (TeO2 + Li2O + TiO2) were prepared by conventional melt-quenching method to study the influence of the Er3+ concentration on the luminescence quantum efficiency (η) at 1.5 µm. Absorption and luminescence data were used to characterize the samples, and the η parameter was measured using the well-known thermal lens spectroscopy. For low Er3+ concentration, the measured values are around 76%, and the concentration behavior of η shows Er-Er and Er-OH- interactions, which agreed with the measured lifetime values.

Characterization of polysaccharides from Hypnea spinella (Gigartinales) and Halopithys incurva (Ceramiales) and their effect on RAW 264.7 macrophage activity

[EN] Red algae have been reported to be an important source of polysaccharides with potential immunomodulatory properties. The objective of this study was to characterize the polysaccharides from Halopithys incurva and Hypnea spinella and to evaluate their effect on the synthesis of cytokines by murine cell line RAW 264.7 macrophages. Polysaccharides were obtained by N-cetylpyridiniumbromide precipitation and characterized by Fourier transform-infrared spectroscopy. Their effect on the activity of RAW 264.7 macrophages was examined by quantification of tumor necrosis factor (TNF)-α, interleukin (IL)-6, and nitric oxide (NO) production using enzyme-linked immunosorbent assays. The activation of the cytokine IL-6 and NO increased linearly as the concentration of polysaccharides from H. incurva and Hy. spinella increased. In general, the activation of IL-6 and NO was tenfold greater when macrophages were exposed to polysaccharides from H. incurva than when exposed to polysaccharides from Hy. spinella. In contrast, TNF-α concentration did not increase when macrophages were exposed to increasing polysaccharide levels. These results indicate that polysaccharides are strong cytokine IL-6 inducers.

Studio del comportamento meccanico di smalti porcellanati per substrati metallici

Composite porcelain enamels are inorganic coatings for metallic components based on a special ceramic-vitreous matrix in which specific additives are randomly dispersed. The ceramic-vitreous matrix is made by a mixture of various raw materials and elements and in particular it is based on boron-silicate glass added with metal oxides(1) of titanium, zinc, tin, zirconia, alumina, ecc. These additions are often used to improve and enhance some important performances such as corrosion(2) and wear resistance, mechanical strength, fracture toughness and also aesthetic functions. The coating process, called enamelling, depends on the nature of the surface, but also on the kind of the used porcelain enamel. For metal sheets coatings two industrial processes are actually used: one based on a wet porcelain enamel and another based on a dry-silicone porcelain enamel. During the firing process, that is performed at about 870°C in the case of a steel substrate, the enamel raw material melts and interacts with the metal substrate so enabling the formation of a continuous varying structure. The interface domain between the substrate and the external layer is made of a complex material system where the ceramic vitreous and the metal constituents are mixed. In particular four main regions can be identified, (i) the pure metal region, (ii) the region where the metal constituents are dominant compared with the ceramic vitreous components, (iii) the region where the ceramic vitreous constituents are dominant compared with the metal ones, and the fourth region (iv) composed by the pure ceramic vitreous material. It has also to be noticed the presence of metallic dendrites that hinder the substrate and the external layer passing through the interphase region. Each region of the final composite structure plays a specific role: the metal substrate has mainly the structural function, the interphase region and the embedded dendrites guarantee the adhesion of the external vitreous layer to the substrate and the external vitreous layer is characterized by an high tribological, corrosion and thermal shock resistance. Such material, due to its internal composition, functionalization and architecture can be considered as a functionally graded composite material. The knowledge of the mechanical, tribological and chemical behavior of such composites is not well established and the research is still in progress. In particular the mechanical performances data about the composite coating are not jet established. In the present work the Residual Stresses, the Young modulus and the First Crack Failure of the composite porcelain enamel coating are studied. Due to the differences of the porcelain composite enamel and steel thermal properties the enamelled steel sheets have residual stresses: compressive residual stress acts on the coating and tensile residual stress acts on the steel sheet. The residual stresses estimation has been performed by measuring the curvature of rectangular one-side coated specimens. The Young modulus and the First Crack Failure (FCF) of the coating have been estimated by four point bending tests (3-7) monitored by means of the Acoustic Emission (AE) technique(5,6). In particular the AE information has been used to identify, during the bending tests, the displacement domain over which no coating failure occurs (Free Failure Zone, FFZ). In the FFZ domain, the Young modulus has been estimated according to ASTM D6272-02. The FCF has been calculated as the ratio between the displacement at the first crack of the coating and the coating thickness on the cracked side. The mechanical performances of the tested coated specimens have also been related and discussed to respective microstructure and surface characteristics by double entry charts.

Determination of bioactive and potentially toxic compounds in food: raw material analysis and shelf life evaluation

"Bioactive compounds" are extranutritional constituents that typically occur in small quantities in food. They are being intensively studied to evaluate their effects on health. Bioactive compounds include both water soluble compounds, such as phenolics, and lipidic substances such as n-3 fatty acids, tocopherols and sterols. Phenolic compounds, tocopherols and sterols are present in all plants and have been studied extensively in cereals, nuts and oil. n-3 fatty acids are present in fish and all around the vegetable kingdom. The aim of the present work was the determination of bioactive and potentially toxic compounds in cereal based foods and nuts. The first section of this study was focused on the determination of bioactive compounds in cereals. Because of that the different forms of phytosterols were investigated in hexaploid and tetraploid wheats. Hexaploid cultivars were the best source of esterified sterols (40.7% and 37.3% of total sterols for Triticum aestivum and Triticum spelta, respectively). Significant amounts of free sterols (65.5% and 60.7% of total sterols for Triticum durum and Triticum dicoccon, respectively) were found in the tetraploid cultivars. Then, free and bound phenolic compounds were identified in barley flours. HPLCESI/ MSD analysis in negative and positive ion mode established that barley free flavan-3- ols and proanthocyanidins were four dimers and four trimers having (epi)catechin and/or (epi)gallocatechin (C and/or GC) subunits. Hydroxycinnamic acids and their derivatives were the main bound phenols in barley flours. The results obtained demonstrated that barley flours were rich in phenolic compounds that showed high antioxidant activity. The study also examined the relationships between phenolic compounds and lipid oxidation of bakery. To this purpose, the investigated barley flours were used in the bakery production. The formulated oven products presented an interesting content of phenolic compounds, but they were not able to contain the lipid oxidation. Furthermore, the influence of conventional packaging on lipid oxidation of pasta was evaluated in n-3 enriched spaghetti and egg spaghetti. The results proved that conventional packaging was not appropriated to preserve pasta from lipid oxidation; in fact, pasta that was exposed to light showed a high content of potentially toxic compounds derived from lipid oxidation (such as peroxide, oxidized fatty acids and COPs). In the second section, the content of sterols, phenolic compounds, n-3 fatty acids and tocopherols in walnuts were reported. Rapid analytical techniques were used to analyze the lipid fraction and to characterize phenolic compounds in walnuts. Total lipid chromatogram was used for the simultaneous determination of the profile of sterols and tocopherols. Linoleic and linolenic acids were the most representative n-6 and n-3 essential dietary fatty acids present in these nuts. Walnuts contained substantial amounts of γ- and δ-tocopherol, which explained their antioxidant properties. Sitosterol, Δ5-avenasterol and campesterol were the major free sterols found. Capillary electrophoresis coupled to DAD and microTOF was utilized to determine phenolic content of walnut. A new compound in walnut ((2E,4E)- 8-hydroxy-2,7-dimethyl-2,4-decadiene-1,10-dioic acid 6-O-β-D-glucopiranosyl ester, [M−H]− 403.161m/z) with a structure similar to glansreginins was also identified. Phenolic compounds corresponded to 14–28% of total polar compounds quantified. Aglycone and glycosylated ellagic acid represented the principal components and account for 64–75% of total phenols in walnuts. However, the sum of glansreginins A, B and ((2E,4E)-8-hydroxy- 2,7-dimethyl-2,4-decadiene-1,10-dioic acid 6-O-β-D-glucopiranosyl ester was in the range of 72–86% of total quantified compounds.

Length scales of dynamic heterogeneities of low and high molecular weight glass formers from multidimensional NMR

Das Ziel der vorliegenden Arbeit ist die Untersuchung der räumlichen und zeitlichen Aspekte der heterogenen Dynamik in Modellglasbildnern. Dabei wird vor allem die langsame alpha-Relaxationsdynamik oberhalb des Glasüberganges Tg untersucht. Die nukleare Magnetresonanz zeigt ihre einmalige Vielseitigkeit bei der Untersuchung molekularer Dynamik, wenn die angewandten Techniken und Experimente durch Simulationen unterstützt werden. Die räumliche Aspekt dynamischer Heterogenitäten wird untersucht durch ein reduziertes vierdimensionales Spindiffusionsexperiment (4D3CP), ein Experiment, das Reorientierungsraten örtlich korreliert. Eine Simulation dieses Experimentes an einem System harter Kugeln liefert wertvolle Informationen über die Auswertemethode des 4D3CP Experiments. Glycerol und o-terphenyl werden durch das 4D3CP Experiment untersucht. Die erhaltenen Resultate werden mit bereits publizierten Daten des polymeren Glasbildners PVAc verglichen. Während PVAc und o-terphenyl eine Längenskale von 3.7 nm bzw. 2.9 nm aufweisen, ist die Längenskale von Glycerol signifikant kleiner bei 1.1 nm. Ein neues Experiment, welches sensitiv auf Translationsbewegung reagiert, wird vorgestellt. Durch Verwendung eines pi-Impulszuges kann eine separate Evolution unter dem Hamiltonian der dipolaren Kopplung und der chemischen Verschiebungsanisotropie erreicht werden.

The Dynamics of a Small Model Glass Former as Viewed from Its Potential Energy Landscape

Despite intensive research during the last decades, thetheoreticalunderstanding of supercooled liquids and the glasstransition is stillfar from being complete. Besides analytical investigations,theso-called energy-landscape approach has turned out to beveryfruitful. In the literature, many numerical studies havedemonstratedthat, at sufficiently low temperatures, all thermodynamicquantities can be predicted with the help of the propertiesof localminima in the potential-energy-landscape (PEL). The main purpose of this thesis is to strive for anunderstanding ofdynamics in terms of the potential energy landscape. Incontrast to the study of static quantities, this requirestheknowledge of barriers separating the minima.Up to now, it has been the general viewpoint that thermallyactivatedprocesses ('hopping') determine the dynamics only belowTc(the critical temperature of mode-coupling theory), in thesense that relaxation rates follow from local energybarriers.As we show here, this viewpoint should be revisedsince the temperature dependence of dynamics is governed byhoppingprocesses already below 1.5Tc.At the example of a binary mixture of Lennard-Jonesparticles (BMLJ),we establish a quantitative link from the diffusioncoefficient,D(T), to the PEL topology. This is achieved in three steps:First, we show that it is essential to consider wholesuperstructuresof many PEL minima, called metabasins, rather than singleminima. Thisis a consequence of strong correlations within groups of PELminima.Second, we show that D(T) is inversely proportional to theaverageresidence time in these metabasins. Third, the temperaturedependenceof the residence times is related to the depths of themetabasins, asgiven by the surrounding energy barriers. We further discuss that the study of small (but not toosmall) systemsis essential, in that one deals with a less complex energylandscapethan in large systems. In a detailed analysis of differentsystemsizes, we show that the small BMLJ system consideredthroughout thethesis is free of major finite-size-related artifacts.

Vegetables biofortified with iodine: chemical, agronomic and qualitative aspects of raw and fried potatoes

Iodine is an essential microelement for human health because it is a constituent of the thyroid hormones that regulate growth and development of the organism. Iodine Deficiency Disorders (IDDs) are believed to be one of the commonest preventable human health problems in the world today, according to the World Health Organization: that diseases include endemic goiter, cretinism and fetal abnormalities, among others, and they are caused by lack of iodine in the diet, that is the main source of iodine. Since iodine intake from food is not enough respect to human needs, this can be remedied through dietary diversification, mineral supplementation, food fortification, or increasing the concentration and/or bioavailability of mineral elements in the edible portions of crops through agricultural intervention or genetic selection (biofortification). The introduction of iodized salt is a strategy widely used and accepted to eradicate iodine deficiency, because it is an inexpensive source of stable iodine. Since the intake of salt, though iodized, must still be limited according to the risk of cardiovascular disease, so the increase of iodine content in plants for the production of functional foods is representing a field of study of particular interest and a potential market. In Italy potatoes enriched with iodine are produced by a patented procedure of agronomic biofortification for the fresh market since several years, furthermore they are recently accepted and recommended by Italian Thyroid Association, as an alternative source of iodine. Researches performed during the PhD course intended to characterize this innovative vegetables products, focusing the attention on different aspects, such as chemistry, agriculture, and quality of fresh and fried potatoes. For this purpose, lipid fraction of raw material was firstly investigated, in order to assess whether the presence of iodine in plant metabolism can affect fatty acid or sterol biosynthesis, according to the hypothesis that iodine can be bounded to polyunsaturated fatty acids of cell membranes, protecting them from peroxydation; phytosterols of plant sterol are also studied because their importance in reducing serum cholesterol, especially in potato plant sterols are also involved in synthesis of glycoalkaloid, a family of steroidal toxic secondary metabolites present in plants of the Solanaceae family. To achieve this goal chromatographic analytical techniques were employed to identify and quantify fatty acids and sterols profile of common and iodine enriched row potatoes. Another aim of the project was to evaluate the effects of frying on the quality of iodine-enriched and common potatoes. Since iodine-enriched potatoes are nowadays produced only for the fresh market, preliminary trials of cultivation under controlled environment were carried out to verify if potato varieties suitable for processing were able to absorb and accumulate iodine in the tuber. In a successive phase, these varieties were grown in the field, to evaluate their potential productivity and quality at harvest and after storage. The best potato variety to be destined for processing purposes, was finally subjected to repeated frying cycles; the effects of lipid oxidation on the composition and quality of both potatoes and frying oil bath were evaluated by chromatographic and spectrophotometric analytical techniques. Special attention were paid on volatile compounds of fried potatoes.

Development of empirical potentials for amorphous silica

Development of empirical potentials for amorphous silica Amorphous silica (SiO2) is of great importance in geoscience and mineralogy as well as a raw material in glass industry. Its structure is characterized as a disordered continuous network of SiO4 tetrahedra. Many efforts have been undertaken to understand the microscopic properties of silica by classical molecular dynamics (MD) simulations. In this method the interatomic interactions are modeled by an effective potential that does not take explicitely into account the electronic degrees of freedom. In this work, we propose a new methodology to parameterize such a potential for silica using ab initio simulations, namely Car-Parrinello (CP) method [Phys. Rev. Lett. 55, 2471 (1985)]. The new potential proposed is compared to the BKS potential [Phys. Rev. Lett. 64, 1955 (1990)] that is considered as the benchmark potential for silica. First, CP simulations have been performed on a liquid silica sample at 3600 K. The structural features so obtained have been compared to the ones predicted by the classical BKS potential. Regarding the bond lengths the BKS tends to underestimate the Si-O bond whereas the Si-Si bond is overestimated. The inter-tetrahedral angular distribution functions are also not well described by the BKS potential. The corresponding mean value of theSiOSi angle is found to be ≃ 147◦, while the CP yields to aSiOSi angle centered around 135◦. Our aim is to fit a classical Born-Mayer/Coulomb pair potential using ab initio calculations. To this end, we use the force-matching method proposed by Ercolessi and Adams [Europhys. Lett. 26, 583 (1994)]. The CP configurations and their corresponding interatomic forces have been considered for a least square fitting procedure. The classical MD simulations with the resulting potential have lead to a structure that is very different from the CP one. Therefore, a different fitting criterion based on the CP partial pair correlation functions was applied. Using this approach the resulting potential shows a better agreement with the CP data than the BKS ones: pair correlation functions, angular distribution functions, structure factors, density of states and pressure/density were improved. At low temperature, the diffusion coefficients appear to be three times higher than those predicted by the BKS model, however showing a similar temperature dependence. Calculations have also been carried out on crystalline samples in order to check the transferability of the potential. The equilibrium geometry as well as the elastic constants of α-quartz at 0 K are well described by our new potential although the crystalline phases have not been considered for the parameterization. We have developed a new potential for silica which represents an improvement over the pair potentials class proposed so far. Furthermore, the fitting methodology that has been developed in this work can be applied to other network forming systems such as germania as well as mixtures of SiO2 with other oxides (e.g. Al2O3, K2O, Na2O).