Stability of clavulanic acid under variable pH, ionic strength and temperature conditions. A new kinetic approach

Clavulanic acid (CA) is a beta-lactam antibiotic that alone exhibits only weak antibacterial activity, but is a potent inhibitor of beta-lactamases enzymes. For this reason it is used as a therapeutic in conjunction with penicillins and cephalosporins. However, it is a well-known fact that it is unstable not only during its production phase, but also during downstream processing. Therefore, the main objective of this study was the evaluation of CA long-term stability under different conditions of pH and temperature, in the presence of variable levels of different salts, so as to suggest the best conditions to perform its simultaneous production and recovery by two-phase polymer/salt liquid-liquid extractive fermentation. To this purpose, the CA stability was investigated at different values of pH (4.0-8.0) and temperature (20-45 degrees C), and the best conditions were met at a pH 6.0-7.2 and 20 degrees C. Its stability was also investigated at 30 degrees C in the presence of NaCl, Na(2)SO(4), CaCl(2) and MgSO(4) at concentrations of 0.1 and 0.5 M in Mcllvaine buffer (pH 6.5). All salts led to increased CA instability with respect to the buffer alone, and this effect decreased in following sequence: Na(2)SO(4) > MgSO(4) > CaCl(2) > NaCl. Kinetic and thermodynamic parameters of CA degradation were calculated adopting a new model that took into consideration the equilibrium between the active and a reversibly inactivated form of CA after long-time degradation. (C) 2009 Elsevier B.V. All rights reserved.

Effect of Test Environment and Microstructure on the Flexural Strength of Dental Porcelains

Purpose: The objective of this study was to verify the influence of test environment on the flexural strength of dental porcelains with distinct microstructures. Material and Methods: Disk-shaped specimens from three dental porcelains with distinct leucite content (VM: zero; CE: 12; NS: 22 vol%) were manufactured and tested for biaxial flexural strength in air and immersed in artificial saliva. The results were analyzed by means of two-way ANOVA and Tukey`s test (alpha = 0.05). Results: The flexural strength (MPa) obtained for ambient air and artificial saliva environments, respectively, were: 110.0 +/- 16.0 and 81.5 +/- 10.8 for VM; 51.9 +/- 4.0 and 42.0 +/- 4.7 for CE; 72.0 +/- 11.5 and 63.6 +/- 5.8 for NS. A numerical decrease in the mean flexural strength was observed for all groups when specimens were tested under artificial saliva; however, the difference was only statistically significant for VM. Conclusions: The results indicate that the effect of water immersion on the flexural strength of dental porcelains varies according to their leucite content, as only the material without leucite in its microstructure (VM) showed significant strength degradation when tested under water.

Degradation of the resin-dentin bonds after simulated and inhibited cariogenic challenge in an in situ model

The aim of this study was to evaluate the resindentin bonds of two simplified etch-and-rinse adhesive after simulated cariogenic and inhibited cariogenic challenge in situ. Dental cavities (4 mm wide, 4 mm long, and 1.5 mm deep) were prepared in 60 bovine teeth with enamel margins. Restorations were bonded with either adhesive Adper Single Bond 2 (3MESPE) or Optibond Solo Plus (Kerr). Forty restorations were included in an intra-oral palatal appliance that was used for 10 adult volunteers while the remaining 20 dental blocks were not submitted to any cariogenic challenge [NC group] and tested immediately. For the simulated cariogenic challenge [C+DA], each volunteer dropped 20% sucrose solution onto all blocks four times a day during 14 days and distilled water twice a day. In the inhibited cariogenic challenge group [C + FA], the same procedure was done, but slurry of fluoride dentifrice (1.100 ppm) was applied instead of water. The restored bovine blocks were sectioned to obtain a slice for cross-sectional Vickers microhardness evaluation and resindentin bonded sticks (0.8 mm2) for resindentin microtensile evaluation. Data were evaluated by two-way ANOVA and Tukey's tests (a = 0.05). Statistically lower microhardness values and degradation of the resindentin bonds were only found in the C + DW group for both adhesives. The in situ model seems to be a suitable short-term methodology to investigate the degradation of the resindentin bonds under a more realistic condition. (c) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 100B: 14661471, 2012.

Influence of pH on slow crack growth of dental porcelains

Objectives. To evaluate the effect of pH of storage medium on slow crack growth (SCG) parameters of dental porcelains. Methods. Two porcelains were selected: with (UD) and without (VM7) leucite particles, in order to assess if the microstructure would affect the response of the material to the pH variation. Disc specimens were produced following manufacturers` instructions. Specimens were stored in artificial saliva in pHs 3.5, 7.0 or 10.0 for 10 days and after that the fatigue parameters (n: SCG susceptibility coefficient and sigma(0): scaling parameter) were obtained by the dynamic fatigue test using the same pH of storage. Microstructural analysis of the materials was also performed. Results. For VM7, the values of n obtained in the different pHs were similar and varied from 29.9 to 31.2. The sigma(0) value obtained in pH 7.0 for VM7 was higher than that obtained in the other pHs, which were similar. For porcelain UD, n values obtained in pHs 7.0 and 10.0 were similar (40.8 and 39.6, respectively), and higher than that obtained in pH 3.5 (26.5). With respect to sigma(0), the value obtained for porcelain UD in pH 10.0 was lower than those obtained in pHs 3.5 and 7.0, which were similar. Significance. The effect of pH on the stress corrosion susceptibility (n) depended on the porcelain studied. While the n value of VM7 was not affected by the pH, UD presented lower n value in acid pH. For both porcelains, storage in acid or basic pH resulted in strength degradation. (C) 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Monolithic CAD/CAM Lithium Disilicate Versus Veneered Y-TZP Crowns: Comparison of Failure Modes and Reliability After Fatigue

Purpose: The aim of this research was to evaluate the fatigue behavior and reliability of monolithic computer-aided design/computer-assisted manufacture (CAD/CAM) lithium disilicate and hand-layer-veneered zirconia all-ceramic crowns. Materials and Methods: A CAD-based mandibular molar crown preparation, fabricated using rapid prototyping, served as the master die. Fully anatomically shaped monolithic lithium disilicate crowns (IPS e.max CAD, n = 19) and hand-layer-veneered zirconia-based crowns (IPS e.max ZirCAD/Ceram, n = 21) were designed and milled using a CAD/CAM system. Crowns were cemented on aged dentinlike composite dies with resin cement. Crowns were exposed to mouth-motion fatigue by sliding a WC-indenter (r = 3.18 mm) 0.7 mm lingually down the distobuccal cusp using three different step-stress profiles until failure occurred. Failure was designated as a large chip or fracture through the crown. If no failures occurred at high loads (> 900 N), the test method was changed to staircase r ratio fatigue. Stress level probability curves and reliability were calculated. Results: Hand-layer-veneered zirconia crowns revealed veneer chipping and had a reliability of < 0.01 (0.03 to 0.00, two-sided 90% confidence bounds) for a mission of 100,000 cycles and a 200-N load. None of the fully anatomically shaped CAD/CAM-fabricated monolithic lithium disilicate crowns failed during step-stress mouth-motion fatigue (180,000 cycles, 900 N). CAD/CAM lithium disilicate crowns also survived r ratio fatigue (1,000,000 cycles, 100 to 1,000 N). There appears to be a threshold for damage/bulk fracture for the lithium disilicate ceramic in the range of 1,100 to 1,200 N. Conclusion: Based on present fatigue findings, the application of CAD/CAM lithium disilicate ceramic in a monolithic/fully anatomical configuration resulted in fatigue-resistant crowns, whereas hand-layer-veneered zirconia crowns revealed a high susceptibility to mouth-motion cyclic loading with early veneer failures. Int J Prosthodont 2010; 23: 434-442.

Robustness of corroded reinforced concrete structures. A structural performance approach

Structure and Infrastructure Engineering, 1-17

Chemical and Morphological Features of Dental Composite Resin: Influence of Light Curing Units and Immersion Media

Aims: The study evaluated the influence of light curing units and immersion media on superficial morphology and chemistry of the nanofilled composite resin Supreme XT (3M) through the EDX analysis and SEM evaluation. Light curing units with different power densities and mode of application used were XL 3000 (480 mW/cm(2)), Jet Lite 4000 Plus (1230mW/cm(2)), and Ultralume Led 5 (790 mW/cm(2)) and immersion media were artificial saliva, Coke(R), tea and coffee, totaling 12 experimental groups. Specimens (10 mm X 2 mm) were immersed in each respective Solution for 5 min, three times a day, during 60 days and stored in artificial saliva at 37 degrees C +/- 1 degrees C between immersion periods. Topography and chemical analysis was qualitative. Findings: Groups immersed in artificial saliva, showed homogeneous degradation of matrix and deposition of calcium at the material surface. Regarding coffee, there was a reasonable chemical degradation with loss of load particles and deposition of ions. For tea, superficial degradation occurred in specific areas with deposition of calcium, carbon. potassium and phosphorus. For Coke(R), excessive matrix degradation and loss of load particles with deposition of calcium, sodium, and potassium. Conclusion: Light curing units did not influence the superficial morphology of composite resin tested, but the immersion beverages did. Coke(R) affected material`s surface more than did the other tested drinks. Microsc. Res. Tech. 73:176-181, 2010. (c) 2009 Wiley-Liss Inc.

Discussion of "Simplified Model of Low Cycle Fatigue for RC Frames"

To model strength degradation due to low cycle fatigue, at least three different approaches can be considered. One possibility is based on the formulation of a new free energy function and damage energy release rate, as was proposed by Ju(1989). The second approach uses the notion of bounding surface introduced in cyclic plasticity by Dafalias and Popov (1975). From this concept, some models have been proposed to quantify damage in concrete or RC (Suaris et al. 1990). The model proposed by the author to include fatigue effects is based essentially in Marigo (1985) and can be included in this approach.

Implications of high power losses in IR femtosecond laser inscribed fibre Bragg gratings

We report on high power issues related to the reliability of fibre Bragg gratings inscribed with an infrared femtosecond laser using the point-by-point writing method. Conventionally, fibre Bragg gratings have usually been written in fibres using ultraviolet light, either holographically or using a phase mask. Since the coating is highly absorbing in the UV, this process normally requires that the protective polymer coating is stripped prior to inscription, with the fibre then being recoated. This results in a time consuming fabrication process that, unless great care is taken, can lead to fibre strength degradation, due to the presence of surface damage. The recent development of FBG inscription using NIR femtosecond lasers has eliminated the requirement for the stripping of the coating. At the same time the ability to write gratings point-by-point offers the potential for great flexibility in the grating design. There is, however, a requirement for reliability testing of these gratings, particularly for use in telecommunications systems where high powers are increasingly being used in long-haul transmission systems making use of Raman amplification. We report on a study of such gratings which has revealed the presence of broad spectrum power losses. When high powers are used, even at wavelengths far removed from the Bragg condition, these losses produce an increase in the fibre temperature due to absorption in the coating. We have monitored this temperature rise using the wavelength shift in the grating itself. At power levels of a few watts, various temperature increases were experienced ranging from a few degrees up to the point where the buffer completely melts off the fibre at the grating site. Further investigations are currently under way to study the optical loss mechanisms in order to optimise the inscription mechanism and minimise such losses.

Time-dependency of Rocks and Implications Associated with Tunnelling

The formulation of a geotechnical model and the associated prediction of the mechanical behaviour is a challenge engineers need to overcome in order to optimize tunnel design and meet project requirements. Special challenges arise in cases where rocks and rockmasses are susceptible to time-effects and time-dependent processes govern. Progressive rockmass deformation and instability, time-dependent overloading of support and delayed failures are commonly the result of time-dependent phenomena. The research work presented in this thesis serves as an attempt to provide more insight into the time-dependent behaviour of rocks. Emphasis is given on investigating and analyzing creep deformation and time-dependent stress relaxation phenomenon at the laboratory scale and in-depth analyses are presented. This thesis further develops the understanding of these phenomena and practical yet scientific tools for estimating and predicting the long-term strength and the maximum stress relaxation of rock materials are proposed. The identification of the existence of three distinct behavioural stages during stress relaxation is presented and discussed. The main observations associated with time-dependent behaviour are employed in numerical analyses and applied at the tunnel scale. A new approach for simulating and capturing the time-dependent behaviour coupled with the tunnel advancement effect is also developed and analyzed. Guidance is provided to increase the understanding of the support-rockmass interaction and the main implications and significance of time-dependent behaviour associated with rock tunnelling are discussed. The work presented in this thesis advances the scientific understanding of time-dependent rock and rockmass behaviour, increases the awareness of how such phenomena are captured numerically, and lays out a framework for dealing with such deformations when predicting tunnel deformations. Practical aspects of this thesis are also presented, which will increase their usage in the associated industries and close the gap between the scientific and industry communities.

Towards a performance based design of shear walls based on damage criteria = Vers un dimensionnement performanciel des murs de refend basé sur des critères d'endommagement

Le dimensionnement basé sur la performance (DBP), dans une approche déterministe, caractérise les objectifs de performance par rapport aux niveaux de performance souhaités. Les objectifs de performance sont alors associés à l'état d'endommagement et au niveau de risque sismique établis. Malgré cette approche rationnelle, son application est encore difficile. De ce fait, des outils fiables pour la capture de l'évolution, de la distribution et de la quantification de l'endommagement sont nécessaires. De plus, tous les phénomènes liés à la non-linéarité (matériaux et déformations) doivent également être pris en considération. Ainsi, cette recherche montre comment la mécanique de l'endommagement pourrait contribuer à résoudre cette problématique avec une adaptation de la théorie du champ de compression modifiée et d'autres théories complémentaires. La formulation proposée adaptée pour des charges monotones, cycliques et de type pushover permet de considérer les effets non linéaires liés au cisaillement couplé avec les mécanismes de flexion et de charge axiale. Cette formulation est spécialement appliquée à l'analyse non linéaire des éléments structuraux en béton soumis aux effets de cisaillement non égligeables. Cette nouvelle approche mise en œuvre dans EfiCoS (programme d'éléments finis basé sur la mécanique de l'endommagement), y compris les critères de modélisation, sont également présentés ici. Des calibrations de cette nouvelle approche en comparant les prédictions avec des données expérimentales ont été réalisées pour les murs de refend en béton armé ainsi que pour des poutres et des piliers de pont où les effets de cisaillement doivent être pris en considération. Cette nouvelle version améliorée du logiciel EFiCoS a démontrée être capable d'évaluer avec précision les paramètres associés à la performance globale tels que les déplacements, la résistance du système, les effets liés à la réponse cyclique et la quantification, l'évolution et la distribution de l'endommagement. Des résultats remarquables ont également été obtenus en référence à la détection appropriée des états limites d'ingénierie tels que la fissuration, les déformations unitaires, l'éclatement de l'enrobage, l'écrasement du noyau, la plastification locale des barres d'armature et la dégradation du système, entre autres. Comme un outil pratique d'application du DBP, des relations entre les indices d'endommagement prédits et les niveaux de performance ont été obtenus et exprimés sous forme de graphiques et de tableaux. Ces graphiques ont été développés en fonction du déplacement relatif et de la ductilité de déplacement. Un tableau particulier a été développé pour relier les états limites d'ingénierie, l'endommagement, le déplacement relatif et les niveaux de performance traditionnels. Les résultats ont démontré une excellente correspondance avec les données expérimentales, faisant de la formulation proposée et de la nouvelle version d'EfiCoS des outils puissants pour l'application de la méthodologie du DBP, dans une approche déterministe.

Inhibition of proteasomal degradation by the Gly-Ala repeat of Epstein–Barr virus is influenced by the length of the repeat and the strength of the degradation signal

The Gly-Ala repeat (GAr) of the Epstein–Barr virus nuclear antigen-1 is a transferable element that inhibits in cis ubiquitin/proteasome-dependent proteolysis. We have investigated this inhibitory activity by using green fluorescent protein-based reporters that have been targeted for proteolysis by N end rule or ubiquitin-fusion degradation signals, resulting in various degrees of destabilization. Degradation of the green fluorescent protein substrates was inhibited on insertion of a 25-aa GAr, but strongly destabilized reporters were protected only partially. Protection could be enhanced by increasing the length of the repeat. However, reporters containing the Ub-R and ubiquitin-fusion degradation signals were degraded even in the presence of a 239-aa GAr. In accordance, insertion of a powerful degradation signal relieved the blockade of proteasomal degradation in Epstein–Barr virus nuclear antigen-1. Our findings suggest that the turnover of natural substrates may be finely tuned by GAr-like sequences that counteract targeting signals for proteasomal destruction.

Microtensile Bond Strength Of Methacrylate And Silorane Resins To Enamel And Dentin.

The aim of this study was to evaluate the microtensile bond strength (µTBS) of two substrates (enamel and dentin) considering two study factors: type of composite resin [methacrylate-based (Filtek Supreme) or silorane-based (Filtek LS)] and aging time (24 h or 3 months). Twenty human molars were selected and divided into 2 groups (n=10) considering two dental substrates, enamel or dentin. The enamel and dentin of each tooth was divided into two halves separated by a glass plate. Each tooth was restored using both tested composite resins following the manufacturer's instructions. The samples were sectioned, producing 4 sticks for each composite resin. Half of them were tested after 24 h and half after 3 months. µTBS testing was carried out at 0.05 mm/s. Data were analyzed by three-way ANOVA and Tukey's HSD tests at α=0.05. Significant differences between composite resins and substrates were found (p<0.05), but no statistically significant difference was found for aging time and interactions among study factors. The methacrylate-based resin showed higher µTBS than the silorane-based resin. The µTBS for enamel was significantly higher than for dentin, irrespective of the composite resin and storage time. Three months of storage was not sufficient time to cause degradation of the bonding interaction of either of the composite resins to enamel and dentin.

Dentin Bond Strength Of A Fluoride-releasing Adhesive System Submitted To Ph-cycling.

To evaluate the microtensile bond strength (µTBS) of a fluoride-containing adhesive system submitted to a pH-cycling and storage time regimen for primary outcomes. As secondary outcomes the fluoride released amount was evaluated. Twelve dentin surfaces from sound third molar were divided into 2 groups according to adhesive systems: Clearfil SE Protect (PB) and Clearfil SE Bond (SE). Sticks obtained (1.0 mm2) from teeth were randomly divided into 3 subgroups according to storage regimen model: immediate (24h); 5-month deionized water (W); and pH-cycling model (C). All sticks were tested for µTBS in a universal testing machine. Fluoride concentration was obtained from 1-4 days and 30-day in W and 1-4 days in demineralization (DE)/remineralization (RE) solutions from C, using a fluoride-specific electrode. µTBS and fluoride released data were, respectively, submitted to ANOVA in a split plot design and Tukey, and Friedman' tests (a=0.05). There was no significant interaction between adhesive system and storage regimen for µTBS. W showed the lowest µTBS values. There was no significant difference between 24 h and C models for µTBS. There was no significant difference between adhesive systems. Failure mode was predominantly cohesive within composite for the 24 h and W, for the C group it was mixed for SE and cohesive within composite for PB adhesive system. Fluoride concentrations in the DE/RE solutions were less than 0.03125 ppm and not detected in W. In conclusion, the fluoride-containing adhesive system performed similarly to the regular one. Hydrolytic degradation is the main problem with both adhesive systems, regardless of fluoride contents.

Theoretical and experimental study of the thermal degradation of Eucalyptus timber

Thermal action on timber causes it to degrade through combustion of its chemical components, which leads to the release of vapors, combustible gases and surface char. This diminishes its load capacity, due to the reduction of its cross section by charring and to changes in its mechanical properties of strength and stiffness as a function of its exposure to high temperatures. This paper reports the charring rates observed on Eucalyptus structural beams and presents a numerical and experimental study of the behavior of these beams when exposed to fire, in which the properties of strength and stiffness were evaluated as a function of rising temperatures, allowing an analysis of the effect of the section factor on the internal rise in temperature of structural Eucalyptus beams.