Evaluating resin-enamel bonds by microshear and microtensile bond strength tests: effects of composite resin

OBJECTIVES: The aims of this study were to evaluate the effect of resin composite (Filtek Z250 and Filtek Flow Z350) and adhesive system [(Solobond Plus, Futurabond NR (VOCO) and Adper Single Bond (3M ESPE)] on the microtensile (μTBS) and microshear bond strength (μSBS) tests on enamel, and to correlate the bond strength means between them. MATERIAL AND METHODS: Thirty-six extracted human molars were sectioned to obtain two tooth halves: one for μTBS and the other one for μSBS. Adhesive systems and resin composites were applied to the enamel ground surfaces and light-cured. After storage (37(0)C/24 h) specimens were stressed (0.5 mm/min). Fracture modes were analyzed under scanning electron microscopy. The data were analyzed using two-way ANOVA and Tukey's test (α=0.05). RESULTS: The correlation between tests was estimated with Pearson's product-moment correlation statistics (α =0.05). For both tests only the main factor resin composite was statistically significant (p<0.05). The correlation test detected a positive (r=0.91) and significant (p=0.01) correlation between the tests. CONCLUSIONS: The results were more influenced by the resin type than by the adhesives. Both microbond tests seem to be positive and linearly correlated and can therefore lead to similar conclusions.

Mechanistic aspects of the isomerization of Z-vinylic tellurides double bonds in the synthesis of potassium Z-vinyltrifluoroborate salts

Through direct transmetalation reaction of Z-vinylic tellurides with nBuLi was observed the unexpected isomerization of double bonds leading to potassium E-vinyltrifluoroborates salts in low to moderate yields. Using EPR spin trapping experiments the radical species that promoted the stereoinversion of Z-vinylic organometallic species during the preparation of potassium vinyltrifluoroborate salts was identified. The experiments support the proposed mechanism, which is based on the homolytic cleavage of the TenBu bond.

Pricing corporate bonds in Brazil: 2000 to 2004

This paper analyzes the factors that influence the issuing price of debentures in Brazil in the period from year 2000 to 2004, applying a factor model, in which exogenous variables explain return and price behavior. The variables in this study include: rating, choice of index, maturity, country risk, basic interest rate, long-term and short-term rate spread, the stock market index, and the foreign exchange rate. Results indicate that the index variable, probability of default and bond`s maturity influence pricing and points out associations of long-term bonds with better rating issues. (C) 2008 Elsevier Inc. All rights reserved.

An insight into the thermostability of a pair of xylanases: the role of hydrogen bonds

Xylanases are enzymes that are very tolerant to temperature. Their potential use in several biotechnological applications, such as animal food manufacture and pulp bleaching, is due to their intrinsic thermostability. The present report deals with two xylanases, the mesophilic xylanase from Bacillus circulans, BCX, and the thermophilic xylanase from Thermomyces lanuginosus,TLX. These enzymes belong to family 11, and they are the most structurally similar mesophilic-thermophilic pair. Molecular dynamics simulations were employed to investigate the factors responsible for the different thermostabilities exhibited by these structurally similar enzymes. Their active site is their most rigid region, and it is equally rigid at all temperatures. Inter and intramolecular interactions, hydrogen bonds in particular, are the key to the main differences between BCX and TLX. The intramolecular hydrogen bonds and salt bridges are important for maintenance of the backbone rigidity even at high temperature, and the highly solvated surface is a clear optimization in TLX compared with BCX. The main differences between these two enzymes can be found on the fingers domain, which indicates that this domain must be the target for the site-directed mutagenesis responsible for improving the temperature tolerance of this family of enzymes.

Effect of prolonged application times on the durability of resin-dentin bonds

Objectives. To examine the effect of prolonged application time on the early and 3-year resin-dentin microtensile bond strength. Methods. Water/ethanol (Single Bond [SB]) and acetone-based systems (One Step [OS]) were employed. A flat superficial dentin surface was exposed in third human molars by wet abrasion. The adhesives were applied to a delimited area of 52 mm(2) on wet surfaces, for 40, 90, 150 and 300s. Four teeth were assigned for each experimental condition. Composite build-ups were constructed incrementally After water storage at 37 degrees C for 24 h, teeth were sectioned to obtain sticks with cross-sectional areas of 0.8 mm(2) to be tested in tension (0.5 mm/min) either immediately (IM) or after 3 years (3Y) of water storage. The microtensile bond strength (mu TBS) values were analyzed by two way repeated measures ANOVA and Tukey`s test (alpha = 0.05). Results. The 90- and 150-s groups achieved the highest IM mu TBS for OS (p < 0.01). For SB, the highest IM mu TBS values were observed after 300-s application (p < 0.01). Significant decreases in mu TBS were observed for OS in the 40- and 90-s groups after 3Y, except for the 150-s group. With regard to SB, after 3Y significant drops in mu TBS values were observed for the 40- and 150-s groups, except for the 300-s group. Significance. Prolonged application times can increase the immediate LTBS of two-step etch-and-rinse adhesive systems and make the adhesive layer more stable over time. (c) 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Long-term effect of carbodiimide on dentin matrix and resin-dentin bonds

Objectives: To characterize the interaction of 1-Ethyl-3-[3-dimethylaminopropyl] carbodiimide Hydrochloride (EDC) with dentin matrix and its effect on the resin-dentin bond. Methods: Changes to the stiffness of demineralized dentin fragments treated with EDC/N-hydroxysuccinimide (NHS) in different solutions were evaluated at different time points. The resistance against enzymatic degradation was indirectly evaluated by ultimate tensile strength (UTS) test of demineralized dentin treated or not with EDC/NHS and subjected to collagenase digestion. Short- and long-term evaluations of the strength of resin-dentin interfaces treated with EDC/NHS for 1 h were performed using microtensile bond strength (mu TBS) test. All data (MPa) were individually analyzed using ANOVA and Tukey HSD tests (alpha = 0.05). Results: The different exposure times significantly increased the stiffness of dentin (p < 0.0001, control-5.15 and EDC/NHS-29.50), while no differences were observed among the different solutions of EDC/NHS (p = 0.063). Collagenase challenge did not affect the UTS values of EDC/NHS group (6.08) (p > 0.05), while complete degradation was observed for the control group (p = 0.0008, control-20.84 and EDC/NHS-43.15). EDC/NHS treatment did not significantly increase resin-dentin mu TBS, but the values remained stable after 12 months water storage (p < 0.05). Conclusions: Biomimetic use of EDC/NHS to induce exogenous collagen cross-links resulted in increased mechanical properties and stability of dentin matrix and dentin-resin interfaces. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 94B: 250-255, 2010.

One-year stability of resin-dentin bonds created with a hydrophobic ethanol-wet bonding technique

Dentin bonding performed with hydrophobic resins using ethanol-wet bonding should be less susceptible to degradation but this hypothesis has never been validated. Objectives. This in vitro study evaluated stability of resin-dentin bonds created with an experimental three-step BisGMA/TEGDMA hydrophobic adhesive or a three-step hydrophilic adhesive after one year of accelerated aging in artificial saliva. Methods. Flat surfaces in mid-coronal dentin were obtained from 45 sound human molars and randomly divided into three groups (n = 15): an experimental three-step BisGMA/TEGDMA hydrophobic adhesive applied to ethanol (ethanol-wet bonding-GI) or water-saturated dentin (water-wet bonding-GII) and Adper Scotchbond Multi-Purpose [MP-GIII] applied, according to manufacturer instructions, to water-saturated dentin. Resin composite crowns were incrementally formed and light-cured to approximately 5 mm in height. Bonded specimens were stored in artificial saliva at 37 degrees C for 24h and sectioned into sticks. They were subjected to microtensile bond test and TEM analysis immediately and after one year. Data were analyzed with two-way ANOVA and Tukey tests. Results. MP exhibited significant reduction in microtensile bond strength after aging (24 h: 40.6 +/- 2.5(a); one year: 27.5 +/- 3.3(b); in MPa). Hybrid layer degradation was evident in all specimens examined by TEM. The hydrophobic adhesive with ethanol-wet bonding preserved bond strength (24 h: 43.7 +/- 7.4(a); one year: 39.8 +/- 2.7(a)) and hybrid layer integrity, with the latter demonstrating intact collagen fibrils and wide interfibrillar spaces. Significance. Coaxing hydrophobic resins into acid-etched dentin using ethanol-wet bonding preserves resin-dentin bond integrity without the adjunctive use of MMPs inhibitors and warrants further biocompatibility and patient safety`s studies and clinical testing. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Differential bonds degradation of two resin-modified glass-ionomer cements in primary and permanent teeth

Objectives: To evaluate the effect of chemical degradation on bond strength of resin-modified glass-ionomer cements bonded to primary and permanent dentin. Methods: Class I cavities of permanent and primary extracted human molars were restored with two resin-modified glass-ionomer cements: Fuji 11 LC and Vitremer, and stored in water for 24 h. Half samples were immersed in 10% NaOCl aqueous solution for 5 h. Teeth were sectioned into beams and tested for microtensile bond strengths. Results were analyzed with multiple ANOVA and Tukey`s tests (p < 0.05). Analysis of debonded surfaces was performed by SEM. Results: 24 h bond strengths for Vitremer and Fuji 11 LC were similar. For Fuji 11, bond strength values were higher for primary than for permanent dentin. Vitremer bond strength was similar for both. Chemical degradation did not affect Fuji I] LC bond strength to dentin. However, decreases in bond strength were found for Vitremer groups after NaOCl immersion. Signs of glass ionomer-dentin interaction were evident by SEM analysis for Fuji 11 LC specimens. Conclusions: Vitremer and Fuji II presented similar bond strength at 24. Vitremer dentin bonds were prone to chemical degradation. Fuji II LC-dentin bonds showed typical features of glass-ionomer dentin interaction at the bonded interfaces, and were resistant to in vitro degradation. (C) 2009 Elsevier Ltd. All rights reserved.

Resistance to degradation of resin-modified glass-ionomer cements dentine bonds

Objective: To evaluate the effect of EDTA pre-treatment of dentine on resistance to degradation of the bond between dentine and resin-modified glass-ionomer cements. Methods: Sixty non-carious human molars underwent cavity preparations. Teeth were restored with Fuji II LC or Vitremer. Half of the cavities were restored following manufacturers` instructions whereas the other half was pre-treated with EDTA (0.1 M, pH 7.4) for 60 s. Teeth were stored in water at 37 degrees C for 24 h, 3 months or submitted to 10% NaOCl immersion for 5 h. Teeth were sectioned into beams (1 +/- 0.1 mm) and tested to failure in tension at 0.5 mm/min. Bond strength data (MPa) were analyzed by ANOVA and SNK multiple-comparisons tests (p < 0.05). Results: When EDTA was used for pre-treatment of dentine, higher bond strengths were observed for both cements. Degradation challenges produced a decrease in bond strength values only in the Vitremer group. This decrease was avoided when EDTA was used for dentine treatment before restoring with Vitremer. Conclusions: EDTA pre-treatment of dentine increases bond strength of resin modified glass-ionomers cements to dentine and improves resistance to degradation of the bond between Vitremer and dentine. (C) 2009 Elsevier Ltd. All rights reserved.

Role of Halogen Bonds in Thyroid Hormone Receptor Selectivity: Pharmacophore-Based 3D-QSSR Studies

Most physiological effects of thyroid hormones are mediated by the two thyroid hormone receptor subtypes, TR alpha and TR beta. Several pharmacological effects mediated by TR beta might be beneficial in important medical conditions such as obesity, hypercholesterolemia and diabetes, and selective TR beta activation may elicit these effects while maintaining an acceptable safety profile, To understand the molecular determinants of affinity and subtype selectivity of TR ligands, we have successfully employed a ligand- and structure-guided pharmacophore-based approach to obtain the molecular alignment of a large series of thyromimetics. Statistically reliable three-dimensional quantitative structure-activity relationship (3D-QSAR) and three-dimensional quantitative structure-selectivity relationship (3D-QSSR) models were obtained using the comparative molecular field analysis (CoMFA) method, and the visual analyses of the contour maps drew attention to a number of possible opportunities for the development of analogs with improved affinity and selectivity. Furthermore, the 3D-QSSR analysis allowed the identification of a novel and previously unmentioned halogen bond, bringing new insights to the mechanism of activity and selectivity of thyromimetics.

Structural effects and hydrogen bonds on N,N `-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, studied by experimental and theoretical methods

Pure N,N`-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, is quantitatively prepared by the hydrolysis reaction of CH(3)OC(O)SNCO and characterized by (1)H NMR, GC-MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach with data obtained from X-ray diffraction, vibrational spectra and theoretical calculation methods. The IR and Raman spectra for normal and deuterated species are reported. The crystal structure of [CH(3)OC(O)SNH](2)CO was determined by X-ray diffraction methods. The substance crystallizes in the orthorhombic P2(1)2(1)2 space group with a = 9.524(2), b = 12.003(1), c = 4.481 (1) angstrom, and Z = 2 moieties in the unit cell. The molecule is sited on a twofold crystallographic axis (C(2)) parallel to c and shows the anti-anti conformation (S-N single bonds antiperiplanar with respect to the opposite C-N single bonds in sulfenyl-urea-sic group). Neighboring molecules are arranged in a chain motif that extends along the C(2)-axis and is held by bifurcated NH center dot center dot center dot O center dot center dot center dot HN intermolecular bonds. A local planar symmetry is observed in the crystal for the central -SN(H)C(O)N(H)S- skeleton. Experimental and calculated data allow to trace this structural feature to the occurrence of N-H center dot center dot center dot O=C hydrogen bonding interactions. Calculated vibrational and structural properties are in good agreement with the experimentally determined features. (C) 2008 Elsevier B.V. All rights reserved.

Heterodinuclear Fe(III)Zn(II)-Bioinspired Complex Supported on 3-Aminopropyl Silica. Efficient Hydrolysis of Phosphate Diester Bonds

Presented herein is the synthesis and characterization of a new Fe(III)Zn(II) complex containing a Fe(III)-bound phenolate with a carbonyl functional group, which was anchored to 3-aminopropylfunctionalized silica as the solid support. The catalytic efficiency of the immobilized catalyst in the hydrolysis of 2,4-bis (dinitrophenyl) phosphate is comparable to the homogeneous reaction, and the supported catalyst can be reused for subsequent diester hydrolysis reactions.

Investigating the Nature of Noble Gas-Copper Bonds by the Quantum Theory of Atoms in Molecules

We investigated noble gas copper bonds in linear complexes represented by the NgCuX general formula in which Ng and X stand for a noble gas (neon, argon, krypton, or xenon) and a halogen (fluorine, chlorine or bromine), respectively, by coupled cluster methods and modified cc-pVQZ basis sets. The quantum theory of atoms in molecules (QTAIM) shows a linear relation between the dissociation energy or noble gas-copper bonds and the amount of electronic charge transferred mainly from the noble gas to copper during complexation. Large changes in the QTAIM quadrupole moments of copper and noble gases resulting from this bonding and a comparison between NgCuX and NgNaCl systems indicate that these noble gas-copper bonds should be better interpreted as predominantly covalent. Finally, QTAIM atomic dipoles of noble gases in NgNaCl systems agree satisfactorily with atomic dipoles given by a simple model for these NgNa van der Waals bonds.

Effect of therapeutic dose X rays on mechanical and chemical properties of esthetic dental materials

The aim of this study was to investigate the influence of therapeutic dose X rays on the microhardness (MH) and degree of conversion (DC) of two different esthetic restorative dental materials. The materials were photo-activated with a LED light-curing unit using three cure-times: 5, 20 and 40 seconds. The photo-activation was carried out in two distinct periods: before and after irradiation with doses of 5, 35 and 70 Gy, from a 6 MV X rays beam. In accordance with the methodology used, it was conclude that a therapeutic dose does not have a detrimental effect on the photoinitiator molecules, because the photo-activation occurred after they were irradiated. When the irradiation was applied before photo-activation, the materials showed MH improvement, but when photo-activation was performed after irradiation, there was less improvement. However, there was no correlation between MH and DC. Thus, a therapeutic dose applied to cured material can promote linking and breaking of chain bonds in a non-linear way.

Modified silicas covalently bounded to 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrinato iron(III): synthesis, spectroscopic and EPR characterization. Catalytic studies

In this work we have studied cyclooctene epoxidation with PhIO, using a new iron porphyrin, 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrinato iron(III), supported on silica matrices via eletrostatic interaction and / or covalent bonds as catalyst. These catalysts were obtained and immobilized on the solid supports propyltrimethylammonium silica (SiN+); propyltrimethylammonium and propylimidazole silica [SiN+(IPG)] and chloropropylsilica (CPS) via elestrostatic interactions and covalent binding. Characterization of the supported catalysts by UV-Vis spectroscopy and EPR (Electron paramagnetic resonance) indicated the presence of a mixture of FeII and FeIII species in all of the three obtained catalysts. In the case of (Z)-cyclooctene epoxidation by PhIO the yields observed for cis-epoxycyclooctane were satisfactory for the reactions catalyzed by the three materials (ranging from 68% to 85%). Such results indicate that immobilization of metalloporphyrins onto solid supports via groups localized on the ortho positions of their mesophenyl rings can lead to efficient catalysts for epoxidation reactions. The catalyst 1-CPS is less active than 1-SiN and 1-SiN(IPG), this argues in favour of the immobilization of this metalloporphyrin onto solids via electrostatic interactions, which is easier to achieve and results in more active oxidation catalysts. Interestingly, the activity of the supported catalysts remained the same even after three successive recyclings; therefore, they are stable under the oxidizing conditions.