Push-out bond strength of CAD/CAM-ceramic luted to dentin with self-adhesive resin cements

OBJECTIVES: This study evaluated the initial and the artificially aged push-out bond strength between ceramic and dentin produced by one of five resin cements. METHODS: Two-hundred direct ceramic restorations (IPS Empress CAD) were luted to standardized Class I cavities in extracted human molars using one of four self-adhesive cements (SpeedCEM, RelyX Unicem Aplicap, SmartCem2 and iCEM) or a reference etch-and-rinse resin cement (Syntac/Variolink II) (n=40/cement). Push-out bond strength (PBS) was measured (1) after 24h water storage (non-aged group; n=20/cement) or (2) after artificial ageing with 5000 thermal cycles followed by 6 months humid storage (aged group; n=20/cement). Nonparametrical ANOVA and pairwise Wilcoxon rank-sum tests with Bonferroni-Holm adjustment were applied for statistical analysis. The significance level was set at alpha=0.05. In addition, failure mode and fracture pattern were analyzed by stereomicroscope and scanning electron microscopy. RESULTS: Whereas no statistically significant effect of storage condition was found (p=0.441), there was a significant effect of resin cement (p<0.0001): RelyX Unicem showed significantly higher PBS than the other cements. Syntac/Variolink II showed significantly higher PBS than SmartCEM2 (p<0.001). No significant differences were found between SpeedCEM, SmartCem2, and iCEM. The predominant failure mode was adhesive failure of cements at the dentin interface except for RelyX Unicem which in most cases showed cohesive failure in ceramic. SIGNIFICANCE: The resin cements showed marked differences in push-out bond strength when used for luting ceramic restorations to dentin. Variolink II with the etch-and-rinse adhesive Syntac did not perform better than three of the four self-adhesive resin cements tested.

Further Quantum Mechanical Evidence that Difluorotoluene does not Hydrogen Bond

Calculations were run on the methylated DNA base pairs adenine:thymine and adenine:difluorotoluene to further investigate the hydrogen-bonding properties of difluorotoluene (F). Geometries were optimized using hybrid density functional theory. Single-point calculations at the MP2(full) level were performed to obtain more rigorous energies. The functional counterpoise method was used to correct for the basis set superposition error (BSSE), and the interaction energies were also corrected for fragment relaxation. These corrections brought the B3LYP and MP2 interaction energies into excellent agreement. In the gas phase, the Gibbs free energies calculated at the B3LYP and MP2 levels of theory predict that A and T will spontaneously form an A:T pair while A:F spontaneously dissociates into A and F. Solvation effects on the pairing of the bases were explored using implicit solvent models for water and chloroform. In aqueous solution, both A:T and A:F are predicted to dissociate into their component monomers. Semiempirical calculations were performed on small sections of B-form DNA containing the two pairs, and the results provide support for the concept that base stacking is more important than hydrogen bonding for the stability of the A:F pair within a DNA helix.

An engineered disulfide bond reversibly traps the IgE-Fc3-4 in a closed, nonreceptor binding conformation

IgE antibodies interact with the high affinity IgE Fc receptor, FcεRI, and activate inflammatory pathways associated with the allergic response. The IgE-Fc region, comprising the C-terminal domains of the IgE heavy chain, binds FcεRI and can adopt different conformations ranging from a closed form incompatible with receptor binding to an open, receptor-bound state. A number of intermediate states are also observed in different IgE-Fc crystal forms. To further explore this apparent IgE-Fc conformational flexibility and to potentially trap a closed, inactive state, we generated a series of disulfide bond mutants. Here we describe the structure and biochemical properties of an IgE-Fc mutant that is trapped in the closed, non-receptor binding state via an engineered disulfide at residue 335 (Cys-335). Reduction of the disulfide at Cys-335 restores the ability of IgE-Fc to bind to its high affinity receptor, FcεRIα. The structure of the Cys-335 mutant shows that its conformation is within the range of previously observed, closed form IgE-Fc structures and that it retains the hydrophobic pocket found in the hinge region of the closed conformation. Locking the IgE-Fc into the closed state with the Cys-335 mutation does not affect binding of two other IgE-Fc ligands, omalizumab and DARPin E2_79, demonstrating selective blocking of the high affinity receptor binding.

Microwave-Assisted Bond Forming Reactions

ABSTRACT FOR PART I: PHOSPHA-MICHAEL ADDITIONS TO ACTIVATED INTERNAL ALKENES: STERIC AND ELECTRONIC EFFECTS A method for the phospha-Michael addition of bis(4-methyl)phenyl phosphine oxide to activated internal alkenes has been developed. Michael acceptors including cinnamates, crotonates, chalcones, and internal alkenes containing multiple activating groups were all successfully utilized in this reaction. The reaction was fairly tolerant of electron-donating and electron-withdrawing substituents on the Michael acceptor, and moderate to excellent yields (49-96%) of the adducts were isolated. When steric bulk was increased by a second substituent on the -position of the Michael-acceptor the reaction was suppressed. This was usually overcome by adding a second activating substituent to the -position. ABSTRACT FOR PART II: MICROWAVE-ASSISTED ARYLGOLD BOND FORMATION A microwave-assisted method was developed for the formation of arylgold complexes containing (2-Biphenyl)di-tert-butylphosphine (JohnPhos) as the supporting phosphine ligand. Arylboronic acids with increasingly bulky aromatic groups were screened to determine the steric limitations of the reaction. Arylgold complexes (JohnPhos)Au(p-methoxyphenyl), (JohnPhos)Au(2,4,6-trimethylphenyl), and (JohnPhos)Au(4-bromo-10-anthracene) were all synthesized by microwave irradiation at 70ºC in the presence of Cs2CO3 in either THF or iPrOH. Reactions performed with arylboronic acids containing unhindered ortho positions were carried out in THF. Arylboronic acids with substituents on the ortho position required iPrOH as the reaction solvent. Arylboronic acids with extreme steric hindrance on the ortho position of the aryl substituent, 2,4,6-triisopropylpphenylboronic acid, were unreactive. It was determined that increasing the irradiation temperature increased the formation of side products, therefore to promote conversion to the arylgold complex the duration of the reaction time was increased while maintaining a temperature of 70ºC. Arylgold complexes (JohnPhos)Au(p-methoxyphenyl), (JohnPhos)Au(2,4,6-trimethylphenyl), and (JohnPhos)Au(4-bromo-10-anthracene) were synthesized with moderate yields (40-69%).

Peroxide bond-dependent antiplasmodial specificity of artemisinin and OZ277 (RBx11160)

Using nonperoxidic analogs of artemisinin and OZ277 (RBx11160), the strong in vitro antiplasmodial activities of the latter two compounds were shown to be peroxide bond dependent. In contrast, the weak activities of artemisinin and OZ277 against six other protozoan parasites were peroxide bond independent. These data support the iron-dependent artemisinin alkylation hypothesis.

Shear bond strength of resin cements to human dentin

OBJECTIVES: The objectives of this in vitro study were (1) to assess the bond strength of the universal cement RelyX Unicem to dentin and to compare it with three conventional resin cements, (2) to test the influence of aging on their bonding capacity and (3) to test the influence of the operator on bonding quality by performing the same test in two different centers. METHODS: 160 third molars, divided into 80 for tests at the University of Zurich (Z) and 80 for tests at the University of Berne (B), were assigned to 2 x 8 subgroups of 10 teeth each. The specimens were prepared with the corresponding bonding agents and acrylic rods were luted either with RelyX Unicem (U), RelyX ARC (A), Multilink (M) or Panavia 21 (P). All specimens were stored in water for 24h (W) and half of the specimens were subjected to 1500 cycles of thermocycling (5 degrees C and 55 degrees C) (T). Bond strength was measured by means of a shear test. RESULTS: After water storage RelyX Unicem exhibited lowest bond strength (UWZ: 9.2+/-1.6 MPa, UWB: 9.9+/-1.2 MPa, AWZ: 15.3+/-6.0 MPa, AWB: 12.2+/-4.3 MPa, MWZ: 15.6+/-3.3 MPa, MWB: 12.4 MPa+/-2.4, PWZ: 13.4+/-2.9 MPa, PWB: 14.9+/-2.6 MPa). Thermocycling affected the bonding performance of all four cements. However, bond strength of RelyX Unicem was least influenced by thermocycling (UTZ: 9.4+/-2.9 MPa, UTB: 8.6+/-1.3 MPa, ATZ: 11.4+/-6.3 MPa, ATB: 13.3+/-3.7 MPa, MTZ: 15.4+/-3.1 MPa, MTB: 10.3+/-2.4 MPa, PTZ: 11.1+/-2.8 MPa, PTB: 11.3+/-2.8 MPa). SIGNIFICANCE: Although the bond strength of RelyX Unicem to dentin was lower in comparison to RelyX ARC, Multilink and Panavia 21, its bond strength was less sensitive to variations in handling and aging.

Compatibility of ultra high performance concrete as repair material : bond characterization with concrete under different loading scenarios

The rehabilitation of concrete structures, especially concrete bridge decks, is a major challenge for transportation agencies in the United States. Often, the most appropriate strategy to preserve or rehabilitate these structures is to provide some form of a protective coating or barrier. These surface treatments have typically been some form of polymer, asphalt, or low-permeability concrete, but the application of UHPC has shown promise for this application mainly due to its negligible permeability, but also as a result of its excellent mechanical properties, self-consolidating nature, rapid gain strength, and minimal creep and shrinkage characteristics. However, for widespread acceptance, durability and performance of the composite system must be fully understood, specifically the bond between UHPC and NSC often used in bridge decks. It is essential that the bond offers enough strength to resist the stress due to mechanical loading or thermal effects, while also maintaining an extended service-life performance. This report attempts to assess the bond strength between UHPC and NSC under different loading configurations. Different variables, such as roughness degree of the concrete substrates, age of bond, exposure to freeze-thaw cycles and wetting conditions of the concrete substrate, were included in this study. The combination of splitting tensile test with 0, 300, 600 and 900 freeze-thaw cycles was carried out to assess the bond performance under severe ambient conditions. The slant-shear test was utilized with different interface angles to provide a wide understanding of the bond performance under different combinations of compression and shear stresses. The pull-off test is the most accepted method to evaluate the bond strength in the field. This test which studies the direct tensile strength of the bond, the most severe loading condition, was used to provide data that can be correlated with the other tests that only can be used in the laboratory. The experimental program showed that the bond performance between UHPC and NSC is successful, as the strength regardless the different degree of roughness of the concrete substrate, the age of the composite specimens, the exposure to freeze-thaw cycles and the different loading configurations, is greater than that of concrete substrate and largely satisfies with ACI 546.3R-06.