Electronic Structure and Spectro-Structural Correlations of Fe(III)Zn(II) Biomimetics for Purple Acid Phosphatases: Relevance to DNA Cleavage and Cytotoxic Activity

Purple acid phosphatases (PAPs) are a group of metallohydrolases that contain a dinuclear Fe(II)M(II) center (M(II) = Fe, Mn, Zn) in the active site and are able to catalyze the hydrolysis of a variety of phosphoric acid esters. The dinuclear complex [(H(2)O)Fe(III)(mu-OH)Zn(II)(L-H)](CIO(4))(2) (2) with the ligand 2-[N-bis(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N-(2-pyridylmethyl)(2-hydroxybenzyl) aminomethyl]phenol (H(2)L-H) has recently been prepared and is found to closely mimic the coordination environment of the Fe(III)Zn(II) active site found in red kidney bean PAP (Neves et al. J. Am. Chem. Soc. 2007, 129, 7486). The biomimetic shows significant catalytic activity in hydrolytic reactions. By using a variety of structural, spectroscopic, and computational techniques the electronic structure of the Fe(III) center of this biomimetic complex was determined. In the solid state the electronic ground state reflects the rhombically distorted Fe(III)N(2)O(4) octahedron with a dominant tetragonal compression align ad along the mu-OH-Fe-O(phenolate) direction. To probe the role of the Fe-O(phenolate) bond, the phenolate moiety was modified to contain electron-donating or -withdrawing groups (-CH(3), -H, -Br, -NO(2)) in the 5-position. Tie effects of the substituents on the electronic properties of the biomimetic complexes were studied with a range of experimental and computational techniques. This study establishes benchmarks against accurate crystallographic struck ral information using spectroscopic techniques that are not restricted to single crystals. Kinetic studies on the hydrolysis reaction revealed that the phosphodiesterase activity increases in the order -NO(2)<- Br <- H <- CH(3) when 2,4-bis(dinitrophenyl)phosphate (2,4-bdnpp) was used as substrate, and a linear free energy relationship is found when log(k(cat)/k(0)) is plotted against the Hammett parameter a. However, nuclease activity measurements in the cleavage of double stranded DNA showed that the complexes containing the electron-withdrawing -NO(2) and electron-donating CH3 groups are the most active while the cytotoxic activity of the biomimetics on leukemia and lung tumoral cells is highest for complexes with electron-donating groups.

Influence of pulse repetition rate of Er : YAG laser and dentin depth on tensile bond strength of dentin-resin interface

The study evaluated the in vitro influence of pulse-repetition rate of Er:YAG laser and dentin depth on tensile bond strength of dentin-resin interface. Dentin surfaces of buccal or lingual surfaces from human third molars were submitted to tensile test in different depths (superficial, 1.0 and 1.5 mm) of the same dental area, using the same sample. Surface treatments were acid conditioning solely (control) and Er:YAG laser irradiation (80 mJ) followed by acid conditioning, with different pulse-repetition rates (1, 2, 3, or 4 Hz). Single bond/Z-250 system was used. The samples were stored in distilled water at 37 degrees C for 24 h, and then the first test (superficial dentine) was performed. The bond failures were analyzed. Following, the specimens were identified, grounded until 1.0- and 1.5-mm depths, submitted again to the treatments and to the second and, after that, to third-bond tests on a similar procedure and failure analysis. ANOVA and Tukey test demonstrated a significant difference (p < 0.001) for treatment and treatment X depth interaction (p < 0.05). The tested depths did not show influence (p > 0.05) on the bond strength of dentin-resin interface. It may be concluded that Er:YAG laser with 1, 2, 3, or 4 Hz combined with acid conditioning did not increase the resin tensile bond strength to dentin, regardless of dentin depth. (C) 2007 Wiley Periodicals, Inc.

Tensile bond strength of cast commercially pure titanium and cast gold-alloy posts and cores cemented with two luting agents

Statement of problem. In vitro studies on the retentive strengths of various cements used to retain posts have reported conflicting results. Purpose. The purpose of this study was to compare the tensile strength of commercially pure titanium and type III cast gold-alloy posts and cores cemented with zinc phosphate or resin cement. Material and methods. Forty-two extracted human canines were endoclontically treated. The root preparations were accomplished using Largo reamers (10 mm in depth and 1.7 mm in diameter). Acrylic resin patterns for the posts and cores were made, and specimens were cast in commercially pure titanium and in type III gold alloy (n=7). Fourteen titanium cast posts and cores were submitted to surface treatment with Kroll acid solution and to scanning electron microscopy (SEM), before and after acid etching. The groups (n=7) were cemented with zinc phosphate cement or resin cement (Panavia F). Tensile strengths were measured in a universal testing machine at a crosshead speed of 0.5 mm/min. The results (Kgf) were statistically analyzed by 2-way ANCIVA (alpha=.05). Results. The 2-way ANOVA indicated that there were no significant differences among the groups tested. Retentive means for zinc phosphate and Panavia F cements were statistically similar. The bond strength was not Influenced by the alloy, the luting material, or the etching treatment. SEM analysis indicated that the etched surfaces were smoother than those that did not receive surface treatment, but this fact did not influence the results. Conclusions. Commercially pure titanium cast posts and cores cemented with zinc phosphate and resin cements demonstrated similar mean tensile retentive values. Retentive values were also similar to mean values recorded for cast gold-alloy posts and cores cemented with zinc phosphate cement and resin cements.

Effect of blood contamination on the shear bond strength at resin/dentin interface in primary teeth

Purpose: To assess in vitro the shear bond strength at the resin/dentin interface in primary teeth after contamination with fresh human blood. Methods: 75 crowns of primary molars were embedded in acrylic resin and mechanically ground to expose a flat dentin surface. The specimens were randomly assigned to five groups (n=15), according to the surface treatment. Group I (control) had no blood contamination. The other groups were blood-contaminated and subjected to different post-contamination protocols: in Group 2, the surfaces were rinsed with water; in Group 3, the surfaces were air-dried; in Group 4, the surfaces were rinsed and air-dried; and in Group 5, no post-contamination treatment was done. In all groups, a 3-mm dentin bonding site was demarcated, Single Bond adhesive system was applied and resin composite cylinders were bonded. After 24 hours in distilled water, shear bond strength was tested at a crosshead speed of 0.5 mm/minute. Results: Means (in MPa) were: Group 1: 7.1 (+/- 4.2); Group 2: 4.0 (+/- 1.8); Group 3: 0.9 (+/- 0.7); Group 4: 3.9 (+/- 2.2) and Group 5: 1.3 (+/- 1.5). Data were analyzed statistically by the Kruskal-Wallis test at 5% significance level. Groups 2 and 4 were similar to each other (P > 0.05) and both ware similar to Group 1 (P > 0.05). These groups (2, 3 and 4) had statistically significantly higher bond strengths than Groups 3 and 5 (P < 0.05). Blood contamination negatively affected the shear bond strength to primary tooth dentin. Among the blood-contaminated groups, water-rinsed specimens had higher bond strengths than those that were exclusively air-dried or not submitted to any post-contamination protocol before adhesive application.

Shear strength of the bond to primary dentin: influence of Er:YAG laser irradiation distance

The aim of this study was to assess in vitro the influence of Er:YAG laser irradiation distance on the shear strength of the bond between an adhesive restorative system and primary dentin. A total of 60 crowns of primary molars were embedded in acrylic resin and mechanically ground to expose a flat dentin surface and were randomly assigned to six groups (n = 10). The control group was etched with 37% phosphoric acid. The remaining five groups were irradiated (80 mJ, 2 Hz) at different irradiation distances (11, 12, 16, 17 and 20 mm), followed by acid etching. An adhesive agent (Single Bond) was applied to the bonding sites, and resin cylinders (Filtek Z250) were prepared. The shear bond strength tests were performed in a universal testing machine (0.5 mm/min). Data were submitted to statistical analysis using one-way ANOVA and the Kruskal-Wallis test (p < 0.05). The mean shear bond strengths were: 7.32 +/- 3.83, 5.07 +/- 2.62, 6.49 +/- 1.64, 7.71 +/- 0.66, 7.33 +/- 0.02, and 9.65 +/- 2.41 MPa in the control group and the groups irradiated at 11, 12, 16, 17, and 20 mm, respectively. The differences between the bond strengths in groups II and IV and between the bond strengths in groups II and VI were statistically significant (p < 0.05). Increasing the laser irradiation distance resulted in increasing shear strength of the bond to primary dentin.

Bond strength of fibre glass and carbon fibre posts to the root canal walls using different resin cements

The aim of the study was to evaluate the bond strength of fibre glass and carbon fibre posts in the root canal walls cemented with self-adhesive (RelyX-Unicem) and chemical (Cement-Post) resin cements. Forty maxillary canines were divided into four groups according to the cement and post used and submitted to the push-out test (0.5 mm min(-1)). The data were submitted to statistical analysis (2-way ANOVA, Bonferroni - P < 0.05) and fracture analysis by Scanning Electronic Microscopy. Fibre glass presented the best results when cemented with RelyX-Unicem and Cement-Post (P < 0.05). RelyX-Unicem presented the highest bond strength values for both posts (P < 0.05). Fracture analysis showed predominance of cohesive fracture of post for RelyX-Unicem and adhesive fracture between dentin/cement and mixed for Cement-Post. The bond strength values were significantly affected by the type of post and cement used and the highest values were found for fibre glass posts and RelyX-Unicem.

Bond durability in erbium:yttrium-aluminum-garnet laser-irradiated enamel

This study sought to evaluate the influence of thermocycling and water storage on the microtensile bond strength of composite resin bonded to erbium:yttrium-aluminum-garnet (Er:YAG)-irradiated and bur-prepared enamel. Eighty bovine incisors were selected and sectioned. Specimens were ground to produce a flat enamel surface. Samples were randomly assigned according to cavity preparation device: (I) Er:YAG laser and (II) high-speed turbine, and were subsequently restored with composite resin. They were subdivided according to the duration of water storage (WS)/number of thermocycles (TCs): 24 h WS/no TCs; 7 days WS/500 TCs; 1 month WS/2,000 TCs; 6 months WS/12,000 TCs. The teeth were sectioned into 1.0 mm(2)-thick slabs and subjected to tensile stress in a universal testing machine. Data were submitted to two-way analysis of variance (ANOVA) and Tukey`s test at a 0.05 significance level. The different periods of water storage and thermocycling did not influence the microtensile bond strength (A mu TBS) values in the Er:YAG laser-prepared groups. In bur-prepared enamel, the group submitted to 12,000 TCs/6 months` WS (IID) showed a significant decrease in bond strength values when compared to the group stored in water for 24 h and not submitted to thermocycling (IIA), but values were statistically similar to those obtained in all Er:YAG laser groups and in the bur- prepared groups degraded with 500 TCs/1 week WS (IIB) or 2,000 TCs/1 month WS (IIC). It may be concluded that adhesion of an etch-and-rinse adhesive to Er:YAG laser-irradiated enamel was not affected by the methods used to simulate degradation of the adhesive interface and was similar to adhesion in the bur-prepared groups in all periods of water storage and thermocycling.

Influence of water flow rate on shear bond strength of resin composite to Er : YAG cavity preparation

Purpose: To evaluate in vitro the influence of water flow rate on shear bond strength of a resin composite to enamel and dentin after Er:YAG cavity preparation. Methods: Ten bovine incisors were selected and roots removed. Crowns were sectioned in four pieces, resulting in 40 samples that were individually embedded in polyester resin (n=10), and ground to plane the enamel and expose the dentin. The bonding site was delimited and samples were randomly assigned according to cavity preparation: (1) Er:YAG/1.0 mL/minute; (2) Er:YAG/1.5 mL/minute; (3) Er:YAG/2.0 mL/minute and (4) High speed handpiece/bur (control group). Samples were fixed to a metallic device, where composite resin cylinders were prepared. Subsequently, they were stored for 24 hours and subjected to a shear bond strength test (500N at 0.5 mm/minute). Results: Means (MPa) were: enamel: 1: 12.8; 2: 16.8; 3: 17.5; 4: 36.0 and Dentin: 1: 13.6; 2: 18.7; 3: 12.1; 4: 21.3. Data were submitted to ANOVA and Tukey`s test. Adhesion to enamel was more efficient than for dentin. The cavities prepared with conventional bur (control) presented higher statistically significant bond strength values (P<0.05) than for Er:YAG laser for both enamel and dentin. No significant differences were observed between water flow rates employed during enamel ablation. For dentin, the shear bond strength of 2.0 mL/minute water flow rate was lower than for 1.5 mL/minute and 1.0 mL/minute rates. The Er:YAG laser adversely affected shear bond strength of resin composite to both enamel and dentin, regardless of the water flow rate used.

Bond Strength of Fiber Posts in Different Root Thirds Using Resin Cement

Purpose: The aim of the study was to assess the in vitro bond strength (BS) of glass fiber posts (GF) and carbon fiber posts (CF) in the cervical, middle, and apical thirds of root canals cemented with RelyX-Unicem (RX) and Cement-Post (CP). Materials and Methods: Forty maxillary canines were divided into 4 groups (n = 10) according to the cement and post used: group 1: GF and RX; group 2: CF and RX; group 3: GF and CP; group 4: CF and CP. The push-out test was applied in the cervical, middle and apical thirds of each specimen to assess bond strength of the cement/post complex to the root canal wall. The data obtained were submitted to ANOVA (Bonferroni test, p < 0.05), and fracture analysis was done with SEM. Results: The GF posts presented the best results when cemented with RX and with CF (p < 0.05). RX presented the highest BS values for both GF and CF (p < 0.05). For all the groups, BS was higher in the cervical third, followed by the middle and apical thirds. Fracture analysis showed a predominance of cohesive fracture of posts for RX, and a predominance of adhesive fracture between dentin/cement, and mixed failure mode for CP. Conclusion: GF posts cemented with RX presented the highest BS values in all root thirds.

Messenger RNA expression of Pabpnl1 and Mbd3l2 genes in oocytes and cleavage embryos

Objective: To identify genes specifically expressed in mammalian oocytes using an in silico subtraction, and to characterize the mRNA patterns of selected genes in oocytes, embryos, and adult tissues. Design: Comparison between oocyte groups and between early embryo stages. Setting: Laboratories of embryo manipulation and molecular biology from Departamento de Genetica (FMRP) and Departamento de Ciencias Basicas (FZEA) - University of Sao Paulo. Sample(s): Oocytes were collected from slaughtered cows for measurements, in vitro fertilization, and in vitro embryo culture. Somatic tissue, excluding gonad and uterus tissue, was collected from male and female cattle. Main Outcome Measure(s): Messenger RNA levels of poly(A)-binding protein nuclear-like 1 (Pabpnl1) and methyl-CpG-binding domain protein 3-like 2 (Mbd3l2). Result(s): Pabpnl1 mRNA was found to be expressed in oocytes, and Mbd3l2 transcripts were present in embryos. Quantification of Pabpnl1 transcripts showed no difference in levels between good-and bad-quality oocytes before in vitro maturation (IVM) or between good-quality oocytes before and after IVM. However, Pabpnl1 transcripts were not detected in bad-quality oocytes after IVM. Transcripts of the Mbd3l2 gene were found in 4-cell, 8-cell, and morula-stage embryos, with the highest level observed in 8-cell embryos. Conclusion(s): Pabpnl1 gene expression is restricted to oocytes and Mbd3l2 to embryos. Different Pabpnl1 mRNA levels in oocytes of varying viability suggest an important role in fertility involving the oocyte potential for embryo development. (Fertil Steril (R) 2010; 93: 2507-12. (C) 2010 by American Society for Reproductive Medicine.)

Influence of dentin cavity surface finishing on micro-tensile bond strength of adhesives

The current trend toward minimal-invasive dentistry has introduced innovative techniques for cavity preparation. Chemical vapor deposition (CVD) and laser-irradiation technology have been employed as an alternative to the common use of regular burs in high-speed turbines. Objectives. The purpose of this study was to assess the influence of alternative techniques for cavity preparation on the bonding effectiveness of different adhesives to dentin, and to evaluate the morphological characteristics of dentin prepared with those techniques. Methods. One etch&rinse adhesive (OptiBond FL, Kerr) and three self-etch systems (Adper Prompt L-Pop, 3M ESPE; Clearfil SE Bond, Kuraray; Clearfil S3 Bond, Kuraray) were applied on dentin prepared with a regular bur in a turbine, with a CVD bur in a turbine, with a CVD tip in ultrasound and with an ErCr:YSGG laser. The micro-tensile bond strength (mu TBS) was determined after storage in water for 24 h at 37 degrees C, and morphological evaluation was performed by means of field -emission -gun scanning electron microscopy (Feg-SEM). Results. Feg-SEM evaluation revealed different morphological features on the dentin surface after the usage of both the conventional and alternative techniques for cavity preparation, more specifically regarding smear-layer thickness and surface roughness. CVD bur-cut, CVD ultra-sonoabraded and laser-irradiated dentin resulted in lower mu TBSs than conventionally bur-cut dentin, irrespective of the adhesive employed. Significance. The techniques, such as CVD diamond-bur cutting, CVD diamond ultra-sonoabrasion and laser-irradiation, used for cavity preparation may affect the bonding effectiveness of adhesives to dentin, irrespective of their acidity or approach. (C) 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Influence of Er,Cr : YSGG laser treatment on the microtensile bond strength of adhesives to dentin

Purpose: In light of the concept of minimally invasive dentistry, erbium lasers have been considered as an alternative technique to the use of diamond burs for cavity preparation. The purpose of this study was to assess the bonding effectiveness of adhesives to Er,Cr:YSGG laser-irradiated dentin using irradiation settings specific for cavity preparation. Materials and Methods: Fifty-four midcoronal dentin surfaces, obtained from sound human molars, were irradiated with an Er,Cr:YSGG laser or prepared with a diamond bur using a high-speed turbine. One etch-and-rinse (Optibond FL/Kerr) and three self-etching adhesives (Adper Prompt L-Pop/3M ESPE, Clearfil SE Bond/Kuraray, and Clearfil S-3 Bond/Kuraray) were used to bond the composite to dentin. The microtensile bond strength (mu TBS) was determined after 24 h of storage in water at 37 degrees C. The Kruskal-Wallis test was used to determine pairwise statistical differences (p < 0.05). Prepared dentin surfaces, adhesive interfaces, and failure patterns were analyzed using a stereo microscope and Field-emission gun Scanning Electron Microscopy (Feg-SEM). Results: Significantly lower mu TBS was observed to laser-irradiated than to bur-cut dentin (p < 0.05), irrespective of the adhesive employed. Feg-SEM photomicrographs of lased dentin revealed an imbricate patterned substrate and the presence of microcracks at the dentin surface. Conclusion: Morphological alterations produced by Er,Cr:YSGG laser-irradiation adversely influence the bonding effectiveness of adhesives to dentin. Keywords: dentin, adhesion, adhesives, laser, ErCr:YSGG.

Bond Strength of Dental Adhesive Systems Irradiated with Ionizing Radiation

Purpose: The aim of the present paper was to determine the effect of different types of ionizing radiation on the bond strength of three different dentin adhesive systems. Materials and Methods: One hundred twenty specimens of 60 human teeth (protocol number: 032/2007) sectioned mesiodistally were divided into 3 groups according to the adhesives systems used: SB (Adper Single Bond Plus), CB (Clearfil SE Bond) and AP (Adper Prompt Self-Etch). The adhesives were applied on dentin and photo-activated using LED (Lec 1000, MMoptics, 1000 mW/cm(2)). Customized elastomer molds (0.5 mm thickness) with three orifices of 1.2 mm diameter were placed onto the bonding areas and filled with composite resin (Filtek Z-250), which was photo-activated for 20 s. Each group was subdivided into 4 Subgroups for application of the different types of ionizing radiation: ultraviolet radiation (UV), diagnostic x-ray radiation (DX), therapeutic x-ray radiation (TX) and without irradiation (control group, CG). Microshear tests were carried out (Instron, model 4411), and afterwards the modes of failure were evaluated by optical and scanning electron microscope and classified using 5 scores: adhesive failure, mixed failures with 3 significance levels, and cohesive failure. The results of the shear bond strength test were submitted to ANOVA with Tukey`s test and Dunnett`s test, and the data from the failure pattern evaluation were analyzed with the Mann Whitney test (p = 0.05). Results: No change in bond strength of CB and AP was observed after application of the different radiation types, only SB showed increase in bond strength after UV (p = 0.0267) irradiation. The UV also changed the failure patterns of SB (p = 0.0001). Conclusion: The radio-induced changes did not cause degradation of the restorations, which means that they can be exposed to these types of ionizing radiation without weakening the bond strength.

Orthodontic brackets removal under shear and tensile bond strength resistance tests - a comparative test between light sources

We have investigated if a new LEDs system has enough efficient energy to promote efficient shear and tensile bonding strength resistance under standardized tests. LEDs 470 +/- 10 nm can be used to photocure composite during bracket fixation. Advantages considering resistance to tensile and shear bonding strength when these systems were used are necessary to justify their clinical use. Forty eight human extracted premolars teeth and two light sources were selected, one halogen lamp and a LEDs system. Brackets for premolar were bonded through composite resin. Samples were submitted to standardized tests. A comparison between used sources under shear bonding strength test, obtained similar results; however, tensile bonding test showed distinct results: a statistical difference at a level of 1% between exposure times (40 and 60 seconds) and even to an interaction between light source and exposure time. The best result was obtained with halogen lamp use by 60 seconds, even during re-bonding; however LEDs system can be used for bonding and re-bonding brackets if power density could be increased.

N-H...S=C hydrogen bond in O-alkyl N-methoxycarbonyl thiocarbamates, ROC(S)N(H)C(O)O)CH(3) (R = CH(3)(-), CH(3)CH(2)-)

Pure O-methyl N-methoxycarbonyl thiocarbamate CH(3)OC(S)N(H)C(O)OCH(3) (I) and O-ethyl N-methoxycarbonyl thiocarbamate, CH(3)CH(2)OC(S)N(H)C(O)OCH(3) (II), are quantitatively prepared by the addition reaction between the CH(3)OC(O)NCS and the corresponding alcohols. The compounds are characterized by multinuclear ((1)H and (13)C) and bi-dimensional ((13)C HSQC) NMR, GC-MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach involving crystallographic data, vibration spectra and theoretical calculations. The low-temperature (150 K) crystal structure of II was determined by X-ray diffraction methods. The substance crystallizes in the monoclinic space group P2(1)/n with a = 4.088(1)angstrom. b = 22.346(1)angstrom, c = 8.284(1)angstrom, beta = 100.687(3)degrees and Z = 4 molecules per unit cell. The conformation adopted by the thiocarbamate group -OC(S)N(H)- is syn (C=S double bond in synperiplanar orientation with respect to the N-H single bond), while the methoxycarbonyl C=O double bond is in antiperiplanar orientation with respect to the N-H bond. The non-H atoms in II are essentially coplanar and the molecules are arranged in the crystal lattice as centro-symmetric dimeric units held by N-H center dot center dot center dot S=C hydrogen bonds Id(N center dot center dot center dot S) = 3.387(1)angstrom, <(N-H center dot center dot center dot S) = 166.4(2)degrees]. Furthermore, the effect of the it electronic resonance in the structural and vibrational properties is also discussed. (C) 2009 Elsevier Ltd. All rights reserved.