Exploring new molecular species on the (1)[H, Se, F] singlet potential energy surface: Energetics, structures, IR spectra, and heats of formation

Structural, energetic, and vibrational properties of new molecular species, HSeF and HFSe, the associated transition state, and dissociation fragments are investigated using a state-of-the-art theoretical approach, CCSD(T)/CBS. HSeF is a normal covalently bonded molecule 38.98 kcal mol (1) more stable than the complex HF-Se, which shows an unusual structure with a central fluorine atom and a bond angle of 101.8 degrees.A barrier (Delta G(#)) of 49.01 kcal mol (1) separates the two species. Vibrational frequencies are also quite distinct. Heats of formation are evaluated for the diatomic fragments and HSeF. Final Delta(f)H values depend on the experimental accuracy of those of Se(g) and H(2)Se. (c) 2009 Elsevier B.V. All rights reserved.

In vitro morphogenesis and cell suspension culture establishment in Piper solmsianum C. DC. (Piperaceae)

In vitro morphogenesis and cell suspension culture establishment in Piper solmsianum C. DC. (Piperaceae)). Piper solmsianum is a shrub from Southeast Brazil in which many biologically active compounds were identified. The aim of this work was to establish a cell suspension culture system for this species. With this in mind, petiole and leaf explants obtained from in vitro plantlets were cultured in the presence of different plant growth regulator combinations (IAA, NAA, 2,4-D and BA). Root and indirect shoot adventitious formation, detected by histological analysis, was observed. Besides the different combinations of plant growth regulators, light regime and the supplement of activated charcoal (1.5 mg.l(-1)) were tested for callus induction and growth. Cultures maintained in light, on a 0.2 mg.l(-1) 2,4-D and 2 mg.l(-1) BA supplemented medium, and in the absence of activated charcoal, showed the highest calli fresh matter increment. From a callus culture, cell suspension cultures were established and their growth and metabolite accumulation studied. The achieved results may be useful for further characterization of the activated secondary metabolites pathways in in vitro systems of P. solmsianum.

PtSnCe/C electrocatalysts for ethanol oxidation: DEFC and FTIR ""in-situ"" studies

The ethanol oxidation reaction (EOR) was investigated using PtSnCe/C electrocatalysts in different mass ratios (72:23:5, 68:22:10 and 64:21:15) that were prepared by the polymeric precursor method. Transmission electron microscopy (TEM) showed that the particles ranged in size from approximately 2 to 5 nm. Changes in the net parameters observed for Pt suggest the incorporation of Sn and Ce into the Pt crystalline network with the formation of an alloy between Pt, Sn and/or Ce. Among the PtSnCe catalysts investigated, the 68:22:10 composition showed the highest activity toward ethanol oxidation, and the current time curves obtained in the presence of ethanol in acidic media showed a current density 50% higher than that observed for commercial PtSn/C (E-Tek). During the experiments performed on single direct ethanol fuel cells, the power density for the PtSnCe/C 68:22:10 anode was nearly 40% higher than the one obtained using the commercial catalyst. Data from Fourier transform infrared (FTIR) spectroscopy showed that the observed behavior for ethanol oxidation may be explained in terms of a double mechanism. The presence of Sn and Ce seems to favor CO oxidation, since they produce an oxygen-containing species to oxidize acetaldehyde to acetic acid. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Pt monolayer electrocatalysts for O-2 reduction: PdCo/C substrate-induced activity in alkaline media

We measured the activity of electrocatalysts, comprising Pt monolayers deposited on PdCo/C substrates with several Pd/Co atomic ratios, in the oxygen reduction reaction in alkaline solutions. The PdCo/C substrates have a core-shell structure wherein the Pd atoms are segregated at the particle`s surface. The electrochemical measurements were carried out using an ultrathin film rotating disk-ring electrode. Electrocatalytic activity for the O-2 reduction evaluated from the Tafel plots or mass activities was higher for Pt monolayers on PdCo/C compared to Pt/C for all atomic Pd/Co ratios we used. We ascribed the enhanced activity of these Pt monolayers to a lowering of the bond strength of oxygenated intermediates on Pt atoms facilitated by changes in the 5d-band reactivity of Pt. Density functional theory calculations also revealed a decline in the strength of PtOH adsorption due to electronic interaction between the Pt and Pd atoms. We demonstrated that very active O-2 reduction electrocatalysts can be devised containing only a monolayer Pt and a very small amount of Pd alloyed with Co in the substrate.

Ethanol oxidation reactions using SnO(2)@Pt/C as an electrocatalyst

This paper presents a study on the ethanol oxidation reaction using SnO(2)@Pt/C core-shell structures as electrocatalysts. All the materials used, including Pt/C and PtSn/C E-tek, were 20% (w/w) metal on carbon. The formation of core-shell nanoparticles (SnO(2)@Pt/C) was measured by UV-vis spectrophotometry. X-ray diffraction measurements showed Pt (shell) diffraction patterns without influence from the SnO(2) core and without any shift in 2 theta values for Pt. The diameters of the core-shell particle structures, measured using high-resolution transmission electron microscopy images, were in the range of 3-16 nm. The electrochemical profile for SnO(2)@Pt/C in an acidic medium (H(2)SO(4) at a concentration of 0.5 mol L(-1)) was almost the same as the typical electrochemical behavior for Pt in an acidic medium. Furthermore, the onset potential for the ethanol oxidation reaction using SnO(2)@Pt/C was almost the same as that for PtSn/C E-tek (0.23 V versus the reversible hydrogen electrode). However, the mass current peak densities for ethanol oxidation were 50% higher on SnO(2)@Pt/C than on PtSn/C E-tek. In the polarization curve, the mass current density for ethanol oxidation was higher at all potentials for SnO(2)@Pt/C when compared to Pt/C and PtSn/C E-tek. At 0.5 V, the current mass density for ethanol oxidation on SnO(2)@Pt was 2.3 times of that for the same process on the commercial material. The electrocatalytic activity of SnO(2)@Pt/C for ethanol oxidation was associated with an increase in the electrochemically active surface area. However, an electronic effect should also be considered because the Pt shell changes its electronic structure in the presence of the foreign core. (C) 2010 Elsevier B.V. All rights reserved.

Effect of cement type and water storage time on the push-out bond strength of a glass fiber post

This study investigated the effects of the cement type and the water storage time on the push-out bond strength of a glass fiber post. Glass fiber posts (Fibrekor, Jeneric Pentron) were luted to post spaces using a self-cured resin cement (C&B Cement [CB]), a glass ionomer cement (Ketac Cem [KC]) or a resin-modified glass ionomer cement (GC FujiCEM [FC]) according to the manufacturers’ instructions. For each luting agent, the specimens were exposed to one of the following water storage times (n=5): 1 day (T1), 7 days (T7), 90 days (T90) and 180 days (T180). Push-out tests were performed after the storage times. Control specimens were not exposed to water storage, but subjected to the push-out test 10 min after post cementation. Data (in MPa) were analyzed by Kruskal-Wallis and Dunn`s test (α=0.05). Cement type and water storage time had a significant effect (p<0.05) on the push-out bond strength. CB showed significantly higher values of retention (p<0.05) than KC and FC, irrespective of the water storage time. Water storage increased significantly the push-out bond strength in T7 and T90, regardless of the cement type (p<0.05). The results showed that fiber posts luted to post spaces with the self-cured resin cement exhibited the best bonding performance throughout the 180-day water storage period. All cements exhibited a tendency to increase the bond strength after 7 and 90 days of water storage, decreasing thereafter.

Influence of different adhesive systems on the pull-out bond strength of glass fiber posts

This in vitro study evaluated the tensile bond strength of glass fiber posts (Reforpost - Angelus-Brazil) cemented to root dentin with a resin cement (RelyX ARC - 3M/ESPE) associated with two different adhesive systems (Adper Single Bond - 3M/ESPE and Adper Scotchbond Multi Purpose (MP) Plus - 3M/ESPE), using the pull-out test. Twenty single-rooted human teeth with standardized root canals were randomly assigned to 2 groups (n=10): G1- etching with 37% phosphoric acid gel (3M/ESPE) + Adper Single Bond + #1 post (Reforpost - Angelus) + four #1 accessory posts (Reforpin - Angelus) + resin cement; G2- etching with 37% phosphoric acid gel + Adper Scotchbond MP Plus + #1 post + four #1 accessory posts + resin cement. The specimens were stored in distilled water at 37°C for 7 days and submitted to the pull-out test in a universal testing machine (EMIC) at a crosshead speed of 0.5 mm/min. The mean values of bond strength (kgf) and standard deviation were: G1- 29.163 ± 7.123; G2- 37.752 ±13.054. Statistical analysis (Student's t-test; a=0.05 showed no statistically significant difference (p<0.05) between the groups. Adhesive bonding failures between resin cement and root canal dentin surface were observed in both groups, with non-polymerized resin cement in the apical portion of the post space when Single Bond was used (G1). The type of adhesive system employed on the fiber post cementation did not influence the pull-out bond strength.

Effect of deproteinization and tubular occlusion on microtensile bond strength and marginal microleakage of resin composite restorations

Dentin adhesion procedure presents limitations, especially regarding to lifetime stability of formed hybrid layer. Alternative procedures have been studied in order to improve adhesion to dentin. OBJECTIVE: The aim of this study was to evaluate in vitro the influence of deproteinization or dentin tubular occlusion, as well as the combination of both techniques, on microtensile bond strength (µTBS) and marginal microleakage of composite resin restorations. MATERIAL AND METHODS: Extracted erupted human third molars were randomly divided into 4 groups. Dentin surfaces were treated with one of the following procedures: (A) 35% phosphoric acid gel (PA) + adhesive system (AS); (B) PA + 10% NaOCl + AS; (C) PA + oxalate + AS and (D) PA + oxalate + 10% NaOCl + AS. Bond strength data were analyzed statistically by two-way ANOVA and Tukey's test. The microleakage scores were analyzed using Kruskal-Wallis and Mann-Whitney non-parametric tests. Significance level was set at 0.05 for all analyses. RESULTS: µTBS data presented statistically lower values for groups D and B, ranking data as A>C>B>D. The use of oxalic acid resulted in microleakage reduction along the tooth/restoration interface, being significant when used alone. On the other hand, the use of 10% NaOCl alone or in combination with oxalic acid, resulted in increased microleakage. CONCLUSIONS: Dentin deproteinization with 10% NaOCl or in combination with oxalate significantly compromised both the adhesive bond strength and the microleakage at interface. Tubular occlusion prior to adhesive system application seems to be a useful technique to reduce marginal microleakage.

Bonding agent underneath sealant: shear bond strength to oil-contaminated

This study evaluated in vitro the shear bond strength of a resin-based pit-and-fissure sealant (Fluroshield - F) associated with either an ethanol-based (Adper Single Bond 2 - SB) or an acetone-based (Prime & Bond - PB) adhesive system under conditions of oil contamination. Mesial and distal enamel surfaces from 30 sound third molars were randomly assigned to 2 groups (n=30): I - no oil contamination; II - oil contamination. Contamination (0.25 mL during 10 s) was performed after 37% phosphoric acid etching with an air/oil spray. The specimens were randomly assigned to subgroups, according to the bonding protocol adopted: subgroup A - F was applied to enamel without an intermediate bonding agent layer; In subgroups B and C, SB and PB, respectively, were applied, light-cured, and then F was applied and light-cured. Shear bond strength was tested at a crosshead speed of 0.5 mm/min in a universal testing machine. Means (± SD) in MPa were: IA-11.28 (±1.84); IIA-12.02 (±1.15); IB-9.73 (±2.38); IIB-9.62 (±2.29); IC-28.30 (±1.63); and IIC-25.50 (±1.91). It may be concluded that the oil contamination affected negatively the sealant bonding to enamel and the acetone-based adhesive system (PB) layer applied underneath the sealant was able to prevent its deleterious effects to adhesion.

Effect of laser welding on the titanium composite tensile bond strength

The aim of this study was to analyze the shear bond strength between commercially pure titanium, with and without laser welding, after airbone-particle abrasion (Al2O3) and 2 indirect composites. Sixty-four specimens were cast and divided into 2 groups with and without laser welding. Each group was divided in 4 subgroups, related to Al2O3 grain size: A - 250 µm; B - 180 µm; C- 110 µm; and D - 50 µm. Composite rings were formed around the rods and light polymerized using UniXS unit. Specimens were invested and their shear bond strength at failure was measured with a universal testing machine at a crosshead speed of 2.0 mm/min. Statistical analysis was carried out with ANOVA and Tukey's test (α=0.05). The highest bond strength means were recorded in 250 µm group without laser welding. The lowest shear bond strength means were recorded in 50 µm group with laser welding. Statistically significant differences (p<0.05) were found between all groups. In conclusion, airborne particle abrasion yielded significantly lower bond strength as the Al2O3 particle size decreased. Shear bond strength decreased in the laser welded specimens.

Influence of specimens' design and manufacturing process on microtensile bond strength to enamel: laboratory and FEA comparison

This study evaluated the effect of specimens' design and manufacturing process on microtensile bond strength, internal stress distributions (Finite Element Analysis - FEA) and specimens' integrity by means of Scanning Electron Microscopy (SEM) and Laser Scanning Confocal Microscopy (LCM). Excite was applied to flat enamel surface and a resin composite build-ups were made incrementally with 1-mm increments of Tetric Ceram. Teeth were cut using a diamond disc or a diamond wire, obtaining 0.8 mm² stick-shaped specimens, or were shaped with a Micro Specimen Former, obtaining dumbbell-shaped specimens (n = 10). Samples were randomly selected for SEM and LCM analysis. Remaining samples underwent microtensile test, and results were analyzed with ANOVA and Tukey test. FEA dumbbell-shaped model resulted in a more homogeneous stress distribution. Nonetheless, they failed under lower bond strengths (21.83 ± 5.44 MPa)c than stick-shaped specimens (sectioned with wire: 42.93 ± 4.77 MPaª; sectioned with disc: 36.62 ± 3.63 MPa b), due to geometric irregularities related to manufacturing process, as noted in microscopic analyzes. It could be concluded that stick-shaped, nontrimmed specimens, sectioned with diamond wire, are preferred for enamel specimens as they can be prepared in a less destructive, easier, and more precise way.

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.

Effect of chlorhexidine concentration on the bond strength to dentin in primary teeth

PURPOSE: To evaluate the effect of the use of 0.5% and 2% chlorhexidine digluconate on the immediate bond strength of a conventional adhesive system to dentin in primary teeth. METHODS: Twenty-one healthy primary molars were divided into three groups (n=7), being one control (A) and two experimental groups (B and C). After dentin exposure, in Group (A) the adhesive procedure was performed using 37% phosphoric acid gel (15 s); dentin was washed (15 s), air dried (30 s) and rehydrated with water. Groups B and C followed similar procedures but for re-hydration with 0.5% and 2% chlorhexidine, respectively, for 30 s. A resin composite block was built simulating a restoration, and the teeth were stored in distilled water at 37°C for 24 h before the microtensile bond strength test. The bond strength data were analyzed by analysis of variance. RESULTS: No statistically significant difference in bond strength was found among the tested groups (P>0.05) CONCLUSION: The 0.5% and 2% concentrations of chlorhexidine presented similar behavior and caused no adverse effects on the bond strength to dentin in primary teeth.

Estabilidade oxidativa e microbiológica em carne de galinha mecanicamente separada e adicionada de antioxidantes durante período de armazenamento a -18 °C

Com o objetivo de acompanhar a estabilidade físico-química e microbiológica da carne mecanicamente separada (CMS) de diferentes origens e estocada durante 99 dias a -18 °C, foi realizada prévia mistura de conservante (nitrito de sódio) e antioxidante (eritorbato de sódio) em CMS obtida de duas linhagens de aves: galinhas matrizes de corte e galinhas poedeiras comerciais brancas. Na CMS de cada linhagem foram realizados três diferentes tratamentos: 1) controle (sem aditivos); 2) adição de 150 ppm de nitrito; e 3) adição de 150 ppm de nitrito e 500 ppm de eritorbato. Os resultados encontrados demonstraram que a adição de nitrito isoladamente não impediu a oxidação lipídica, avaliada através do índice de TBARS, nem a alteração na cor, avaliada em colorímetro. Por outro lado, a adição de nitrito juntamente com eritorbato foi efetiva na redução dos problemas de oxidação lipídica na CMS de galinhas matrizes, e em menor grau, na CMS de poedeiras. A adição de nitrito e eritorbato na CMS também melhorou a preservação da cor vermelha desejável (a*) ao longo do tempo. A avaliação da estabilidade microbiológica da CMS, realizada no primeiro e último dia de estocagem congelada, para microrganismos mesófilos, Escherichia coli, Staphylococcus aureus, Clostridium perfringens e Pseudomonas spp., e quinzenalmente para microrganismos psicrotróficos, indicou que não houve uma variação significativa nas contagens em função do tratamento utilizado (diferentes aditivos adicionados). Não foi detectada Salmonella spp. em nenhuma das amostras analisadas. Em função da melhoria da estabilidade oxidativa, recomenda-se a adição de nitrito (150 ppm) e eritorbato (500 ppm) em CMS de galinhas matrizes a ser estocada congelada por um período prolongado.

Vitaminas D e C para poedeiras na fase inicial de produção de ovos

Um experimento foi conduzido com o objetivo de avaliar os efeitos de duas fontes de vitamina D e três níveis de vitamina C sobre as características de desempenho, a qualidade interna e externa dos ovos, os níveis de cálcio total e iônico séricos e a resistência óssea de poedeiras. Foram utilizadas 288 galinhas da linhagem ISA Babcock B300® com 23 semanas de idade, durante um período experimental de 12 semanas. Utilizou-se o delineamento inteiramente ao acaso em arranjo fatorial 2 × 3, com os fatores: fontes de vitamina D (colecalciferol e 25-hidroxicolecalciferol - 25(OH)D3) e de vitamina C (0, 100 e 200 ppm), totalizando seis tratamentos com oito repetições de seis aves. O nível basal de colecalciferol foi de 2.756 UI/kg, correspondendo a 5,51 g do produto comercial Hy.D®/t de ração, como fonte de 25(OH)D3. Os fatores estudados não influenciaram o consumo de ração, a produção, o peso e a massa de ovos. Observou-se efeito da interação de fontes de vitamina sobre a conversão alimentar, que foi melhor quando utilizado metabólito 25(OH)D3 na ausência de vitamina C. Interações foram observadas para porcentagem de albúmen e porcentagem de gema, que aumentaram na presença de 200 ppm de vitamina C. O peso específico dos ovos, as concentrações de cálcio sérico, cinzas ósseas e a resistência à quebra não foram influenciadas pelas fontes de vitamina D e C. Houve interação para porcentagem e espessura de casca, cujos maiores valores foram obtidos com a suplementação de vitamina C na presença de 25(OH)D3. Em poedeiras na fase inicial de produção, a conversão alimentar é melhor com a utilização do 25(OH)D3 e a espessura e porcentagem de casca também melhoram com a utilização de 25(OH)D3 e a suplementação de vitamina C nas dietas (100 ou 200 ppm, respectivamente).