Raman investigation of structural photoinduced irreversible changes of Ga10Ge25S65 chalcogenide glasses

The influence of time exposure, when exposed to above band gap light (3,52 eV) and annealing, on Ga10Ge25S65 glasses has been studied through their effects on the structure and optical properties. To evaluate the photostructural change infrared and Raman spectra for bulk Ga10Ge25S65 glasses have been measured before and after exposure. The Raman spectra are interpreted in terms of models in which the Ge atoms are fourfold coordinated and the S atoms are two fold coordinated. The observed changes in the spectral region of (S-S) stretching vibration (470-490 cm (-1)) is a direct evidence for the occurrence of important structural changes in local bonding configuration caused by optical irradiation. It is shown that the dominant photostrucural changes are chain formation tendency of the chalcogenide atoms under the laser irradiation rather than rings.

Influence of the bonding substrate in dental composite polymerization stress testing

Our objective was to compare the polymerization stress (sigma(pol)) of a series of composites obtained using poly(methyl methacrylate) (PMMA) or glass as bonding substrates, and to compare the results with those from in vitro microleakage of composite restorations. The tested hypothesis was that stress values obtained in a less rigid testing system (i.e. using PMMA) would show a better relationship with microleakage data. Five dental composites were tested: Filtek Z250 (FZ), Z100 (Z1), Concept (CO), Durafill (DU) and Heliomolar (HM). sigma(pol) was determined in 1 mm high specimens inserted between two rods (empty set = 5 mm) of either PMMA or glass. The composite elastic modulus (E) was obtained by three-point bending. sigma(pol) and E data were submitted to a one-way analysis of variance/Tukey test (alpha = 0.05). For the microleakage test (MI), bovine incisors received cylindrical cavities (empty set = 5 mm, h = 2 mm), which were restored in bulk. After storage for 24 h in water, specimens were subjected to dye penetration using AgNO(3) as tracer. Specimens were sectioned twice, perpendicularly, and microleakage was measured (in millimeters) under 20x magnification. Data from MI were submitted to the Kruskal-Wallis test. Means (SD) of sigma(pol) (MPa) using glass/PMMA were FZ: 7.5(1.8)(A)/2.5(0.2)(bc); Z1: 7.3(0.5)(A)/2.8(0.3)(ab); CO: 6.8(1.1)(A)/3.2(0.5)(a); DU: 4.5(0.7)(B)/2.0(0.2)(bc); HM: 3.5(0.2)(B)/2.3(0.3)(c). sigma(pol) obtained using PMMA rods were 34-67% lower than with glass. Means (SD) for tooth average/tooth maximum microleakage were FZ: 0.92(0.19)(B)/1.53(0.30)(a); Z1: 1.19(0.21)(A)/1.75(0.20)(a); CO: 1.26(0.25)(A)/1.78(0.24)(a); DU: 0.83(0.30)(B)/1.68(0.46)(a): HM: 0.81(0.27)(B)/1.64(0.54)(a). The tested hypothesis was confirmed, as the composites showed the same ordering both in the polymerization stress test using PMMA rods and in the microleakage test. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Pi*-pi* bonding interactions generated by halogen oxidation of zirconium(IV) redox-active ligand complexes.

The new complex, [Zr(pda)2]n (1, pda2- = N,N'-bis(neo-pentyl)-ortho-phenylenediamide, n = 1 or 2), prepared by the reaction of 2 equiv of pdaLi2 with ZrCl4, reacts rapidly with halogen oxidants to afford the new product ZrX2(disq)2 (3, X = Cl, Br, I; disq- = N,N'-bis(neo-pentyl)-ortho-diiminosemiquinonate) in which each redox-active ligand has been oxidized by one electron. The oxidation products 3a-c have been structurally characterized and display an unusual parallel stacked arrangement of the disq- ligands in the solid state, with a separation of approximately 3 A. Density functional calculations show a bonding-type interaction between the SOMOs of the disq- ligands to form a unique HOMO while the antibonding linear combination forms a unique LUMO. This orbital configuration leads to a closed-shell-singlet ground-state electron configuration (S = 0). Temperature-dependent magnetism measurements indicate a low-lying triplet excited state at approximately 750 cm-1. In solution, 3a-c show strong disq--based absorption bands that are invariant across the halide series. Taken together these spectroscopic measurements provide experimental values for the one- and two-electron energies that characterize the pi-stacked bonding interaction between the two disq- ligands.

Evidence for two different bonding mechanisms of Al on Si(111)

By means of the ab initio cluster-model approach, we present theoretical evidence for two different mechanisms of bonding of atomic Al to Si(111). On the atop site (T1) the interaction of atomic Al to Si(111) is characteristic of an ionic bond whereas interaction above the threefold eclipsed site (T4) leads to the formation of a typical covalent bond. Moreover, both sites have a similar interaction energy if electronic correlation effects are included. While the conclusions regarding the nature of the chemisorption bond in the two sites do not depend either on the cluster-model size, the kind of embedding hydrogen atoms used, or the quality of the wave function (Hartree-Fock or configuration interaction), the chemisorption energy depends strongly on the wave function used. In fact, inclusion of correlation energy is necessary to properly describe the interaction energies.

Electronic Structure and Chemical Bonding in the Ground and Low-Lying Electronic States of Ta(2)

The electronic structure and chemical bonding of the ground and low-lying Lambda - S and Omega states of Ta(2) were investigated at the multiconfiguration second-order perturbation theory (CASSCF//CASPT2) level. The ground state of Ta(2) is computed to be a X(3)Sigma(-)(g) state (R(e) = 2.120 angstrom, omega(e) = 323 cm(-1), and D(e) = 4.65 eV), with two low-lying singlet states close to it (a(1) Sigma(+)(g) : T(e) = 409 cm(-1), R(e) = 2.131 angstrom, and omega(e) = 313 cm(-1); b(1) Gamma(g): T(e) = 1, 038 cm(-1), R(e) = 2.127 angstrom, and omega(e) = 316 cm(-1)). These electronic states are derived from the same electronic configuration: vertical bar 13 sigma(2)(g)14 sigma(2)(g)7 delta(2)(g)13 pi(4)(u)>. The effective bond order of the X(3) Sigma(-)(g) state is 4.52, which indicates that the Ta atoms are bound by a quintuple chemical bond. The a(1) Sigma(+)(g) state interacts strongly with the X(3)Sigma(-)(g) g ground state by a second-order spin-orbit interaction, giving rise to the (1)0(g)(+) (ground state) (dominated by the X(3)Sigma(-)(g) Lambda - S ground state) and (9)0(g)(+) (dominated by the a(1) Sigma(+)(g) Lambda - S state) Omega states. These results are in line with those reported for the group 5B homonuclear transition metal diatomics. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1306-1315, 2011

Inhibitory Effects Of A Cured Antibacterial Bonding System On Viability And Metabolic Activity Of Oral Bacteria.

To evaluate the antimicrobial efficacy of Clearfil SE Protect (CP) and Clearfil SE Bond (CB) after curing and rinsed against five individual oral microorganisms as well as a mixture of bacterial culture prepared from the selected test organisms. Bacterial suspensions were prepared from single species of Streptococcus mutans, Streptococcus sobrinus, Streptococcus gordonii, Actinomyces viscosus and Lactobacillus lactis, as well as mixed bacterial suspensions from these organisms. Dentin bonding system discs (6 mm×2 mm) were prepared, cured, washed and placed on the bacterial suspension of single species or multispecies bacteria for 15, 30 and 60 min. MTT, Live/Dead bacterial viability (antibacterial effect), and XTT (metabolic activity) assays were used to test the two dentin system's antibacterial effect. All assays were done in triplicates and each experiment repeated at least three times. Data were submitted to ANOVA and Scheffe's f-test (5%). Greater than 40% bacteria killing was seen within 15 min, and the killing progressed with increasing time of incubation with CP discs. However, a longer (60 min) period of incubation was required by CP to achieve similar antimicrobial effect against mixed bacterial suspension. CB had no significant effect on the viability or metabolic activity of the test microorganisms when compared to the control bacterial culture. CP was significantly effective in reducing the viability and metabolic activity of the test organisms. The results demonstrated the antimicrobial efficacy of CP both on single and multispecies bacterial culture. CP may be beneficial in reducing bacterial infections in cavity preparations in clinical dentistry.

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.

Shear bond strength of self-etch and total-etch bonding systems at different dentin depths

The purpose of this study was to evaluate the dentin shear bond strength of four adhesive systems (Adper Single Bond 2, Adper Prompt L-Pop, Magic Bond DE and Self Etch Bond) in regards to buccal and lingual surfaces and dentin depth. Forty extracted third molars had roots removed and crowns bisected in the mesiodistal direction. The buccal and lingual surfaces were fixed in a PVC/acrylic resin ring and were divided into buccal and lingual groups assigned to each selected adhesive. The same specimens prepared for the evaluation of superficial dentin shear resistance were used to evaluate the different depths of dentin. The specimens were identified and abraded at depths of 0.5, 1.0, 1.5 and 2.0 mm. Each depth was evaluated by ISO TR 11405 using an EMIC-2000 machine regulated at 0.5 mm/min with a 200 Kgf load cell. We performed statistical analyses on the results (ANOVA, Tukey and Scheffé tests). Data revealed statistical differences (p < 0.01) in the adhesive and depth variation as well as adhesive/depth interactions. The Adper Single Bond 2 demonstrated the highest mean values of shear bond strength. The Prompt L-Pop product, a self-etching adhesive, revealed higher mean values compared with Magic Bond DE and Self Etch Bond adhesives, a total and self-etching adhesive respectively. It may be concluded that the shear bond strength of dentin is dependent on material (adhesive system), substrate depth and adhesive/depth interaction.

Comparative study of chemical and mechanical retentive systems for bonding of indirect composite resin to commercially pure titanium

This study evaluated the effect of chemical and mechanical surface treatments for cast metal alloys on the bond strength of an indirect composite resin (Artglass) to commercially pure titanium (cpTi). Thirty cylindrical metal rods (3 mm diameter x 60 mm long) were cast in grade-1 cpTi and randomly assigned to 6 groups (n=5) according to the received surface treatment: sandblasting; chemical treatment; mechanical treatment - 0.4 mm beads; mechanical treatment - 0.6 mm beads; chemical/mechanical treatment - 0.4 mm; and chemical/mechanical treatment - 0.6 mm beads. Artglass rings (6.0 mm diameter x 2.0 mm thick) were light cured around the cpTi rods, according manufacturer's specifications. The specimens were invested in hard gypsum and their bond strength (in MPa) to the rods was measured at fracture with a universal testing machine at a crosshead speed of 2.0 mm/min and 500 kgf load cell. Data were analyzed statistically by one-way ANOVA and Tukey test (a=5%). The surface treatments differed significantly from each other (p<0.05) regarding the recorded bond strengths. Chemical retention and sandblasting showed statistically similar results to each other (p=0.139) and both had significantly lower bond strengths (p<0.05) than the other treatments. In conclusion, mechanical retention, either associated or not to chemical treatment, provided higher bond strength of the indirect composite resin to cpTi.

Morphological analysis of glass, carbon and glass/carbon fiber posts and bonding to self or dual-cured resin luting agents

OBJECTIVE: The aim of this study was to evaluate the morphology of glass (GF), carbon (CF) and glass/carbon (G/CF) fiber posts and their bond strength to self or dual-cured resin luting agents. MATERIAL AND METHODS: Morphological analysis of each post type was conducted under scanning electron microscopy (SEM). Bond strength was evaluated by microtensile test after bisecting the posts and re-bonding the two halves with the luting agents. Data were subjected to two-way ANOVA and Tukey's test (α=0.05). Failure modes were evaluated under optical microscopy and SEM. RESULTS: GF presented wider fibers and higher amount of matrix than CF, and G/CF presented carbon fibers surrounded by glass fibers, and both involved by matrix. For CF and GF, the dual-cured material presented significantly higher (p<0.05) bond strength than the self-cured agent. For the dual agent, CF presented similar bond strength to GF (p>0.05), but higher than that of G/CF (p<0.05). For the self-cured agent, no significant differences (p>0.05) were detected, irrespective of the post type. For GF and G/CF, all failures were considered mixed, while a predominance of adhesive failures was detected for CF. CONCLUSION: The bonding between fiber posts and luting agents was affected by the type of fibers and polymerization mode of the cement. When no surface treatment of the post is performed, the bonding between glass fiber post and dual-cured agent seems to be more reliable.

Hydrogen bonding in 2-(2-oxothiazolidin-3-yl)-4,5-dihydrothiazolium hydrogen sulfate monohydrate

The asymmetric unit of the title compound, C(6)H(9)N(2)OS(2)(+)center dot-HSO(4)(-)center dot H(2)O, contains a heterocyclic cation, a hydrogen sulfate anion and a water molecule. There are strong hydrogen bonds between the hydrogen sulfate anions and water molecules, forming an infinite chain along the [010] direction, from which the cations are pendent. The steric, electronic and geometric features are compared with those of similar compounds. In this way, structural relationships are stated in terms of the influence of the sulfate group on the protonation of the heterocycle and on the tautomeric equilibrium in the solid state.

Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M(13). First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first- principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M(13) structures. Several new lower energy configurations were identified, e. g., Pd(13), W(13), Pt(13), etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au(13), we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.

Regional scale analysis of landform configuration with base-level (isobase) maps

Base-level maps (or ""isobase maps"", as originally defined by Filosofov, 1960), express a relationship between valley order and topography. The base-level map can be seen as a ""simplified"" version of the original topographic surface, from which the ""noise"" of the low-order stream erosion was removed. This method is able to identify areas with possible tectonic influence even within lithologically uniform domains. Base-level maps have been recently applied in semi-detail scale (e.g., 1:50 000 or larger) morphotectonic analysis. In this paper, we present an evaluation of the method's applicability in regional-scale analysis (e.g., 1:250 000 or smaller). A test area was selected in northern Brazil, at the lower course of the Araguaia and Tocantins rivers. The drainage network extracted from SRTM30_PLUS DEMs with spatial resolution of approximately 900 m was visually compared with available topographic maps and considered to be compatible with a 1:1,000 000 scale. Regarding the interpretation of regional-scale morphostructures, the map constructed with 2nd and 3rd-order valleys was considered to present the best results. Some of the interpreted base-level anomalies correspond to important shear zones and geological contacts present in the 1:5 000 000 Geological Map of South America. Others have no correspondence with mapped Precambrian structures and are considered to represent younger, probably neotectonic, features. A strong E-W orientation of the base-level lines over the inflexion of the Araguaia and Tocantins rivers, suggest a major drainage capture. A N-S topographic swath profile over the Tocantins and Araguaia rivers reveals a topographic pattern which, allied with seismic data showing a roughly N-S direction of extension in the area, lead us to interpret this lineament as an E-W, southward-dipping normal fault. There is also a good visual correspondence between the base-level lineaments and geophysical anomalies. A NW-SE lineament in the southeast of the study area partially corresponds to the northern border of the Mosquito lava field, of Jurassic age, and a NW-SE lineament traced in the northeastern sector of the study area can be interpreted as the Picos-Santa Ines lineament, identifiable in geophysical maps but with little expression in hypsometric or topographic maps.

E-contracting with price configuration for Web services and QoS

The large amount of information in electronic contracts hampers their establishment due to high complexity. An approach inspired in Software Product Line (PL) and based on feature modelling was proposed to make this process more systematic through information reuse and structuring. By assessing the feature-based approach in relation to a proposed set of requirements, it was showed that the approach does not allow the price of services and of Quality of Services (QoS) attributes to be considered in the negotiation and included in the electronic contract. Thus, this paper also presents an extension of such approach in which prices and price types associated to Web services and QoS levels are applied. An extended toolkit prototype is also presented as well as an experiment example of the proposed approach.

Characterization of micro-bubble size distribution and flow configuration in DAF contact zone by a non-intrusive image analysis system and tracer tests

This paper aims to investigate the influence of some dissolved air flotation (DAF) process variables (specifically: the hydraulic detention time in the contact zone and the supplied dissolved air concentration) and the pH values, as pretreatment chemical variables, on the micro-bubble size distribution (BSD) in a DAF contact zone. This work was carried out in a pilot plant where bubbles were measured by an appropriate non-intrusive image acquisition system. The results show that the obtained diameter ranges were in agreement with values reported in the literature (10-100mm), quite independently of the investigated conditions. The linear average diameter varied from 20 to 30mm, or equivalently, the Sauter (d(3,2)) diameter varied from 40 to 50mm. In all investigated conditions, D(50) was between 75% and 95%. The BSD might present different profile (with a bimodal curve trend), however, when analyzing the volumetric frequency distribution (in some cases with the appearance of peaks in diameters ranging from 90-100mm). Regarding volumetric frequency analysis, all the investigated parameters can modify the BSD in DAF contact zone after the release point, thus potentially causing changes in DAF kinetics. This finding prompts further research in order to verify the effect of these BSD changes on solid particle removal efficiency by DAF.