Effect of Different Radiopacifying Agents on the Physicochemical Properties of White Portland Cement and White Mineral Trioxide Aggregate

Introduction: The aim of this study was to evaluate the pH, calcium ion release, setting time, and solubility of white mineral trioxide aggregate (WMTA) and white Portland cement (WPC) combined with the following radiopacifying agents: bismuth oxide (BO), calcium tungstate (CT), and zirconium oxide (ZO). Methods: Fifty acrylic teeth with root-end filling material were immersed in ultrapure water for measurement of pH and calcium release (atomic absorption spectrophotometry) at 3, 24, 72, and 168 hours. For evaluation of setting time, each material was analyzed according to the American Society for Testing and Materials guidelines 266/08. The solubility test was performed according to American National Standards Institute/American Dental Association specification no. 57/2000. Solubility, setting time, and pH values were compared by using analysis of variance and Tukey test, and the values of calcium release were compared by the Kruskal-Wallis and Miller tests. The significance level was set at 5%. Results: The pH and calcium release were higher at 3 and 24 hours. WPC was the material with the higher values for both properties. WMTA had the greatest solubility among all materials (P < .05). All radiopacifiers increased the setting time of WPC, and WMTA had the shortest setting time among all materials (P < .05). Conclusions: All materials released calcium ions. Except for WPC/CT at 168 hours, all materials promoted an alkaline pH. On the basis of the obtained results, ZO and CT can be considered as potential radiopacifying agents to be used in combination with Portland cement. (J Endod 2012;38:394-397)

Consensus hologram QSAR modeling for the prediction of human intestinal absorption

Consistent in silico models for ADME properties are useful tools in early drug discovery. Here, we report the hologram QSAR modeling of human intestinal absorption using a dataset of 638 compounds with experimental data associated. The final validated models are consistent and robust for the consensus prediction of this important pharmacokinetic property and are suitable for virtual screening applications. (C) 2012 Elsevier Ltd. All rights reserved.

Evaluation of the propylene glycol association on some physical and chemical properties of mineral trioxide aggregate

Duarte MAH, Alves de Aguiar K, Zeferino MA, Vivan RR, Ordinola-Zapata R, Tanomaru-Filho M, Weckwerth PH, Kuga MC. Evaluation of the propylene glycol association on some physical and chemical properties of mineral trioxide aggregate. International Endodontic Journal, 45, 565570, 2012. Abstract Aim To evaluate the influence of propylene glycol (PG) on the flowability, setting time, pH and calcium ion release of mineral trioxide aggregate (MTA). Methodology Mineral trioxide aggregate was mixed with different proportions of PG, as follows: group 1: MTA + 100% distilled water (DW); group 2: MTA + 80% DW and 20% PG; group 3: MTA + 50% DW and 50% PG; group 4: MTA + 20% DW and 80% PG; group 5: MTA + 100% PG. The ANSI/ADA No. 57 was followed for evaluating the flowability and the setting time was measured by using ASTM C266-08. For pH and calcium release analyses, 50 acrylic teeth with root-end cavities were filled with the materials (n = 10) and individually immersed in flasks containing 10 mL deionized water. After 3 h, 24 h, 72 h and 168 h, teeth were placed in new flasks and the water in which each specimen was immersed had its pH determined by a pH metre and the calcium release measured by an atomic absorption spectrophotometer with a calcium-specific hollow cathode lamp. Data were analysed by using one-way anova test for global comparison and by using Tukeys test for individual comparisons. Results The highest value of flowability was observed with MTA + 20% DW and 80% PG and the lowest values were found with MTA + 100% DW. They were significantly different compared to the other groups (P < 0.05). The presence of PG did not affect the pH and calcium release. The MTA + 100% PG favoured the highest (P < 0.05) pH and calcium release after 3 h. Increasing the PG proportion interfered (P < 0.05) with the setting time; when used at the volume of 100% setting did not occur. Conclusion The addition of PG to MTA-Angelus increased its setting time, improved flowability and increased the pH and calcium ion release during the initial post-mixing periods. The ratio of 80% DW 20% PG is recommended.

Synthesis, spectroscopic characterization, photochemical and photophysical properties and biological activities of ruthenium complexes with mono- and bi-dentate histamine ligand

The monodentate cis-[Ru(phen)(2)(hist)(2)](2+) 1R and the bidentate cis-[Ru(phen)(2)(hist)](2+) 2A complexes were prepared and characterized using spectroscopic (H-1, (H-1-H-1) COSY and (H-1-C-13) HSQC NMR, UV-vis, luminescence) techniques. The complexes presented absorption and emission in the visible region, as well as a tri-exponential emission decay. The complexes are soluble in aqueous and non-aqueous solution with solubility in a buffer solution of pH 7.4 of 1.14 x 10(-3) mol L-1 for (1R + 2A) and 6.43 x 10(-4) mol L-1 for 2A and lipophilicity measured in an aqueous-octanol solution of -1.14 and -0.96, respectively. Photolysis in the visible region in CH3CN converted the starting complexes into cis-[Ru(phen)(2)(CH3CN)(2)](2+). Histamine photorelease was also observed in pure water and in the presence of BSA (1.0 x 10(-6) mol L-1). The bidentate coordination of the histamine to the ruthenium center in relation to the monodentate coordination increased the photosubstitution quantum yield by a factor of 3. Pharmacological studies showed that the complexes present a moderate inhibition of AChE with an IC50 of 21 mu mol L-1 (referred to risvagtini, IC50 181 mu mol L-1 and galantamine IC50 0.006 mu mol L-1) with no appreciable cytotoxicity toward to the HeLa cells (50% cell viability at 925 mu mol L-1). Cell uptake of the complexes into HeLa cells was detected by fluorescence confocal microscopy. Overall, the observation of a luminescent complex that penetrates the cell wall and has low cytotoxicity, but is reactive photochemically, releasing histamine when irradiated with visible light, are interesting features for application of these complexes as phototherapeutic agents.

Effect of Solvent-Induced Coil to Helix Conformational Change on the Two-Photon Absorption Spectrum of Poly(3,6-phenanthrene)

This paper investigates the effect of solvent-induced conformational changes of poly(3,6-phenanthrene) on their two-photon absorption (2PA). Such effect was studied employing the wavelength-tunable femtosecond Z-scan technique and modeled using the sum-over-essential states approach. We observed a strong reduction of the 2PA cross-section when the sample was prepared in hexane (poor solvent) in comparison to chloroform (good solvent), which is related to the conformation adopted by the polymer in each case. In chloroform it adopts a random coil conformation, as opposed to the one-handed helix conformation in hexane. Our results pointed out that the coil to helix conformation change decreases the degree of molecular planarity of the polymer pi-conjugated backbone, which is primarily responsible for their optical nonlinearity, contributing to diminishing the effective transition dipole moments and, consequently, the 2PA cross-section. Moreover, by studying the nonlinear response with different light polarization, we showed that, although the solvent-induced conformational change does not alter the molecular symmetry of the polymer, it modifies considerably the direction of the transition dipole moments between the excited states.

Structure and electronic properties of hydrated mesityl oxide: a sequential quantum mechanics/molecular mechanics approach

The hydration of mesityl oxide (MOx) was investigated through a sequential quantum mechanics/molecular mechanics approach. Emphasis was placed on the analysis of the role played by water in the MOx syn-anti equilibrium and the electronic absorption spectrum. Results for the structure of the MOx-water solution, free energy of solvation and polarization effects are also reported. Our main conclusion was that in gas-phase and in low-polarity solvents, the MOx exists dominantly in syn-form and in aqueous solution in anti-form. This conclusion was supported by Gibbs free energy calculations in gas phase and in-water by quantum mechanical calculations with polarizable continuum model and thermodynamic perturbation theory in Monte Carlo simulations using a polarized MOx model. The consideration of the in-water polarization of the MOx is very important to correctly describe the solute-solvent electrostatic interaction. Our best estimate for the shift of the pi-pi* transition energy of MOx, when it changes from gas-phase to water solvent, shows a red-shift of -2,520 +/- 90 cm(-1), which is only 110 cm(-1) (0.014 eV) below the experimental extrapolation of -2,410 +/- 90 cm(-1). This red-shift of around -2,500 cm(-1) can be divided in two distinct and opposite contributions. One contribution is related to the syn -> anti conformational change leading to a blue-shift of similar to 1,700 cm(-1). Other contribution is the solvent effect on the electronic structure of the MOx leading to a red-shift of around -4,200 cm(-1). Additionally, this red-shift caused by the solvent effect on the electronic structure can by composed by approximately 60 % due to the electrostatic bulk effect, 10 % due to the explicit inclusion of the hydrogen-bonded water molecules and 30 % due to the explicit inclusion of the nearest water molecules.

Influence of the relative amounts of crystalline and amorphous phases on the mechanical properties of polyamide-6 nanocomposites

The relative amounts of amorphous and crystalline ?- and a-phases in polyamide-6 nanocomposites, estimated from the deconvolution of X-ray diffraction peaks using Gaussian functions, correlates with their mechanical, thermomechanical, and barrier properties. The incorporation of organoclay platelets (Cloisite 15A and 30B) induced the crystallization of the polymer in the ? form at expense of the amorphous phase, such that 12 wt % of Cloisite is enough to enhance the mechanical and the thermomechanical properties. However, higher nanofiller loads were necessary to achieve good barrier effects, because this property is mainly dependent on the tortuous path permeation mechanism of the gas molecules through the nanocomposite films. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Polyazomethine with vinylene and phenantridine moieties in the main chain: Synthesis, characterization, opto(electrical) properties and theoretical calculations

The opto(electrical) properties and theoretical calculations of polyazomethine with vinylene and phenantridine moieties in the main chain were investigated in the present study. 2,5-Bis(hexyloxy)-1,4-bis[(2,5-bis(hexyloxy)-4-formyl-phenylenevinylene]benzene was polymerized in solution with 3,8-diamino-6-phenylphenanthridine (PAZ-PV-Ph). The temperatures of 5% weight loss (T-5%) of the polyazomethine was observed at 356 degrees C in nitrogen. Electrochemical properties of thin film of the polymer were studied by differential pulse voltammetry. The HOMO level of the PAZ-PV-Ph was at -4.97 eV. The energy band gap (E-g) was detected of approximately similar to 1.9 eV. Energy band gap (E-gopt) was additionally calculated from absorption spectrum and absorption coefficient alpha. The absorption UV-vis spectra of polyazomethine recorded in solution showed a blue shift in comparison with the solid state. HOMO-LUMO levels and E-g were additionally calculated theoretically by density functional theory and molecular simulations of PAZ-PV-Ph are presented. Current density-voltage (J-U) measurements were performed on ITO/PAZ-PV-Ph/Al, ITO/TiO2/PAZ-PV-Ph/Al and ITO/PEDOT/PAZ-PV-Ph:TiO2/Al devices in the dark and during irradiation with light (under illumination of 1000 W m(-2)). The polymer was tested using AFM technique and roughness (R-a, R-ms) along with skew and kurtosis are presented.

Synthesis, characterization, optical absorption, luminescence and defect centres in Er3+ and Yb3+ co-doped MgAl2O4 phosphors

The Er3+-Yb3+ co-doped MgAl2O4 phosphor powders have been prepared by the combustion method. The phosphor powders are well characterized by X-ray diffraction (XRD) and energy dispersive (EDX) techniques. The absorption spectrum of Er3+/Er3+-Yb3+ doped/co-doped phosphor powder has been recorded in the UV-Vis-NIR region of the electro-magnetic spectrum. The evidence for indirect pumping under 980 nm excitation of Er3+ from Yb3+ was observed in the MgAl2O4 matrix material. Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process in MgAl2O4:Er3+ phosphor. Three defect centres were identified in irradiated phosphor by ESR measurements which were carried out at room temperature and these were assigned to an O- ion and F+ centres. O- ion (hole centre) appears to correlate with the low temperature TSL peak at 210 A degrees C and one of the F+ centres (electron centre) is related to the high temperature peak at 460 A degrees C.

Synthesis and Characterization of Gold/Alanine Nanocomposites with Potential Properties for Medical Application as Radiation Sensors

Radiation dose assessment is essential for several medical treatments and diagnostic procedures. In this context, nanotechnology has been used in the development of improved radiation sensors, with higher sensitivity as well as smaller sizes and energy dependence. This paper deals with the synthesis and characterization of gold/alanine nanocomposites with varying mass percentage of gold, for application as radiation sensors. Alanine is an excellent stabilizing agent for gold nanoparticles because the size of the nanoparticles does not augment with increasing mass percentage of gold, as evidenced by UV-vis spectroscopy, dynamic light scattering, and transmission electron microscopy. X-ray diffraction patterns suggest that the alanine crystalline orientation undergoes alterations upon the addition of gold nanoparticles. Fourier transform infrared spectroscopy indicates that there is interaction between the gold nanoparticles and the amine group of the alanine molecules, which may be the reason for the enhanced stability of the nanocomposite. The application of the nanocomposites as radiation detectors was evaluated by the electron spin resonance technique. The sensitivity is improved almost 3 times in the case of the nanocomposite containing 3% (w/w) gold, so it can be easily tuned by changing the amount of gold nanoparticles in the nanocomposites, without the size of the nanoparticles influencing the radiation absorption. In conclusion, the featured properties, such as homogeneity, nanoparticle size stability, and enhanced sensitivity, make these nanocomposites potential candidates for the construction of small-sized radiation sensors with tunable sensitivity for application in several medical procedures.

Structural Refinement and Photoluminescence Properties of MnWO4 Nanorods Obtained by Microwave-Hydrothermal Synthesis

Manganese tungstate (MnWO4) nanorods were prepared at room temperature by the co-precipitation method and synthesized after processing in a microwave-hydrothermal (MH) system at 140 degrees C for 6-96 min. These nanorods were structurally characterized by X-ray diffraction (XRD), Rietveld refinements and Fourier transform (FT)-Raman spectroscopy. The growth direction, shape and average size distribution of nanorods were observed by means of transmission electron microscopy (TEM) and high resolution TEM (HR-TEM). The optical properties of the nanorods were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. XRD patterns, Rietveld refinement data and FT-Raman spectroscopy indicate that the MnWO4 precipitate is not a single phase structure while the nanorods synthesized by MH processing have a wolframite-type monoclinic structure without deleterious phases. FT-Raman spectra exhibited the presence of 17 Raman-active modes from 50 to 1,000 cm(-1). TEM and HR-TEM micrographs indicated that the nanorods are aggregated due to surface energy by Van der Waals forces and grow along the [100] direction. UV-vis absorption measurements confirmed non-linear values for the optical band gap (from 3.2 to 2.72 eV), which increased as the MH processing time increased. The structural characterizations indicated that the presence of defects in the MnWO4 precipitate promotes a significant contribution to maximum PL emission, while MnWO4 nanorods obtained by MH processing decrease the PL emission due to the reduction of defects in the lattice.

Cluster Coordination and Photoluminescence Properties of alpha-Ag2WO4 Microcrystals

In this paper, we report our initial research to obtain hexagonal rod-like elongated silver tungstate (alpha-Ag2WO4) microcrystals by different methods [sonochemistry (SC), coprecipitation (CP), and conventional hydrothermal (CH)] and to study their cluster coordination and optical properties. These microcrystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements, Fourier transform infrared (FT-IR), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies. The shape and average size of these alpha-Ag2WO4 microcrystals were observed by field-emission scanning electron microscopy (FE-SEM). The optical properties of these microcrystals were investigated by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) measurements. XRD patterns and Rietveld refinement data confirmed that alpha-Ag2WO4 microcrystals have an orthorhombic structure. FT-IR spectra exhibited four IR-active modes in a range from 250 to 1000 cm(-1). XANES spectra at the W L-3-edge showed distorted octahedral [WO6] clusters in the lattice, while EXAFS analyses confirmed that W atoms are coordinated by six O atoms. FE-SEM images suggest that the alpha-Ag2WO4 microcrystals grow by aggregation and the Ostwald ripening process. PL properties of alpha-Ag2WO4 microcrystals decrease with an increase in the optical band-gap values (3.19-3.23 eV). Finally, we observed that large hexagonal rod-like alpha-Ag2WO4 microcrystals prepared by the SC method exhibited a major PL emission intensity relative to alpha-Ag2WO4 microcrystals prepared by the CP and CH methods.

Structural refinement, growth process, photoluminescence and photocatalytic properties of (Ba1-xPr2x/3)WO4 crystals synthesized by the coprecipitation method

Barium praseodymium tungstate (Ba1-xPr2x/3)WO4 crystals with (x = 0, 0.01, and 0.02) were prepared by the coprecipitation method. These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements, Fourier-transform Raman (FT-Raman) and Fourier-transform infrared (FT-IR) spectroscopies. The shape and size of these crystals were observed by field emission scanning electron microcopy (FE-SEM). Their optical properties were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. Moreover, we have studied the photocatalytic (PC) activity of crystals for degradation of rhodamine B (RhB) dye. XRD patterns, Rietveld refinements data, FT-Raman and FT-IR spectroscopies indicate that all crystals exhibit a tetragonal structure without deleterious phases. FT-Raman spectra exhibited 13 Raman-active modes in a range from 50 to 1000 cm(-1), while FT-IR spectra have 8 infrared active modes in a range from 200 to 1050 cm(-1). FE-SEM images showed different shapes (bonbon-, spindle-, rice-and flake-like) as well as a reduction in the crystal size with an increase in Pr3+ ions. A possible growth process was proposed for these crystals. UV-vis absorption measurements revealed a decrease in optical band gap values with an increase of Pr3+ into the matrix. An intense green PL emission was noted for (Ba1-xPr2x/3)WO4 crystals (x = 0), while crystals with (x = 0.01 and 0.02) produced a reduction in the wide band PL emission and the narrow band PL emission which is related to f-f transitions from Pr3+ ions. High photocatalytic efficiency was verified for the bonbon-like BaWO4 crystals as a catalyst in the degradation of the RhB dye after 25 min under UV-light. Finally, we discuss possible mechanisms for PL and PC properties of these crystals.

Spatial-temporal variations in phytoplankton size and colored detrital matter absorption at global and regional scales, as derived from twelve years of SeaWiFS data (1998-2009)

A procedure has been proposed by Ciotti and Bricaud (2006) to retrieve spectral absorption coefficients of phytoplankton and colored detrital matter (CDM) from satellite radiance measurements. This was also the first procedure to estimate a size factor for phytoplankton, based on the shape of the retrieved algal absorption spectrum, and the spectral slope of CDM absorption. Applying this method to the global ocean color data set acquired by SeaWiFS over twelve years (1998-2009), allowed for a comparison of the spatial variations of chlorophyll concentration ([Chl]), algal size factor (S-f), CDM absorption coefficient (a(cdm)) at 443 nm, and spectral slope of CDM absorption (S-cdm). As expected, correlations between the derived parameters were characterized by a large scatter at the global scale. We compared temporal variability of the spatially averaged parameters over the twelve-year period for three oceanic areas of biogeochemical importance: the Eastern Equatorial Pacific, the North Atlantic and the Mediterranean Sea. In all areas, both S-f and a(cdm)(443) showed large seasonal and interannual variations, generally correlated to those of algal biomass. The CDM maxima appeared in some occasions to last longer than those of [Chl]. The spectral slope of CDM absorption showed very large seasonal cycles consistent with photobleaching, challenging the assumption of a constant slope commonly used in bio-optical models. In the Equatorial Pacific, the seasonal cycles of [Chl], S-f, a(cdm)(443) and S-cdm, as well as the relationships between these parameters, were strongly affected by the 1997-98 El Ni o/La Ni a event.

Local order and electronic structure of Pb1-xLaxZr0.40Ti0.60O3 materials and its relation with ferroelectric properties

The knowledge of electronic and local structures is a fundamental step towards understanding the properties of ferroelectric ceramics. X-ray absorption near-edge structure (XANES) of Pb1-xLaxZr0.40Ti0.60O3 ferroelectric samples was measured in order to know how the local order and electronic structure are related to their ferroelectric property, which was tailored by the substitution of lead by lanthanum atoms. The analysis of XANES spectra collected at Ti K- and L-edges XANES showed that the substitution of Pb by La leads to a decrement of local distortion around Ti atoms on the TiO6 octahedron. The analysis of O K-edge XANES spectra showed that the hybridization between O 2p and Pb 6sp states is related to the displacement of Ti atoms in the TiO6 octahedra. Based on these results, it is possible to determine that the degree of ferroelectricity in these samples and the manifestation of relaxor behavior are directly related to the weakening of O 2p and Pb 6sp hybridization. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720472]