Synthesis, spectroscopic characterization and X-ray structures of five-coordinate diorganotin(IV) complexes containing 5-hydroxypyrazoline derivatives as ligands

Four new diorganotin(IV) complexes have been prepared from R(2)SnCl(2) (R = Me, Ph) with the ligands 5-hydroxy-3-metyl-5-phenyl-1-(S-benzildithiocarbazate)-pyrazoline (H(2)L(1)) and 5-hydroxy-3-methyl-5-phenyl-1-(2-thiophenecarboxylic)-pyrazoline (H(2)L(2)). The complexes were characterized by elemental analysis, IR. (1)H (13)C, (119)Sn NMR and Mossbauer spectroscopes The complexes [Me(2)SnL(1)], [Ph(2)SnL(1)] and [Me(2)SnL(2)] were also studied by single crystal X-ray diffraction and the results showed that the Sn(IV) central atom of the complexes adopts a distorted trigonal bipyramidal (TBP) geometry with the N atom of the ONX-tridentate (X = O and S) ligand and two organic groups occupying equatorial sites. The C-Sn-C angles for [Me(2)Sn(L(1))] and [Ph(2)Sn(L(1))] were calculated using a correlation between (119)Sn Mossbauer and X-ray crystallographic data based on the point-charge model Theoretical calculations were performed with the B3LYP density functional employing 3-21G(*) and DZVP all electron basis sets showing good agreement with experimental findings General and Sn(IV) specific IR harmonic frequency scale factors for both basis sets were obtained from comparison with selected experimental frequencies (C) 2010 Elsevier B V All rights reserved

Evaluation of phenolic compounds in mate (Ilex paraguariensis) processed by gamma radiation

The radiation food processing has been demonstrating great effectiveness in the attack of pathogenic agents, while little compromising nutritional value and sensorial properties of foods. The mate (Ilex paraguariensis), widely consumed product in South America, generally in the form of infusions with hot or cold water, calls of chimarrao or terere, it is cited in literature as one of the best sources phenolic compounds. The antioxidants action of these constituent has been related to the protection of the organism against the free radicals, generated in alive, currently responsible for the sprouting of some degenerative illness as cancer, arteriosclerosis, rheumatic arthritis and cardiovascular clutters among others. The objective of that work was to evaluate the action of the processing for gamma radiation in phenolic compounds of terere beverage in the doses of 0, 3, 5, 7 and 10 kGy. The observed results do not demonstrate significant alterations in phenolic compounds of terere beverage processed by gamma radiation. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

Synthesis of chitosan/hydroxyapatite membranes coated with hydroxycarbonate apatite for guided tissue regeneration purposes

Chitosan, which is a non-toxic, biodegradable and biocompatible biopolymer, has been widely researched for several applications in the field of biomaterials. Calcium phosphate ceramics stand out among the so-called bioceramics for their absence of local or systemic toxicity, their non-response to foreign bodies or inflammations, and their apparent ability to bond to the host tissue. Hydroxyapatite (HA) is one of the most important bioceramics because it is the main component of the mineral phase of bone. The aim of this work was to produce chitosan membranes coated with hydroxyapatite using the modified biomimetic method. Membranes were synthesized from a solution containing 2% of chitosan in acetic acid (weight/volume) via the solvent evaporation method. Specimens were immersed in a sodium silicate solution and then in a 1.5 SBF (simulated body fluid) solution. The crystallinity of the HA formed over the membranes was correlated to the use of the nucleation agent (the sodium silicate solution itself). Coated membranes were characterized by means of scanning electron microscopy - SEM, X-ray diffraction - XRD, and Fourier transform infrared spectroscopy - FTIR. The results indicate a homogeneous coating covering the entire surface of the membrane and the production of a semi-crystalline hydroxyapatite layer similar to the mineral phase of human bone. (C) 2010 Elsevier B.V. All rights reserved.

Phase equilibria study of systems composed of refined babassu oil, lauric acid, ethanol, and water at 303.2 K

Deacidification of vegetable oils can be performed using liquid-liquid extraction as an alternative method to the classical chemical and physical refining processes. This paper reports experimental data for systems containing refined babassu oil, lauric acid, ethanol, and water at 303.2 K with different water mass fractions in the alcoholic solvent (0, 0.0557, 0.1045, 0.2029, and 0.2972). The dilution of solvent with water reduced the distribution coefficient values, which indicates a reduction in the loss of neutral oil. The experimental data were used to adjust the NRTL equation parameters. The global deviation between the observed and the estimated compositions was 0.0085, indicating that the model can accurately predict the behavior of the compounds at different levels of solvent hydration. (C) 2011 Elsevier Ltd. All rights reserved.

Extracts from pitanga (Eugenia uniflora L.) leaves: Influence of extraction process on antioxidant properties and yield of phenolic compounds

Different extraction processes were employed to extract the polyphenolic compounds from pitanga (Eugenia uniflora L) leaves: a one-step process using water, ethanol or supercritical CO(2) as solvents, and a two-step process using supercritical CO(2) followed by either water or ethanol. The total polyphenolic compounds, total flavonoids and antioxidant activity were determined in all the extracts obtained. The process performance was evaluated with respect to three variables: global extraction yield, concentration and yield of both polyphenols and flavonoids in the extracts. For the one-step extraction, the results showed that the extraction yield increased with solvent polarity. For the two-step process, the results suggested that water was more efficient in extracting the phenolic compounds from E. uniflora when the matrix was previously extracted with scCO(2). With respect to the antioxidant activity, the ethanolic extracts obtained from both processes, using either the DPPH radical scavenging method or the beta-carotene bleaching method, presented high antioxidant activities. (C) 2010 Elsevier B.V. All rights reserved.

Liquid-liquid equilibria for systems composed of refined soybean oil, free fatty acids, ethanol, and water at different temperatures

Soybean oil can be deacidified by liquid-liquid extraction with ethanol. In the present paper, the liquid-liquid equilibria of systems composed of refined soybean oil, commercial linoleic acid, ethanol and water were investigated at 298.2 K. The experimental data set obtained from the present study (at 298.2 K) and the results of Mohsen-Nia et al. [1] (at 303.2 K) and Rodrigues et al. [2] (at 323.2 K) were correlated by applying the non-random two liquid (NRTL) model. The results of the present study indicated that the mutual solubility of the compounds decreased with an increase in the water content of the solvent and a decrease in the temperature of the solution. Among variables, the water content of the solvent had the strongest effect on the solubility of the components. The maximum deviation and average variance between the experimental and calculated compositions were 1.60% and 0.89%, indicating that the model could accurately predict the behavior of the compounds at different temperatures and degrees of hydration. (C) 2010 Elsevier B.V. All rights reserved.

Phase transitions of cassava starch dispersions prepared with glycerol solutions

The aim of this work was to study the glass transition, the glass transition of the maximally freeze-concentrated fractions, the ice melting and the gelatinization phenomenon in dispersions of starch prepared using glycerol- water solutions. The starch concentration was maintained constant at 50 g cassava starch/100 g starch dispersions, but the concentration of the glycerol solutions was variable (C-g= 20, 40, 60, 80 and 100 mass/mass%). The phase transitions of these dispersions were studied by calorimetric methods, using a conventional differential scanning calorimeter (DSC) and a more sensitive equipment (micro-DSC). Apparently, in the glycerol diluted solutions (20 and 40%), the glycerol molecules interacted strongly with the glucose molecules of starch. While in the more concentrated glycerol domains (C-g> 40%), the behaviour was controlled by migration of water molecules from the starch granules, due to a hypertonic character of glycerol, which affected all phase transitions.

Supercritical CO(2) extraction of carotenoids from pitanga fruits (Eugenia uniflora L.)

Supercritical carbon dioxide (SC-CO(2)) extraction was employed to extract carotenoids from the freeze-dried pulp of pitanga fruits (Eugenia uniflora L.), an exotic fruit, rich in carotenoids and still little explored commercially. The SC-CO(2) extraction was carried out at two temperatures, 40 and 60 degrees C, and seven pressures, 100, 150, 200, 250, 300, 350 and 400 bar. The carotenoids were determined by high-performance liquid chromatography connected to photodiode array and mass spectrometry detectors. Lycopene, rubixanthin and P-cryptoxanthin were the main carotenoids present in the freeze-dried pitanga pulp, whereas beta-cryptoxanthin concentration was negligible in the SC-CO(2) extracts, for all the investigated state conditions. The maximum recovery of carotenoids was obtained at 60 degrees C and 250 bar, extracting 55% of the total carotenoid content, 74% of the rubixanthin and 78% of the lycopene from the pulp. Under these state conditions, the total carotenoid concentration in the extract was 5474 mu g/g, represented by 66% lycopene and 32% rubixanthin. The experimental state conditions produced different SC-CO(2) extracts with respect to the extraction yield and concentration of different carotenoids, indicating that the supercritical carbon dioxide was selective in the extraction of the pitanga carotenoids as a function of temperature and pressure. (C) 2008 Elsevier B.V. All rights reserved.

Polymorphism, crystallinity and hydrophilic-lipophilic balance of stearic acid and stearic acid-capric/caprylic triglyceride matrices for production of stable nanoparticles

There is an increasing interest in lipid nanoparticles because of their suitability for several administration routes. Thus, it becomes even more relevant the physicochemical characterization of lipid materials with respect to their polymorphism, lipid miscibility and stability, as well as the assessment of the effect of surfactant on the type and structure of these nanoparticles. This work focuses on the physicochemical characterization of lipid matrices composed of pure stearic acid or of mixtures of stearic acid-capric/caprylic triglycerides, for drug delivery. The lipids were analyzed by Differential Scanning Calorimetry (DSC), Wide Angle X-ray Diffraction (WAXD), Polarized Light Microscopy (PLM) and hydrophilic-lipophilic balance (HLB) in combination with selected surfactants to determine the best solid-to-liquid ratio. Based on the results obtained by DSC and WAXD, the selected qualitative and quantitative composition contributed for the production of stable nanoparticles, since the melting and the tempering processes provided important information on the thermodynamic stability of solid lipid matrices. The best HLB value obtained for stearic acid-capric/caprylic triglycerides was 13.8, achieved after combining these lipids with accepted surfactants (trioleate sorbitan and polysorbate 80 in the ratio of 10:90). The proposed combinations were shown useful to obtain a stable emulsion to be used as intermediate form for the production of lipid nanoparticles. (C) 2011 Elsevier B.V. All rights reserved.

Observing the Solubilization of Lipid Bilayers by Detergents with Optical Microscopy of GUVs

The solubilization of lipid bilayers by detergents was studied with optical microscopy of giant unilamellar vesicles (GUVs) composed of palmitoyl oleoyl phoshatidylcholine (POPC). A solution of the detergents Triton X-100 (TX-100) and sodium dodecyl sulfate (SDS) was injected with a micropipette close to single GUVs. The solubilization process was observed with phase contrast and fluorescence microscopy and found to be dependent on the detergent nature. In the presence of TX-100, GUVs initially showed an increase in their surface area, due to insertion of TX-100 with rapid equilibration between the two leaflets of the bilayer. Then, above a solubility threshold, several holes opened, rendering the bilayer a lace fabric appearance, and the bilayer gradually vanished. On the other hand, injection of SDS caused initially an increase in the membrane spontaneous curvature, which is mainly associated with incorporation of SDS in the outer layer only. This created a stress in the membrane, which caused either opening of transient macropores with substantial decrease in vesicle size or complete vesicle bursting. In another experimental setup, the extent of solubilization/destruction of a collection of GUVs was measured as a function of either TX-100 or SDS concentration.

Improvement in the Reduction Behavior of Novel ZrO(2)-CeO(2) Solid Solutions with a Tubular Nanostructure by Incorporation of Pd

In this work, 1 wt % Pd/ZrO(2)-CeO(2) mixed oxide nanotubes with 90 mol % CeO(2) were synthesized following a very simple, high-yield procedure and their properties were characterized by synchrotron radiation X-ray diffraction, X-ray absorption near-edge spectroscopy (XANES), and scanning and high-resolution transmission electron microscopy (SEM and HRTEM). In situ XANES experiments were carried out under reducing conditions to investigate the reduction behavior of these novel nanotube materials. The Pd/CeO(2)-based nanotubes exhibited the cubic phase (Fm3m space group). The nanotube walls were composed of nanoparticles with an average crystallite size of about 7 nm, and the nanotubes exhibited a large specific surface area (85 m(2).g(-1)). SEM and HRTEM studies showed that individual nanotubes were composed of a curved sheet of these nanoparticles. Elemental analysis showed that the Ce:Zr:Pd ratios appeared to be approximately constant across space, suggesting compositional homogeneity in the samples. XANES results indicated that the extent of reduction of these materials is low and that the Ce(4+) state is in the majority over the reduced Ce(3+) state. The results suggest that Pd cations-most likely Pd(2+)-form a Pd-Ce-Zr oxide solid solution and that the Pd(2+) is stabilized against reduction in this phase. However, incorporation of the Pd (1 wt %) into the crystal lattice of the nanotubes also appeared to destabilize Ce(4+) against reduction to Ce(3+) and caused a significant increase in its reducibility.

Factorial design to optimize microwave-assisted synthesis of FDU-1 silica with a new triblock copolymer

The synthesis of FDU-1 silica with large cage-like mesopores prepared with a new triblock copolymer Vorasurf 504 (R) (Eo)(38)(BO)(46)(EO)(38) was developed. The hydrothermal treatment temperature, the dissolution of the copolymer in ethanol, the HCl concentration, the solution stirring time and the hydrothermal treatment time in a microwave oven were evaluated with factorial design procedures. The dissolution in ethanol is important to produce a material with better porous morphology. Increases in the hydrothermal temperature (100 degrees C) and HCl concentration (2 M) improved structural, textural and chemical properties of the cubic ordered mesoporous silica. Also, longer times induced better physical and chemical property characteristics. (C) 2010 Elsevier Inc. All rights reserved.

Melting Regime of the Anionic Phospholipid DMPG: New Lamellar Phase and Porous Bilayer Model

Aqueous dispersions of the anionic phospholipid dimyristoyl phosphatidylglycerol (DMPG) at pH above the apparent pK of DMPG and concentrations in the interval 70-300 mM have been investigated by small (SAXS) and wide-angle X-ray scattering, differential scanning calorimetry, and polarized optical microscopy. The order. disorder transition of the hydrocarbon chains occurs along an interval of about 10 degrees C (between T(m)(on) similar to 20 degrees C and T(m)(off) similar to 30 degrees C). Such melting regime was previously characterized at lower concentrations, up to 70 mM DMPG, when sample transparency was correlated with the presence of pores across the bilayer. At higher concentrations considered here, the melting regime persists but is not transparent. Defined SAXS peaks appear and a new lamellar phase L(p) with pores is proposed to exist above 70 mM DMPG, starting at similar to 23 degrees C (similar to 3 degrees C above T(m)(on)) and losing correlation after T(m)(off). A new model for describing the X-ray scattering of bilayers with pores, presented here, is able to explain the broad band attributed to in-plane correlation between pores. The majority of cell membranes have a net negative charge, and the opening of pores across the membrane tuned by ionic strength, temperature, and lipid composition is likely to have biological relevance.

Structural characterization of supported nanocrystalline ZnO thin films prepared by dip-coating

Nanocrystalline ZnO thin films prepared by the sol-gel dip-coating technique were characterized by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). The structures of several thin films subjected to (i) isochronous annealing at 350, 450 and 550 degrees C, and (ii) isothermal annealing at 450 degrees C during different time periods, were characterized. The studied thin films are composed of ZnO nanocrystals as revealed by analysing several GIXD patterns, from which their average sizes were determined. Thin film thickness and roughness were determined from quantitative analyses of AFM images and XR patterns. The analysis of XR patterns also yielded the average density of the studied films. Our GISAXS study indicates that the studied ZnO thin films contain nanopores with an ellipsoidal shape, and flattened along the direction normal to the substrate surface. The thin film annealed at the highest temperature, T = 550 degrees C, exhibits higher density and lower thickness and nanoporosity volume fraction, than those annealed at 350 and 450 degrees C. These results indicate that thermal annealing at the highest temperature (550 degrees C) induces a noticeable compaction effect on the structure of the studied thin films. (C) 2011 Elsevier B.V. All rights reserved.

Retention at room temperature of the tetragonal t ``-form in Sc(2)O(3)-doped ZrO(2) nanopowders

Synchrotron X-ray powder diffraction was applied to the study of the effect of crystallite size on the crystal structure of ZrO(2)-10 mol% Sc(2)O(3) nanopowders synthesized by a nitrate-lysine gel-combustion route Nanopowders with different average crystallite sizes were obtained by calcination at several temperatures, ranging from 650 to 1200 degrees C The metastable t""-form of the tetragonal phase, exhibiting a cubic unit cell and tetragonal P4(2)/nmc spatial symmetry, was retained at room temperature in fine nanocrystalline powders, completely avoiding the presence of the stable rhombohedral beta phase. Differently, this phase was identified in samples calcined at high temperatures and its content increased with increasing crystallite size The critical maximum crystallite size for the retention of the mestastable t""-form resulted of about 35 nm (C) 2009 Elsevier B.V All rights reserved