Improvement of the Mo/TiO2-Al2O3 catalyst by the control of the sol-gel synthesis

Traditional hydrotreating catalysts are constituted by molybdenum deposited on Al2O3 promoted by nickel and phosphorous. Several studies have shown that TiO2-Al2O3 mixed oxides are excellent supports for the active phases. Results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, the titanium one chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal molar ratio [Ti]/[Ti+Al] on the microstructural features of nanometric particles was analyzed by X-Ray Diffraction, N-2 Adsorption Isotherms and Transmission Electron Microscopy. The catalytic activity of Mo impregnated supports was evaluated using the thiophene hydrodesulfurization at different temperatures and atmospheric pressure. The pores size distribution curve moves from the micropores to the mesopores by increasing the Ti contents, allowing the fine tuning of average size from 2.5 to 6 nm. Maximal (367 m(2).g(-1)) and minimal (127 m(2).g(-1)) surface area were found for support containing [Ti]/[Ti+Al] ratio equal to 0.1 and 1, respectively. The good mesopore texture of alumina-titania support with [Ti]/[Ti+Al] molar ratio between 0.3 and 0.5 was found particularly valuable for the preparation of well dispersed MoS2 active phase, leading to HDS catalyst with somewhat higher activity than that prepared using a commercial alumina support.

A nonisothermal study of the kinetics of the nanoporosity elimination in sonogels-derived silica xerogels

A nonisothermal study of the kinetics of the nanoporosity elimination in monolithic silica xerogels, prepared from acid and ultrasound catalyzed hydrolysis of tetraethylortosilicate (TEOS), has been carried out by means of in situ linear shrinkage measurements performed with different heating rates. The study could be applied up to almost alpha similar to 0.6 of the volume fraction alpha of eliminated pores. The activation energy was found increasing from about 3.2 x 10(2) kJ/mol for alpha similar to 0.06 up to about 4.4 x 10(2) kJ/mol for alpha. similar to 0.44. The sintering process accompanying the nanopore elimination in this set of xerogels is in agreement with a viscous flux sintering process with the hydroxyl content diminishing with the volume fraction of eliminated pores. All the volume fraction of eliminated pores versus temperature (T) curves can be matched onto a unique curve with an appropriate rescaling of the T axis, independent of the heating rate. This scaling property suggests that the path of sintering seems the same, regardless of the heating rate; the difference is that the rate is faster at higher temperature.

X-ray reflectivity of zirconia based sol-gel coatings on borosilicate glasses

In this work the technique of X-ray reflectometry was applied to study zirconiumsulfate films deposited by sol-gel dip-coating process on a borosilicate glass surface. The influence of withdrawal speed and temperature of thermal treatment on the film structure are analyzed. The thermal evolution of the density and thickness of the film was compared with these properties measured for a monolithic xerogel by helium picnometry and thermomechanical analysis. The fitting of experimental curves by classical reflectivity model showed the presence of an additional layer at the top surface of the coating. Layer thickness increases with increase of withdrawal speed in agreement with the Landau-Levich model. The apparent and real densities are similar for coatings fired below 400 degrees C, which shows that the films are free of pores. The shrinkage during firing is anisotropic, occurring essentially perpendicular to the coating surface. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Anindobothrium n. gen. (Eucestoda : Tetraphyllidea) inhabiting marine and freshwater potamotrygonid stingrays

Anindobothrium n. gen. is proposed to accommodate Caulobothrium anacolum inhabiting Himanturu schmardae from Colombia, and 2 new species, one inhabiting Potamotrygon orbigny in Brazil and the other inhabiting Paratrygon aereiba in Venezuela. Members of the new genus resemble members of Pararhinebothroides, Rhinebothroides, and Anthocephalum by having bothridia with poorly differentiated apical suckers and vasa deferentia expanded into external seminal vesicles. It further resembles Pararhinebothroides, Rhinebothroides, and Anthocephalum cairae by having vas deferens inserted near the poral rather than aporal end of the cirrus sac. The 3 species assigned to the new genus form an apparent monophyletic group, based on the possession of 3 putative synapomorphies: (1) genital pores in the anterior 1/4 of the proglottid, a trait that is unusual, but not unique, among phyllobothriids; (2) anteroventral ovarian lobes converging to the center of the proglottid, a character not previously reported for phyllobothriids; and (3) ovarian lobes comprising a loose network of digitiform processes.

Isothermal structural evolution of SnO2 monolithic porous xerogels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Model peptides mimic the structure and function of the N-terminus of the pore-forming toxin sticholysin II

To investigate the role of the N-terminal region in the lytic mechanism of the pore-forming toxin sticholysin II (St II), we studied the conformational and functional properties of peptides encompassing the first 30 residues of the protein. Peptides containing residues 1-30 (P1-30) and 11-30 (P11-30) were synthesized and their conformational properties were examined in aqueous solution as a function of peptide concentration, pH, ionic strength, and addition of the secondary structure-inducing solvent trifluoroethanol (TFE). CD spectra showed that increasing concentration, pH, and ionic strength led to aggregation of P1-30; as a consequence, the peptide acquired beta-sheet conformation. In contrast, P11-30 exhibited practically no conformational changes under the same conditions, remaining essentially structureless. Moreover, this peptide did not undergo aggregation. These differences clearly point to the modulating effect of the first 10 hydrophobic residues on the peptides aggregation and conformational properties. In TFE both the first ten hydrophobic peptides acquired alpha-helical conformation, albeit to a different extent, P11-30 displayed lower alpha-helical content. P1-30 presented a larger-fraction of residues in alpha-helical conformation in TFE than that found in St II's crystal structure for that portion of the protein. Since TFE mimics the membrane em,, such increase in helical content could also occur upon toxin binding to membranes and represent a step in the mechanism of pore formation. The peptides conformational properties correlated well with their functional behaviour. Thus, P1-30 exhibited much higher hemolytic activity than P11-30. In addition, P11-30 was able to block the toxin's hemolytic activity. The size of pores formed in red blood cells by P 1-30 was estimated by measuring the permeability PEGs of different molecular mass. The pore radius (0.95 +/- 0.01 nm) was very similar to that of the PEGs of different pore formed by the toxin. The results demonstrate that the synthetic peptide P1-30 is a good model of St 11 conformation and function and emphasize the contribution of the toxin's N-terminal region, and, in particular, the hydrophobic residues 1-10 to pore formation. (c) 2005 Wiley Periodicals, Inc.

Phase separation in pyrex glass by hydrothermal treatment: evidence from micro-Raman spectroscopy

In this work, we investigated the formation of porous silica matrix obtained by hydrothermal treatment under saturated steam condition from Pyrex (R) glass. This investigation was carried out by scanning electron microscopy (SEM), infrared spectroscopy (IR), X-ray powder diffractometry (XRD) and Raman microscopy. We observed the presence of connected and homogeneously distributed pores in a non-crystalline silica phase and a detectable interface between silica and remnant glass phases resulting in a framework similar to asymmetric membranes. The results indicate that the process of phase separation takes place at lower temperature than that of glass-transition on the surface of the glass phase. Essential reaction between water and silica at supercritical condition together with the formation and leaching of soluble phase contribute to obtain porous silica matrix, (C) 2001 Elsevier B.V. B.V. All rights reserved.

Structure of SnO2 alcosols and films prepared by sol-gel dip coating

To obtain SnO2 films to be used for surface protection of fluoride glasses, a non-aqueous sol-gel route for the preparation was developed. An ethanolic SnO2 colloidal suspension was prepared by thermohydrolysis of SnCl4 solution at 70 degreesC. By using this procedure, redispersable powders with nanometer sized particles were obtained. Films were obtained by dip coating on glass and mica substrates. The structures of the ethanolic precursor suspension and films were compared to those of similar samples prepared by the classical aqueous sol-gel route. Comparative analyses performed by photon correlation spectroscopy demonstrated that the powders obtained by freeze-drying are fully redispersable either in aqueous or in alcoholic solutions at pH greater than or equal to 8. As prepared sols and redispersed colloidal suspensions have hydrodynamic radius distribution (2-14 nm) with an average size close to 7 nm. The variations in film structures with firing temperature were investigated by small-angle X-ray scattering and X-ray reflectometry. The experimental results show that the films have a two level porous structure composed of agglomerates of primary colloidal particles. The sintering of the primary particles leads to the densification of agglomerates and to the formation of inter-agglomerate spatially correlated pores. The volume fraction of intra-agglomerate pores is reduced from approximate to 50% to approximate to 30% by the precipitation of precursor salts partially hydrolyzed in ethanolic solution. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Structural evolution up to 1100 degrees C of xerogels prepared from TEOS sonohydrolysis and liquid phase exchanged by acetone

Silica xerogels were prepared from sonohydrolysis of tetraethoxysilane and exchange of the liquid phase of the wet gel by acetone. Monolithic xerogels were obtained by slow evaporation of acetone. The structural characteristics of the xerogels were studied as a function of temperature up to 1100 degrees C by means of bulk and skeletal density measurements, linear shrinkage measurements and thermal analyses (DTA, TG and DL). The results were correlated with the evolution in the UV-Vis absorption. Particularly, the initial pore structure of the dried acetone-exchanged xerogel was studied by small-angle X-ray scattering and nitrogen adsorption. The acetone-exchanged xerogels exhibit greater porosity in the mesopore region presenting greater mean pore size (similar to 4 nm) when compared to non-exchanged xerogels. The porosity of the xerogels is practically stable in the temperature range between 200 degrees C and 800 degrees C. Evolution in the structure of the solid particles (silica network) is the predominant process upon heating up to about 400 degrees C and pore elimination is the predominant process above 900 degrees C. At 1000 degrees C the xerogels are still monolithic and retain about 5 vol.% pores. The xerogels exhibited foaming phenomenon after hold for 10 h at 1100 degrees C. This temperature is even higher than that found for foaming of non-exchanged xerogels. (c) 2005 Elsevier B.V. All rights reserved.

Red and blue emissions of europium doped gadolinium silicate from porous silica matrix and hydroxide carbonate with spherical shaped particles

In this work, Eu(III) and Eu(II) doped gadolinium silicates has been obtained as compact tubes starting from spherical gadolinium hydroxide carbonate using the pores of silica matrix as support and its surface as reagent. Eu(III) doped gadolinium silicate with hexagonal phase shows an interesting visible shifted charge transfer band when compared to disilicate with orthorhombic phase that was also obtained. Eu(II) gadolinium silicate has been prepared using CO atmosphere presenting an intense blue emission. The divalent europium system shows a potential application as an UV-blue converter. The samples were characterized by scanning electron microscopy (SEM), X-ray powder diffractometry (XRD) and photoluminescence spectroscopy. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Modulation of intercellular communication in macrophages: possible interactions between GAP junctions and P2 receptors

Gap junctions are connexin-formed channels that play an important role in intercellular communication in most cell types. In the immune system, specifically in macrophages, the expression of connexins and the establishment of functional gap junctions are still controversial issues. Macrophages express P2X(7) receptors that, once activated by the binding of extracellular ATP, lead to the opening of transmembrane pores permeable to molecules of up to 900 Da. There is evidence suggesting an interplay between gap junctions and P2 receptors in different cell systems. Thus, we used ATP-sensitive and -insensitive J774.G8 macrophage cell lines to investigate this interplay. To study junctional communication in J774-macrophage-like cells, we assessed cell-to-cell communication by microinjecting Lucifer Yellow. Confluent cultures of ATP-sensitive J774 cells (ATP-s cells) are coupled, whereas ATP-insensitive J774 cells (ATP-i cells), derived by overexposing J774 cells to extracellular ATP until they do not display the phenomenon of ATP-induced permeabilization, are essentially uncoupled. Western-blot and reverse-transcription polymerase chain reaction assays revealed that ATP-s and ATP-i cells express connexin43 (Cx43), whereas only ATP-s cells express the P2X(7) receptor. Accordingly, ATP-i cells did not display any detectable ATP-induced current under whole-cell patch-clamp recordings. Using immunofluorescence microscopy, Cx43 reactivity was found at the cell surface and in regions of cell-cell contact of ATP-s cells, whereas, in ATP-i cells, Cx43 immunoreactivity was only present in cytosolic compartments. Using confocal microscopy, it is shown here that, in ATP-s cells as well as in peritoneal macrophages, Cx43 and P2X(7) receptors are co-localized to the membrane of ATP-s cells and peritoneal macrophages.

Effects of self-assembly process of latex spheres on the final topology of macroporous silica

This paper surveys the topology of macroporous silica prepared using latex templates covering the submicrometric range (0.1-0.7 mu m). The behavior of latex spheres in aqueous dispersion has been analyzed by dynamic light scattering (DLS) measurement indicating the most appropriate conditions to form well-defined cubic arrays. The optical behavior of latex spheres has been analyzed by transmittance and reflectance measurements in order to determine their diameter and filling factor when they were assembled in bidimensional arrays. Macroscopic templates have been obtained by a centrifugation process and their crystalline ordering has been confirmed by porosimetry and scanning electron microscopy. These self-assembled structures have been used to produce macroporous silica, whose final topology depends on the pore size distribution of the original template. It has been seen that latex spheres are ordered in a predominant fcc arrangement with slipping of tetragonal pores due to the action of attractive electrostatic interactions. The main effect is to change the spherical shape of voids in macroporous silica into a hexagonal configuration with possible applications to fabricate photonic devices with novel optical properties. (c) 2005 Elsevier B.V. All rights reserved.

Zirconia foams prepared by integration of the sol-gel method and dual soft template techniques

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Isochronal sintering of the blended elemental Ti-35Nb alloy

Titanium alloy parts are ideally suited for advanced aerospace systems and surgical implants because of their unique combination of high specific strength at both room temperature and moderately elevated temperature, in addition to excellent corrosion resistance. In this work, results of the Ti-35Nb alloy sintering are presented. This alloy, due to its lower modulus of elasticity and high biocompatibility, is a promising candidate for surgical and aerospace applications. Samples were produced by mixing of initial metallic hydride powders followed by uniaxial and cold isostatic pressing with subsequent densification by isochronal sintering between 700 and 1500 degrees C, in vacuum. Sintering behavior was studied by means of microscopy and density. Sintered samples were characterized for phase composition, microstructure and microbardness by X-ray diffraction, scanning electron microscopy and Vickers indentation, respectively. Samples sintered at high temperatures display a fine plate-like a structure and intergranular P. A few remaining pores are still found, and density above 97% for specimens sintered at 1500 degrees C is reached. (c) 2007 Elsevier B.V. All rights reserved.

Electrochemical Behavior of Cu-9% Al-5% Ni-2% Mn Alloy in Chloride Media

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)