Zirconia needles synthesized inside hexagonal swollen liquid crystals

We report the synthesis of zirconia microneedles by the direct nucleation of particles inside a hexagonal swollen liquid crystal (SLC) (cell parameter a = 27 nm) prepared by mixing with the proper ratio, an aqueous solution of sulfated zirconium colloids, a cationic surfactant (cetylpyridinium chloride), cychlohexane as swelling agent with an oil over water ratio of 2.5 (vol.), and 1-pentanol as cosurfactant. After a slow crystallogenesis that can be enhanced by an initial induction step under moderate temperature, particles in the centimeter range can be obtained, with a very high shape ratio (over 100). These particles are made of crystalline octahydrate zirconium oxychloride containing pores of 20 nm diameter, aligned along the main axis of the liquid crystal, as the fingerprint of the oil cylinders present in the hexagonal phase. The morphology of these particles confirms that the shaping mechanism is based on true liquid crystal templating (TLCT). Further thermal treatment of these particles, after extraction from the SLC, leads to the crystallization of zirconia with the same needlelike morphology as the zirconium oxychloride.

Comparison of different clean-up procedures for the determination of N-methylcarbamate insecticides in vegetable matrices by high-performance liquid chromatography with UV detection

Several clean-up procedures which included the use of glass chromatography columns (silica gel, alumina, Florisil, silanized Celite-charcoal), Sep-Pak cartridges and standard solutions were compared for the determination of the following N-methylcarbamate (NMC) insecticides: aldicarb, carbaryl, carbofuran, methomyl and propoxur. According to recovery results of the compounds after elution in a glass column, the most efficient systems employed 4.6% deactivated alumina and a silanized Celite-charcoal (4:1) as adsorbents, using dichloromethane-methanol (99:1) and toluene-acetonitrile (75:25) mixtures, respectively, as binary eluents. The recoveries of the compounds studied varied from 84 to 120%. Comparable recoveries (75-100%) for Sep-Pak cartridges in normal phase (NH2, CN) and reversed phase (C-8) were observed. Different temperatures were tested during the concentration step in a rotary evaporator, and we verified a strong influence of this parameter on the stability of some compounds, such as carbofuran and carbaryl. Recovery studies employing the best clean up procedures were performed at the Brazilian agricultural level in potato and carrot samples; Validation methodology of the US Food and Drug Administration was adapted for the N-methylcarbamate analysis. Their recoveries ranged between 79 and 93% with coefficients of variation of 2.3-8%. (C) 1998 Elsevier B.V. B.V.

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.

THE FLUID SYSTEMS FOR THE SLD CHERENKOV RING IMAGING DETECTOR

We describe the design and operation of the fluid delivery, monitor and control systems for the SLD barrel Cherenkov Ring Imaging Detector (CRID). The systems deliver drift gas (C2H6+TMAE), radiator gas (C5F12+N2) and radiator liquid (C6F14). MeasUred critical quantities such as electron lifetime in the drift gas and ultra-violet (UV) transparencies of the radiator fluids, together with the operational experience, are also reported.

Preparation of new glass systems by the polymeric precursor method for dental applications

Glass ionomer cements (GICs) are largely employed in Dentistry for several applications, such as luting cements for the attachment of crowns, bridges, and orthodontic brackets as well as restorative materials. The development of new glass systems is very important in Dentistry to improve of the mechanical properties and chemical stability. The aim of this study is the preparation of two glass systems containing niobium in their compositions for use as GICs. Glass systems based on the composition SiO2,Al2O3-Nb2O5-CaO were prepared by chemical route at 700degreesC. The XRD and DTA results confirmed that the prepared materials are glasses. The structures of the obtained glasses were compared to commercial material using FTIR, Al-27 and Si-29 MAS-NMR. The analysis of FTIR and MAS-NMR spectra indicated that the systems developed and commercial material are formed by SiO4 and AlO4 linked tetrahedra. These structures are essential to get the set time control and to have cements. These results encourage further applications of the experimental glasses in the formation of GICs. (C) 2004 Elsevier B.V. All rights reserved.

Highly swollen liquid crystals as new reactors for the synthesis of nanomaterials

Synthesis and self-assembly of nanomaterials can be controlled by the properties of soft matter. on one hand, dedicated nanoreactors such as reverse microemulsions or miniemulsions can be designed. on the other hand, direct shape control can be provided by the topology of liquid crystals that confine the reacting medium within a specific geometry. In the first case, the preparation of micro- or miniemulsions generally requires energetic mechanical stirring. The second approach uses thermodynamically stable systems, but it remains usually limited to binary (water + surfactant) systems. We report the preparation of different families of materials in highly ordered quaternary mediums that exhibit a liquid crystal structure with a high cell parameter. They were prepared with the proper ratios of salted water, nonpolar solvent, surfactant. and cosurfactants that form spontaneously swollen hexagonal phases. These swollen liquid crystals can be prepared from all classes of surfactants (cationic, anionic, and nonionic). They contain a regular network of parallel cylinders, whose diameters can be swollen with a nonpolar solvent, that are regularly spaced in a continuous aqueous salt solution. We demonstrate in the present report that both aqueous and organic phases can be used as nanoreactors for the preparation of materials. This property is illustrated by various examples such as the synthesis of platinum nanorods prepared in the aqueous phase or zirconia needles or the photo- or gamma-ray-induced polymerization of polydiacetylene in the organic phase. In all cases, materials can be easily extracted and their final shapes are directed by the structure-directing effect imposed by the liquid crystal.

Miniaturized structures for removal or selection of particles from liquid flow

The aim of this work was the development of miniaturized structures useful for retention and/or selection of particles and viscous substances from a liquid flow. The proposed low costs structures are similar to macroscopic wastewater treatment systems, named baffles, and allow disassemble. They were simulated using FEMLAB 3.2b package and manufactured in acrylic with conventional tools. Tests for retention or selection of particles in water or air and viscous fluids in water were carried out. Either in air or water particles with 50 mu m diameter will be retained but not with 13 mu m diameter. In aqueous flow, it is also possible the retention of viscous samples, such as silicone 350 cSt. The simulated results showed good agreement with experimental measurements. These miniaturized structures can be useful in sample pretreatment for chemical analysis and microorganism manipulation. (C) 2007 Elsevier B.V. All rights reserved.

Microstructural development of ZnO varistor during reactive liquid phase sintering

The microstructural evolution, grain growth and densification for the varistor systems ZnO-Bi2O3 (ZB), ZnO-Bi2O3-Sb2O3 (ZBS), ZnO-Bi2O3-Sb2O3-MnO-Cr 2O3-CoO (ZBSCCM) were studied using constant heating rate sintering, scanning electron microscopy (SEM) and in situ phase formation measurement by high temperature X-ray diffraction (HT-XRD). The results showed that the densifying process is controlled by the formation and decomposition of the Zn2Bi3Sb3O14 pyrochlore (PY) phase for the ZBS and ZBSCCM systems. The addition of transition metals (ZBSCCM system) alters the formation and decomposition reaction temperatures of the pyrochlore phase and the morphology of the Zn7Sb2O12 spinel phase. Thus, the spinel grains act as inclusions and decrease the ZnO grain growth rate. Spinel grain growth kinetics in the ZBSCCM system showed an n value of 2.6, and SEM and HT-XRD results indicate two grain growth mechanisms based on coalescence and Ostwald ripening. © 1996 Chapman & Hall.

Absence of Cooper-type bound states in three- and few-electron systems

It is shown that the appearance of a fixed-point singularity in the kernel of the two-electron Cooper problem is responsible for the formation of the Cooper pair for an arbitrarily weak attractive interaction between two electrons. This singularity is absent in the problem of three and few superconducting electrons at zero temperature on the full Fermi sea. Consequently, such three- and few-electron systems on the full Fermi sea do not form Cooper-type bound states for an arbitrarily weak attractive pair interaction.

Microstructure, crystalline phase, and dielectric property analyses of TiO2 composition with ZrO2 addition

For microwave applications, including mobile and satellite communications, ceramic resonators should have a high dielectric constant, low dielectric losses, and high frequency stability. In this sense, TiO2-ZrO 2 ceramics have been investigated as a function of sintering behavior, phase composition, and microstructure. The ceramics were densified reaching a value of about 86% of theoretical density at 1400°C sintering temperature. The ceramics are prepared by mixing raw materials with the following TiO2-ZrO2 weight % ratio: 100 to 0, 90 to 10, and 80 to 20, respectively. The measured dielectric constants are between 79 and 88 values, while the quality factor due to dielectric losses are between 2820 and 5170. These results point out the influence of Ti/Zr ratio on controlling the dielectric properties. © (2010) Trans Tech Publications.

A comparative study of aquifer systems occurring at the Paraná sedimentary basin, Brazil: U-isotopes contribution

The radioactivity due to 238U and 234U in three aquifer systems occurring within the Paraná sedimentary basin, South America, has been investigated. Uranium is much less dissolved from fractured igneous rocks than from the porous sedimentary rocks as indicated by the U-mobility coefficients between 7. 6 × 10-6 and 1. 2 × 10-3 g cm-3. These values are also compatible with the U preference ratios relative to Na, K, Ca, Mg and SiO2, which showed that U is never preferentially mobilized in the liquid phase during the flow occurring in cracks, fissures, fractures and faults of the igneous basaltic rocks. Experimental dissolution of diabase grains on a time-scale laboratory has demonstrated that the U dissolution appeared to be a two-stage process characterized by linear and second-order kinetics. The U dissolution rate was 8 × 10-16 mol m-2 s-1 that is within the range of 4 × 10-16-3 × 10-14 mol m-2 s-1 estimated for other rock types. The 234U/238U activity ratio of dissolved U in solutions was higher than unity, a typical result expected during the water-rock interactions when preferential 234U-leach from the rock surfaces takes place. Some U-isotopes data allowed estimating 320 ka for the groundwater residence time in a sector of a transect in São Paulo State. A modeling has been also realized considering all U-isotopes data obtained in Bauru (35 samples), Serra Geral (16 samples) and Guarani (29 samples) aquifers. The results indicated that the Bauru aquifer waters may result from the admixture of waters from Guarani (1. 5 %) and Serra Geral (98. 5 %) aquifers. © 2012 Springer-Verlag.

Nanotechnology-based drug delivery systems for treatment of hyperproliferative skin diseases - a review

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nasal administration of liquid crystal precursor mucoadhesive vehicle as an alternative antiretroviral therapy

The purpose of this study was to develop a mucoadhesive stimuli-sensitive drug delivery system for nasal administration of zidovudine (AZT). The system was prepared by formulating a low viscosity precursor of a liquid crystal phase, taking advantage of its lyotropic phase behavior. Flow rheology measurements showed that the formulation composed of PPG-5-CETETH-20, oleic acid and water (55, 30, 15% w/w), denominated P, has Newtonian flow behavior. Polarized light microscopy (PLM) revealed that formulation P is isotropic, whereas its 1:1 (w/w) dilution with artificial nasal mucus (ANM) changed the system to an anisotropic lamellar phase (PD). Oscillatory frequency sweep analysis showed that PD has a high storage modulus (G′) at nasal temperatures. Measurement of the mucoadhesive force against excised porcine nasal mucosa or a mucin disk proved that the transition to the lamellar phase tripled the work of mucoadhesion. Ex vivo permeation studies across porcine nasal mucosa exhibited an 18-fold rise in the permeability of AZT from the formulation. The Weibull mathematical model suggested that the AZT is released by Fickian diffusion mechanisms. Hence, the physicochemical characterization, combined with ex vivo studies, revealed that the PPG-5-CETETH-20, oleic acid, and water formulation could form a mucoadhesive matrix in contact with nasal mucus that promoted nasal absorption of the AZT. For an in vivo assessment, the plasma concentrations of AZT in rats were determined by HPLC method following intravenous and intranasal administration of AZT-loaded P formulation (PA) and AZT solution, respectively, at a dose of 8 mg/kg. The intranasal administration of PA resulted in a fast absorption process (Tmax = 6.7 min). Therefore, a liquid crystal precursor formulation administered by the nasal route might represent a promising novel tool for the systemic delivery of AZT and other antiretroviral drugs. In the present study, the uptake of AZT absorption in the nasal mucosa was demonstrated, providing new foundations for clinical trials in patients with AIDS. © 2012 Elsevier B.V. All rights reserved.

Liquid foam templates associated with the sol-gel process for production of zirconia ceramic foams

The unique properties of ceramic foams enable their use in a variety of applications. This work investigated the effects of different parameters on the production of zirconia ceramic foam using the sol-gel process associated with liquid foam templates. Evaluation was made of the influence of the thermal treatment temperature on the porous and crystalline characteristics of foams manufactured using different amounts of sodium dodecylsulfate (SDS) surfactant. A maximum pore volume, with high porosity (94%) and a bimodal pore size distribution, was observed for the ceramic foam produced with 10% SDS. Macropores, with an average size of around 30 μm, were obtained irrespective of the SDS amount, while the average size of the supermesopores increased systematically as the SDS amount was increased up to 10%, after which it decreased. X-ray diffraction analyses showed that the sample treated at 500 °C was amorphous, while crystallization into a tetragonal metastable phase occurred at 600 °C due to the presence of sulfate groups in the zirconia structure. At 800 and 1000 °C the monoclinic phase was observed, which is thermodynamically stable at these temperatures. © 2013 by the authors; licensee MDPI, Basel, Switzerland.

Analise de viabilidade técnica-econômica na substituição de um sistema combinado de geração de vapor-vácuo por bombas secas

Pós-graduação em Engenharia Mecânica - FEG