Alcóxidos como precursores na síntese de novos materiais através do processo sol-gel

An overview about the role of alkoxides in the most recent uses of the sol-gel process in the synthesis of new materials is presented. Special attention is focused on the uses of silicon, aluminum, zirconium and titanium alkoxides. This review shows that the alkoxides enable the synthesis of new matrices with controlled surface area, acidity and porosity, as well as some unusual properties. The property associated with the solubility of metal alkoxides opens enormous possibilities of combining them for the synthesis films of powders with a very large range of metal compositions.

Ultra-trace monitoring of copper in environmental and biological samples by inductively coupled plasma atomic emission spectrometry after separation and preconcentration by using octadecyl silica membrane disks modified by a new schiff's base

Ultra-trace amounts of Cu(II) were separated and preconcentrated by solid phase extraction on octadecyl-bonded silica membrane disks modified with a new Schiff,s base (Bis- (2-Hydroxyacetophenone) -2,2-dimethyl-1,3-propanediimine) (SBTD) followed by elution and inductively coupled plasma atomic emission spectrometric detection. The method was applied as a separation and detection method for copper(II) in environmental and biological samples. Extraction efficiency and the influence of sample matrix, flow rate, pH, and type and minimum amount of stripping acid were investigated. The concentration factor and detection limit of the proposed method are 500 and 12.5 pg mL-1, respectively.

A novel method for fast enrichment and monitoring of hexavalent and trivalent chromium at the ppt level with modified silica MCM-41 and its determination by inductively coupled plasma optical emission spectrometry

Chromium(III) at the ng L-1 level was extracted using partially silylated MCM-41 modified by a tetraazamacrocyclic compound (TAMC) and determined by inductively coupled plasma optical emision spectrometry (ICP OES). The extraction time and efficiency, pH and flow rate, type and minimum amount of stripping acid, and break- through volume were investigated. The method's enrichment factor and detection limit are 300 and 45.5 pg mL-1, respectively. The maximum capacity of the 10 mg of modified silylated MCM-41 was found to be 400.5±4.7 µg for Cr(III). The method was applied to the determination of Cr(III) and Cr(VI) in the wastewater of the chromium electroplating industry and in environmental and biological samples (black tea, hot and black pepper).

O emprego de quitosana quimicamente modificada com anidrido succínico na adsorção de azul de metileno

The adsorption capacity of alpha-chitosan and its modified form with succinic anhydride was compared with the traditional adsorbent active carbon by using the dye methylene blue, employed in the textile industry. The isotherms for both biopolymers were classified as SSA systems in the Giles model, more specifically in L class and subgroup 3. The dye concentration in the supernatant in the adsorption assay was determined through electronic spectroscopy. By calorimetric titration thermodynamic data of the interaction between methyene blue and the chemically modified chitosan at the solid/liquid interface were obtained. The enthalpy of the dye/chitosan interaction gave 2.47 ± 0.02 kJ mol-1 with an equilibrium constant of 7350 ± 10 and for the carbon/dye interaction this constant gave 5951 ± 8. The spontaneity of these adsorptions are reflected by the free Gibbs energies of -22.1 ± 0.4 and -21.5 ± 0.2 kJ mol-1, respectively, found for these systems. This new adsorbent derived from a natural polysaccharide is as efficient as activated carbon. However 97% of the bonded dye can be eluted by sodium chloride solution, while this same operation elutes only 42% from carbon. Chitosan is efficient in dye removal with the additional advantage of being cheap, non-toxic, biocompatible and biodegradable.

Determinação das propriedades catalíticas em meio aquoso e orgânico da lipase de Candida rugosa imobilizada em celulignina quimicamente modificada por carbonildiimidazol

Microbial lipase from Candida rugosa was immobilized by covalent binding on wood cellulignin (Eucaliptus grandis) chemically modified with carbonyldiimidazole. The immobilized system was fully evaluated in aqueous (olive oil hydrolysis) and organic (ester synthesis) media. A comparative study between free and immobilized lipase was carried out in terms of pH, temperature and thermal stability. A higher pH value (8.0) was found optimal for the immobilized lipase. The optimal reaction temperature shifted from 37 °C for the free lipase to 45 °C for the immobilized lipase. The pattern of heat stability indicated that the immobilization process tends to stabilize the enzyme. Kinetics tests at 37 °C following the hydrolysis of olive oil obeyed the Michaelis-Menten rate equation. Values for Km = 924.9 mM and Vmax = 198.3 U/mg were lower than for free lipase, suggesting that the affinity towards the substrate changed and the activity of the immobilized lipase decreased during the course of immobilization. The immobilized derivative was also tested in the ester synthesis from several alcohols and carboxylic acids.

Biomateriais: deposição de hidroxiapatita sobre superfície de Ti-cp modificada por aspersão térmica

The osseointegrated titanium implants are reliable and safe alternatives to treatments for long periods of time. For surface modification, thermal aspersion of TiO2 was used. The samples with and without TiO2 were treated with NaOH and SBF in order to obtain a layer of HA. Characterization was done by SEM and FTIR. The images of HA obtained by SEM show a uniform morphology and a porous structure with spherical particles. The IR spectra show that the surface of Ticp/ TiO2 is more favorable for the HA deposit, as can be seen by the increase of the crystalline structure and the very intense and defined bands of the OH group of HA that is verified about 3571 and 630 cm-1. Thus the Ticp/ TiO2 surface presents a satisfactory nucleation of HA when compared to Ticp.

Síntese e estudo de ortossilicatos de zinco luminescentes com aplicação da técnica sol-gel

Usually, the concepts of the Sol-Gel technique are not applied in experimental chemistry courses. This work presents a feasible experiment for chemistry instruction, which involves the synthesis of luminescent materials - Zn2SiO4, with and without Mn2+ as a dopant - by the Sol-Gel technique. The obtained materials were analyzed by scanning electron microscopy, X-Ray diffraction, IR spectroscopy and luminescence measures by UV-vis spectroscopy. The results allow the students to confirm the luminescent properties of the zinc orthosilicate luminophores as well as the structural features expected from literature data.

Nióbia sintética modificada como catalisador na oxidação de corante orgânico: utilização de H2O2 e O2 atmosférico como oxidantes

In this work synthetic niobia was used to promote the oxidation of methylene blue dye in aqueous medium. The niobia was characterized by N2 adsorption/desorption, XRD and TG measurements. The presence of reactive species on the niobia surface strongly increased the oxidation rate of the methylene blue dye. The reaction mechanism was studied by ESI-MS suggesting that the oxidation of the organic dye involve oxidizing species generated mainly after previous treatment with H2O2. It can be observed that the catalyst is a good material in the activation of gas (atmospheric oxygen) or liquid (hydrogen peroxide) oxidant agent with a total discoloration of the dye solution after only 1 h of reaction.

Estudo de liberação e permeação in vitro do diclofenaco de dietilamônio em microemulsão gel-like

The goal of this study was to produce and characterize a new microemulsion gel-like carrier system (MEG) by using the pseudo-ternary phase-diagram concept. The diclofenac diethylamine (DDA) was incorporated in the MEG and its in vitro release and permeation profiles were performed using Franz-type diffusion cells. The results revealed that the commercial DDA emulgel provided significantly higher Kp of DDA (2.2-fold) as compared to the MEG. Similar data were obtained in the permeation studies in which DDA Kp 4.7-fold higher. Therefore, MEG presents higher potential as a topical delivery system for DDA when compared to the commercial DDA emulgel.

Obtaining high purity silica from rice hulls

Many routes for extracting silica from rice hulls are based on direct calcining. These methods, though, often produce silica contaminated with inorganic impurities. This work presents the study of a strategy for obtaining silica from rice hulls with a purity level adequate for applications in electronics. The technique is based on two leaching steps, using respectively aqua regia and Piranha solutions, which extract the organic matrix and inorganic impurities. The material was characterized by Fourier-transform infrared spectroscopy (FTIR), powder x-ray diffraction (XRD), x-ray fluorescence (XRF), scanning electron microscopy (SEM), particle size analysis by laser diffraction (LPSA) and thermal analysis.

Degradação de corantes reativos por processo foto-fenton envolvendo o uso de peneira molecular 4A modificada com Fe3+

In this work the preparation and characterization of a supported catalyst intended for degradation of reactive dyes by Fenton-like processes is described. The photocatalyst was prepared by immobilization of Fe3+ into the molecular sieve (4A type) surface and characterized by x-ray diffractometry and infrared, Mössbauer and EPR spectroscopy. The solid containing 0.94% (w/w) of ferric ions was used in degradation studies of aqueous reactive-dyes samples with really promissory results. Generally, Vis-assisted photochemical processes leads to almost total decolorization of all tested dyes at reaction times lower than 30 min. It was also observed that the iron-molecular sieve matrix can be reused.

Reator de UV-Ozônio com lâmpada a vapor de mercúrio a alta pressão modificada para tratamento superficial de óxidos transparentes condutivos utilizados em dispositivos poliméricos eletroluminescentes

An UV-Ozone reactor was developed with an ignition tube extracted into HID mercury lamp used to irradiation on zinc oxide (ZnO) and fluorinated tin oxide (FTO) films for PLEDs devices. Different exposures times were used. In contact angle measurements revealed better results for ZnO and FTO by 15 and 5 min, respectively. In Diffuse Reflectance Infra-red Fourier Transformed (DRIFT) spectroscopy allowed the observation of water, hydrocarbon and carbon dioxide adsorbed on the untreated TCO surfaces. After the UV-Ozone treatment the contaminants were significantly reduced or eliminated and the PLEDs devices decreased threshold voltages in comparison with respectively untreated TCOs.

Properties of silica from rice husk and rice husk ash and their utilization for zeolite y synthesis

This study compared properties of silica (SiO2) from rice husk (RH) and rice husk ash (RHA) extracted by acid- and heat-treatment. The SiO2 from RH was in amorphous phase with nearly 100% purity while that from RHA was in crystalline phase with 97.56% purity. Both extracted SiO2 were used in the synthesis of zeolite NaY but that from RH was better due to the efficiency in product recovery and simplicity of extraction. After the NaY was exchanged to NH4Y and calcined to convert to HY, the product did not carry over the textural properties of the parent NaY and NH4Y.

Synthesis of indium tin oxide nanoparticles by a nonhydrolytic sol-gel method

Indium tin oxide nanoparticles were synthesized in two different sizes by a nonhydrolytic sol-gel method. These powders were then transformed into ITO via an intermediate metastable state at between 300 and 600 ºC. The presence of characteristic O-In-O and O-Sn-O bands at 480 and 670 cm-1 confirmed the formation of ITO. The X-ray diffraction patterns indicated the preferential formation of metastable hexagonal phase ITO (corundum type) as opposed to cubic phase ITO when the reflux time was less than 3 h and the heat treatment temperature was below 600 ºC. Particle morphology and crystal size were examined by scanning electron microscopy.

Remoção de íons Pb2+ de solução de bateria automotiva por caulinita modificada com óxido de manganês

Nine absorbents were prepared using a mixture of Amazonian kaolinite and MnO2 at three temperatures (600, 700 and 900 ºC) in order to retain Pb2+ ions contained in the battery solutions. The batch experiments carried out with the batteries used water for 3 h and the kinetic isotherm was fitted with the pseudo-second order Lagergren equation. Findings show that synthesized adsorbents AD4, AD5 and AD7 performed well in reducing the Pb2+ ion content from 0.36 to 0.00 mg g-1. The better performance for removing the Pb2+ ions occurred for adsorbents synthesized in the temperature range from 600 to 700 ºC.