INTRATRACHEAL INJECTION OF NICKEL CHLORIDE AND COPPER-ZINC SUPEROXIDE-DISMUTASE ACTIVITY IN LUNG OF RATS

Superoxide radical (O2-) is a free radical that may be involved in various toxic processes. Cu-Zn superoxide dismutase catalyses the dismutation of the superoxide free radical and protects cells from oxidative damage, and it has been used clinically. The concentration of Ni2+ and Cu-Zn superoxide dismutase activity were measured in lungs of rats at time intervals of 5, 12, 19, 26, 33, and 40 days following an intratracheal injection of 127 nmol of NiCl2. Nickel chloride increased nickel content and resulted in a significant increase of Cu-Zn superoxide dismutase activity in lungs. This elevation of Cu-Zn superoxide dismutase activity was highest on the 12th day (approximately threefold) and is at levels comparable to controls rats on day 40 onwards. Since Cu-Zn superoxide dismutase activity was increased in lung throughout our experimental period without corresponding increases of Cu2+ and Zn2+, we speculate that the elevation of Cu-Zn superoxide dismutase activity might be due to an increased half-life of the enzyme, induced by nickel.

Titanium(IV)-EDTA complex - Kinetics of thermal decomposition by non-isothermal procedures

This work aims the evaluation of the kinetic triplets corresponding to the two successive steps of thermal decomposition of Ti(IV)-ethylenediaminetetraacetate complex. Applying the isoconversional Wall-Flynn-Ozawa method on the DSC curves, average activation energy: E=172.4 +/- 9.7 and 205.3 +/- 12.8 kJ mol(-1), and pre-exponential factor: logA = 16.38 +/- 0.84 and 18.96 +/- 1.21 min(-1) at 95% confidence interval could be obtained, regarding the partial formation of anhydride and subsequent thermal decomposition of uncoordinated carboxylate groups, respectively.From E and logA values, Dollimore and Malek methods could be applied suggesting PT (Prout-Tompkins) and R3 (contracting volume) as the kinetic model to the partial formation of anhydride and thermal decomposition of the carboxylate groups, respectively.

Cobalt(II) and nickel(II) complexes with djenkolic acid

Cobalt(II) and nickel(II) djenkolates CoC7H12N2O4S2. H2O (I) and NiC7H12N2O4S2. H2O (II) were synthesized by the reaction of potassium djenkolate with the respective chlorides. LR spectra suggested coordination via the COO- and NH2 groups for the ligands in both compounds. Visible absorption spectra confirmed the octahedral structure of the complexes. X-ray powder diffraction patterns were indexed in the orthorhombic and monoclinic unit cells with parameters: a = 11.35, b = 7.35, c = 6.85 Angstrom for I and a = 11.54, b = 7.45, c = 6.90 Angstrom, beta = 94.95 degrees for II.

Response of rat bone marrow cells to commercially pure titanium submitted to different surface treatments

Objectives. Alterations in the commercially pure titanium (cpTi) surface may be undertaken to improve its biological properties. The aim of this study is to investigate the biocompatibility of cpTi submitted to different surface treatments.Methods. The cpTi surfaces were prepared so that machined and blasted surfaces, either acid etched or not, were compared using rat bone marrow cells cultured to differentiated into osteoblast. For attachment evaluation, cells were cultured for 4 and 24 h. Cell morphology was evaluated after 3 days. After 7, 14, and 21 days cell proliferation was evaluated. Total protein content and alkaline phosphatase (ALP) activity were evaluated after 14 and 21 days. For bone-like nodule formation, cells were cultured for 21 days. Data were compared by analysis of variance.Results. Cell attachment, cell morphology, cell proliferation, and ALP activity were not affected by surface treatments. Total. protein content was reduced by blasted and acid etched surface. Bone-Like nodule formation was significantly reduced by blasted, acid etched, and a combination of both blasted and acid etched surfaces.Conclusions. Based on these results, it can be suggested that cpTi surfaces that were submitted only to machining treatment favor the final event of osteoblastic differentiation of the rat bone marrow cells, evidenced by increased bone-Like nodule formation. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Dye-sensitized solar cell architecture based on indium-tin oxide nanowires coated with titanium dioxide

A new architecture for dye-sensitized solar cells is employed, based on a nanostructured transparent conducting oxide protruding from the substrate, covered with a separate active oxide layer. The objective is to decrease electron-hole recombination. The concept was tested by growing branched indium-tin oxide nanowires on glass using pulsed laser deposition followed by deposition of a sputtered titanium dioxide layer covering the wires. The separation of charge generation and charge transport functions opens many possibilities for dye-sensitized solar cell optimization. (c) 2007 Acta Materialia. Inc. Published by Elsevier Ltd. All rights reserved.

Thermal studies on nickel(II) 4-iodopyrazole complexes

This work describes the synthesis, IR and UV-Vis spectroscopic characterization as well the thermal behavior of the [NiCl2(HIPz)(4)]center dot C3H6O (1), [Ni(H2O)(2)(HIPz)(4)](NO3)(2) (2), [Ni(NCS)(2)(HIPz)(4)] (3) and [Ni(N-3)(2)(HIPz)(4)] (4) (HIPz = 4-iodopyrazole) pyrazolyl complexes. TG experiments reveal that the compounds 1-4 undergo thermal decomposition in three or four mass loss steps yielding NiO as final residue, which was identified by X-ray powder diffraction.

Polymerization of ethylene by the tris(pyrazolyl)borate titanium(IV) compound immobilized on MAO-modified silicas

The immobilization of soluble catalyst {Tp(Ms)}TiCl3 (Tp(Ms*)HB(3-mesityl-pyrazolyl)(2)(5-mesityl-pyrazolyl)(-)) on silica and MAO-modified silicas containing 4.0, 8.0 and 23.0 wt.% Al/SiO2 yields active supported catalysts for ethylene polymerization. Among the supported catalysts studied by XRF spectroscopy, higher titanium content was obtained using MAO-modified silica containing 8.0 wt.% Al/SiO2 as support. For the ethylene polymerization reactions carried out in hexane at 60degreesC using a combination of triisobutylaluminum (TiBA) and methylaluminoxane (MAO) (1:1), the activities varied between 24.4 and 113.5 kg of PE/mol [Ti] h. The highest activity is reached using MAO-modified silica containing 4.0 wt.% Al/SiO2 as support. The viscosity-average molecular weights ((M) over bar (v)) of the PE's produced with the supported catalysts varying from 1.44 to 9.94 x 10(5) g/mol with melting temperatures in the range of 125-140degreesC. The use of other Lewis acid cocatalysts, including TiBA, diethylaluminium chloride (DEAC), and trimethylaluminum (TMA) resulted also in the formation of active catalysts for ethylene polymerization. However, the activities are lower than that one using a combination of TiBA and MAO. The viscosity-average molecular weights (R,) of PE's are influenced by varying the cocatalysts as well as the Al/Ti molar ratio. The supported catalyst generated in situ under ethylene atmosphere is roughly four times more active than supported one containing 4.0 wt.% Al/SiO2. (C) 2003 Elsevier B.V. All rights reserved.

Characterization of nickel doped Zn7Sb2O12 spinel phase using Rietveld refinement

Zn7Sb2O12 is known to adopt an inverse spinel crystal structure, in which Zn2+ occupies the eight tetrahedral positions and Sb5+ and Zn2+ randomly occupy the 16 octahedral positions. Samples of Zn7-xNixSb2O12 (X = 0, 1, 2, 3, and 4) were synthesized using a modified polymeric precursor method, known as the Pechini method. The crystal structure of the powders was characterized by Rietveld refinement with X-ray diffraction data. The results show that for X = 0, 1, and 2 Ni substitutes for Zn2+ in the octahedral sites, and that for X = 3 and 4 it is assumed that Ni2+ replaces Zn2+ ions in both the octahedral and tetrahedral positions. It is also observed for x = 3 and 4 the formation of two spinel phases. (C) 2003 International Centre for Diffraction Data.

Highly selective nickel ethylene oligomerization catalysts based on sterically hindered tris(pyrazolyl)borate ligands

The reaction of TlTp' (Tp' = HB(3-mesitylpyrazolyl)(3)(-) (Tp(Ms)), HB(3-mesitylpyrazolyl)(2)(5-mesitylpyrazolyl)(-) (Tp(Ms)*)) with NiCl(2).6H(2)O affords Tp(Ms)NiCl (1) and Tp(Ms)*NiCl (2) in good yield. The compound 2 undergoes an isomerization process to form [{Tp(Ms)**}NiCl](2) (3) (Tp(Ms)** = HB(5-mesitylpyrazolyl)(2)(3-mesitylpyrazolyl)(-)) in 68% yield. Treatment of the tris(pyrazolyl)-borate nickel compounds 1 and 2 with alkylaluminum cocatalysts such as methylalumoxane (MAO) and trimethylaluminum (TMA) in toluene generates active catalysts for ethylene oligomerization. The compound 1 shows turnover frequencies in the range of (2.2-43.1) x 10(3) h(-1). Oligomerization reaction conditions can be adjusted that lead to selectivities as high as 81% for butene-1.

Effects of nitrogen ion irradiation on plasma polymerized films produced from titanium tetraiso pro poxide-oxygen-helium mixtures

In this work films were produced by the plasma enhanced chemical vapor deposition (PECVD) of titanium tetraisopropoxide-oxygen-helium mixtures and irradiated with 150 keV singly-charged nitrogen ions (N(+)) at fluences, phi, between 10(14) and 10(16) cm(-2). Irradiation resulted in compaction, which reached about 40% (measured via the film thickness) at the highest fluence. Infrared reflection-absorption spectroscopy (IRRAS) revealed the presence of Ti-O bonds in all films. Both O-H and C-H groups were present in the as-deposited films, but the density of each of these decreased with increasing phi and was absent at high phi, indicating a loss of hydrogen. X-ray photoelectron spectroscopy (XPS) analyses revealed an increase in the C to Ti atomic ratio as phi increased, while the O to Ti ratio hardly altered, remaining at around 2.8. The optical gap of the films, derived from data obtained by ultraviolet-visible spectroscopy (UVS), remained at about 3.6 eV for all fluences except the highest, for which an abrupt fall to around 1.0 eV was observed. For the irradiated films, the electrical conductivity, measured using the two-point method, showed a systematic increase with increasing phi. (c) 2008 Elsevier B.V. All rights reserved.

Plasma enhanced chemical vapor deposition of titanium(IV) ethoxide-oxygen-helium mixtures

Thin films were deposited by plasma enhanced chemical vapor deposition from titanium (IV) ethoxide (TEOT)-oxygen-helium mixtures. Actinometric optical emission spectroscopy was used to obtain the relative plasma concentrations of the species H, CH, O and CO as a function of the percentage of oxygen in the feed, R(ox). The concentrations of these species rise with increasing R(ox) and tend to fall for R(ox) greater than about 45%. As revealed by a strong decline in the emission intensity of the actinometer Ar as R(ox) was increased, the electron mean energy or density (or both) decreased as greater proportions of oxygen were fed to the chamber. This must tend to reduce gas-phase fragmentation of the monomer by plasma electrons. As the TEOT flow rate was fixed, however, and since the species H and CH do not contain oxygen, the rise in their plasma concentrations with increasing R(ox) is explained only by intermediate reactions involving oxygen or oxygen-containing species. Transmission infrared (IRS) and X-ray photoelectron (XPS) spectroscopies were employed to investigate film structure and composition. The presence of CH(2), CH(3), C=C, C-O and C=O groups was revealed by IRS. In addition, the presence of C-O and C=O groups was confirmed by XPS, which also revealed titanium in the +4 valence state. The Ti content of the films, however, was found to be much less than that of the monomer material itself. (C) 2007 Elsevier B.V. All rights reserved.

Influence of the morphology and microstructure on the photocatalytic properties of titanium oxide films obtained by sparking anodization in H3PO4

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A Simple Method Based on ICP-MS for Estimation of Background Levels of Arsenic, Cadmium, Copper, Manganese, Nickel, Lead, and Selenium in Blood of the Brazilian Population

Throughout the world, biomonitoring has become the standard for assessing exposure of individuals to toxic elements as well as for responding to serious environmental public health problems. However, extensive biomonitoring surveys require rapid and simple analytical methods. Thus, a simple and high-throughput method is proposed for the determination of arsenic (As), cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se) in blood samples by using inductively coupled plasma-mass spectrometry (ICP-MS). Prior to analysis, 200 l of blood samples was mixed with 500 l of 10% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 10 min, and subsequently diluted to 10 ml with a solution containing 0.05% w/v ethylenediamine tetraacetic acid (EDTA) + 0.005% v/v Triton X-100. After that, samples were directly analyzed by ICP-MS (ELAN DRC II). Rhodium was selected as an internal standard with matrix-matching calibration. Method detection limits were 0.08, 0.04, 0.5, 0.09, 0.12, 0.04, and 0.1 g//L for As, Cd, Cu, Mn, Ni, Pb, and Se, respectively. Validation data are provided based on the analysis of blood samples from the trace elements inter-\comparison program operated by the Institut National de Sante Publique du Quebec, Canada. Additional validation was provided by the analysis of human blood samples by the proposed method and by using electrothermal atomic absorption spectrometry (ETAAS). The method was subsequently applied for the estimation of background metal blood values in the Brazilian population. In general, the mean concentrations of As, Cd, Cu, Mn, Ni, Pb, and Se in blood were 1.1, 0.4, 890, 9.6, 2.1, 65.4, and 89.3 g/L, respectively, and are in agreement with other global populations. Influences of age, gender, smoking habits, alcohol consumption, and geographical variation on the values were also considered. Smoking habits influenced the levels of Cd in blood. The levels of Cu, Mn, and Pb were significantly correlated with gender, whereas Cu and Pb were significantly correlated with age. There were also interesting differences in Mn and Se levels in the population living in the north of Brazil compared to the south.

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L-1 H2SO4 solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA](n), polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases ill solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L-1 H2SO4 in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper. (C) 2007 Elsevier Ltd. All rights reserved.

Processing and mechanical characterization of titanium-graphite hybrid laminates

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