Indole ring oxidation by activated leukocytes prevents the production of hypochlorous acid

Hypochlorous acid (HOCl) released by activated leukocytes has been implicated in the tissue damage that characterizes chronic inflammatory diseases. In this investigation, 14 indole derivatives, including metabolites such as melatonin, tryptophan and indole-3-acetic acid, were screened for their ability to inhibit the generation of this endogenous oxidant by stimulated leukocytes. The release of HOCl was measured by the production of taurine-chloramine when the leukocytes (2 x 10(6) cells/mL) were incubated at 37ºC in 10 mM phosphate-buffered saline, pH 7.4, for 30 min with 5 mM taurine and stimulated with 100 nM phorbol-12-myristate acetate. Irrespective of the group substituted in the indole ring, all the compounds tested including indole, 2-methylindole, 3-methylindole, 2,3-dimethylindole, 2,5-dimethylindole, 2-phenylindole, 5-methoxyindole, 6-methoxyindole, 5-methoxy-2-methylindole, melatonin, tryptophan, indole-3-acetic acid, 5-methoxy-2-methyl-3-indole-acetic acid, and indomethacin (10 µM) inhibited the chlorinating activity of myeloperoxidase (MPO) in the 23-72% range. The compounds 3-methylindole and indole-3-acetic acid were chosen as representative of indole derivatives in a dose-response study using purified MPO. The IC50 obtained were 0.10 ± 0.03 and 5.0 ± 1.0 µM (N = 13), respectively. These compounds did not affect the peroxidation activity of MPO or the production of superoxide anion by stimulated leukocytes. By following the spectral change of MPO during the enzyme turnover, the inhibition of HOCl production can be explained on the basis of the accumulation of the redox form compound-II (MPO-II), which is an inactive chlorinating species. These results show that indole derivatives are effective and selective inhibitors of MPO-chlorinating activity.

Sistema TS-FF-AAS com chama acetileno-ar como alternativa em relação à chama acetileno-óxido nitroso em FAAS na determinação de estanho

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

Cúrcuma: planta medicinal, condimentar e de outros usos potenciais

A cúrcuma (Curcuma longa L.), espécie originária do sudeste asiático, é considerada uma preciosa especiaria. Com a proibição do uso de pigmentos sintéticos nos principais países da América do Norte e Europa, têm sido procuradas alternativas naturais. A cúrcuma, além de sua principal utilização como condimento, possui substâncias antioxidantes, antimicrobianas e corantes (curcumina) que lhe conferem possibilidade de emprego nas áreas de cosméticos, têxtil, medicinal e alimentício. Até o presente momento, poucos estudos foram realizados com a cúrcuma no Brasil, fato que determina baixa produtividade. Entretanto, recentes resultados de pesquisa mostram a possibilidade de obtenção de produtividades semelhantes às de seu país de origem, ainda que maiores estudos sejam necessários para definição de estande, adubação e outras práticas culturais. Os objetivos do presente trabalho são apresentar a versatilidade mercadológica da cúrcuma, caracterizar a espécie quanto a aspectos botânicos, nutricionais e químicos, bem como reunir e discutir informações técnicas para melhoria da produtividade e qualidade dos rizomas.

Determinação de rotina do crômio em fezes, como marcador biológico, pelo método espectrofotométrico ajustado da 1,5-difenilcarbazida

O objetivo deste estudo foi ajustar o método espectrofotométrico da 1,5-difenilcarbazida à determinação do crômio em fezes, como marcador biológico, adequando-o à rotina laboratorial. Fatores que poderiam exercer interferência na transformação do crômio (III) à crômio (VI) foram testados, como a recuperação do metal, quantidade de amostra, quantidade e ordem de emprego dos ácidos oxidantes da digestão úmida, temperatura e tempo de digestão e perda por volatilização do crômio como cloreto de cromila, porém não se determinou estatisticamente interferência destes fatores. No método ajustado, a amostra é digerida pela clássica mistura ácida nítrica/perclórica, levando a oxidação do crômio (III) a crômio (VI), e alíquota do extrato diluído é usado para reação com 1,5-difenilcarbazida; as absorbâncias são medidas a 550nm, utilizando-se de cubetas de um centímetro de caminho óptico, contra prova em branco conduzida simultaneamente. Dicromato de potássio foi empregado como substância de referência para obtenção da curva padrão na faixa de 0,25 - 2,5mg.mL-1 de Cr2O3 (1mg Cr2O3 º 1,9355mg K2Cr2O7).

Alterações hematológicas induzidas por poluição industrial em moradores e industriários de Cubatão, SP (Brasil)

Foram analisados 496 indivíduos de Cubatão, SP (Brasil), cidade com alto teor de poluição industrial, com o objetivo de verificar alterações hematológicas induzidas por poluentes industriais. Dos estudos citológicos dos eritrócitos dessa população estudada, foram observadas 188 (38%) com alterações, isoladas ou combinadas em um único indivíduo, das quais 26% apresentaram policromatofilia, 24% com pontilhados basófilos, 15% com corpos de Heinz, e 8% com reticulocitose. As freqüências de metahemoglobinemia e sulfohemoglobinemia foram,respectivamente, de 35% e 32% em moradores da vila Parisi - um bairro cercado pela maioria das indústrias de Cubatão - 15% e 5% em operários das indústrias, e 12% e 4% em habitantes de áreas distantes entre 3 e 8 km do polo industrial. Esses resultados indicam que as alterações são causadas por poluentes tóxico-oxidantes e que as conseqüências fisio-patológicas no sangue dos moradores de Cubatão parecem indicar que estão relacionadas com o tempo de exposição e com a proximidade dos focos emissores de poluentes.

Electrochemical noise analysis of chalcopyrite carbon paste electrodes by Acidithiobacillus ferrooxidans

The electrochemical response of chalcopyrite was studied using electrochemical noise analysis (ENA). The assay was carried out under constant aeration using 30 mL in two electrochemical cells containing iron-free mineral salts solution. These cells were initially monitored for 56 hours, After 72 hours, 7.25x 10(10) cells mL(-1) of A, ferrooxidans strain LR were added in both cells and monitored until 128 h. Subsequent to this period, 0.927 mmol L-1 of silver ions and 400 mmol L-1 of chloride ions were added each one separately. Both conditions were monitored until 168 hours. According to results obtained, it was observed that Cl- ions addition induced an accelerated corrosion process. However, there is a tendency of the system to reach the stationary state due to repassivation of the electrodic surface. In the other side, the Ag+ addition contributed for the maintenance of the oxidant atmosphere, in spite of controversial effect caused by considerable variations in the R-n values, resulting in a instability in the chalcopyrite reactivity.

Increase on incineration capacity and NOx control for air enrichment in the experimental simulation of aqueous residue incineration

An experimental investigation of air enrichment in a combustion chamber designed to incinerate aqueous residues is presented. Diesel fuel and liquefied petroleum gas (LPG) were used independently as fuels. An increase of 85% in the incineration capacity was obtained with nearly 50% O-2 in the oxidant gas, in comparison to incineration with air only. The incineration capacity continues increasing for enrichment levels above 50% O-2 , although at a lower pace. For complete oxy-flame combustion (100% O-2 ), the increase of the incineration capacity was about 110% relative to the starting conditions and about 13.5% relative to the condition with 50% O-2 . The CO concentration measured near the flame front decreases drastically with the increase of O-2 content in the oxidant gas. At the chamber exit, the CO concentration was always near zero, indicating that the chamber residence time was sufficient to complete fuel oxidation in any test setting. For diesel fuel, the NOx was entirely formed in the first region of the combustion chamber. For diesel fuel, there was some increase in the NOx concentration up to 35% of O-2 ; this increase became very sharp after that. From 60 ppm, at operation with air only, the NOx concentration raises to 200 ppm at 35% O-2 , and then to 2900 ppm at 74% O-2 . The latter corresponds to six times more NOx in terms of the ratio of mass of NO to mass of residue, compared to the situation of combustion with air only. For LPG, the NOx concentrations reached 4200 ppm at 80% O-2 , corresponding to nine times more, also in terms of the ratio of mass of NO to mass of residue, in comparison with combustion with air only. Results of different techniques used to control the NOx emission during air enrichment are discussed: (a) variation of the recirculated zone intensity, (b) increase of the spray Sauter mean diameter, (c) fuel staging, (d) oxidizer staging, and (e) ammonia injection. The present paper shows that NOx emission may be controlled without damage of the increase of incineration capacity by the enrichment and with low emission of partial oxidation pollutants such as CO.

BaTiO3 obtained through metallic stearate precursors

Metallic stearates were used as precursors to obtain BaTiO3. Barium and titanium stearate mixtures were homogenized in ball mill containing some amount of ammonium stearate. The mixture of the precursors was evaluated by simultaneous TG/ DTA and TMA, and residues from thermal decomposition were characterized by XRD and SEM. It could be verified that the residues from the thermal decomposition in both oxidant and inert atmospheres were the BaTiO3 but with characteristic morphological and crystalline aspects depending on the experimental conditions in which the mixtures of precursors were obtained. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Oxidation of chalcopyrite by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans in shake flasks

Chalcopyrite oxidation was evaluated with two acidophilic thiobacilli that are important in bioleaching processes. Acidithiobacillus thiooxidans in pure culture did not oxidize CuFeS2 but oxidized externally added S in the presence of CuFeS2. Acidithiobacillus ferrooxidans released Cu2+ and soluble Fe from chalcopyrite, and the time course lead to a gradual passivation of chalcopyrite whereby Cu2+ dissolution leveled off. Fe3+ acted as a chemical oxidant in CuFeS2 leaching and was reduced to Fe2+. Parallel bacterial re-oxidation of Fe2+ contributed to a high Fe3+/Fe2+ ratio and an increase in redox potential. Chemical oxidation of chalcopyrite was slow compared with A. ferrooxidans-initiated solubilization. X-ray analysis revealed new solid phases: (i) jarosite, found in solids from A. ferrooxidans cultures and in chemical controls that initially received Fe2+ or Fe3+, and (ii) S-0, found mostly in iron-amended A. ferrooxidans culture and the corresponding chemical controls. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Thermal behaviour of Tin(II) complex with 8-hydroxyquinolinate in the solid state

Tin(II) complexes with 8-hydroxyquinolinate in solid state have been obtained by adding aqueous ammonium to a solution containing stannous chloride and 8-hydroxiquinoline in medium of HCl and acetone up to pH 5 and 9, respectively. The products obtained show the same composition, Sn(C9H6ON)(2); however there are some differences regarding both the thermal behaviour in an oxidant atmosphere and morphology. These products were characterised by elemental and complexometric analysis, TG and DTA curves, infrared and X-ray diffractometry. TG curves show, above 448 K, the partial oxidation on air atmosphere of Sn(II) complexes to Sn(IV) complexes, SnO(C9H6ON)(2). This behaviour does not depend only on pH in which the compounds were obtained but also on the heating rate in TG curves. Sn(II) complexes volatilise almost completely on nitrogen atmosphere and partially on air atmosphere depending on the oxidation degree of the compound.

Antioxidant activity of the melanin pigment extracted from Aspergillus nidulans

Melanins are pigments of high molecular weight formed by oxidative polymerization of phenolic or indolic compounds. A number of fungi, including Aspergillus nidulans, produce pigments related or identical to melanin, which are located on cell walls or exist as extracellular polymers. The aim of the present study was to assess the antioxidant activity of synthetic melanin and of the pigment extracted from the mycelium and culture medium after growth of the highly melanized strain (MEL1) from A. nidulans. The ability of the melanin pigment to scavenge the oxidants HOCl and H2O2 was evaluated by inhibition of the oxidation of 5-thio-2-nitrobenzoic acid (TNB) using several melanin concentrations. The results showed that the pigment of the MEL1 strain competes with TNB for H2O2 and HOCl, inhibiting TNB oxidation in a concentration-dependent manner. For the HOCl oxidant, this inhibition was comparable to that of synthetic melanin, whose IC50 values were quite close for both pigments. Thus, our results suggest that the melanin from A. nidulans is a potential HOCl scavenger and may be considered a promising material for the cosmetic industry for the formulation of creams that protect the skin against possible oxidative damage.

Non-isothermal kinetic of oxidation of tungsten carbide

Tungsten carbide, WC, has shown dissimilar thermal behavior when it is heated on changeable heating rate and flow of oxidant atmosphere. The oxidation of WC to WO3 tends to be in a single and slow kinetic step on slow heating rate and/or low flux of air. Kinetic parameters, on non-isothermal condition, could be evaluated to the oxidation of WC to heating rate below 15 degrees C min(-1) or low flow of air (10 mL min(-1)). The reaction is governed by nucleation and growth at 5 to 10 degrees C min(-1) then the tendency is to be autocatalytic, JMA and SB, respectively.

Tuning the acidic properties of aluminas via sol-gel synthesis: New findings on the active site of alumina-catalyzed epoxidation with hydrogen peroxide

This study answers several pending questions about alumina-catalyzed epoxidation with aqueous 70 wt% H2O2. To evaluate the effect of the water-to-aluminum tri-sec-butoxide molar ratio, this was systematically changed from 1 to 24. The xerogels were calcined at 450 degrees C and gave different gamma-Al2O3's with distinct textural and acidic properties. A combination of Al-27 MAS NMR and TPD-NH3 results of calcined aluminas allowed us to assign the type la. Al-OH sites as the catalytic sites for epoxidation. The type Ib Al-OH sites have no function in catalytic epoxidation, because ethyl acetate poisons these sites. The strong acid sites of types IIa, IIb, and III Al-OH groups are responsible for the undesired H2O2 decomposition and decreased oxidant selectivity. (c) 2006 Elsevier B.V. All rights reserved.

Preparation and characterization of nanosized SrBi2Nb2O9 powder by the combustion synthesis

This work presents the preparation of SrBi2Nb2O9 (SBN) directly by the combustion synthesis. Strontium nitrate, niobium ammonium oxalate (NH4H2[NbO-(C2O4)(3)].3H(2)O) and bismuth oxide were used as oxidant reactants and urea as fuel. The influence of the fuel was evaluated by the addition of different fuel amounts (50%, 100%, 200% and 300%), 100% being the stoichiometric proportion. The XRD patterns showed that the SBN perovskite crystallized as the majority phase. The as-synthesized stoichiometric powder presented a specific surface area of around 13 m(2)/g and a mean grain size of around 16 nm. Dilatometric measurements showed that the maximum sintering rate occurs at 1275degreesC. The determination of the ferroparaelectric transition showed a Curie temperature (T-c) of 429degreesC. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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.