Matrix effects observed during pesticides residue analysis in fruits by GC

The influence of the sample matrix in the CC-electron-capture detection analysis of the pesticides dimethoate, diazinon, chlorothalonil.. parathion methyl and fenitrothion in fruits samples has been studied. Experiments have been carried out where the pesticide responses in standard solutions prepared in selected solvent were compared with their response when present in apple, mango, papaya, banana, pineapple and melon extracts. The presence of matrix effects (MEs) and their extent were shown to be simultaneously influenced by several factors (matrix concentration, matrix type, pesticide concentration, analytical range). Pronounced MEs were observed particularly for dimethoate and diazinon in all matrices tested; in lower concentrations, all pesticides presented significant ME. The other pesticides presented variable ME. Higher ME enhancement was detected at lower pesticide concentration levels of and/or at higher matrix concentration solutions. The ME detected for fenitrothion, in the analytical range evaluated, were dependent on matrix type. For each pesticide, solvent and matrix-matched calibrations were compared for all fruit samples, and it could be concluded that quantitation based on standard solutions prepared in blank matrix extract (matrix-matched calibration) should be used to compensate the MEs and to obtain more accurate results for the pesticides studied.

Chemical Composition of Lipids Present in Cat and Dog Oocyte by Matrix-Assisted Desorption Ionization Mass Spectrometry (MALDI- MS)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Kinetic Analysis of Substrate Utilization by Native and TNAP-, NPP1-, or PHOSPHO1-Deficient Matrix Vesicles

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

Experimental poisoning by Senecio brasiliensis in calves: quantitative and semi-quantitative study on changes in the hepatic extracellular matrix and sinusoidal cells

A matriz extracelular (MEC) desempenha um papel importante em lesões hepáticas crônicas e tem sido estudada em modelos de intoxicação experimental. em bovinos, no entanto, não há estudos específicos sobre a MEC hepática normal ou com lesões crônicas. Por isso, foi desenvolvido um modelo de intoxicação experimental hepático usando Senecio brasilliensis, uma planta que contém alcalóides pirrolizidínicos e causa lesão hepática dependente da dose. Cinco bezerros receberam por via oral, 0.38g/kg de folhas secas por 24 dias. Biópsias hepáticas foram obtidas a cada 15 dias durante 60 dias. Sinais clínicos de complicações digestivas surgiram da terceira semana do experimento. Um bezerro morreu aos 45 dias e os outros quatro foram avaliados até os 60 dias. As biópsias hepáticas foram processadas para microscopia óptica, imuno-histoquímica e microscopia eletrônica de transmissão. No trigésimo dia, as lesões hepáticas eram progessivas caracterizadas por vacuolização hepatocelular, necrose, apoptose, megalocitose, e fibrose centrolobular, pericelular e portal. Foram realizadas avaliações quantitativas e semi-quantitativas de componentes da MEC hepática antes e após o aparecimento das lesões. Foi realizada morfometria do colágeno total e do sistema de fibras elásticas. Colágeno total e colágenos tipos I e III aumentaram progressivamente em todos os locais do fígado. Mudanças na localização, quantidade e disposição do sistema de fibras elásticas foram também observadas. Houve um aumento significativo de células de Kupffer aos 30 dias e de células sinusoidais totais aos 45 e 60 dias. As lesões hepáticas neste experimento foram progressivas mesmo após a remoção da planta. Lesões de fibrose severa foram localizadas principalmente nos espaços porta, seguido por fibrose veno-oclusiva e pericelular. Os colágenos tipo I e tipo III foram observados no fígado normal e no fígado dos bezerros afetados, com predomínio do tipo I. Nos bezerros afetados o aumento do colágeno total e do sistema de fibras elásticas foi paralelo ao aumento no número das células sinusoidais.

Characterization of silica-carbon mesoporous matrix with embedded nickel nanoparticles synthesized by the polymeric precursor method

Nickel nanoparticles into silica-carbon matrix composites were prepared by using the polymeric precursor method. The effects of the polyester type and the time of pyrolysis on the mesoporosity and nickel particle dispersion into non-aqueous amorphous silica-carbon matrix were investigated by thermogravimetric analysis, adsorption/desorption isotherms and TEM. A well-dispersed metallic phase could be only obtained by using ethylene glycol. Weightier polyesters affected the pyrolysis process due to a combination of more amounts of carbonaceous residues and delaying of pyrolysis process. The post-pyrolyzed composites were successfully cleaned at 200 degrees C for I h in oxygen atmosphere leading to an increase in the surface area and without the occurrence of carbon combustion or nickel nanoparticles oxidation. The matrix composites presented predominantly mesoporous with pore size well defined in 38 angstrom, mainly when tetraethylene glycol was used as polymerizing agent. (C) 2007 Elsevier B.V. All rights reserved.

Coordination polymer adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO(3)-BaF(2)-WO(3) and the binary system NaPO(3)-WO(3) with high concentrations of WO(3) (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L(I) and L(III) absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO(6)) and that these films are free of tungstate tetrahedral units (WO(4)). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO(3) increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO(6) octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO(3) concentrated samples (above 40% molar) attributed to the formation of WO(6) clusters. (C) 2008 Elsevier B.V. All rights reserved.

Benzoate ion determination in beverages by using a potentiometric sensor immobilized in a graphite matrix

The characteristics, performance, and application of an electrode, namely. Pt\Hg\Hg-2(Bzt)(2)\graphite, where Bzt stands for benzoate ion. are described. This electrode responds to Bzt with sensitivity of 57.7 +/- 1.0 mV/decade over the range 5 x 10(-4)-1 x 10(-1) mol l(-1) at pH 6.0-8.0 with a detection limit of 1.6 x 10(-4) mol l(-1). The electrode shows easy construction, fast response rime (between 10-30 s), low-cost, acid excellent response stability (lifetime > 6 months, in continuous use), the proposed sensor displayed good selectivity for benzoate in the presence of several carboxylate and inorganic anions. It was used to determine benzoate in various beverages by means of the standard additions method. The results obtained by using this electrode compared very favorably with those given by the official AOAC spectrophotometric method and by a HPLC procedure as well. (C) 2001 Elsevier B.V. B.V. All rights reserved.

p-Aminobenzoate ion determination in pharmaceutical formulations by using a potentiometric sensor immobilized in a graphite matrix

The characteristics, performance, and application of an electrode, namely, Pt\Hg\Hg-2(PABzt)(2)\ graphite, where PABzt stands for p-aminobenzoate ion, are described. This electrode responds to PABzt with sensivity of (58.1 +/- 1.0) mV per decade over the range 1.0 x 10(-4) to 1.0 x 10(-1) mol l(-1) at pH 6.5-8.0 and a detection limit of 3.2 x 10(-5) mol l(-1). The electrode shows easy construction, fast response time (within 10-30 s), low-cost, and excellent response stability (lifetime greater than 6 months, in continuous use). The proposed sensor displayed good selectivity for p-aminobenzoate in the presence of several substances, especially, concerning carboxylate and inorganic anions. It was used to determine p-aminobenzoate in pharmaceutical formulations by means of the standard additions method. The results obtained by using this electrode compared very favorably with those given by an HPLC procedure. (C) 2004 Elsevier B.V. All rights reserved.

Evaluation of Bi as internal standard to minimize matrix effects on the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru permanent modifier with co-injection of Pd/Mg(NO3)(2)

Bismuth was evaluated as an internal standard for the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru as a permanent modifier with co-injection of Pd/Mg(NO3)(2). The correlation coefficient of the graph plotted from the non-nalized absorbance signals of Bi versus Pb was r=0.989. Matrix effects were evaluated by analyzing the slope ratios between the analytical curve, and analytical curves obtained from Pb additions in red and white wine vinegar obtained from reference solutions prepared in 0.2% (v/v) HNO3, samples. The calculated ratios were around 1.04 and 1.02 for analytical curves established applying an internal standard and 1.3 and 1.5 for analvtical curves without. Analytical curves in the 2.5-15 pg L-1 Pb concentration interval were established using the ratio Pb absorbance to Bi absorbance versus analvte concentration, and typical linear correlations of r=0.999 were obtained. The proposed method was applied for direct determination of Pb in 18 commercial vinegar samples and the Pb concentration varied from 2.6 to 31 pg L-1. Results were in agreement at a 95% confidence level (paired t-test) with those obtained for digested samples. Recoveries of Pb added to vinegars varied from 96 to 108% with and from 72 to 86% without an internal standard. Two water standard reference materials diluted in vinegar sample were also analyzed and results were in agreement with certified values at a 95% confidence level. The characteristic mass was 40 pg Pb and the useful lifetime of the tube was around 1600 firings. The limit of detection was 0.3 mu g L-1 and the relative standard deviation was <= 3.8% and <= 8.3% (n = 12) for a sample containing, 10 mu L-1 Pb with and without internal standard, respectively. (C) 2007 Elsevier B.V. All rights reserved.

Isolation and sequence determination of peptides in the venom of the spider wasp (Cyphononyx dorsalis) guided by matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry

Micro-scale (sub-pmol) isolation and sequence determination of three peptides from the venom of the solitary spider wasp Cyphononyx dorsalis is described. We isolated two novel peptides Cd-125 and Cd-146 and a known peptide Thr(6)-bradykinin from only two venom sacs of solitary spider wasp Cyphononyx dorsalis without bioassay-guided fractionation. but instead guided by MALDI-TOF MS. The MALDI-TOF MS analysis of each fraction showed the purity and molecular weight of the components, which led to the isolation of the peptides virtually without loss of sample amount. The sequences of the novel peptides Cd-125 (Asp-Thr-Ala-Arg-Leu-Lys-Trp-His) and Cd-146 (Ser-Glu-Thr-Gly-Asn-Thr-Val-Thr-Val-Lys-Gly-Phe-Ser-Pro-Leu-Arg) were determined by Edman degradation together with mass spectrometry. and finally corroborated by solid-phase synthesis. The known peptide Thr(6)-bradykinin (Arg-Pro-Pro-Gly-Phe-Thr-Pro-Phe-Arg) was identified by comparison with the synthetic authentic specimen. This is the first example for any kinins to be found in Pompilidae wasp venoms. The procedure reported here can be applicable to studies on many other components of solitary wasp venoms with limited sample availability. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Degradation of tetracycline by photo-Fenton process - Solar irradiation and matrix effects

The degradation of the antibiotic tetracycline (TC) by the photo-Fenton process was evaluated under black-light and solar irradiation. The influences of iron source (Fe(NO3)(3) or ferrioxalate), hydrogen peroxide and matrix (pure water, surface water and a sewage treatment plant effluent-STP) were evaluated. Under black-light irradiation, TC degradation was favored in the presence of Fe(NO3)(3), achieving total degradation after 1 min irradiation, while under solar light the use of ferrioxalate favors the degradation. Nevertheless, no significant difference in total organic carbon removal was observed between these two iron sources, achieving a residual concentration of around 5 mg L-1 under black-light and 2 mg L-1 under solar light irradiation. No decrease of the degradation efficiency relative to pure water was observed when TC was irradiated in a sample of surface water, under either black-light or solar irradiation. However, lower efficiency was obtained under black-light when TC was present in a sample of STP effluent, indicating the interference of the constituents of this sample on the overall efficiency of the process. on the other hand, under solar irradiation in the presence of ferrioxalate, no influence of the matrix was observed, even in the sample of STP effluent, achieving total degradation of TC in 1.5 min. (c) 2006 Elsevier B.V. All rights reserved.

Step by step analyses of Clarke's matrix correction procedure for untransposed three-phase transmission line cases

The correction procedure for Clarke's matrix, considering three-phase transmission line analyzes, is analyzed step by step in this paper, searching to improve the application of this procedure. Changing the eigenvectors as modal transformation matrices, Clarke's matrix has been applied to analyses for transposed and untransposed three-phase transmission line cases. It is based on the fact that Clarke's matrix is an eigenvector matrix for transposed three-phase transmission lines considering symmetrical and asymmetrical cases. Because of this, the application of this matrix has been analyzed considering untransposed three-phase transmission lines. In most of these cases, the errors related to the eigenvalues can be considered negligible. It is not true when it is analyzed the elements that are not in main diagonal of the quasi-mode matrix. This matrix is obtained from the application of Clarke's matrix. The quasi-mode matrix is correspondent to the eigenvalue matrix. Their off-diagonal elements represent couplings among the quasi-modes. So, the off-diagonal quasi-mode element relative values are not negligible when compared to the eigenvalues that correspond to the coupled quasi-modes. Minimizing these relative values, the correction procedure is analyzed in detail, checking some alternatives for the correction procedure application.

Porphyromonas gingivalis-mediated shedding of extracellular matrix metalloproteinase inducer (EMMPRIN) by oral epithelial cells: a potential role in inflammatory periodontal disease

Extracellular matrix metalloproteinase inducer (EMMPRIN) or CD 147 is a transmembrane glycoprotein expressed by various cell types, including oral epithelial cells. Recent studies have brought evidence that EMMPRIN plays a role in periodontitis. In the present study, we investigated the effect of Porphyromonas gingivalis, a major pathogen in chronic periodontitis, on the shedding of membrane-anchored EMMPRIN and on the expression of the EMMPRIN gene by oral epithelial cells. A potential contribution of shed EMMPRIN to the inflammatory process of periodontitis was analyzed by evaluating the effect of recombinant EMMPRIN on cytokine and matrix metalloproteinase (MMP) secretion by human gingival fibroblasts. ELISA and immunofluorescence analyses revealed that P. gingivalis mediated the shedding of epithelial cell-surface EMMPRIN in a dose- and time-dependent manner. Cysteine proteinase (gingipain)-deficient P. gingivalis mutants were used to demonstrate that both Arg- and Lys-gingipain activities are involved in EMMPRIN shedding. Real-time PCR showed that P. gingivalis had no significant effect on the expression of the EMMPRIN gene in epithelial cells. Recombinant EMMPRIN induced the secretion of IL-6 and MMP-3 by gingival fibroblasts, a phenomenon that appears to involve mitogen activated protein kinases. The present study brought to light a new mechanism by which P. gingivalis can promote the inflammatory response during periodontitis. (C) 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.