Multiresidue determination of pesticides in honey samples by gas chromatography-mass spectrometry and application in environmental contamination

A simple and fast multiresidue method has been developed to determine 48 pesticides within the major groups of pesticides (organohalogen, organophosphorous, pyrethroids and organonitrogen) in representative samples of locally produced honey, in Bauru (State of São Paulo, Brazil) during 2003-2004. The recovery results found ranged from 76% to 95% and the limits of detection were lower than 0.01 mg/kg for gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). The results indicated that most pesticides found in the samples belonged to the organohalogen and organophosphorous groups and lower levels of residues of some organonitrogen and pyretroids were also detected. Malathion residues were detected in all the samples, in a high concentration, owing to its applications to control dengue mosquitoes in the area studied. (c) 2005 Elsevier Ltd. All rights reserved.

Screening Brazilian automotive gasoline quality through quantification of saturated hydrocarbons and anhydrous ethanol by gas chromatography and exploratory data analysis

In this paper a set of Brazilian commercial gasoline representative samples from São Paulo State, selected by HCA, plus six samples obtained directly from refineries were analysed by a high-sensitive gas chromatographic (GC) method ASTM D6733. The levels of saturated hydrocarbons and anhydrous ethanol obtained by GC were correlated with the quality obtained from Brazilian Government Petroleum, Natural Gas and Biofuels Agency (ANP) specifications through exploratory analysis (HCA and PCA). This correlation showed that the GC method, together with HCA and PCA, could be employed as a screening technique to determine compliance with the prescribed legal standards of Brazilian gasoline.

Rapid and sensitive method for the determination of acetaldehyde in fuel ethanol by high-performance liquid chromatography with UV-Vis detection

A high-performance liquid chromatography (HPLC) method for the determination of acetaldehyde in fuel ethanol was developed. Acetaldehyde was derivatized with 0.900 mL 2,4-dinitrophenylhydrazine (DNPHi) reagent and 50 mu L phosphoric acid 1 mol L-1 at a controlled room temperature of 15 degrees C for 20 min. The separation of acetaldehyde- DNPH (ADNPH) was carried out on a Shimadzu Shim-pack C-18 column, using methanol/LiCl(aq) 1.0 mM (80/20, v/v) as a mobile phase under isocratic elution and UV-Vis detection at 365 nm. The standard curve of ADNPH was linear in the range 3-300 amg L-1 per injection (20 mu L) and the limit of detection (LOD) for acetaldehyde was 2.03 mu g L-1, with a correlation coefficient greater than 0.999 and a precision (relative standard deviation, RSD) of 5.6% (n=5). Recovery studies were performed by fortifying fuel samples with acetaldehyde at various concentrations and the results were in the range 98.7-102%, with a coefficient of variation (CV) from 0.2% to 7.2%. Several fuel samples collected from various gas stations were analyzed and the method was successfully applied to the analysis of acetaldehyde in fuel ethanol samples.

High-resolution aquifer analog of fluvial-aeolian sediments of the Guarani aquifer system

The Guarani aquifer system (GAS) represents one of the biggest aquifers in the world and is the most relevant groundwater resource in South America. For the first time, by combining field and laboratory measurements, a high-resolution aquifer analog model of fluvial-aeolian sediments of the GAS in São Paulo State (Brazil) is constructed. Three parallel sections of frontal outcrops, 28 m × 5.8 m, and two parallel sections of lateral outcrops, 7 m × 5.8 m, are recorded during open-pit mining of sandy sediments and describe in detail the three-dimensional distribution of the local lithofacies and hydrofacies. Variations of hydraulic conductivity, K, and porosity, n, are resolved on the centimeter scale, and the most permeable units of the fluvial-aeolian facies association are identified. The constructed aquifer analog model shows moderate hydraulic heterogeneity and a mean K value of 1.36 × 10-4 m/s, which is greater than the reported range of K values for the entire GAS in São Paulo State. The results suggest that the examined sedimentary unit constitutes a relevant portion of the GAS in São Paulo State in the context of groundwater extraction and pollution. Moreover, the constructed aquifer analog is considered an ideal basis for future numerical model experiments, aiming at in-depth understanding of the groundwater flow and contaminant transport patterns at this GAS portion or at comparable fluvial-aeolian facies associations. © 2013 Springer-Verlag Berlin Heidelberg.

A C2-continuous high-resolution upwind convection scheme

A bounded upwinding scheme for numerical solution of hyperbolic conservation laws and Navier-Stokes equations is presented. The scheme is based on convection boundedness criterion and total variation diminishing stability criteria and developed by employing continuously differentiable functions. The accuracy of the scheme is verified by assessing the error and observed convergence rate on 1-D benchmark test cases. A comparative study between the new scheme and conventional total variation diminishing/convection boundedness criterion-based upwind schemes to solve standard nonlinear hyperbolic conservation laws is also accomplished. The scheme is then examined in the simulation of Newtonian and non-Newtonian fluid flows of increasing complexity; a satisfactory agreement has been observed in terms of the overall behavior. Finally, the scheme is used to study the hydrodynamics of a gas-solid flow in a bubbling fluidized bed. © 2013 John Wiley & Sons, Ltd.

Plasma Steroid Dynamics in Late- and Near-term Naturally and Artificially Conceived Bovine Pregnancies as Elucidated by Multihormone High-resolution LC-MS/MS

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

Determination of furanic aldehydes in sugarcane bagasse by high-performance liquid chromatography with pulsed amperometric detection using a modified electrode with nickel nanoparticles

A glassy carbon electrode chemically modified with nickel nanoparticles coupled with reversed-phase chromatography with pulsed amperometric detection was used for the quantitative analysis of furanic aldehydes in a real sample of sugarcane bagasse hydrolysate. Chromatographic separation was carried out in isocratic conditions (acetonitrile/water, 1:9) with a flow rate of 1.0 mL/min, a detection potential of -50 mV vs. Pd, and the process was completed within 4 min. The analytical curves presented limits of detection of 4.0 × 10(-7) mol/L and 4.3 × 10(-7) mol/L, limits of quantification of 1.3 × 10(-6) and 1.4 × 10(-6) mol/L, amperometric sensitivities of 2.2 × 10(6) nA mol/L and 2.7 × 10(6) nA mol/L for furfural and 5-hydroxymethylfurfural, respectively. The values obtained in this sample by the standard addition method were 1.54 ± 0.02 g/kg for 5-hydroxymethylfurfural and 11.5 ± 0.2 g/kg for furfural. The results demonstrate that this new proposed method can be used for the quick detection of furanic aldehydes without the interference of other electroactive species, besides having other remarkable merits that include excellent peak resolution, analytical repeatability, sensitivity, and accuracy.

Development and validation of a simple, rapid and stability-indicating high performance liquid chromatography method for quantification of norfloxacin in a pharmaceutical product

A stability-indication high performance liquid chromatographic method has been developed for the determination of norfloxacin in tablet dosage forms. Optimum separation was achieved in less than 7 minutes using Eclipse Plus Zorbax C18 Agilent, 150 mm×4.6 mm i.d., 5 μm particle size column. The analyte was resolved by using a mobile phase 5% acetic acid aqueous solution and methanol (80:20, v/v) at a flow rate 1.0 ml/min on an isocratic high performance liquid chromatographic system at a wavelength of 277 nm. Linearity, system suitability, precision, sensitivity, selectivity, specific, and robustness were established by International Conference Harmonization guidelines. For stress studies the drug was subjected to photolysis, oxidation, acid, alkaline and neutral conditions. The analytical conditions and the solvent developed provided good resolution within a short analysis time and economic advantages. The proposed method not required sophisticated and expensive instrumentation.

High-resolution electrocardiography in dogs under doxorubicin-induced cardiomyopathy

Determinaram-se a ocorrência de potencial tardio em cães com cardiomiopatia induzida pela doxorrubicina e sua relação com o desenvolvimento de arritmias ventriculares ou morte súbita. Sete cães adultos, sem raça definida, de ambos os sexos foram utilizados. A cardiomiopatia foi induzida por infusão venosa lenta de doxorrubicina (30mg/m²) em intervalos de 21 dias, até uma dose total cumulativa de 240mg/m². Os animais foram monitorados ecocardiograficamente. Após a confirmação da cardiomiopatia, foi feito o registro da eletrocardiografia de alta resolução. Potenciais tardios foram observados em dois animais que morreram subitamente poucos dias após.

High-resolution electrocardiography in the diagnosis of arrhythmogenic right ventricular cardiomyopathy in Boxer dogs

Com o objetivo de avaliar a importância da eletrocardiografia de alta resolução no diagnóstico da cardiomiopatia arritmogênica do ventrículo direito do Boxer, 20 cães sem evidências de doença cardíaca estrutural à avaliação ecodopplercardiográfica foram agrupados de acordo com a frequência de arritmias ventriculares, avaliadas pela eletrocardiografia ambulatorial de 24 horas, e submetidos ao exame eletrocardiográfico de alta resolução. Duração do complexo QRS filtrado, duração dos sinais de baixa amplitude (menor que 40µV) dos últimos 40 milissegundos do complexo QRS e raiz quadrada média da voltagem ao quadrado dos últimos 40 milissegundos do complexo QRS (RMS40) foram as variáveis avaliadas. Não foram observadas diferenças significativas entre os grupos em relação às variáveis estudadas. Sendo assim, os resultados do presente estudo sugerem que a eletrocardiografia de alta resolução não é uma ferramenta útil no auxílio diagnóstico da cardiomiopatia arritmogênica do ventrículo direito dos cães da raça Boxer que não apresentam alterações miocárdicas evidentes ou disfunção sistólica.

Comparison of the quantification of caffeine in human plasma by gas chromatography and ELISA

In the present study we evaluated the precision of the ELISA method to quantify caffeine in human plasma and compared the results with those obtained by gas chromatography. A total of 58 samples were analyzed by gas chromatography using a nitrogen-phosphorus detector and routine techniques. For the ELISA test, the samples were diluted to obtain a concentration corresponding to 50% of the absorbance of the standard curve. To determine whether the proximity between the I50 of the standard curve and that of the sample would bring about a more precise result, the samples were divided into three blocks according to the criterion of difference, in modulus, of the I50 of the standard curve and of the I50 of the sample. The samples were classified into three groups. The first was composed of 20 samples with I50 up to 1.5 ng/ml, the second consisted of 21 samples with I50 ranging from 1.51 to 3 ng/ml, and the third of 17 samples with I50 ranging from 3.01 to 13 ng/ml. The determination coefficient (R² = 0.999) showed that the data obtained by gas chromatography represented a reliable basis. The results obtained by ELISA were also reliable, with an estimated Pearson correlation coefficient of 0.82 between the two methods. This coefficient for the different groups (0.88, 0.79 and 0.49 for groups 1, 2 and 3, respectively) showed greater reliability for the test with dilutions closer to I50.

Three-Dimensional Semiautomatic Road Extraction From a High-Resolution Aerial Image by Dynamic-Programming Optimization in the Object Space

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

Determination of gatifloxacin in bulk and tablet preparations by high-performance liquid chromatography

A sensitive, precise, and specific high-performance liquid chromatographic (HPLC) method was developed for the assay of gatifloxacin (GATX) in raw material and tablets. The method validation parameters yielded good results and included the range, linearity, precision, accuracy, specificity, and recovery. It was also found that the excipients in the commercial tablet preparation did not interfere with the assay. The HPLC separation was carried out by reversed-phase chromatography on a C18 absorbosphere column (250 x 4.6 mm id, 5 pm particle size) with a mobile phase composed of acetic acid 50/o--acetonitrile-methanol (70 + 15 + 15, v/v/v) pumped isocratically at a flow rate of 1.0 mL/min. The effluent was monitored at 287 nm. The calibration graph for GATX was linear from 4.0 to 14.0 mu g/mL. The interday and intraday precisions (relative standard deviation) were less than 1.05%.

Plasmid-based controls to detect rpoB mutations in Mycobacterium tuberculosis by quantitative polymerase chain reaction-high-resolution melting

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