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.

Off line extraction of phenol from human urine sample with isoamyl alcohol and determination by HPLC

This method has been developed for extraction and determination of phenol in a urine sample by high performance liquid chromatography.After acid hydrolysis, the free phenol was extracted with isoamyl alcohol solvent, followed by back extraction with 0.5 mol.L-1 sodium hydroxide solution and analyzed by an isocratic HPLC Varian System, equipped with reverse-phase column (MicroPak-C-18). The mobile phase was acetonitrile in 0.01 mol.L-1 hydrochloric acid solution, (20:80 v/v), and at a now-rate of 1.0 mL.min-1. The chromatogram was monitored at 220 nm in room temperature. The identification was based on retention time and the quantification was performed by automatic peak-area determination, corrected for the external standards method.The recovery was higher than 99.5 % for phenol and reproducibility of method was shown to be 2.3% standard deviation and 5.6% coefficient of variance (n=20). The limit detection was 0.05 mgL(-1) and a range of 0.05 to 20.0 mgL(-1) of phenol for linearity.

Validação de metodologia para análise de aminas bioativas em camarão utilizando cromatografia de íons

In this study, we worked with the validation of a methodology for analysis of bioactive amines in shrimp, considering it to be one of the main products of the northriograndense trade balance, maintaining the state of Rio Grande do Norte topped the list of Brazilian exports of this product the last decade. The sector of the Brazilian shrimp works exclusively with gray shrimp Litopenaeus Vannamei since the late 1990s. This study used liquid chromatography with conductimetric detector, using as the mobile phase methylsulfonic 3 mM acid (MSA) with gradient and phase C18 column with reverse the development of methodology for the analysis of bioactive amines in shrimp. In the sample preparation was used as 5% trichloroacetic acid (TCA) extraction solution. Validation analysis of biotativas amines (putrescine - PUT, histamine - HIST, agmatine - AGM, spermidine - EPD and spermine - EPN) in shrimp, the linear working range was 0.1 to 2.0 mg L-1 to was sensitive, homoscedastic, in effect, selective, accurate and precise array. Thus, considered feasible for these determinations bioactive amines in this array. Determined the concentration of these amines in fresh shrimps (AGM = 0.61 ± 0.05 mg kg- 1 EPD = 2.57 ± 0.14 mg kg-1 and EPN = 1.79 ± 0.11 mg kg-1), and freezing weather predetermined in cooked shrimp (AGM = 6.28 ± 0.18 mg kg-1, EPD = 12.72 ± 0.02 mg kg- 1 and EPN = 22.30 ± 0.60 mg kg-1), the shrimp with twenty-four hour stay at room temperature (PUT = 879.52 ± 28.12 mg kg-1, AGM = 848.13 ± 19.40 mg kg-1, ESPD = 13.59 ± 0.97 mg kg-1 and ESPN = 18.47 + 1.57 mg kg-1). In shrimp subjected to freezing for a week, two weeks, three weeks and four weeks, the results showed that there is an increase in the content of agmatine (7.31 ± 0.21 mg kg-1) while in spermine ( 1.22 ± 0.14 mg kg-1) and spermidine (below limit of quantification) there was a decrease in the freeze time, while there is a decrease in the level of spermidine not reaching detectad. The putrescine was only found in shrimp that remained for 24 hours at room temperature and histamine was not found in any of the samples

Aplicabilidade da voltametria de pulso diferencial na quantificação de ácido fólico e ácido oxálico: um método comparativo

The development of more selective and sensitive analytical methods is of great importance in different areas of knowledge, covering, for example, food, biotechnological, environmental and pharmaceutical sectors. The study aimed to employ the technique electroanalytical differential pulse voltammetry (DPV) as an innovative and promising alternative for identification and quantification of organic compounds. The organic compounds were investigated in this study oxalic acid (OA) and folic acid (FA). The electrochemical oxidation of oxalic acid has been extensively studied as a model reaction in the boundary between the organic and inorganic electrochemistry. Since the AF, an essential vitamin for cell multiplication in all tissues, which is essential for DNA synthesis. The AF has been investigated using analytical techniques, liquid chromatography and molecular absorption spectrophotometry. The results obtained during the experimental procedure indicated that the process of electrochemical oxidation of oxalic acid is strongly dependent on the nature of the anode material and the oxidation mechanism, which affects their detection. Efficient removal was observed in Ti/PbO2 anodes, graphite, BDD and Pt 90, 85, 80 and 78% respectively. It was also shown that the DPV employing glassy carbon electrode offers a fast, simple, reliable and economical way to determine the AO during the process of electrochemical oxidation. Furthermore, electroanalytical methods are more expensive than commonly used chromatographic analysis and other instrumental methods involving toxic reagents and higher cost. Compared with the classical method of titration and DPV could be a good fit, confidence intervals and detection limits confirming the applicability of electroanalytical technique for monitoring the degradation of oxalic acid. For the study of AF was investigated the electrocatalytic activity of the carbon paste electrode for identification and quantification in pharmaceutical formulations by applying the DPV. The results obtained during the experimental procedure showed an irreversible oxidation peak at 9.1 V characteristic of FA. The carbon paste sensor showed low detection limit of 5.683×10−8 mol L-1 reducing matrix effects. The spectrophotometric analysis showed lower concentrations of HF compared with those obtained by HPLC and DPV. The levels of AF were obtained according to the methodology proposed by the Brazilian Pharmacopoeia. The electroanalytical method (DPV) proposed is cheaper than GC analysis commonly used by the pharmaceutical industry. The results demonstrated the potential of these electroanalytical techniques for future applications in environmental, chemical and biological sensors

Development of an HPLC-UV/Vis method for the determination of dyes in a gasoline sample employing different pre-treatments

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

Chemical and Antidiarrheal Studies of Plinia cauliflora

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

Identificação de alguns constituintes químicos de Indigofera hirsuta Linn. (Fabaceae) por CLAE-IES-EM (TOF) e avaliação da atividade antirradicalar

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

Validação de metodologia analítica por cromatografia líquida de alta eficiência para quantificação de bupivacaína (S75-R25) em nanoesferas de poli(lactídeo-co-glicolídeo)

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

Extraction and clean-up procedure for analysis of organochlorine pesticide residues in ethoxylated lanolin

In the present study an evaluation was made of a method for the determination of organochlorine pesticide residues in ethoxylated lanolin. Samples were homogenized with Celite, transferred to chromatographic columns, prepacked with silica gel deactivated to 10%. The pesticide elution was processed with n-hexane-dichloromethane and the concentrated eluate was analyzed using gas-liquid chromatography (GC) with electron capture detection (ECD). The composition of the elution solvent was a significant factor for the recovery of the pesticides. Mean recoveries obtained for fortified samples ranged from 87 to 94% for p,p'-DDE, dieldrin, endrin, p,p'-DDD and p,p'-DDT. Optimization of the experimental conditions resulted in a small-scale method that combines extraction and cleanup in a single step. (C) 2000 Elsevier B.V. S.A. All rights reserved.

On-line extraction and determination of carbofuran in raw milk by direct HPLC injection on an ISRP column

A method has been developed for extraction and determination of carbofuran in milk. The method involved direct injection of raw milk on to a human serum albumin dimethyloctyl-silica gel (HSA-Cs) column and the use of 80:20 (v/v) 0.01 M phosphate buffer pH 5.5 - acetonitrile as mobile phase. UV spectrophotometric detection was performed at 220 nm. Identification was based on retention time. Quantification was performed by automatic peak-area determination and was calibrated by use of an external standard.

Metodologia rápida e eficiente para análise de pesticidas organoclorados em fubá

A rapid and efficient analytical method is presented for the quantitative analysis of 10 organochlorine pesticides in corn meal. The extraction and clean up steps are combined into one step by transferring the sample to a chromatographic column prepacked with alumina and silica gel. The pesticides are eluted with n-hexane-dichloromethane 9:1 (v/v) and the extracts analized by gas-liquid chromatography with electron capture detection, the average recoveries were between 78% and 98% and the detection limits were between 1 and 5 ng/g.

Correlation between acidic ninhydrin and HPLC methods to evaluate fraudulent addition of whey in milk

The acidic ninhydrin spectrophotometric method (ANSM) for quantitative determination of free and bound sialic acid of milk glycoprotein has been proved to be fast and efficient for routine detection of fraudulent addition of rennet whey to fluid milk. In this research the ANSM was compared with the high performance liquid chromatography (HPLC) method, internationally recommended for caseinomacropeptide (CMP) determination, which besides its high accuracy is more sophisticated and requires trained personnel. For several sample conditions (raw milk and milk with variable added amounts of rennet cheese whey), the methods showed an excellent linear correlation, with r = 0.981 when milk was deproteinized with a 120 g.L-1 final concentration of trichloroacetic acid (TCA) concentration. The best correlations could be seen with final concentrations of 100 g.L-1 and 80 g.L-1 TCA; respectively, r = 0.992 and 0.993.

Determination of carbamate residues in crop samples by cholinesterase-based biosensors and chromatographic techniques

An amperometric biosensor based on cholinesterase (ChE) has been used for the determination of selected carbamate insecticides in vegetable samples. The linear range of the biosensor for the N-methylcarbamates (aldicarb, carbaryl, carbofuran, methomyl and propoxur) varied from 5 x 10(-5) to 50 mg kg(-1). Limits of detection were calculated on the basis that the ChE enzymes were 10% inhibited and varied, depending of the combination ChE (as acetyl- or butyrylcholinesterase) vs. inhibitor (pesticide), from 1 x 10(-4) to 3.5 mg kg(-1). The biosensor-based carbamate determination was compared to liquid chromatography/UV methods. Three vegetable samples were spiked with carbofuran and propoxur at 125 mu g kg(-1) followed by conventional procedures. Good correlations were observed for carbofuran in the vegetable extracts (79, 96 and 91% recoveries for potato, carrot and sweet pepper, respectively), whereas for propoxur unsatisfactory results were obtained. Potato and carrot samples were spiked with 10, 50 and 125 mu g kg(-1) carbofuran, followed by direct determination by the amperometric biosensor. The fortified sampler; resulted in very high inhibition values, and recoveries were: 28, 34 and 99% for potato, and 140, 90 and 101% for carrot, respectively, at these three fortification levels. (C) 1998 Elsevier B.V. B.V.

Determination of cocaine in samples of hair using the chromatographic column, ISRP-C-18

A method has been developed for the determination of the cocaine levels in samples of hair, using a chromatographic column internal surface reverse phase (ISRP)-C-18, for direct injection of the extracts of hair, without purification or derivation of the sample. The method allows monitoring an individual stopped for using or making cocaine. This method allowed the determination of levels of cocaine concentration in 75% of the analyzed samples of chemical dependents' hair, with cocaine detected at levels of 0.37-16.85 mug g(-1). In the other analyzed samples (25%), the drug was not detected, because the corresponding individuals told us that they consumed cocaine infrequently and in small amounts. The detection

Synthesis of the stationary phase IS-Anionic (internal surface-anionic) for extraction of ochratoxin A and B from samples of beers

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