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Biomedical subjects

M Valcárcel

Publications and source records attributed to M Valcárcel.

At least 37 records · Page 2Linked to original sources
PubMed2001

Selective enrichment of 17 pyrethroids from lyophilised agricultural samples.

The screening of agricultural samples to determine 17 synthetic pyrethroids was investigated. Samples were lyophilised without losses of the insecticides, and then extracted with n-hexane. A simple, continuous preconcentration-elution system was developed, which included a silica sorbent column (packed with 50 mg) and used an air stream to carry the eluent (ethyl acetate) which minimised the eluate volume thus increasing the preconcentration factor; so no evaporation step was required. Pyrethroids were determined by gas chromatography-electron capture detection (GC-ECD) by using a 5% phenylmethylpolysiloxane-coated fused-silica capillary column; gas chromatography-mass spectrometry was used to identify the pyrethroids detected by GC-ECD monitoring. Limits of detection varied between 0.1 and 0.8 ng/ml (except for piperonyl butoxide, 25 ng/ml) with linear ranges from 1 to 200 ng/ml; the precision of the method was high (3-6%). Recoveries of 17 insecticides from 14 different agricultural samples fortified at levels of 20-100 ng/g ranged from 66 to 102% (bifenthrin and deltamethrin were those providing the lowest values, 66-87%). Pyrethroids were detected in eight samples (from the 100 unfortified agricultural samples tested) at concentrations lower than the established maximum residue limits (MRLs).

Chromatography, Gas↗
PubMed2001

Determination of nonsteroidal anti-inflammatory drugs in biological fluids by automatic on-line integration of solid-phase extraction and capillary electrophoresis.

A new, automatic method for the clean-up, preconcentration, separation, and quantitation of nonsteroidal anti-inflammatory drugs (NSAIDs) in biological samples (human urine and serum) using solid-phase extraction coupled on-line to capillary electrophoresis is proposed. Automatic pretreatment is carried out by using a continuous flow system operating simultaneously with the capillary electrophoresis equipment, to which it is linked via a laboratory-made mechanical arm. This integrated system is controlled by an electronic interface governed via a program developed in GWBasic. Capillary electrophoresis is conducted by using a separation buffer consisting of 20 mM NaHPO4, 20 mM beta-cyclodextrin and 50 mM SDS at pH 9.0, an applied potential of 20 kV and a temperature of 20 degrees C. The analysis time is 10 min and the detection limits were between 0.88 and 1.71 microg mL(-1). Automatic clean-up and preconcentration is accomplished by using a C-18 minicolumn and 75% methanol as eluent. The limit of detection of NSAIDs can be up to 400-fold improved when using sample clean-up. The extraction efficiency for these compounds is between 71.1 and 109.7 microg mL(-1) (RSD 2.0-7.7%) for urine samples and from 77.2 to 107.1 microg mL(-1) (RSD 3.5-7.1%) for serum samples.

Anti-Inflammatory Agents, Non-Steroidal↗
PubMed2001

Determination of phenolic constituents in citrus samples by on-line coupling of a flow system with capillary electrophoresis.

Phenolic compounds extracted from different citrus were determined. Calibration, extraction, elution, and introduction into the sample vial was carried out automatically by a continuous flow system (CFS) coupled to capillary electrophoresis (CE) equipment via a programmable arm. The only manual operation was the centrifugation of the sample to remove the pulp. The supernatant solutions were introduced into the CFS-CE system. A C-18 minicolumn coupled into the CFS was used to perform cleanup of the samples. The analytes were eluted from the minicolumn using methanol. Quantitative analysis was carried out by the standard addition method. The method presented allows a fast, quantitative, and reproducible determination of six main phenolic compounds in citrus samples, with precision in the range of 3.0-6.5%, expressed as relative standard deviations.

Citrus↗
PubMed2001

A solid phase extraction method for the screening and determination of pyrethroid metabolites and organochlorine pesticides in human urine.

A screening method has been developed for the determination of 23 organochlorine pesticides (OCPs) and 3-pyrethroid metabolities [cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-(1-cyclopropane) carboxylic acid, cis-3-(2,2-dibromovinyl)-2,2-dimethyl-(1-cyclopropane) carboxylic acid and 3-phenoxybenzoic acid] from human urine. OCPs were directly detected in urine samples while pyrethroid metabolites required acid-induced hydrolysis to convert their conjugates into free acids; all compounds were then cleaned-up/preconcentrated using solid phase extraction. Determination and quantitation was achieved by gas chromatography with a mass spectrometer detector operating in selected ion monitoring mode. Limits of detection varied between 0.1 and 0.3 ng/mL with linear ranges from 0.3 to 700 ng/mL; the precision of the method was high (4.3-7.2%). Recoveries of all analytes from urine samples fortified at levels of 30 ng/mL for each OCP and 15 ng/mL for each pyrethroid metabolite ranged from 88 to 101% (captan gave the lowest recovery). The results obtained from the analysis of real urine samples show the suitability of the proposed method for monitoring people exposed to organochlorine and pyrethroid pesticides.

Biotransformation↗
PubMed2001

Automated flow-injection spectrophotometric determination of nitrosamines in solid food samples.

A spectrophotometric method using a flow-injection system is proposed for the determination of nitrosamines in foods (cured-meats). The method is based on the photochemical cleavage of the N-NO bond of the nitrosamine to yield the corresponding amine and nitrite. The nitrite is then detected spectrophotometrically, at 542 nm, by use of its reaction with a modified Griess reagent. Different linear ranges between 0.8 and 2000 ng mL(-1) are obtained for the method, depending on the time of exposure of the sample to the UV radiation. The relative standard deviation varies between 2.0 and 3.9% and the sample throughput is between three and seven samples per hour, depending on the experimental conditions. The proposed method was successfully applied to the analysis of N-nitrosodimethylamine in cured ham and loin, bacon, and sausages.

Animals↗
PubMed2001

Multiresidue screening of pesticides in fruits using an automatic solid-phase extraction system.

About 20 pesticides were determined in lyophilized fruits using a semiautomatic multiresidue method, based on solid-phase extraction (SPE) with a silica column. The lyophilization of the sample, besides the SPE procedure selected, provided clean extracts despite the complexity of the matrixes studied. In addition, the lyophilization process allows sample preservation for at least three months without changes in the concentrations of the pesticides. Determination and quantitation of organochlorine and pyrethroid residues was carried out using a gas chromatograph equipped with an electron capture detector (GC-ECD), and a mass spectrometric detector (GC-MS) was used for confirmation purposes. Organochlorine pesticides provided average recoveries (spiked at three concentration levels in eight different fruits) near 93 +/- 4%, being lower (89 +/- 8%) for pyrethroids as a consequence of their higher degradation and interaction with the sample matrix. On the other hand, the detection limits achieved for all pesticides (0.5-8 ng per g of lyophilized fruit) allow their determination at the MRLs established by the European Union, with good precision ( approximately 5%). Finally, from the 100 different fruits screened, only 10 positive responses were obtained, which were further confirmed by GC-MS.

Automation↗
PubMed2001

Determination of fat in leather by the use of supercritical fluid extraction combined with on-line piezoelectric detection.

Leather samples were prepared and characterized as 'in house' matrix standards for the determination of fat. The Soxhlet standard method was used to establish the reference fat content in every standard sample. Sample homogeneity and stability were examined under specific storing conditions. The materials were subsequently used as matrix standards for the determination of fat in leather samples, using supercritical fluid extraction (SFE) with on-line piezoelectric detection. Real samples were weighed in the extraction SFE thimble, previously loaded with 1 g of diatomaceous earth. A temperature of 45 degrees C and a CO2 fluid density of 0.85 g ml-1 were used for extraction. The linear calibration range thus achieved was 0.001-0.040% m/m total fat (related to the weight of the leather) and the relative standard deviation +/- 3% (n = 11; P = 0.05). The results were compared with those obtained with the Soxhlet method and no significant differences were found.

Journal Article↗
PubMed2000

Automatic on-line coupling of supercritical fluid extraction and capillary electrophoresis.

An interface for the automatic coupling of a supercritical fluid extractor (SFE) with capillary electrophoretic (CE) equipment, both commercially available, was developed with a view to improving sample treatment, which is a crucial step in capillary electrophoresis. Extracted analytes were collected in a trap following depressurization in the SFE and were transferred to the CE equipment across the interface. The key elements of the experimental assembly are a laboratory-made programmable arm and the autosampler of the CE equipment, both of which are controlled by a built-in microprocessor using an appropriate electronic interface and customized software. This combined system was successfully used to determine cresols and chlorophenols in liquid samples (river water and human urine) with increased precision, throughput, and automatability. The proposed arrangement opens up interesting prospects for the direct determination of analyte traces in solid samples without human intervention.

Journal Article↗
PubMed2000

Continuous microwave-assisted extraction, solvent changeover and preconcentration of monophenols in agricultural soils.

An automatic extraction, preconcentration and clean-up module for the extraction of phenolic compounds from soils was developed; the separation and quantitation of each phenol is accomplished by GC-MS. The sorption-desorption of thirteen phenols on soils containing variable amounts of organic carbon (0.05-3.4%) and clay minerals (2-43%) at pH 5.7-8.6 was investigated. For this purpose, uncontaminated soils were spiked with 5 or 20 microg of each phenol per g of soil; the soils were then stored at 4 degrees C for at least 3 months prior to analysis in order to simulate analyte-matrix interactions other than material losses and environmental degradation in actual contaminated soils. The organic carbon content in acid and alkaline soils affects the sorption of chlorophenols but not that of alkylphenols. On the other hand, alkylphenols are preferentially sorbed by neutral soils, the process being influenced by the clay mineral content. Based on the results, alkylphenols interact more strongly with agricultural soils than do chlorophenols; also, both types of compound are less strongly sorbed by loamy sand soils owing to their increased sand contents.

Agriculture↗
PubMed2000

Simplified method for the determination of chlorinated fungicides and insecticides in fruits by gas chromatography.

A fast, reliable method for the determination of more than twenty chlorinated fungicides and insecticides in a variety of fruit samples is presented. The pesticides are extracted from chopped samples with magnetic stirring, after adding 13 ml of acetone-phosphate buffer-brine solution (12:1, v/v) with 5 ml of n-hexane. The continuous module employed allows sequential decolourization of the organic phase, solvent changeover and solid-phase extraction for clean-up and preconcentration purposes. A 1-microl aliquot of the pesticides in ethyl acetate (eluent) is finally injected into the gas chromatograph for separation and identification. The method provides excellent clean-up despite the complexity of the matrices involved. Fruit samples (5-20 g) containing 0.1-1250 ng/g pesticides were analysed with a high precision (4-6%). After contamination of the fruit samples for 12 h, average recoveries >90% at fortification levels of 5-25 ng/g were obtained for most of the pesticides. Positive findings of these pesticides in fruits purchased at local markets were confirmed by GC-MS.

Chromatography, Gas↗
PubMed2000

Automatic microgravimetric determination of fats in milk products by use of supercritical fluid extraction with on-line piezoelectric detection.

An on-line supercritical fluid extraction-piezoelectric detection system was developed and applied to the quantitative gravimetric determination of total fat in food samples (skimmed milk and cocoa). The proposed assembly provides all the advantages of an on-line system as regards automation, in addition to acceptable sensitivity and precision. Its strength lies in the design of the interface between the supercritical fluid extractor and the piezoelectric detector. Samples of skimmed milk and cocoa are weighed in the extraction thimble, previously loaded with I g of diatomaceous earth. A temperature of 100 degrees C and a CO2 fluid density of 0.60 mg/ml are used for extraction. The linear calibration range thus achieved is 0.005-0.07% w/w total fat, and the relative standard deviation is +/-2.3% (n=11; P=0.05). The throughput is six samples h(-1) (for the overall process). The proposed method was used to determine the total fat in food samples (milk, cocoa), the results being competitive with those of the Soxhlet methods for the same purpose.

Animals↗
PubMed2000

Analytical potential of fullerene as adsorbent for organic and organometallic compounds from aqueous solutions.

In this work, the analytical potential of C60 fullerene as a sorbent for organic and organometallic compounds from aqueous solutions was studied for the first time. Fullerene adsorbs many types of organic substances (e.g., N-methylcarbamates, phenols, polycyclic aromatic hydrocarbons, amines) with efficiencies that depend on the nature of the compound concerned and never exceed 60%. Conventional sorbents such as XAD-2 or polyurethane foam are more efficient than C60 for this purpose. Organometallic compounds (viz. metalocenes and organoleads) are quantitatively adsorbed on C60 via the formation of neutral complexes or chelates; the adsorption constant is dramatically increased by the use of classical reagents such as pyrrolidinedithiocarbamate or diethyldithiocarbamate. A complementary comparative study on the adsorption of organometallic complexes on RP-C18 and silica gel 100, among others, showed C60 to be superior as sorbent. All experiments in this work were carried out by using continuous flow configurations and gas chromatography-atomic absorption spectrometry techniques.

Adsorption↗
PubMed2000

Determination of pesticides in waters by automatic on-line solid-phase extraction-capillary electrophoresis.

The separation of seven pesticides by micellar electrokinetic capillary chromatography in spiked water samples is described, allowing the analysis of pesticides mixtures down to a concentration of 50 microg l(-1) in less than 13 min. Calibration, pre-concentration, elution and injection into the sample vial was carried out automatically by a continuous flow system (CFS) coupled to a capillary electrophoresis system via a programmable arm. The whole system was electronically coupled by a micro-processor and completely controlled by a computer. A C18 solid-phase mini-column was used for the pre-concentration, allowing a 12-fold enrichment (as an average value) of the pesticides from fortified water samples. Under the optimal extraction conditions, recoveries between 90 and 114% for most of the pesticides were obtained.

Automation↗
PubMed2000

Automatic calibration in capillary electrophoresis.

A direct, completely automated calibration procedure in capillary electrophoresis (CE) is presented. The manual calibration operations involved in analytical methods, such as external calibration, standard addition, and internal standard, were accomplished with a continuous flow system (CFS) coupled to commercial capillary electrophoresis equipment via a programmable arm. The system was managed by the proper CE microprocessor and allowed automatic calibration and direct quantification of the analytes in the sample without any manual pretreatment, therefore avoiding or minimizing manually associated errors. The whole system including peristaltic pumps and the programmable arm was connected via an electronic interface and completely controlled by a computer using a program written in GW-BASIC. The potential of this new CFS-CE arrangement was assessed by applying it to samples containing selected compounds.

Automation↗
PubMed2000

Flow injection spectrophotometric determination of ascorbic acid in soft drinks and beer.

Two spectrophotometric methods, a photochemical and a non-photochemical, for the determination of ascorbic acid in soft drinks and beer using a flow-injection system are proposed. The non-photochemical method is based on the redox reaction that takes place between ascorbic acid and Fe(III), yielding dehydroascorbic acid and Fe(II). Fe(II) reacts with 1,10-phenantroline, originating the reddish orange Fe(phen)3(2+) complex (ferroin). This complex is spectrophotometrically monitored at 512 nm, and the signal is directly related to the concentration of ascorbic acid in the sample. The photochemical method has the same basis, nevertheless, uses the irradiation with visible light to enhance the redox reaction and so achieve higher sensitivities in the analysis. The non-photochemical method shows a linear range between 5 and 80 microg mL(-1), with a relative standard deviation of 1.6% (n = 11), a detection limit of 2.7 microg mL(-1) and a sample throughput of 60 samples h(-1). The photochemical method shows a linear range between 1 and 80 microg mL(-1), with a relative standard deviation of 1.0% (n = 11 ), a detection limit of 0.5 microg mL(-1) and a sample throughput of 40 samples h(-1).

Ascorbic Acid↗
PubMed2000

Continuous sorbent preconcentration for the electrothermal atomic absorption spectrometric determination of ultratrace amounts of cobalt in milled wheat fractions.

A method for the rapid determination of cobalt at ultratrace levels was applied in flour and flour byproducts (shorts and bran) obtained from various types of wheat that includes on-line preconcentration and electrothermal atomic absorption spectrometry is proposed. Solutions in 0.1 mol/L HNO(3) of milled wheat fractions subjected to wet ashing are preconcentrated in a straightforward flow-injection system by sorption on a RP-C(18) column following chelation. The eluent, ethanol, is carried by an air stream, and the chelate is eluted and collected in a 500 microL PTFE autosampler cup. The determination of cobalt features a precision (RSD) of 6% for a concentration of 0.2 ng/mL and a sensitivity (slope of the calibration graph) of 0.38 +/- 0.03 A s x ng/mL. The cobalt content in each type of wheat was found to be influenced by its geographical origin and texture. Also, it was found to depend on the amount of bran present in the milled wheat fraction. On the other hand, it is not significantly affected by the technological processes involved in wheat milling at a flour-producing factory.

Cobalt↗