Biomedical subjects

M Valcárcel

Publications and source records attributed to M Valcárcel.

At least 55 records · Page 3Linked to original sources

PubMed2000

Fast urinary screening for paracetamol using on-line microwave assisted hydrolysis and spectrophotometric detection.

A fully automated urinary screening system for paracetamol and its metabolites is proposed. The method comprises on-line acid microwave assisted hydrolysis of the drug to p-aminophenol followed by reaction with o-cresol in alkaline medium. The indophenol blue dye formed can be continuously monitored at 620 nm. The detection limit achieved, 0.1 microgram ml-1, allows a high dilution of the samples, thus reducing potential interferences from the sample matrix (mainly protein degradation during urine hydrolysis). The proposed screening system also possesses an adequate selectivity, as the major interferent, epinephrine, is tolerated at concentrations higher than those that could be found in the positive urine samples. The reproducibility, expressed as relative standard deviation, was 3.0% and the sample frequency 20 h-1. The reliability of the method was established at five concentrations (between 0.5 and 4 times the detection limit). Finally, it was applied to the screening of several human urine samples. The results obtained were compared with those provided by batch acid hydrolysis, and were similar in all instances.

Acetaminophen↗

PubMed2000

Use of supported liquid membranes incorporated in a flow system for the direct determination of eugenol in spice samples.

A method for the determination of eugenol in spice samples based on the use of supported liquid membranes coupled to a flow system was developed. The solid sample is placed directly in the membrane unit without any treatment and the analyte is extracted from the sample, passes through the membrane and is conducted to the flow cell by the acceptor stream. This stream flows through the detector, allowing the measurement of the analyte by using a PVC-graphite composite electrode, versus Ag/AgCl/3 M KCl at +0.3 V, placed in a well-jet flow cell as amperometric detector. The method allowed the determination of eugenol in the range 0.5-30 micrograms ml-1 with a relative standard deviation of 5%. Results provided by the proposed procedure when applied to clove and seasoning samples agreed well with those obtained by a reference method.

Electrochemistry↗

PubMed1999

Enantiomeric separation of D- and L-carnitine by integrating on-line derivatization with capillary zone electrophoresis.

A new capillary zone electrophoretic method has been developed for the enantiomeric separation and quantification of enantiomers of carnitine, D- and L-carnitine were derivatized with 9-fluorenylmethyl chloroformate in a flow system, working on-line with the capillary electrophoretic equipment. The separation was performed using a selective chiral buffer containing 2,6-dimethyl-beta-cyclodextrin (heptakis). Triethanolamine was used as electroosmotic modifier and the separation was carried out in a uncoated capillary. Under the optimal conditions the resolution between D- and L-carnitine was 1.2 and the limits of detection for both isomers were about 5.0 microM. The proposed method was applied to the determination of D-carnitine in excess of L-carnitine in synthetic samples, and the results demonstrated that the maximal D-:L-carnitine ratio determined was approximately 1:100.

Carnitine↗

PubMed1999

Semiautomatic method for the screening and determination of 23 organochlorine pesticides in horticultural samples by gas chromatography with electron-capture detection.

A rapid, simple, efficient device for the extraction-preconcentration of 23 organochlorine pesticides currently applied to vegetables is proposed. Pesticide residues are extracted from chopped samples by using a mixture of distilled water and light petroleum (1:1, v/v). After phase separation, an aliquot of the organic layer is continuously evaporated to dryness under a N2 stream as it is dropped into a glass tube containing distilled water. The aqueous phase, containing the analytes, is then passed through a miniaturized RP-C18 column for preconcentration, clean-up and subsequent elution with 150 microliters of ethyl acetate. A volume of 1 microliter of the extract containing pesticides is injected into the gas chromatograph, fitted with an electron-capture detector, for their selective determination. Limits of detection vary between 0.04 and 10 ng/ml, with linear ranges from 0.2 to 500 ng/ml; the average relative standard deviation at the low nanogram-per-millilitre level is 5.3%. The potential of the proposed method was realized by applying it to the screening/determination of organochlorine pesticides in horticultural commodities.

Automation↗

PubMed1999

Gas chromatographic flow method for the preconcentration and simultaneous determination of antioxidant and preservative additives in fatty foods.

A partially automated gas chromatographic method for the simultaneous determination of antioxidants (tert.-butyl-4-hydroxyanisole, 2,6-di-tert.-butyl-p-hydroxytoluene, tert.-butylhydroquinone, alpha-tocopherol and alpha-tocopheryl acetate) and preservatives (sorbic acid, benzoic acid and their esters) in fatty foods without derivatization is reported. About 95% of triglycerides from lipid material are avoided by manually extracting the samples with a mixture of solvents and the remaining by using a continuous solid-phase extraction system. By using aqueous sample solutions (in 0.1 M HNO3), XAD-2 sorbent and selective elution with 200 microliters of 2-propanol, only ca. 0.03% of total triglycerides present in the original sample remains in the final extract. Manual injection of the extract into a GC-flame ionization detection allows the additives to be determine at concentrations in the range 0.5-100 micrograms/ml with a high precision (ca. 3%). Mass spectrometry in the conventional electron impact mode, in conjunction with library search, permits the unequivocal identification of all the additives. Margarine, oil, cheese, pâté and sauce samples were analysed in this way, all with good results.

Antioxidants↗

PubMed1999

Discrimination of structural isomers of chlorinated phenols in waters using gas chromatography-mass spectrometry in the negative chemical ionization mode.

The analysis and identification of structural isomers of mono-, di- and trichlorophenols is reported. The fragmentation of the phenols was examined by GC-MS in both electron impact (EI) and negative chemical ionization (NCI) modes, using methane as reagent gas. The ability of NCI to discriminate these isomeric compounds from differences in relative intensities for selected peaks is demonstrated. 3- and 4-chlorophenols have similar retention times; however, they can still be discriminated because their negative mass spectra and rather different. In dichlorophenols, the presence of one chlorine atom in the ortho position decreases their retention time and the relative intensity of the fragment ion at m/z 140. The NCI mass spectra for trichlorophenols are different from the rest, particularly for the m/z value corresponding to the chlorine atom. Tetra- and pentachlorophenols were also studied and sequential losses of Cl observed. An automatic solid-phase extraction system can optionally be used to preconcentrate chlorophenols in waters prior to determination at legally established toxic levels.

Gas Chromatography-Mass Spectrometry↗

PubMed1999

Determination of chlorophenols in human urine based on the integration of on-line automated clean-up and preconcentration unit with micellar electrokinetic chromatography.

A new method was developed and validated for the determination of chlorophenols in human urine by using micellar electrokinetic chromatography (MEKC) coupled via a mechanic arm to an on-line automatic clean-up and preconcentration unit for urine samples. Separation is accomplished by using a selective buffer consisting of 15 mM borate, 25 mM phosphate and 100 mM sodium dodecyl sulfate (SDS) at pH 9.1 in addition to a positive power supply of 25 kV at 18 degrees C. The proposed capillary electrophoresis (CE) method allows the separation of 11 chlorophenols within 7 min with a reproducibility as relative standard deviation (RSD) between 2.6% and 7.2%, and limits of detection (LODs) between 0.08 and 0.46 microg/mL for all chlorophenols. Urine samples were previously hydrolyzed with 37% HCl at 80 degrees C for 60 min and then cleaned on a C-18 mini-column. Recoveries ranged from 58% to 103%. The preconcentration treatment affords limits of determination between 4 and 12 ng/mL for all chlorophenols except pentachlorophenol and 4-chlorophenol, which could not be determined. The overall analysis time, including on-line clean-up, preconcentration and electrophoretic separation is 20 min per sample.

Chlorophenols↗

PubMed1998

Determination of anti-carcinogenic polyphenols present in green tea using capillary electrophoresis coupled to a flow injection system.

A capillary electrophoresis (CE) method was developed for the simultaneous determination of a number of major ingredients of green tea. The components analysed were caffeine, adenine, theophylline, epigallocatechin-3 gallate, epigallocatechin, epicatechin-3 gallate, (-)-epicatechin, (+)-catechin, gallic acid, quercetin and caffeic acid. Separation was achieved using a fused capillary column with 0.15 M H3BO3 as buffer at a pH of 8.5, UV detection at 210 nm and 20 kV of voltage. Analysis was carried out after treatment (extraction, filtration and dilution) of the samples in a flow injection system which was coupled to a CE equipment via a programmable arm. The procedure allows the determination of these compounds in less than 20 min. Quantitative analysis was performed by the standard addition method. Limits of detection ranged between 0.04 microgram ml-1 for flavonols and 1.2 micrograms ml-1 for caffeine.

Anticarcinogenic Agents↗

PubMed1998

Gas chromatographic-mass spectrometric confirmation of selected benzophenones from benzodiazepines in human urine following automatic screening.

This paper reports a simple, expeditious procedure for confirming the presence of benzodiazepines in previously screened positive urine samples. Samples are manually hydrolysed to the corresponding benzophenones in an acid medium. The hydrolysis products are continuously aspirated into a photometric flow system for screening; positive samples are then confirmed and benzodiazepines identified by using a different flow system that conditions the analytes for gas chromatographic separation and unequivocal mass spectrometric confirmation. Detection limits for benzodiazepines in the nanogram-per-millilitre region are thus achieved by using 0.5 ml of hydrolysed urine; also, repeatability, as R.S.D., is less than 6.5%. The high specificity and sensitivity of the proposed method enables the confirmation of different benzodiazepines in urine samples obtained from drug addicts and patients from a local hospital.

Benzodiazepines↗

PubMed1998

Direct determination of biogenic amines in wine by integrating continuous flow clean-up and capillary electrophoresis with indirect UV detection.

A flow-injection manifold for automating the determination of biogenic amines in wine using capillary electrophoresis (CE) with indirect UV detection was developed. The ensuing method involves clean-up and solid-phase extraction (SPE) of the target analytes in the sample. Various treatments involving different SPE minicolumns were tested and compared. The C18 minicolumn was chosen to concentrate the amines following addition of ammonium chloride and ammonium hydroxide as buffer to neutralize them. Additions of amine standards were used to determine recoveries. Biogenic amines can be separated and detected after SPE with limits of detection in the range 0.05-0.1 microgram ml-1 by using 4 mM copper(II) sulphate, formic acid and 18-crown-6 as running buffer. All the amines studied are eluted within 15 min under the optimum conditions established. The overall process was successfully used to identify biogenic amines in various types of wine from different Spanish regions.

Biogenic Amines↗

PubMed1998

Sensitive determination of paraquat and diquat at the sub-ng ml-1 level by continuous amperometric flow methods.

Two methodologies are described for the determination of paraquat and diquat. The first is based on the pre-treatment of an electrode with a surfactant solution, which improves the electrochemical determination of the herbicides. Linear calibration graphs were obtained in the ranges 10-80 and 10-100 ng ml-1 for paraquat and diquat, respectively. The limits of detection were 6.32 for paraquat and 4.80 ng ml-1 for diquat. The method was applied to the determination of the herbicides in synthetic water samples. The second methodology is based on the preconcentration of paraquat and diquat in a minicolumn packed with a cation-exchange material. The determination ranges and detection limits depend on the sample volume used (5-50 ml). Thus, 50 ml of sample provides limits of detection of 0.016 and 0.020 ng ml-1 for paraquat and diquat, respectively. The applicability of the method was demonstrated with the determination of the herbicides in both synthetic and real water samples.

Diquat↗

PubMed1997

Rapid solid-phase extraction/derivatization system for sample preparation and gas chromatographic/mass spectrometric determination of drugs in human urine.

A novel automatic system has been developed for the rapid solid-extraction and derivatization of different drugs and their metabolites from urine, prior to further analysis. Manual injection of underivatized/derivatized drugs in a GC/MS system, in which the quadrupole mass filter was operated conventionally, provided high sensitivity and selectivity at the selected m/z value. The precision (2.1-6.8%) is acceptable and the overall recovery from urine was determined to be ca. 95%. The effectiveness of this approach is demonstrated with data obtained from different urine samples which had tested positively.

Calibration↗

PubMed1996

Gas chromatographic determination of cholesterol and tocopherols in edible oils and fats with automatic removal of interfering triglycerides.

An automated gas chromatographic method for the simultaneous determination of cholesterol, alpha-tocopherol and alpha-tocopheryl acetate in edible oils and fats without derivatization is reported. Interferences from lipid material are avoided by using a continuous system to transesterify triglycerides with potassium methylate in methanol. The precision of the method is 1.9, 2.2 and 3.1% for cholesterol, alpha-tocopherol and alpha-tocopheryl acetate, respectively. The proposed methods was validated by analysing a standard reference material of coconut oil (SRM 1563-2) with good results. The method features a high throughput, minimal sample handling and analyte specificity (lipid material does not interfere).

Cholesterol↗

PubMed1996

A partially automated pretreatment module for routine analyses for seventeen non-steroid antiinflammatory drugs in race horses using gas chromatography/mass spectrometry.

A partially automated module for the routine determination of illicit non-steroid antiinflammatory drugs (NSAIDs) in biological fluids from race horses was built, tested, refined, and shown to work. This pretreatment module retains 17 NSAIDs on an Amberlite XAD-2 column before back-elution derivatization with methyl iodide in acetonitrile. Methylated derivatives are manually injected into a gas chromatograph connected to a mass spectrometer. The quantification limits thus achieved are 50-100 ng/mL in 1 mL of urine or plasma. The proposed method is more expeditious than its manual liquid-liquid and liquid-solid extraction counterparts and is similar in speed to a typical gas chromatographic program.

Animals↗

PubMed1996

Flow-injection/pervaporation coupling for the determination of sulphide in Kraft liquors.

A dynamic manifold has been coupled with a pervaporation module for the determination of sulphide ion in complex matrices such as Kraft liquors. The method is based on ethylene blue formation and features detection limits of 0.68 and 0.42 microg mL(-1) of S(2-) for injection and continuous introduction of the sample, respectively, with linear ranges of 1-15 and 1-10 microg mL(-1). The method is highly selective as the interferences from other sulphur species are avoided in the pervaporation process; thus, it has been applied successfully to the determination of the analyte in white and green bleaching liquors.

Journal Article↗

PubMed1996

Automatic determination of total aliphatic amines by on-line photometric liquid-liquid microextraction.

An automatic flow method for the determination of total aliphatic amines has been developed. Using an integrated micro extraction unit at the detection point that allows continuous on-line monitoring of small organic plug from which amines are extracted. It is based on the formation of ion-pairs between aliphatic amines and sodium 1,2-naphthoquinone-5-sulphonate that are subsequently extracted into chloroform. The gradual enrichment of the organic phase with the ion-pair is continuously monitored at 460 nm. Absorbance readings at a fixed time and the slopes of absorbance-time recordings are the measured parameters used for determination purposes. The proposed method has been applied to the determination of total aliphatic amines in both synthetic and real (food) samples.

Journal Article↗

PubMed1995

Automatic gas chromatographic determination of the high-density-lipoprotein cholesterol and total cholesterol in serum.

A new analytical method that combines on-line precipitation-filtration, enzymatic hydrolysis, extraction and gas chromatography was developed for the determination of total cholesterol and high-density-lipoprotein cholesterol in human serum. Very-low-density lipoprotein, intermediate-density lipoprotein and low-density lipoprotein are precipitated with sodium phosphotungstate and magnesium chloride; then, the serum is continuously filtered and unprecipitated high-density-lipoprotein cholesterol is enzymatically hydrolyzed and finally determined as cholesterol by gas chromatography. Total cholesterol is also determined by direct introduction of the serum into the proposed system. The proposed method was validated by analyzing a lipid control serum with certified contents of high-density-lipoprotein cholesterol and total cholesterol. The results obtained were consistent with the certified contents.

Cholesterol↗

PubMed1995

Development and validation of chromatographic methods (HPLC and GC) for the determination of the active components (benzocaine, tyrothricin and menthol) of a pharmaceutical preparation.

Methods are reported for the determination of tyrothricin and benzocaine by HPLC and menthol by GC in the analysis of throat lozenges (tablets) containing all three compounds. After optimization of the variables involved in both HPLC and GC the methods have been characterized and validated according to the guidelines of the Spanish Pharmacopoeia, and applied to both the monitoring of the manufacturing process and the quality control of the final product.

Anesthetics, Local↗