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Biomedical subjects

M Valcárcel

Publications and source records attributed to M Valcárcel.

At least 19 recordsLinked to original sources
PubMed2006

Vanguard/rearguard strategy for the evaluation of the degradation of yoghurt samples based on the direct analysis of the volatiles profile through headspace-gas chromatography-mass spectrometry.

A vanguard/rearguard analytical strategy for the monitoring of the degradation of yoghurt samples is proposed. The method is based on the headspace-gas chromatography-mass spectrometry (HS-GC-MS) instrumental coupling. In this combination, the chromatographic column is firstly used as an interface between the HS and the MS (vanguard mode) avoiding separation of the volatile components by maintaining the chromatographic oven at high, constant temperature. By changing the thermal conditions of the oven, the aldehydes can be properly separated for individual identification/quantification (rearguard mode). In the vanguard method, the quantification of the volatile aldehydes was calculated through partial least square and given as a total index. The rearguard method permits the detection of the aldehydes at concentrations between 12 and 35 ng/g. Both methods were applied to the study of the environmental factors favouring the presence of the volatile aldehydes (C(5)-C(9)) in the yoghurt samples. Principal component analysis of the total concentration of aldehydes with the time (from 0 to 30 days) demonstrates the capability of the HS-MS coupling for the estimation of the quality losses of the samples. The results were corroborated by the HS-GC-MS which also indicates that pentanal was present in the yoghurt from the beginning of the study and the combination of light/oxygen was the most negative influence for sample conservation.

Aldehydes↗
PubMed2006

Alternatives for coupling sequential injection systems to commercial capillary electrophoresis-mass spectrometry equipment.

On-line coupling of an automated flow system with a commercially available capillary electrophoresis (CE) system with an electrospray interface (ESI) for mass spectroscopic (MS) detection is described. The peculiarities of CE-ESI-MS interfaces, in which a high electrical field must be applied to the capillary end where the sample is provided by the flow system, introduce significant difficulties for the appropriate work of the entire arrangement. Experimental strategies are proposed for achieving stable conditions for on-line sample pre-treatment, conditioning of the separation capillary, sample injection, as the proper separation. The versatility and robustness of the proposed arrangement is discussed, taken as example the separation of a variety of amines. Connection of the CE system's pressure to the automated flow system enables hydrodynamic introduction of sample with high precision. The developed hyphenated system is of practical relevance as it opens an avenue for the simplification and automation of the whole analytical process required when using powerful CE-ESI-MS equipments.

Butylamines↗
PubMed2005

Use of non-aqueous capillary electrophoresis for the quality control of commercial saffron samples.

A non-aqueous capillary electrophoresis (NACE) method for quantifying the seven crocin metabolites that are the major biologically active ingredients of saffron was developed. Separation is done by using a fused silica capillary filled with a 12.5 mM H3BO3/37.5 mM sodium tetraborate methanolic solution as background electrolyte. The results obtained were compared with the total index "safranal value", widely used as a quality measure of saffron products. The comparison revealed that the proposed NACE method provides useful information not obtained in the safranal value. Infact, samples with a similar safranal value can contain crocin metabolites in different concentrations and relative proportions. This new method is very useful for quality control in commercial saffron samples.

Carotenoids↗
PubMed2004

Solid-phase extraction-gas chromatography-mass spectrometry using a fullerene sorbent for the determination of inorganic mercury(II), methylmercury(I) and ethylmercury(I) in surface waters at sub-ng/ml levels.

A novel, straightforward solid-phase extraction system for the determination of inorganic mercury and organomercury compounds in water is proposed. The analytes, in a buffer medium at pH 4.5, are sorbed as diethyldithiocarbamate complexes on a C60 fullerene column an subsequently eluted and derivatized with sodium tetra-n-propylborate in ethyl acetate. Following elution, 1 microl of extract is injected into a gas chromatograph-mass spectrometer system. The proposed gas chromatography-mass spectrometry speciation method exhibits a linear range of 4-1 ng/ml, and a detection limit of 1.5 ng/l (sample volume, 50 ml). Its repeatibility, as relative standard deviation (RSD) (from 11 standards containing 50 ng/l for each analyte), is ca. 7%. No interferences from metals ions, such as Zn2+, Fe3+, Sb3+, As3+, Pb2+, Ni2+, Cu2+, Sn2+, Co2+, Mn2+ and Cd2+ were encountered at concentrations 1000 times higher than those of the mercury compounds. The method was used for the speciation of inorganic mercury, methylmercury and ethylmercury in various types of water including sea and waste water.

Ethylmercury Compounds↗
PubMed2004

Combining headspace gas chromatography with mass spectrometry detection for confirmation of hydrocarbon residues in virgin olive oil following automatic screening.

Hydrocarbon residues can be present in virgin olive oils either naturally or as contaminants. Presence of benzene, toluene, ethylbenzene, xylene isomers and styrene (BTEXS) in virgin olive oil, demanded the establishment of a cut-off level to discriminate oil samples containing these residues at normal levels from those at high levels caused by contamination. By introducing volatile components present in the headspace (HS) of the oil samples (without prior chromatographic separation) into the ionization source of a mass spectrometer, samples were classified as containing normal or high levels of BTEXS (recommendable or non-recommendable forhuman consumption). Confirmation and quantification of contaminated virgin olive oils were achieved by combining HS sampling with gas chromatography-mass spectrometry (GC-MS). No sample pretreatment was necessary for the chromatographic method, but the addition of 600 microl of ethyl acetate as chemical modifier for 10 ml of virgin olive oil. Detection limits ranged between 3 and 9 ng/ml. Oil analysis showed the presence of toluene in all samples, as well as the absence of benzene, ethylbenzene and o-xylene.

Automation↗
PubMed2004

Direct automatic screening of soils for polycyclic aromatic hydrocarbons based on microwave-assisted extraction/fluorescence detection and on-line liquid chromatographic confirmation.

An integrated screening-confirmation system for PAHs in soils is presented. The sample screening configuration comprises on-line microwave-assisted extraction of the selected pollutants, followed by continuous preconcentration and sample clean-up on RP-C18. Those samples for which the total concentration is close to or above the threshold limit established (10 microg/g) are subjected to liquid chromatographic separation for confirmation. An evaluation of the qualitative data obtained was also carried out, by calculating the unreliability zone as well as the false positive and false negative rates. The whole method (extraction/determination/confirmation) was validated using industrial soil and harbour sediment certified reference materials (IRMM, European Commission CRM 524 and CRM 535). Application to the screening of solid environmental samples with subsequent confirmation of the results is also presented.

Chromatography, High Pressure Liquid↗
PubMed2004

Monitoring of bacterial contamination in food samples using capillary zone electrophoresis.

A capillary electrophoresis method with UV detection is proposed for the identification and quantitation of bacterial contamination in food samples. The electrophoretic separation relies on the differential mobility of bacteria in the capillary. Electrophoretic resolution is improved by using calcium and myoinositol hexakisphosphate as specific ions that interact with the bacterial surface changing its electrical properties and electrophoretic mobility. The proposed method allows the effective separation of eight different types of bacteria in only 25 min. It was successfully used to detect the presence of bacteria in contaminated food. The precision of the analysis of real spiked samples ranges from 3.3 to 7.0%, and the overall analysis time is 7 h, which is much shorter than the 24-48 h typically required for plate counts. The validity of the method was established by comparison with the standard plate counting method.

Animals↗
PubMed2004

Bioguided extraction of polyphenols from grape marc by using an alternative supercritical-fluid extraction method based on a liquid solvent trap.

The biological activity of polyphenols extracted from grape marc was studied with a view to finding a new use for this winery waste. Polyphenols were extracted by using an alternative supercritical-fluid extraction method based on the use of a liquid trap that allows extracted polyphenols to be retained in a saline buffer, thus avoiding the need for the organic solvent required to elute polyphenols from a solid trap. The major extraction variables influencing the performance of the liquid trap (viz. CO(2) modifier content, flow-rate, extraction time and trap volume) were optimized. The proposed method was applied to the supercritical-fluid extraction extraction of 0.3 g grape marc with CO(2) modified with 3% methanol at 350 bar at 50 degrees C (CO(2) density 0.9 g mL(-1)) for 20 min, using a liquid flow-rate of 0.9 mL min(-1). The polyphenol extracts thus obtained exhibited cytotoxic effects that induced apoptosis in tumour cells.

Apoptosis↗
PubMed2004

Speciation of butyltin compounds in marine sediments by preconcentration on C60 and gas chromatography-mass spectrometry.

A new method for the speciation of butyltin compounds by solid phase extraction and direct injection using gas chromatography-mass spectrometry (GC/MS) is described. The compounds were complexed with sodium diethyldithiocarbamate and retained on a C60 sorbent column. The neutral chelates of butyltin compounds were eluted with ethyl acetate containing NaBPr4 as derivatising reagent. The main analytical figures of merit of the proposed method for 10 ml of sample are: linear range 0.2-35 ng/g expressed as Sn; limits of detection, 0.07, 0.09 and 0.10 ng/g as Sn for monobutyltin, dibutyltin and tributyltin, respectively. No interferences from metal ions such as Zn2+, Fe3+, Sb3t, Pb2+, Ni2+ and Mn2+ were observed in the determination of organotin compounds. The validation of method was performed out by the analysis of a standard reference sediment (CRM 462). The method was also applied to the determination of butyltin compounds in marine sediment samples.

Gas Chromatography-Mass Spectrometry↗
PubMed2002

Screening of aflatoxins in feed samples using a flow system coupled to capillary electrophoresis.

A method is proposed which presents a new approach to the joint use of capillary electrophoresis (CE) commercial equipment and a flow system. This flow system allows the total determination of several compounds by using a fluorimetric screening system. The individual determination for each analyte is performed by the CE proposed method. The screening procedure uses simple equipment and operations and provides a yes/no binary response that occasionally requires confirmation. A fast, simple, and reliable method has been developed in order to determine the most frequent mycotoxins in feed samples using micellar electrokinetic capillary chromatography (MECC). An extraction step followed by a purification step was carried out on the samples in order to remove interference substances before analysis. A C18 column was chosen to concentrate the mycotoxins, and the analytes were eluted from C18 using methanol. The MECC method allows the separation of six mycotoxins within 50 min with a reproducibility as RSD between 7.45 and 13.06%, and a limit of detection (LOD) between 0.02 and 0.06 mg l(-1) for all the mycotoxins. These LODs were clearly below legal limits (0.05 mg l(-1)).

Aflatoxins↗
PubMed2002

Determination of monoterpene hydrocarbons and alcohols in Majorana hortensis Moench by micellar electrokinetic capillary chromatographic.

Micellar electrokinetic capillary chromatography was used to determine the essential oils obtained by steam distillation of different samples of marjoram (Majorana hortensis Moench) dried leaves and flowers. The electrophoretic method consisted of a running buffer of 10 mM NaH2PO4, 6 mM Na2B4O7, 50 mM SDS, 7 mM gamma-cyclodextrin, and 10% acetonitrile, adjusted to pH 8.0 by the addition of 0.1 M H3PO4. The following monoterpene hydrocarbons and alcohol compounds were extracted from real samples and determined by the method proposed: alpha-pinene, gamma-terpinene, alpha-terpinene, terpinolene, p-cymene, linalool, alpha-terpineol, and terpinen-4-ol. The most prominent component of dried leaves, flowers, and commercial samples was terpinen-4-ol in four of the samples analyzed; only in one sample was alpha-terpineol present as the major compound.

Alcohols↗
PubMed2002

Innovations in the speciation of organolead compounds in water: towards a more rational, rapid, and simple analytical process.

Speciation analysis calls for rapid, simple systems for minimizing errors made in the most troublesome of all steps in the analytical process: sample preparation. In this context, continuous-flow systems are of great help. The evolution in the different methodologies enabled solutions to the main shortcomings occurring from the lack of selectivity of using RP-C18 as sorbent material. One solution was a shift to more sensitive and selective, but only partially automated, systems employing C60 fullerene and Grignard's reagent; another was a shift to completely automated systems employing sodium tetrapropylborate; and a final solution was to employ the simplest possible configuration by removing the reagent stream. The analytical methods developed allowed the identification and quantification of different organolead species at the pg/ml levels in rainwater samples, with precision (RSD) of about 5% and recoveries ranging from 92 to 100%.

Automation↗
PubMed2001

Study of the degradation of the herbicides 2,4-D and MCPA at different depths in contaminated agricultural soil.

Two phenoxyacid herbicides (2,4-D and MCPA) and their six corresponding phenols were determined in soil by using gas chomatography with electron impact mass spectrometry (GC/MS) for confirmation/quantitation. An automatic extraction (leaching), preconcentration, and cleanup (sorption) module was developed to extract the eight compounds from soil. The average recovery of all species, spiked to soil at microg/kg-mg/kg levels, was 95% (average standard deviation +/- 5%). A plot of agricultural clayey soil (approximately 12 m2) was contaminated with both herbicides (approximately 96 g/m3, depth 10 cm, density 1.23 g/cm3) and irrigated with (17 mm) at variable time intervals. Both herbicides and their corresponding phenol compounds were monitored at different soil depths over a 50 day period. The degradation of both herbicides in the surface layer (t(1/2) approximately 5 days) is a result of photodecomposition and microbial action; in the deeper layers, the degradation products occur in lower proportions by effect of leaching and are also the result of microbial action. The six phenol metabolites are only detected in the surface layer as they form preferentially by photodecomposition. The main metabolites (viz. 2,4-DCP for 2,4-D and 4-C-2-MP for MCPA) are formed within 24 h after the soil is contaminated; their concentration peaks are at day 8 in the absence of irrigation.

2,4-Dichlorophenoxyacetic Acid↗
PubMed2001

Comparison of three coupled gas chromatographic detectors (MS, MIP-AES, ICP-TOFMS) for organolead speciation analysis.

An automatic unit for the screening of rainwater is used for the determination of organolead compounds using different detectors coupled to a gas chromatograph. A systematic overview is given of the advantages and disadvantages of several detectors (electron ionization mass spectrometry, EI-MS; microwave induced plasma atomic emission spectrometry, MIP-AES; and inductively coupled plasma time-of-flight mass spectrometry, ICP-TOFMS, for the speciation of organolead compounds on the basis of sensitivity, selectivity and reliability. C60 fullerene and RP-C18 were used as sorbent materials for these compounds. The primary assets of the fullerene sorbent, as compared to C18 sorbent, are high sensitivity and selectivity resulting from efficient adsorption due to large surface area and interstitial volume. Among the detection systems, GC/ ICP-TOFMS is the most sensitive, with absolute detection limits of approximately 15 fg of organolead compounds (as lead) using 5-mL sample volumes. Except for diethyllead, similar sensitivities were obtained by MIP-AES. GC/MS is intrinsically the most specific option, because the species are detected directly from molecular information. The precision is similar for all detectors. The screening of rainwater from different locations showed that samples collected in countries in which leaded gasolines are now banned contain organolead species at concentrations below 2 pg/ mL, levels that can be detected only for sample volumes of 25 mL and using MIP-AES or ICP-TOFMS as detectors, their determination being impossible by GC/MS.

Journal Article↗
PubMed2001

Coupling continuous separation techniques to capillary electrophoresis.

One of the weak points of capillary electrophoresis is the need to implement rigorously sample pretreatment because its great impact on the quality of the qualitative and quantitative results provided. One of the approaches to solve this problem is through the symbiosis of automatic continuous flow systems (CFSs) and capillary electrophoresis (CE). In this review a systematic approach to CFS-CE coupling is presented and discussed. The design of the corresponding interface depends on three factors, namely: (a) the characteristics of the CFS involved which can be non-chromatographic and chromatographic; (b) the type of CE equipment: laboratory-made or commercially available; and (c) the type of connection which can be in-line (on-capillary), on-line or mixed off/on-line. These are the basic criteria to qualify the hyphenation of CFS (solid-phase extraction, dialysis, gas diffusion, evaporation, direct leaching) with CE described so far and applied to determine a variety of analytes in many different types of samples. A critical discussion allows one to demonstrate that this symbiosis is an important topic in research and development, besides separation and detection, to consolidate CE as a routine analytical tool.

Chromatography, High Pressure Liquid↗
PubMed2001

Use of eosin as a fluorophore in capillary electrophoresis with laser detection.

Eosin has been used to generate the background signal for indirect fluorimetric detection of inorganic and organic ions, simultaneously separated by capillary zone electrophoresis (CZE). This reagent provides constant fluorescence over the pH range of 5-10 and is compatible with the excitation by an argon ion laser at 488 nm with emission at 520 nm. The use of esosine as fluorophore, H3BO3, and Na2B4O7 as electrolyte and diethylentriamine as modifier of the electroosmotic flow in CZE were optimised. The analytical potential of the studied buffer was tested on a group of 12 anions, used as model compounds. Both, hydrodynamic and electrokinetic injection mode were optimised. The detection limits determined by the last injection mode, were in the range 0.008-0.037 mg l(-1). By using this method, the quantitation of the common anions in tap and mineral water has been carried out successfully.

Electrophoresis, Capillary↗