P. Ortega-Barrales

Investigation by ICP-MS of trace element levels in vegetable edible oils produced in Spain

The content of trace elements (Ag, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, Ti, Tl and V) in edible oils (virgin olive, olive, pomace-olive, sunflower, soybean and corn) from Spain was determined, using inductively-coupled plasma-mass spectrometry (ICP-MS) after microwave digestion, employing only nitric acid in this step. The method has been validated by using both an oil reference material and recovery experiments over different oil samples, obtaining satisfactory results in all cases. Inter-day repeatabilities lower than 10% were observed for all of the analysed elements in the different kinds of oil samples. Studying the content of trace elements, in order to detect tendencies in the samples of the same type of oil, principal components analysis was used. Promising groupings were observed using a model with two principal components and retaining 75.3% of the variance.

Solid-phase spectrophotometric determination of trace amounts of hydrazine at sub-ng ml−1 level

Abstract A very sensitive method for the determination of trace amounts of hydrazine by Solid-phase spectrophotometry has been developed. The method is based on the fixation of an aldazine derivative of hydrazine on a cation-exchange resin and the resin phase absorbance being measured directly. It allows the determination of hydrazine in the range 0.08–1.20 ng ml −1 (with a RSD of 3.4% and an apparent molar absorptivity of 2.7 × 10 8 1 mol −1 cm −1 ). The method was applied to the determination of hydrazine in boiler feed and natural water samples, urine and isoniazid tablets.

Flow-through UV spectrophotometric sensor for determination of (acetyl)salicylic acid in pharmaceutical preparations

The solid phase spectrophotometry technique, in which the absorbance of the species of interest sorbed on a solid support is measured directly, was applied to the determination of salicylic acid using flow injection-analysis. Salicylic acid was determined by monitoring of its intrinsic absorbance at 297 nm sorbed on Sephadex QAE A-25 resin placed in an appropriate flow-through cell. The method proposed improves the selectivity compared with the corresponding solution-phase method and the sensitivity is increased by a factor of 30 or more. The flow-through sensor proposed allows working with several calibration lines simply by varying the sample volume injected. Thus, linear dynamic ranges from 1 to 20 and from 2 to 40 microg ml(-1) can be obtained by using 1000 and 300 microl, respectively, with detection limits being 0.064 and 0.135 microg ml(-1). Relative Standard Deviations (RSDs) of 0.52 and 0.38%, and sampling frequencies of 18 and 25 h(-1), respectively, were also achieved. The sensor also allows the indirect determination of acetylsalicylic acid previous hydrolysis on-line to salicylic acid. For acetylsalicylic acid, a linear dynamic range from 5 to 120 microg ml(-1) and 25 h(-1) of sampling frequency (300 microl of sample volume) were obtained. The proposed flow-through sensor has been successfully applied to the determination of both analytes in pharmaceutical preparations.

Lanthanide-Sensitized Luminescence as a Promising Tool in Clinical Analysis

Abstract The recent applications and novelties of lanthanide-sensitized luminescence (LSL) as a detection technique in clinical analysis are here reviewed. In LSL, lanthanide ions form complexes with organic compounds; in these complexes, the energy absorbed by the organic chromophore (usually the analyte) at its characteristic excitation wavelength is transferred to a triplet state of the molecule and then transferred to a resonance level of the lanthanide ion, which finally emits luminescence at its particular emission wavelength. The characteristics of this process will be reviewed and particular attention will be paid to the development of automatic methods of analysis, fluorescence probes, or flow-through optosensors, due to their potential applications in clinical analysis. A critical discussion of the advantages and handicaps of each analytical method is done and the trends of analytical chemistry in this research field are also presented.

Solid phase Fourier transform near infrared spectroscopy

A novel flow methodology, integrating continuous solid phase spectroscopy with measurements in the near infrared region (NIR) has been developed, the NIR absorbance measurement being carried out on a C18 solid phase located inside a flow-through cell. In this way, a simple and straightforward procedure has been developed for the determination of trace amounts of α-naphthylamine, used as a test molecule, in water samples. The method, based on peak area measurements between 5800 and 6060 cm–1 of the coadded spectra obtained between 4 and 8 min after sample injection, is suitable for α-naphthylamine concentrations from 4 to 30 µg mL–1 with a limit of quantification of 2 µg mL–1. Recovery studies, carried out on natural samples spiked with known concentrations of amine, provided an average recovery value of between 92 and 106% and the relative standard deviation of three independent analyses of a seawater sample spiked at a concentration level of 16 µg mL–1 of α-naphthylamine was 6.4%. The sampling frequency of the method corresponds to 6 h–1.

Fast flow-injection fluorimetric determination of amiloride by using a solid sensing zone

A rapid and simple flow-through solid phase spectrofluorimetric system is described in this paper for the determination of the diuretic amiloride in physiological fluid (serum) and pharmaceuticals. The sensor was developed in conjunction with a monochannel flow-injection analysis system with fluorimetric transduction. Amiloride was transitorily retained on cationic exchanger gel Sephadex SP-C25 placed in the detection area into the cell. The determination is carried out without any derivatization reaction, by measuring directly the intrinsic fluorescence of the analyte and using the peak height as analytical signal. The wavelengths of excitation and emission were 291 and 419 nm, respectively. Amiloride could be determined in the concentration ranges of 10-600 and 4-250 mugl(-1) at a sampling rate of 24 and 30 h(-1), respectively with detection limits of 0.92 and 0.33 mugl(-1) for 100, and 600 mul of sample volume injected, respectively. The relative standard deviations for ten independent determinations were better than 0.65%. The method was satisfactorily applied to the determination of amiloride in spiked biological fluids (serum) and pharmaceutical preparations without any pretreatment of the samples.

Fluorimetric determination of thiabendazole residues in mushrooms using sequential injection analysis

Thiabendazole is a benzimidazole fungicide of general use that is specifically used to control mushroom diseases, mainly cobweb diseases, which is caused by members of the genus Cladobotryum. Although this compound is legislated and its maximum residue limit established at 60mgkg(-1) by Codex Alimentarius, there is almost a complete absence of analytical methods available for its determination in mushrooms. Here, we propose an automated method, using Sequential Injection Analysis with fluorescence detection (λ(exc)/λ(em)=305/345nm) for the determination of thiabendazole in mushrooms. We have developed a flow-through optosensor using C(18) silica gel as solid support placed in the flow-cell where the determination is performed. This method presents a detection limit of 0.5mgkg(-1), and recovery experiments have been carried out in different kinds of mushrooms at levels below the legislated maximum residue limit, demonstrating that the proposed analytical method fulfils the requirements for its applications in quality control of mushrooms.

Environmental Water Samples Analysis of Pesticides by Means of Chemometrics Combined with Fluorimetric Multioptosensing

A single flow-through optosensor spectrofluorimetric system is proposed for the resolution of mixtures of three pesticides, α-naphthol, o-phenylphenol and thiabendazole, at μg l−1 levels using a partial least-squares (PLS) calibration approach. The sensor was developed in conjunction with a monochannel flow-injection analysis system with fluorimetric detection using C18 silicagel as an active sorbent substrate in the flow cell. By using 20% methanol-water (v:v) solution as carrier solution, the multisensor responds linearly in the measuring range without requiring additional reagents or derivatization. First derivative emission spectra of the corresponding analytes recorded during the process of retention-elution were used to provide multivariate data. The different kinetic on the retention process of the analytes on the sensing zone allows the selection of a time matrix for each analyte providing best results in the PLS approach. Accurate prediction results were obtained for the three analytes with RMSEP values of 1.86%, 3.34% and 0.50% were obtained for α-naphtol, o-phenylphenol and thiabendazole respectively. In the analysis of environmental waters samples, a mean recovery of 103% was obtained.

Development of an automated chemiluminescence flow-through sensor for the determination of 5-aminosalicylic acid in pharmaceuticals: a comparative study between sequential and multicommutated flow techniques

This work is aimed at demonstrating the potential of the implementation of automatic flow systems in optosensors using chemiluminescence detection. With this purpose, two automatic methodologies, multicommutation and sequential injection analysis (SIA), have been applied to the analysis of 5-aminosalicylic acid (ASA). The analyte is determined for the first time making use of its chemiluminescence reaction with permanganate anion, previously immobilized on an appropriate solid support in the detection area. First, the study of the most appropriate commercial flow-through cell and the optimum conditions for the reaction were performed. Second, the main differences in terms of flow variables and analytical parameters for multicommutation and SIA approaches were stated. Both methodologies were applied to the determination of the analyte in pharmaceuticals obtaining satisfactory results. Finally, the advantages and disadvantages of both proposed methods and the recoveries obtained from pharmaceuticals were statistically compared.

Lathyrus aureus and Lathyrus pratensis: characterization of phytochemical profiles by liquid chromatography-mass spectrometry, and evaluation of their enzyme inhibitory and antioxidant activities

Different wild plants commonly used in folk medicine, such as different species from the genus Lathyrus, may represent new sources of biologically active compounds. Hence, a study of the composition and (bio)chemical behaviour of extracts from these plants may provide valuable information. To evaluate the phytochemical profile, and the enzyme inhibition and antioxidant activities of the aerial parts of L. pratensis and L. aureus, extracts from both plants were analyzed by high-performance liquid chromatography with electrospray ionization mass spectrometric detection (HPLC-ESI-MSn). The in vitro antioxidant activity (phosphomolybdenum, β-carotene bleaching, DPPH, ABTS, FRAP, CUPRAC and metal chelating) and enzyme inhibitory activity (acetyl cholinesterase, butyrylcholinesterase, tyrosinase, α-amylase and α-glucosidase) were also investigated for these Lathyrus species. Flavonoids and saponins were the main groups of compounds detected in the extracts from both plants. Generally, the methanol and water extracts presented remarkable antioxidant and enzyme inhibitory effects; all the observed results are critically discussed. The content of organic compounds and the antioxidant and enzyme assays suggest that these plants may be further used in phytopharmaceutical or food industry applications.