Direct chiral determination of free amino acid enantiomers by two-dimensional liquid chromatography: application to control transformations in E-beam irradiated foodstuffs

Changes in free amino acids content and its potential racemization in ready-to-eat foods treated with E-beam irradiation between 1 and 8 kGy for sanitation purposes were studied. A simple heart cut two-dimensional high performance liquid chromatographic method (LC–LC) for the simultaneous enantiomeric determination of three pairs of amino acids used as markers (tyrosine, phenylalanine, and tryptophan) is presented. The proposed method involves the use of two chromatographs in an LC–LC achiral–chiral coupling. Amino acids and their decomposition products were firstly separated in a primary column (C₁₈) using a mixture of ammonium acetate buffer (20 mM, pH 6) (94%) and methanol (6%) as the mobile phase. Then, a portion of each peak was transferred by heart cutting through a switching valve to a teicoplanin-chiral column. Methanol (90%)/water (10%) was used as the mobile phase. Ultraviolet detection was at 260 nm. Detection limits were between 0.16 and 3 mg L⁻¹ for each enantiomer. Recoveries were in the range 79–98%. The LC–LC method combined with the proposed sample extraction procedure is suitable for complex samples; it involves an online cleanup, and it prevents degradation of protein, racemization of L-enantiomers, and degradation of tryptophan. Under these conditions, D-amino acids were not found in any of the analyzed samples at detection levels of the proposed method.     

The influence of hydrogen peroxide on carbon monoxide electrooxidation at Pt/C and Pt:Ru/C electrodes

Polymer electrolyte fuel cells constitute one of the most important efficiency energy converters for non-centralised uses. However, the use of fuels arising from reformate processes significantly lowers the current efficiency because of anodic catalytic poison coming from adsorbed carbon monoxide (CO_ad). In this work, the influence of the addition of hydrogen peroxide in the flow current is studied, considering the adsorption and electrochemical oxidation of carbon monoxide on carbon-supported Pt (20% Pt/Vulcan) and Pt:Ru (1:1, 20% Pt:Ru/Vulcan) catalysts in 2 M sulphuric acid. The investigation was conducted applying cyclic voltammetry and on-line differential electrochemical mass spectrometry. A series of experiments has been performed to investigate the influence of the temperature as well as the time of contact and the concentration of hydrogen peroxide. Oxidation of CO_ad to carbon dioxide occurs at lower potentials in the presence of hydrogen peroxide. Moreover, it is possible to remove ca. 70% of CO_ad on Pt/C electrodes. On the other hand, for PtRu/C electrodes, similar charge values to those of Pt/C electrodes were obtained for the CO stripping, but the process occurs at more negative potentials. In this case, the effect of partial desorption for CO_ad by interaction with hydrogen peroxide is added to the bifunctional mechanism usually considered for this alloy. This paper is dedicated to Prof. Francisco Nart, in memoriam.     

Study of the polyphenol content of red and white grape varieties by liquid chromatography-mass spectrometry and its relationship to antioxidant power

There is considerable interest in the analysis of phenolic compounds due to their involvement in the organoleptic characteristics of foods and drinks, and their contribution to protection against cardiovascular diseases and cancers through their antioxidant activity. This article describes studies of the polyphenol content, both total (by means of the Folin-Ciocalteu method) and individual (by means of HPLC, LC-MS and LC-MS-MS) and the antioxidant power, of six varieties of grape over the course of their maturation. A good correlation is found to exist between the total polyphenol content of the samples and their antioxidant power, and both seem diminish along the maturation.     

The chromatographic behaviour of cycloolefins on stationary phases of different polarity. Prediction of their retention indices and boiling points

Summary The retention indices of mono and polycycloolefins with endo or exo double bonds, on squalane or polypropylenglycol 425 are related to their physico-chemical properties such as boiling point, molar volume, molar refraction, and refractive index. Equations have been empirically obtained, from which accurate retention indices of these compounds can be predicted. Unknown boiling points of some of these compounds can also be calculated from their lineal relation with the retention index on squalane.     

Analysis of Low Molecular Weight Carbohydrates in Food and Beverages: A Review

This review presents a study of new advances in chromatographic methods and capillary electrophoresis for the analysis and quantification of carbohydrates in food and drink that have been made in essentially the last seven years (1995–2002). All the main groups of sugars have been considered: monosaccharides, disaccharides, trisaccharides, oligosaccharides, related compounds such as alditols, alditol glycosides, polyols, amino sugars, deoxy sugars, uronic acids and aldonic acids. The chromatographic methods referred to are High Performance Liquid Chromatography (HPLC), Gas Chromatography (GC) and related techniques (AMD-HPTLC: High Performance Thin-Layer Chromatography with Automated Multiple Development). Capillary Electrophoresis (CE) was also discussed.     

Uptake of alpha and beta emitters by mushrooms collected and cultured in Spain

Almost all studies on the radioactive content of mushrooms have been centered on ¹³⁷Cs and, to a lesser extent, on ⁴⁰K. Other alpha and beta emitters have not been fully investigated and, therefore, their contribution to the dose due to consumption of mushrooms is not taken into consideration. We have studied the incorporation of several radionuclides: into mushrooms using two approaches — laboratory and natural conditions. Pleurotus eryngii was cultured under controlled laboratory conditions, and was found that ¹³⁴Cs was incorporated to a greater extent in the mushroom than the rest of radionuclides, and ²³⁹Pu at least. These results were confirmed by the uptake under natural conditions: ¹³⁷Cs > ^228,230,232Th ^234,238U ⁹⁰Sr >> ^239+240Pu. The contribution of thorium and uranium to the dose due to mushroom consumption in Spain is of the same order of magnitude as that of ¹³⁷Cs.This revised version was published online in November 2005 with corrections to the Cover Date.     

Density-Dependent Incompressible Fluids with Non-Newtonian Viscosity

We study the system of PDEs describing unsteady flows of incompressible fluids with variable density and non-constant viscosity. Indeed, one considers a stress tensor being a nonlinear function of the symmetric velocity gradient, verifying the properties of p-coercivity and (p–1)-growth, for a given parameter p > 1. The existence of Dirichlet weak solutions was obtained in [2], in the cases p 12/5 if d = 3 or p 2 if d = 2, d being the dimension of the domain. In this paper, with help of some new estimates (which lead to point-wise convergence of the velocity gradient), we obtain the existence of space-periodic weak solutions for all p 2. In addition, we obtain regularity properties of weak solutions whenever p 20/9 (if d = 3) or p 2 (if d = 2). Further, some extensions of these results to more general stress tensors or to Dirichlet boundary conditions (with a Newtonian tensor large enough) are obtained.     

Understanding higher twist: operator approach to power corrections

A thorough discussion of perturbative QCD for twist-4 is presented from a practical point of view. Misleading uses of intrinsic transverse momentum and mass terms are criticized and corrected in the complete expressions relevant for a model-independent experimental test of power corrections which is proposed. Upper and lower bounds for the twist-4 scale are deduced from a theoretically-consistent analysis of present DIS data with a simplified assumption on twist-4, from which a power-dominatedR=σ _L /R=σ _T is predicted.     

Spectroelectrogravimetry of the electrical conductivity activation in poly(o-toluidine) films

Journal of Solid State Electrochemistry - The study of the first stages of the transformation of conducting films from the insulating to the conducting form by oxidation is essential to understand...