Multiresidue determination of organochlorines in fish oil by GC-MS: A new strategy in the sample preparation

A rapid, economic and environmentally friendly analytical methodology has been implemented for the determination of α-, β-, γ- and δ-HCH, p,p′-DDT, p,p′-DDD and p,p′-DDE, PCBs congeners #28, #52, #101, #153, #138 and #180 and Hexachlorobenzene in fish oil. 1,2,3,4-Tetrachloronaphtalene was used as internal standard. The sample preparation, consisting of a single step of clean-up and fractionation, took place in a column filled with different layers of neutral and sulphuric acid modified silica. The analytes were eluted by vacuum with of hexane. Significant reduction in terms of solvents, sorbents, and analysis time was achieved in comparison with literature.Gas chromatography coupled to mass spectrometry was used for the separation and determination of the analytes. The instrumental limits of detection were from 0.1 to 1.3 ng mL⁻¹ and the response of the detector was linear up to 200 ng mL⁻¹. The separation proved to be precise (RSD < 3.7% in peak area) and robust in terms of peak area, peak efficacy and resolution. The methodology was validated with two certified reference materials of cod liver oil, BCR 598 and BCR 349, obtaining no statistically significant differences between the concentrations found and certified. For the analytes that were not certified, aliquots of the reference materials were spiked and the recoveries obtained were satisfactory. These results were consistent with those found previously for DDTs by gas chromatography with an electron-capture detector.The methodology was applied to the analysis of three fish oil pills sold in Spain as a dietary supplement of vitamins and omega-3 fatty acids. The sum of the analytes studied was from 64 to 80 ng g⁻¹. The most abundant compounds are PCBs, followed by DDTs in all samples.     

Selective linkage detection of O‐sialoglycan isomers by negative electrospray ionization ion trap tandem mass spectrometry

Sialylated O‐linked oligosaccharides are involved in many biological processes, such as cell‐cell interactions, cell‐substance adhesion, and virus‐host interactions. These activities depend on their structure, which is frequently determined by tandem mass spectrometry. However, these spectra are frequently analyzer‐dependent, which makes it difficult to develop widely applicable analytical methods. In order to deepen the origin of this behavior, two couples of isomers of sialylated O‐linked oligosaccharides, NeuAcα2‐3Galβ1‐3GalNAc‐ol/Galβ1‐3(NeuAcα2‐6)GalNAc‐ol and NeuGcα2‐3Galβ1‐3GalNAc‐ol/Galβ1‐3(NeuGcα2‐6)GalNAc‐ol, were analyzed by liquid chromatography/negative electrospray ionization ion trap tandem mass spectrometry (LC/ESI(?)‐MSⁿ) using both an ion trap and a triple quadrupole mass spectrometer. Results clearly showed that while ions obtained in the triple quadrupole instrument fitted very well with the standard fragmentation routes, in the ion trap several intense ions could not be explained by these rules, specially a fragment at m/z 597. Furthermore, this ion was observed in the mass spectrum of those isomers that sialic acid binds to GalNAc by an α2‐6 linkage. From the MS³ spectrum of this ion an unexpected structure was deduced, and it led to propose alternative fragmentation pathways. Molecular mechanics calculations suggested that the found atypical route could be promoted by a hydrogen bond located only in α2‐6‐linked oligosaccharides. It has also been demonstrated that this process follows a slow kinetic, explaining why it cannot be observed using an ion beam‐type mass analyzer. In conclusion, ion traps seem to be more appropriate than triple quadrupoles to develop a reliable analytical method to distinguish between isomeric O‐linked glycans. Copyright © 2010 John Wiley & Sons, Ltd.     

A first step towards variational methods in engineering

In this paper, a didactical proposal is presented to introduce the variational methods for solving boundary value problems to engineering students. Starting from a couple of simple models arising in linear elasticity and heat diffusion, the concept of weak solution for these models is motivated and the existence, uniqueness and continuous dependence on the initial data for these solutions are proved. Finally, the solutions of the above mentioned problems are numerically evaluated by the finite element method.     

Accurate calculation of the eigenvalues of a new simple class of superpotentials in SUSY quantum mechanics

We obtain accurate eigenvalues for two recently derived SUSY partner Hamiltonians. We improve the Rayleigh-Ritz variational method proposed by the authors and show how to apply the Riccati-Padé method to those particular partner potentials.     

Pointwise Fourier Inversion on Rank 1 Symmetric Spaces with Cesaro Means

Conditions for pointwise Fourier inversion using spherical Cesàromeans of a given degree are established on rank 1 noncompactsymmetric spaces.     

On disjoint function systems and complemented subspaces

A sufficient condition for the complementability of subspaces generated by disjoint function systems in rearrangement invariant spaces is given. Orthogonal projections in L _p -spaces are extended to certain rearrangement invariant spaces. Applications to Lorentz spaces are given.     

New basic catalysts obtained from layered double hydroxides nanocomposites

A new route for the preparation of basic mixed oxides using nanocomposite precursors obtained from layered double hydroxides (LDH) was investigated. These nanocomposites have been prepared by intercalation of negatively charged guest entities containing Ca²⁺, Sr²⁺, Ba²⁺ or La³⁺ cations in the interlayer space of host Mg/Al LDH by anionic exchange. The guest entities have been previously prepared by complexation of the required cations in the presence of edta or citrate chelating anions. Intercalation of [Mⁿ⁺(edta)]^(4?n)? or [La(cit)OH]^? complexes is proved by elemental analysis, XRD analysis and FT-IR spectroscopy. However, in order to satisfy the charge equilibrium in the materials, (edta)^4? and (citrate)^3? species are also co-intercalated in the nanocomposites. The basic properties of the mixed oxides obtained after thermal decomposition of the nanocomposites precursors were evaluated in the disproportionation of 2-methyl-3-butyn-2-ol (MBOH) and the transesterification of 1-phenylethanol with diethylcarbonate (DEC). The Sr- and Ba-containing mixed oxides exhibit basicity close to the one of MgO and Mg(La)O mixed oxides. A comparative study of the reactivity of La-containing mixed oxides obtained following different preparation routes, i.e. coprecipitation or anionic exchange, allows to conclude that the nanocomposite route led to the most active samples.