Development and validation of a LC–MS/MS method for the simultaneous determination of aflatoxins, dyes and pesticides in spices

Based on several alerts from European countries over the last years concerning spices, we have been encouraged to establish an accurate method for the determination of dyes, aflatoxins and pesticides in various types of spices using reversed-phase (RP) liquid chromatography–tandem mass spectrometry interfaced with electrospray (LC–ESI–MS/MS). A simple sample treatment procedure entailing the use of an extraction step with acetonitrile without further cleanup has been developed. A C18 column with an aqueous ammonium formate/methanol mixture as the mobile phase was used, and gradient elution was performed. Mass spectral acquisition was done in positive ion mode by applying multiple reaction monitoring of at least two fragmentation transitions per compound to provide a high degree of selectivity. The method was in-house validated in terms of linearity, sensitivity, repeatability, recovery and selectivity on six kinds of spices. Satisfactory results in the majority of the cases were obtained for all analytes and matrices, with practical limits of quantitation acceptable for routine monitoring purposes. Extraction recoveries for most of the compounds ranged from 60% to 140% at spiking levels of 0.05 and 0.5 mg kg⁻¹. The applicability of the method for the simultaneous determination of dyes, aflatoxins and pesticides in several types of spices was demonstrated, and the method successfully applied to a limited number of products from the local market.     

Influence of the nature of the porous confining network on the sorption, diffusion and mechanical properties of hydrogel IPNs

Two series of amphiphilic hydrogels of various compositions were prepared by sequentially interpenetrating two polymer networks, a poly(2-hydroxyethyl acrylate) (PHEA) network inside either a macroporous matrix of poly(methyl methacrylate) (PMMA) or a macroporous poly(ethyl acrylate) (PEA) network. In both cases poly(2-hydroxyethyl acrylate) (PHEA) served as network II, and the firstly formed porous network was a hydrophobic homonetwork, PMMA or PEA, that conferred mechanical strength to the hydrogel. In order to obtain hydrogels with high hydrophilic content, the first network was prepared in the presence of a solvent, thus yielding a macroporous network. The two families of IPNs thus obtained were: (net-PMMA)-ipn-(net-PHEA) and (net-PEA)-ipn-(net-PHEA), with a PHEA content ranging from 36% to 87% and from 64% to 94%, respectively. The novelty of the work consisted in comparing the effect of using as the first macroporous network a polymer which is glassy at room temperature (PMMA) and another of the same family (PEA) but which is in the rubber state at room temperature. Swelling studies showed that the specific equilibrium water content of PHEA falls from 1.6 for pure (unconfined) PHEA to values that range from 0.4 to 1, for the (net-PMMA)-ipn-(net-PHEA), whereas in the second IPNs family, the equilibrium water uptake of PHEA phase is, at least, the same as that of the pure PHEA (in some cases it is greater). This means that the expansion of the PHEA phase is not restricted by the confining hydrophobic component when this last is in the rubber state at room temperature. Whereas for the first IPNs the mechanical properties significantly increased (storage modulus at 37 °C from 0.25 to 2.5 GPa) compared with those of pure PHEA (25.12 MPa), little if any reinforcing effect was observed in the second type of IPNs. This is due to the fact that the glass transition of the PEA network takes place at a lower temperature than that of PHEA, so both components are in the rubbery state at room temperature. Both series behave differently also in dynamic water sorption experiments: the rigid PMMA network hinders the diffusion of water, yielding lower values of the apparent diffusion coefficients. By contrast, with the PEA polymer as network I this diffusion is similar to that of the pure PHEA homonetwork.     

Design and construction of multicrystal analyser detectors using Rowland circles: application to MAD26 at ALBA

A concept is given for describing multicrystal analyser detectors (MADs), as they are in use for synchrotron powder diffraction, on the basis of the Rowland circle construction. The Rowland circle is typically used to describe focusing geometries and can be adapted for the case of MADs working at a single energy as well as in a limited energy range. With this construction it is also possible to quantify and optimize the walk of the beam along non‐central crystals which is inevitable in certain detector designs. The results of this geometrical inspection are correlated with a real detector design that is implemented at the ALBA synchrotron facility in Spain. An error budget is given to estimate the influence and amount of tolerance of the manufacturing process.     

Cooper pairs? magnetic moment in MCFL color superconductivity

We investigate the effect of the alignment of the magnetic moments of Cooper pairs of charged quarks that form at high density in three-flavor quark matter. The high-density phase of this matter in the presence of a magnetic field is known to be the Magnetic Color-Flavor-Locked (MCFL) phase of color superconductivity. We derive the Fierz identities of the theory and show how the explicit breaking of the rotational symmetry by the uniform magnetic field opens new channels of interactions and allows the formation of a new diquark condensate. The new order parameter is a spin-1 condensate proportional to the component in the field direction of the average magnetic moment of the pairs of charged quarks. The magnitude of the spin-1 condensate becomes comparable to the larger of the two scalar gaps in the region of large fields. The existence of the spin-1 condensate is unavoidable, as in the presence of a magnetic field there is no solution of the gap equations with nonzero scalar gaps and zero magnetic moment condensate. This is consistent with the fact that the extra condensate does not break any symmetry that has not already been broken by the known MCFL gaps. The spin-1 condensate enhances the condensation energy of pairs formed by charged quarks and the magnetization of the system. We discuss the possible consequences of the new order parameter on the issue of the chromomagnetic instability that appears in color superconductivity at moderate density.     

Modeling of astigmatic-elliptical beam shaping during fs-laser waveguide writing including beam truncation and diffraction effects

In this work, we report a model for accurately calculating the focal volumes corresponding to astigmatic elliptical beams used in fs-laser waveguide writing. The model is based on the use of the ABCD matrix formalism for the propagation of a Gaussian beam. The code includes the effects of propagation on the astigmatic elliptical beam, and the effects of beam truncation and diffraction at the entrance pupil of the focusing objective due to beam clipping when overfilling the pupil. The results predict that for a given astigmatism value and propagation distance it is possible to efficiently suppress the astigmatic focus closer to the surface. This explains previous experimental results where single structure waveguides with controllable aspect-ratio were fabricated using astigmatic-elliptical beams. Furthermore, we investigate the respective roles of astigmatism and beam propagation, as well as the strong impact of truncation and diffraction effects caused by clipping the beam at the pupil of the focusing optics. Finally, based on the results from our model, we present some practical considerations in terms of beam propagation and phase wrapping constraints.     

On the effect of friend feedbacks

Given ?? an (A,B)‐invariant subspace, we prove that the set of friend feedbacks is a linear variety, which can be considered as the direct sum of the feedbacks of the restriction to ?? and the co‐restriction to ??^⊥. In particular, when the natural controllability hypothesis hold, both pole assignments are simultaneously possible by means of a convenient friend feedback. Copyright © 2010 John Wiley & Sons, Ltd.     

Antioxidant activity of methimazole-copper(II) bioactive species and spectroscopic investigations on the mechanism of its interaction with Bovine Serum Albumin

Free radical-mediated oxidative stress has been implicated in numerous autoimmune disorders including Graves’ disease. Hyperthyroidism results in a marked increase in intracellular antioxidant enzymes including superoxide dismutase. The later activity is significantly increased in untreated Graves’ patients while treatment with methimazole results in normalization of the free radical and antioxidant activity indices. In this context, and considering the findings mentioned above, the aim of the present study was to evaluate unknown biological activities of methimazole and its methimazole-copper(II) complex investigating their superoxide scavenger power. Under the applied experimental conditions, methimazole did not show superoxide dismutase (SOD) activity while the copper complexes exhibited a strong superoxide radical scavenging capacity. Bearing in mind that the capacity of drugs to bind and/or interact with albumin is essential for their pharmacokinetic and pharmacodynamic properties, a complete investigation of the binding ability of both compounds by using Fourier transform infrared (FT-IR), Raman and Fluorescence spectroscopies, and UV-Vis spectrophotometry was included. Besides, in order to probe the copper ligand environment the EPR spectra of such compounds were analyzed.