Characterization of reaction products of iron and iron salts and aqueous plant extracts

The complexes formed in aqueous solution as a result of a reaction of iron and iron salts (Fe²⁺ and Fe³⁺) and some plant extracts were analyzed using Mössbauer spectroscopy and Fourier transform infrared. The extracts were obtained from Opuntia elatior mill., Acanthocereus pentagonus (L.) Britton, Mimosa tenuiflora, Caesalpinia coriaria (Jacq.) Willd., Bumbacopsis quinata (Jacq.) Dugand and Acacia mangium Willd., plants growing wildly in different zones of the Isthmus of Panama. Results suggest the formation of mono- and bis-type complexes, and in some cases, the occurrence of a redox reaction. The feasibility of application of the studied extracts as atmospheric corrosion inhibitors is discussed.     

Determination of sub‐ppb epichlorohydrin levels in water by on‐line solid‐phase extraction liquid chromatography/tandem mass spectrometry

A new sensitive and selective method based on on‐line solid‐phase extraction (SPE) coupled to liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI‐MS/MS) using a triple quadrupole mass spectrometer has been developed for the determination of epichlorohydrin (ECH) in different types of water samples. ECH is not easily determined directly by ESI‐MS as it is not readily ionized, and it has a low molecular mass and high polarity. Thus, prior derivatization of ECH was necessary, employing 3,5‐difluorobenzylamine as a derivatizing agent with Fe(III) as a catalyst. In order to achieve accurate quantification, correcting for matrix effects, losses in the derivatization process and instrumental deviations, isotope labelled ECH (ECH‐d₅) was added as an internal standard (IS) to the water samples. The method was validated based on European SANCO guidelines using drinking and other types of treated water spiked at two concentration levels (0.1 and 1.0 µg/L), the lower level having been established as the limit of quantification (LOQ) of the method. Satisfactory accuracy (recoveries between 70 and 103%), precision (RSD <20%) and linearity (from 0.05 to 50 µg/L, r >0.99) were obtained. The limit of detection (LOD) was set up at 0.03 µg/L. The method was applied to different water samples (drinking water and water samples collected from a municipal treatment water plant). In order to enhance confidence, five selected reaction monitoring (SRM) transitions were acquired, thus obtaining a simultaneous reliable quantification and identification of ECH in water, even at sub‐ppb levels. Copyright © 2009 John Wiley & Sons, Ltd.     

Potential of atmospheric pressure chemical ionization source in GC‐QTOF MS for pesticide residue analysis

The potential applications of a new atmospheric pressure source for GC‐MS analysis have been investigated in this work. A list of around 100 GC‐amenable pesticides, which includes organochlorine, organophosphorus and organonitrogenated compounds, has been used to evaluate their behavior in the new source. Favoring the major formation of the molecular ion in the source has been the main goal due to the wide‐scope screening possibilities that this fact brings in comparison with the traditional, highly fragmented electron ionization spectra. Thus, the addition of water as modifier has been tested as a way to promote the generation of protonated molecules. Pesticides investigated have been classified into six groups according to their ionization/fragmentation behavior. Four of them are characterized by the abundant formation of the protonated molecule in the atmospheric pressure source, mostly being the base peak of the spectrum. These results show that wide‐scope screening could be easily performed with this source by investigating the presence of the protonated molecule ion, MH+. The developed procedure has been applied to pesticide screening in different food samples (nectarine, orange and spinach) and it has allowed the presence of several pesticides to be confirmed such as chlorpyriphos ethyl, deltamethrin and endosulfan sulfate. The availability of a quadrupole time‐of‐flight instrument made it feasible to perform additional MS/MS experiments for both standards and samples to go further in the confirmation of the identity of the detected compounds. Results shown in this paper have been obtained using a prototype source which exhibits promising features that could be applied to other analytical problems apart from those illustrated in this work. Copyright © 2010 John Wiley & Sons, Ltd.     

A new volume of fluid method in three dimensions—Part I: Multidimensional advection method with face‐matched flux polyhedra

A multidimensional advection scheme in 3D based on the use of face‐matched flux polyhedra to integrate the volume fraction evolution equation is proposed. The algorithm tends to reduce the formation of ‘over/undershoots’ by alleviating the over/underlapping of flux polyhedra, thus diminishing the need to use local redistribution algorithms. The accuracy and efficiency of the proposed advection algorithm, which are analyzed using different tests with prescribed velocity field, compare well with other multidimensional advection methods proposed recently. The algorithm is also applied, in combination with a Navier–Stokes solver, to reproduce the impact of a water droplet falling through air on a pool of deep water. The interfacial curvature is calculated using a height‐function technique with adaptive stencil adjustment, which provides improved accuracy in regions of low grid resolution. The comparison of the numerical results with experimental results shows a good degree of agreement. Copyright © 2008 John Wiley & Sons, Ltd.     

Isotropic umbrella based triangulation of regular parametric surfaces

In this paper we propose an advancing front method for generating an isotropic triangular mesh on a regular parametric surface. Starting from a point on the surface, the method computes a set of points in the intersection curve between the surface and the sphere centered at that point with a prescribed radius. From this set we select the vertices of a cell composed by triangles approximately equilateral. The mesh grows repeating the described computation with boundary vertices of the cell as starting points. Compared to methods proposed by other authors, the current method may be considered as an improvement, since it is more efficient and flexible. Furthermore, the resulting mesh is closer to being isotropic. Additionally, we obtain a sufficient condition ensuring that a surface triangulation is of Delaunay type.     

Catalytic asymmetric hydrosilylation of acetophenone with new chiral thiourea ligands containing the (S)-α-phenylethyl group

New chiral thioureas 1–8 containing 1,2-ethylendiamine or trans-1,2-diaminocyclohexane as the carbon skeleton, and containing an (S)-α-phenylethyl group have been prepared (79–98% yield). Thioureas 1–8 were used as ligands for the zinc-based catalyzed asymmetric hydrosilylation of acetophenone with polymethylhydrosiloxane (PMHS). The best result was achieved with monothiourea 1 (up to 75% ee), in toluene and a catalyst load of 5 mol %.     

Performance evaluation of nonsynchronized initial random access for mobile broadband systems

In this paper, a comparative analysis of the performance of the nonsynchronized initial random access channel in Mobile WiMAX and E-UTRA systems under different conditions (fast fading, multiuser interference) is carried out. The analysis is focused on the correlation properties of the code sequences used in each case. We evaluate their ability to provide low values for false alarm and erroneous detection probabilities (detecting a sequence that has not been transmitted) at the same time as guaranteeing low nondetection probabilities of the effectively transmitted sequences. Results show the promising performance of the E-UTRA scheme, even in high mobility scenarios, where the Doppler effect requires additional considerations to guarantee the correct system operation.     

Formation and Evolution of Carbonate Species in Na-Doped Al2O3 and V2O5-Al2O3

A study is carried out by FT-IR spectroscopy of the carbonate species formed upon interaction of CO₂ with alumina and vanadia-alumina catalysts doped with sodium. It is found that the presence of sodium enhances the ability of the catalyst surface to adsorb CO₂, yielding to carbonate formation. The species formed changes in the presence of vanadium, shifting the ν_COO stretching bands towards higher wavenumbers than those recorded in Na-Al₂O₃ systems.