Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry combined with solid phase microextraction as a powerful tool for quantification of ethyl carbamate in fortified wines. The case study of Madeira wine

An analytical methodology based on headspace solid phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography—time-of-flight mass spectrometry (GC × GC–ToFMS) was developed for the identification and quantification of the toxic contaminant ethyl carbamate (EC) directly in fortified wines. The method performance was assessed for dry/medium dry and sweet/medium sweet model wines, and for quantification purposes, calibration plots were performed for both matrices using the ion extraction chromatography (IEC) mode (m/z 62). Good linearity was obtained with a regression coefficient (r²) higher than 0.981. A good precision was attained (R.S.D. <20%) and low detection limits (LOD) were achieved for dry (4.31 μg/L) and sweet (2.75 μg/L) model wines. The quantification limits (LOQ) and recovery for dry wines were 14.38 μg/L and 88.6%, whereas for sweet wines were 9.16 μg/L and 99.4%, respectively. The higher performance was attainted with sweet model wine, as increasing of glucose content improves the volatile compound in headspace, and a better linearity, recovery and precision were achieved. The analytical methodology was applied to analyse 20 fortified Madeira wines including different types of wine (dry, medium dry, sweet, and medium sweet) obtained from several harvests in Madeira Island (Portugal). The EC levels ranged from 54.1 μg/L (medium dry) to 162.5 μg/L (medium sweet).     

Effect of electron beam radiation dose on the foam formation in pre-ceramic polymer

Methylsilicone resin as a polymer precursor for a SiOC ceramic material was cured and foamed by electron beam (EB) irradiation in air prior to the pyrolysis under an inert atmosphere. Methylsilicone foams were obtained without additional foaming agent when exposed to accelerated electrons with radiation doses up to 9 MGy and dose rate of 2.8 kGy/s. During irradiation the polymer was melted and simultaneously gaseous products were formed by the methyl group oxidation and by the poly-condensation crosslinking reactions. The formed gases could not escape from the molten polymer and began to aggregate into bubbles. The effect of the radiation dose on the polymer foam molecular structure, the gel fraction and the ceramic yield was analyzed. The results indicate that the maximum amount of crosslinking in methylsilicone, when EB radiation is used, occurred between 1.0 and 2.0 MGy radiation dose. Methylsilicone foams were pyrolysed in N₂ atmosphere at temperatures of 1200 and 1500 °C, resulting in amorphous SiOC and partially crystalline ceramic foams, respectively. A porosity of ~84% was achieved in the pyrolyzed foams, with cell size ranging from 30 to 300 μm and density of about 0.31 g cm^?3.     

Improving the 1H indirect dimension resolution of 2D CRAMPS NMR spectra: a simulation and experimental investigation

An experimental and simulation investigation regarding the effect of various CRAMPS parameters (delays interleaved with the decoupling shape, z-rotation symmetry and offset frequency) on the DUMBO decoupling performance is presented using two model compounds, glycine and tyrosine·HCl. Although the conclusions of this work may be extended to the other homonuclear-decoupling schemes, this work focuses essentially on the effect of adding interleaved delays to DUMBO decoupling during the indirect dimension using different 2D pulse-scheme architectures. While the simulations revealed an increasing loss of the spectral resolution with longer delays (from 0 to 6 μs), the experimental 2D (1)H DUMBO NMR correlation spectra revealed that the inclusion of delays, during the indirect dimension, improves the (1)H resolution whether the z-rotation symmetry was used or not. The best experimental spectra are obtained when z-rotation symmetry and windows are combined.     

3D elemental distribution images in biological samples by XRFµCT

An X‐ray transmission microtomography (CT) system combined with an X‐ray fluorescence microtomography (XRFµCT) system was implemented in the Brazilian Synchrotron Light Laboratory (LNLS), Campinas, Brazil. The aim of this work was to determine the elemental distribution in biological samples (breast, prostate and lung samples) in order to verify the concentration of some elements correlated with characteristics and pathology of each tissue observed by the transmission CT. The experiments were performed at the X‐ray fluorescence beamline (D09B‐XRF) of the Brazilian Synchrotron Light Laboratory, Campinas, Brazil. A quasi‐monochromatic beam produced by a multilayer monochromator was used as an incident beam. The sample was placed on a high‐precision goniometer and translation stages that allow rotating as well as translating it perpendicularly to the beam. The fluorescence photons were collected with an energy dispersive HPGe detector placed at 90° to the incident beam, while transmitted photons were detected with a fast Na(Tl) scintillation counter placed behind the sample on the beam path. The CT images were reconstructed using a filtered‐back projection algorithm and the XRFµCT images were reconstructed using a filtered‐back projection algorithm with absorption corrections. The 3D images were reconstructed using the 3D‐DOCTOR software. Results from the 3D visualization showed that the distribution of iron, copper and zinc is different and heterogeneous from the analyzed samples. Copyright © 2011 John Wiley & Sons, Ltd.     

Fractional Type Integral Operators on Variable Hardy Spaces

Given certain n × n invertible matrices A ₁, . . . , A _m and 0 ≦ α < n, we obtain the \({H^{p(.)}(\mathbb{R}^n) \to L^{q(.)}(\mathbb{R}^n)}\) boundedness of the integral operator with kernel \({k(x, y) = |x - A_1y|^{-\alpha_1} . . . |x - A_my|^{-\alpha_m}}\) , where α ₁ +  . . . + α _m = n ? α and p(.), q(.) are exponent functions satisfying log-Hölder continuity conditions locally and at infinity related by \({\frac{1}{q(.)} = \frac{1}{p(.)} - \frac{\alpha}{n}}\) . We also obtain the \({H^{p(.)}(\mathbb{R}^n) \to H^{q(.)}(\mathbb{R}^n)}\) boundedness of the Riesz potential operator.     

A genetic algorithm with neural network fitness function evaluation for IMRT beam angle optimization

Intensity Modulated Radiotherapy Treatment (IMRT) is a technique used in the treatment of cancer, where the radiation beams are modulated by a multileaf collimator allowing the irradiation of the patient using non-uniform radiation fields from selected angles. Beam angle optimization consists in trying to find the best set of angles that should be used in IMRT planning. The choice of this set of angles is patient and pathology dependent and, in clinical practice, most of the times it is made using a trial and error procedure or simply using equidistantly distributed angles. In this paper we propose a genetic algorithm that aims at calculating good sets of angles in an automated way, given a predetermined number of angles. We consider the discretization of all possible angles in the interval [0 \(^{\circ }\) , 360 \(^{\circ }\) ], and each individual is represented by a chromosome with 360 binary genes. As the calculation of a given individual’s fitness is very expensive in terms of computational time, the genetic algorithm uses a neural network as a surrogate model to calculate the fitness of most of the individuals in the population. To explicitly consider the estimation error that can result from the use of this surrogate model, the fitness of each individual is represented by an interval of values and not by a single crisp value. The genetic algorithm is capable of finding improved solutions, when compared to the usual equidistant solution applied in clinical practice. The genetic algorithm will be described and computational results will be shown.     

Realization of 2D convolutional codes of rate \frac{1}{n} by separable Roesser models

In this paper, two-dimensional convolutional codes constituted by sequences in $(\mathbb F ^n)^{\mathbb{Z }^{2}}$ where $\mathbb F $ is a finite field, are considered. In particular, we restrict to codes with rate $\frac{1}{n}$ and we investigate the problem of minimal dimension for realizations of such codes by separable Roesser models. The encoders which allow to obtain such minimal realizations, called R-minimal encoders, are characterized.     

PIXE analysis of Tillandsia usneoides for air pollution studies at an industrial zone in Central Mexico

In order to find out if there is a relation between atmospheric particulate matter composition and human health effects, metals and other elements measurement are performed. Analysis of atmospheric aerosols collected in filters is the usual method to achieve this task. Biological monitors provide an advantageous alternative way of sampling, since there is no need of special sampling devices, and accumulation time can be as long as desired. In this study, Tillandsia usneoides a reliable air pollution biological monitor that occurs naturally throughout Mexico was used to monitor air quality of Tula–Tepeji corridor at central Mexico. This area is considered critical zone because of atmosphere contaminants high concentration. Some biomonitors were transplanted from a clean environment to four sites at the Tula corridor. Plants samples were collected every two weeks from February to April 2008. PM₁₀ sampling in filters was also performed simultaneously at three locations where T. usneoides was transplanted, for a comparison. Chemical composition was determined by PIXE. Results showed that T. usneoides incorporates anthropogenic elements reaching maximal levels after 6 to 10 weeks approximately. Since results obtained with biomonitors agree with those obtained with aerosol filters, T. usneoides could be employed as a first approximation to provide insights of the atmospheric pollution level previous to a detailed study using filters.