74 resultados para comprehensive two-dimensional gas chromatography


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Background: We characterized variation and chemical composition of epicuticular hydrocarbons (CHCs) in the seven species of the Drosophila buzzatii cluster with gas chromatography/mass spectrometry. Despite the critical role of CHCs in providing resistance to desiccation and involvement in communication, such as courtship behavior, mating, and aggregation, few studies have investigated how CHC profiles evolve within and between species in a phylogenetic context. We analyzed quantitative differences in CHC profiles in populations of the D. buzzatii species cluster in order to assess the concordance of CHC differentiation with species divergence. Results: Thirty-six CHC components were scored in single fly extracts with carbon chain lengths ranging from C(29) to C(39), including methyl-branched alkanes, n alkenes, and alkadienes. Multivariate analysis of variance revealed that CHC amounts were significantly different among all species and canonical discriminant function (CDF) analysis resolved all species into distinct, non-overlapping groups. Significant intraspecific variation was found in different populations of D. serido suggesting that this taxon is comprised of at least two species. We summarized CHC variation using CDF analysis and mapped the first five CHC canonical variates (CVs) onto an independently derived period (per) gene + chromosome inversion + mtDNA COI gene for each sex. We found that the COI sequences were not phylogenetically informative due to introgression between some species, so only per + inversion data were used. Positive phylogenetic signal was observed mainly for CV1 when parsimony methods and the test for serial independence (TFSI) were used. These results changed when no outgroup species were included in the analysis and phylogenetic signal was then observed for female CV3 and/or CV4 and male CV4 and CV5. Finally, removal of divergent populations of D. serido significantly increased the amount of phylogenetic signal as up to four out of five CVs then displayed positive phylogenetic signal. Conclusions: CHCs were conserved among species while quantitative differences in CHC profiles between populations and species were statistically significant. Most CHCs were species-, population-, and sex-specific. Mapping CHCs onto an independently derived phylogeny revealed that a significant portion of CHC variation was explained by species' systematic affinities indicating phylogenetic conservatism in the evolution of these hydrocarbon arrays, presumptive waterproofing compounds and courtship signals as in many other drosophilid species.

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Context. The enigmatic object HD 45166 is a qWR star in a binary system with an orbital period of 1.596 day, and presents a rich emission-line spectrum in addition to absorption lines from the companion star (B7 V). As the system inclination is very small (i = 0.77 degrees +/- 0.09 degrees), HD 45166 is an ideal laboratory for wind-structure studies. Aims. The goal of the present paper is to determine the fundamental stellar and wind parameters of the qWR star. Methods. A radiative transfer model for the wind and photosphere of the qWR star was calculated using the non-LTE code CMFGEN. The wind asymmetry was also analyzed using a recently-developed version of CMFGEN to compute the emerging spectrum in two-dimensional geometry. The temporal-variance spectrum (TVS) was calculated to study the line-profile variations. Results. Abundances and stellar and wind parameters of the qWR star were obtained. The qWR star has an effective temperature of T(eff) = 50 000 +/- 2000 K, a luminosity of log(L/L(circle dot)) = 3.75 +/- 0.08, and a corresponding photospheric radius of R(phot) = 1.00 R(circle dot). The star is helium-rich (N(H)/N(He) = 2.0), while the CNO abundances are anomalous when compared either to solar values, to planetary nebulae, or to WR stars. The mass-loss rate is. M = 2.2 x 10(-7) M(circle dot) yr(-1), and the wind terminal velocity is v(infinity) = 425 km s(-1). The comparison between the observed line profiles and models computed under different latitude-dependent wind densities strongly suggests the presence of an oblate wind density enhancement, with a density contrast of at least 8: 1 from equator to pole. If a high velocity polar wind is present (similar to 1200 km s(-1)), the minimum density contrast is reduced to 4:1. Conclusions. The wind parameters determined are unusual when compared to O-type stars or to typical WR stars. While for WR stars v(infinity)/v(esc) > 1.5, in the case of HD 45166 it is much smaller (v(infinity)/v(esc) = 0.32). In addition, the efficiency of momentum transfer is eta = 0.74, which is at least 4 times smaller than in a typical WR. We find evidence for the presence of a wind compression zone, since the equatorial wind density is significantly higher than the polar wind. The TVS supports the presence of such a latitude-dependent wind and a variable absorption/scattering gas near the equator.

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This study presents the mass distribution for a sample of 18 late-type galaxies in nine Hickson compact groups. We used Ha rotation curves (RCs) from high-resolution two-dimensional velocity fields of Fabry-Perot observations and the J-band photometry from the Two Micron All Sky Survey, in order to determine the dark halo and the visible matter distributions. The study compares two halo density profiles, an isothermal core-like distribution, and a cuspy one. We also compare their visible and dark matter distributions with those of galaxies belonging to cluster and field galaxies coming from two samples: 40 cluster galaxies of Barnes et al. and 35 field galaxies of Spano et al. The central halo surface density is found to be constant with respect to the total absolute magnitude similar to what is found for the isolated galaxies. This suggests that the halo density is independent of galaxy type and environment. We have found that core-like density profiles better fit the RCs than cuspy-like ones. No major differences have been found between field, cluster, and compact group galaxies with respect to their dark halo density profiles.

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The theory of nonlinear diffraction of intensive light beams propagating through photorefractive media is developed. Diffraction occurs on a reflecting wire embedded in the nonlinear medium at a relatively small angle with respect to the direction of the beam propagation. It is shown that this process is analogous to the generation of waves by a flow of a superfluid past an obstacle. The ""equation of state"" of such a superfluid is determined by the nonlinear properties of the medium. On the basis of this hydrodynamic analogy, the notion of the ""Mach number"" is introduced where the transverse component of the wave vector plays the role of the fluid velocity. It is found that the Mach cone separates two regions of the diffraction pattern: inside the Mach cone oblique dark solitons are generated and outside the Mach cone the region of ""optical ship waves"" (the wave pattern formed by a two-dimensional packet of linear waves) is situated. Analytical theory of the ""optical ship waves"" is developed and two-dimensional dark soliton solutions of the generalized two-dimensional nonlinear Schrodinger equation describing the light beam propagation are found. Stability of dark solitons with respect to their decay into vortices is studied and it is shown that they are stable for large enough values of the Mach number.

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The semiclassical limit of quantum mechanical scattering in two dimensions is developed and the Wentzel-Kramers-Brillouin and eikonal results for two-dimensional scattering is derived. No backward or forward glory scattering is present in two dimensions. Other phenomena, such as rainbows and orbiting, do occur. (C) 2008 American Association of Physics Teachers.

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Magnetoresistance of two-dimensional electron systems with several occupied subbands oscillates owing to periodic modulation of the probability of intersubband transitions by the quantizing magnetic field. In addition to previous investigations of these magnetointersubband (MIS) oscillations in two-subband systems, we report on both experimental and theoretical studies of such a phenomenon in three-subband systems realized in triple quantum wells. We show that the presence of more than two subbands leads to a qualitatively different MIS oscillation picture, described as a superposition of several oscillating contributions. Under a continuous microwave irradiation, the magnetoresistance of triple-well systems exhibits an interference of MIS oscillations and microwave-induced resistance oscillations. The theory explaining these phenomena is presented in the general form, valid for an arbitrary number of subbands. A comparison of theory and experiment allows us to extract temperature dependence of quantum lifetime of electrons and to confirm the applicability of the inelastic mechanism of microwave photoresistance for the description of magnetotransport in multilayer systems.

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An analysis of the effect of an oil spill on mangrove sediments was carried out by contamination of mesocosms derived from two different mangroves, one with a history of contamination and one pristine. The association between N(2) fixers and hydrocarbon degradation was assessed using quantitative PCR (qPCR) for the genes rrs and nifH, nifH clone library sequencing and total petroleum hydrocarbon (TPH) quantification using gas chromatography. TPH showed that the microbial communities of both mangroves were able to degrade the hydrocarbons added; however, whereas the majority of oil added to the mesocosm derived from the polluted mangrove was degraded in the 75 days of the experiment, there was only partially degradation in the mesocosm derived from the pristine mangrove. qPCR showed that the addition of oil led to an increase in rrs gene copy numbers in both mesocosms, having almost no effect on the nifH copy numbers in the pristine mangrove. Sequencing of nifH clones indicated that the changes promoted by the oil in the polluted mangrove were greater than those observed in the pristine mesocosm. The main effect observed in the polluted mesocosm was the selection of a single phylotype which is probably adapted to the presence of petroleum. These results, together with previous reports, give hints about the relationship between N(2) fixation and hydrocarbon degradation in natural ecosystems.

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Five vegetable oils: canola, soybean, corn, cottonseed and sunflower oils were characterized with respect to their composition by gas chromatography and viscosity. The compositions of the vegetable oils suggest that they exhibit substantially different propensity for oxidation following the order of: canola < corn < cottonseed < sunflower approximate to soybean. Viscosities at 40 degrees C and 100 degrees C and the viscosity index (VI) values were determined for the vegetable oils and two petroleum oil quenchants: Microtemp 157 (a conventional slow oil) and Microtemp 153B (an accelerated or fast oil). The kinematic viscosities of the different vegetable and petroleum oils at 40 degrees C were similar. The VI values for the different vegetable oils were very close and varied between 209-220 and were all much higher than the VI values obtained for Microtemp 157 (96) and Microtemp 153B (121). These data indicate that the viscosity variations of these vegetable oils are substantially less sensitive to temperature variation than are the parafinic oil based Microtemp 157 and Microtemp 153B. Although these data suggest that any of the vegetable oils evaluated could be blended with minimal impact on viscosity, the oxidative stability would surely be substantially impacted. Cooling curve analysis was performed on these vegetable oils at 60 degrees C under non-agitated conditions. These results were compared with cooling curves obtained for Microtemp 157, a conventional, unaccelerated petroleum oil, and Microtemp 153B, an accelerated petroleum oil under the same conditions. The results showed that cooling profiles of the different vegetable oils were similar as expected from the VI values. However, no boiling was observed wit any of the vegetable oils and heat transfer occurs only by convection since there is no full-film boiling and nucleate boiling process as typically observed for petroleum oil quenchants, including those of this study. Therefore, high-temperature cooling is considerable faster for vegetable oils as a class. The cooling properties obtained suggest that vegetable oils would be especially suitable fur quenching low-hardenability steels such as carbon steels.

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This paper presents a study of the stationary phenomenon of superheated or metastable liquid jets, flashing into a two-dimensional axisymmetric domain, while in the two-phase region. In general, the phenomenon starts off when a high-pressure, high-temperature liquid jet emerges from a small nozzle or orifice expanding into a low-pressure chamber, below its saturation pressure taken at the injection temperature. As the process evolves, crossing the saturation curve, one observes that the fluid remains in the liquid phase reaching a superheated condition. Then, the liquid undergoes an abrupt phase change by means of an oblique evaporation wave. Across this phase change the superheated liquid becomes a two-phase high-speed mixture in various directions, expanding to supersonic velocities. In order to reach the downstream pressure, the supersonic fluid continues to expand, crossing a complex bow shock wave. The balance equations that govern the phenomenon are mass conservation, momentum conservation, and energy conservation, plus an equation-of-state for the substance. A false-transient model is implemented using the shock capturing scheme: dispersion-controlled dissipative (DCD), which was used to calculate the flow conditions as the steady-state condition is reached. Numerical results with computational code DCD-2D vI have been analyzed. Copyright (C) 2009 John Wiley & Sons, Ltd.

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A two-dimensional numeric simulator is developed to predict the nonlinear, convective-reactive, oxygen mass exchange in a cross-flow hollow fiber blood oxygenator. The numeric simulator also calculates the carbon dioxide mass exchange, as hemoglobin affinity to oxygen is affected by the local pH value, which depends mostly on the local carbon dioxide content in blood. Blood pH calculation inside the oxygenator is made by the simultaneous solution of an equation that takes into account the blood buffering capacity and the classical Henderson-Hasselbach equation. The modeling of the mass transfer conductance in the blood comprises a global factor, which is a function of the Reynolds number, and a local factor, which takes into account the amount of oxygen reacted to hemoglobin. The simulator is calibrated against experimental data for an in-line fiber bundle. The results are: (i) the calibration process allows the precise determination of the mass transfer conductance for both oxygen and carbon dioxide; (ii) very alkaline pH values occur in the blood path at the gas inlet side of the fiber bundle; (iii) the parametric analysis of the effect of the blood base excess (BE) shows that V(CO2) is similar in the case of blood metabolic alkalosis, metabolic acidosis, or normal BE, for a similar blood inlet P(CO2), although the condition of metabolic alkalosis is the worst case, as the pH in the vicinity of the gas inlet is the most alkaline; (iv) the parametric analysis of the effect of the gas flow to blood flow ratio (Q(G)/Q(B)) shows that V(CO2) variation with the gas flow is almost linear up to Q(G)/Q(B) = 2.0. V(O2) is not affected by the gas flow as it was observed that by increasing the gas flow up to eight times, the V(O2) grows only 1%. The mass exchange of carbon dioxide uses the full length of the hollow-fiber only if Q(G)/Q(B) > 2.0, as it was observed that only in this condition does the local variation of pH and blood P(CO2) comprise the whole fiber bundle.

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Dynamic experiments in a nonadiabatic packed bed were carried out to evaluate the response to disturbances in wall temperature and inlet airflow rate and temperature. A two-dimensional, pseudo-homogeneous, axially dispersed plug-flow model was numerically solved and used to interpret the results. The model parameters were fitted in distinct stages: effective radial thermal conductivity (K (r)) and wall heat transfer coefficient (h (w)) were estimated from steady-state data and the characteristic packed bed time constant (tau) from transient data. A new correlation for the K (r) in packed beds of cylindrical particles was proposed. It was experimentally proved that temperature measurements using radially inserted thermocouples and a ring-shaped sensor were not distorted by heat conduction across the thermocouple or by the thermal inertia effect of the temperature sensors.

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This study aimed to establish the optimum level of palm kernel meal in the diet of Santa Ines lambs based on the sensorial characteristics and fatty acid profile of the meat. We used 32 lambs with a starting age of 4 to 6 months and mean weight of 22 2.75 kg, kept in individual stalls. The animals were fed with Tifton-85 hay and a concentrate mixed with 0.0, 6.5, 13.0 or 19.5% of palm kernel meal based on the dry mass of the complete diet. These levels formed the treatments. Confinement lasted 80 days and on the last day the animals were fasted and slaughtered. After slaughter, carcasses were weighed and sectioned longitudinally, along the median line, into two antimeres. Half-carcasses were then sliced between the 12th and 13th ribs to collect the loin (longissimus dorsi), which was used to determine the sensorial characteristics and fatty acid profile of the meat. For sensorial evaluation, samples of meat were given to 54 judges who evaluated the tenderness, juiciness, appearance, aroma and flavor of the meat using a hedonic scale. Fatty acids were determined by gas chromatography. The addition of palm kernel meal to the diet had no effect on the sensorial characteristics of meat juiciness, appearance, aroma or flavor. However, tenderness showed a quadratic relationship with the addition of the meal to the diet. The concentration of fatty acids C12:0, C14:0 and C16:0 increased with the addition of palm kernel meal, as did the sum of medium-chain fatty acids and the atherogenicity index. Up to of 19.5% of the diet of Santa Ines lambs can be made up of palm kernel meal without causing significant changes in sensorial characteristics. However, the fatty acid profile of the meat was altered.

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Introduction - Ayahuasca is obtained by infusing the pounded stems of Banisteriopsis caapi in combination with the leaves of Psychotria viridis. P. viridis is rich in the psychedelic indole N,N-dimethyltryptamine, whereas B. caapi contains substantial amounts of beta-carboline alkaloids, mainly harmine, harmaline and tetrahydroharmine, which are monoamine-oxidase inhibitors. Because of differences in composition in ayahuasca preparations, a method to measure their main active constituents is needed. Objective - To develop a gas chromatographic method for the simultaneous determination of dimethyltryptamine and the main beta-carbolines found in ayahuasca preparations. Methodology - The alkaloids were extracted by means of solid phase extraction (C(18)) and detected by gas chromatography with nitrogen/phosphorous detector. Results - The lower limit of quantification (LLOQ) was 0.02 mg/mL for all analytes. The calibration curves were linear over a concentration range of 0.02-4.0 mg/mL (r(2) > 0.99). The method was also precise (RSD < 10%). Conclusion - A simple gas chromatographic method to determine the main alkaloids found in ayahuasca was developed and validated. The method can be useful to estimate administered doses in animals and humans for further pharmacological and toxicological investigations of ayahuasca. Copyright (C) 2009 John Wiley & Sons, Ltd.

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The effects of acai pulp addition and different probiotic bacteria on the fatty acid profile of stirred yoghurt were examined. Skim milk was divided into two groups: one containing acai pulp and another without the fruit. Batches were inoculated with yoghurt starter culture and divided into five groups according to probiotic addition. Counts of viable microorganisms were measured at days 1, 14 and 28 of cold storage. Fatty acid profile was determined by gas chromatography at day 1. Acai pulp favoured an increase in Lactobacillus acidophilus L10, Bifidobacterium animalis ssp. lactis Bl04 and Bifidobacterium longum Bl05 counts at the end of 4 weeks of cold storage. This study demonstrated that acai pulp addition increased monounsaturated and polyunsaturated fatty acid contents in probiotic yoghurt and enhanced the production of cc-linolenic and conjugated linoleic acids during fermentation of skim milk prepared with B. animalis ssp. lactis Bl04 and B94 strains. (C) 2010 Elsevier Ltd. All rights reserved.

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Poly(pyrrole) (PPY) coating was prepared on a stainless-steel (SS) wire for solid-phase microextraction (SPME) by electrochemical deposition (cyclic voltammetric). The PPY was evaluated by analyzing new-generation antidepressants (mirtazapine, citalopram, paroxetine, duloxetine, fluoxetine, and sertraline) in plasma sample by SPME and liquid chromatography with UV detection (LC-UV). The effect of electrolyte Solution (lithium perchlorate or tetrabutylammonium perchlorate) and the number of cycles (50, 100 or 200) applied during the polymerization process on the SPME performance was evaluated. Important factors in the optimization of SPME efficiency such as extraction time, temperature, pH, influence of plasma proteins on sorption mechanisms, and desorption conditions are discussed. The SPME-PPY/LC method showed to be linear in concentrations ranging from the limit of quantification (LOQ) to 1200 ng mL(-1). The LOQ values range from 16 to 25 ng mL-1. The inter-day precision of the SPME-PPY/LC method presented coefficient of variation (CV) lower than 15%. Based on analytical validation results, the SPME-PPY/LC methodology showed to be adequate for antidepressant analysis, from therapeutic to toxic levels. In order to evaluate the proposed method for clinical use, the SPME-PPY/LC method was applied to the analysis of plasma samples from elderly depressed patients. (c) 2009 Elsevier B.V. All rights reserved,