Propylthiouracil Quantification In Human Plasma By High-performance Liquid Chromatography Coupled With Electrospray Tandem Mass Spectrometry: Application In A Bioequivalence Study.

A rapid, sensitive and specific method for quantifying propylthiouracil in human plasma using methylthiouracil as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using an organic solvent (ethyl acetate). The extracts were analyzed by high performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC-MS/MS) in negative mode (ES-). Chromatography was performed using a Phenomenex Gemini C18 5μm analytical column (4.6mm×150mm i.d.) and a mobile phase consisting of methanol/water/acetonitrile (40/40/20, v/v/v)+0.1% of formic acid. For propylthiouracil and I.S., the optimized parameters of the declustering potential, collision energy and collision exit potential were -60 (V), -26 (eV) and -5 (V), respectively. The method had a chromatographic run time of 2.5min and a linear calibration curve over the range 20-5000ng/mL. The limit of quantification was 20ng/mL. The stability tests indicated no significant degradation. This HPLC-MS/MS procedure was used to assess the bioequivalence of two propylthiouracil 100mg tablet formulations in healthy volunteers of both sexes in fasted and fed state. The geometric mean and 90% confidence interval CI of Test/Reference percent ratios were, without and with food, respectively: 109.28% (103.63-115.25%) and 115.60% (109.03-122.58%) for Cmax, 103.31% (100.74-105.96%) and 103.40% (101.03-105.84) for AUClast. This method offers advantages over those previously reported, in terms of both a simple liquid-liquid extraction without clean-up procedures, as well as a faster run time (2.5min). The LOQ of 20ng/mL is well suited for pharmacokinetic studies. The assay performance results indicate that the method is precise and accurate enough for the routine determination of the propylthiouracil in human plasma. The test formulation with and without food was bioequivalent to reference formulation. Food administration increased the Tmax and decreased the bioavailability (Cmax and AUC).

Profile Of Phenolic Compounds Of Brazilian Virgin Olive Oils By Rapid Resolution Liquid Chromatography Coupled To Electrospray Ionisation Time-of-flight Mass Spectrometry (rrlc-esi-tof-ms).

In recent years, agronomical researchers began to cultivate several olive varieties in different regions of Brazil to produce virgin olive oil (VOO). Because there has been no reported data regarding the phenolic profile of the first Brazilian VOO, the aim of this work was to determine phenolic contents of these samples using rapid-resolution liquid chromatography coupled to electrospray ionisation time-of-flight mass spectrometry. 25 VOO samples from Arbequina, Koroneiki, Arbosana, Grappolo, Manzanilla, Coratina, Frantoio and MGS Mariense varieties from three different Brazilian states and two crops were analysed. It was possible to quantify 19 phenolic compounds belonging to different classes. The results indicated that Brazilian VOOs have high total phenolic content because the values were comparable with those from high-quality VOOs produced in other countries. VOOs from Coratina, Arbosana and Grappolo presented the highest total phenolic content. These data will be useful in the development and improvement of Brazilian VOO.

Authenticity study of Phyllanthus species by NMR and FT-IR Techniques coupled with chemometric methods

The importance of medicinal plants and their use in industrial applications is increasing worldwide, especially in Brazil. Phyllanthus species, popularly known as quebra-pedras in Brazil, are used in folk medicine for treating urinary infections and renal calculus. This paper reports an authenticity study, based on herbal drugs from Phyllanthus species, involving commercial and authentic samples using spectroscopic techniques: FT-IR, ¹H HR-MAS NMR and ¹H NMR in solution, combined with chemometric analysis. The spectroscopic techniques evaluated, coupled with chemometric methods, have great potential in the investigation of complex matrices. Furthermore, several metabolites were identified by the NMR techniques.

Distinção entre cachaças destiladas em alambiques e em colunas usando quimiometria

One hundred fifteen cachaça samples derived from distillation in copper stills (73) or in stainless steels (42) were analyzed for thirty five itens by chromatography and inductively coupled plasma optical emission spectrometry. The analytical data were treated through Factor Analysis (FA), Partial Least Square Discriminant Analysis (PLS-DA) and Quadratic Discriminant Analysis (QDA). The FA explained 66.0% of the database variance. PLS-DA showed that it is possible to distinguish between the two groups of cachaças with 52.8% of the database variance. QDA was used to build up a classification model using acetaldehyde, ethyl carbamate, isobutyl alcohol, benzaldehyde, acetic acid and formaldehyde as chemical descriptors. The model presented 91.7% of accuracy on predicting the apparatus in which unknown samples were distilled.

Multistable behavior above synchronization in a locally coupled Kuramoto model

A system of nearest neighbors Kuramoto-like coupled oscillators placed in a ring is studied above the critical synchronization transition. We find a richness of solutions when the coupling increases, which exists only within a solvability region (SR). We also find that the solutions possess different characteristics, depending on the section of the boundary of the SR where they appear. We study the birth of these solutions and how they evolve when the coupling strength increases, and determine the diagram of solutions in phase space.

Transition to complete synchronization in phase-coupled oscillators with nearest neighbor coupling

We investigate synchronization in a Kuramoto-like model with nearest neighbor coupling. Upon analyzing the behavior of individual oscillators at the onset of complete synchronization, we show that the time interval between bursts in the time dependence of the frequencies of the oscillators exhibits universal scaling and blows up at the critical coupling strength. We also bring out a key mechanism that leads to phase locking. Finally, we deduce forms for the phases and frequencies at the onset of complete synchronization.

The Coupled Aerosol and Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CATT-BRAMS) - Part 1: Model description and evaluation

We introduce the Coupled Aerosol and Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CATT-BRAMS). CATT-BRAMS is an on-line transport model fully consistent with the simulated atmospheric dynamics. Emission sources from biomass burning and urban-industrial-vehicular activities for trace gases and from biomass burning aerosol particles are obtained from several published datasets and remote sensing information. The tracer and aerosol mass concentration prognostics include the effects of sub-grid scale turbulence in the planetary boundary layer, convective transport by shallow and deep moist convection, wet and dry deposition, and plume rise associated with vegetation fires in addition to the grid scale transport. The radiation parameterization takes into account the interaction between the simulated biomass burning aerosol particles and short and long wave radiation. The atmospheric model BRAMS is based on the Regional Atmospheric Modeling System (RAMS), with several improvements associated with cumulus convection representation, soil moisture initialization and surface scheme tuned for the tropics, among others. In this paper the CATT-BRAMS model is used to simulate carbon monoxide and particulate material (PM(2.5)) surface fluxes and atmospheric transport during the 2002 LBA field campaigns, conducted during the transition from the dry to wet season in the southwest Amazon Basin. Model evaluation is addressed with comparisons between model results and near surface, radiosondes and airborne measurements performed during the field campaign, as well as remote sensing derived products. We show the matching of emissions strengths to observed carbon monoxide in the LBA campaign. A relatively good comparison to the MOPITT data, in spite of the fact that MOPITT a priori assumptions imply several difficulties, is also obtained.

New coupled quintessence cosmology

A component of dark energy has been recently proposed to explain the current acceleration of the Universe. Unless some unknown symmetry in Nature prevents or suppresses it, such a field may interact with the pressureless component of dark matter, giving rise to the so-called models of coupled quintessence. In this paper we propose a new cosmological scenario where radiation and baryons are conserved, while the dark energy component is decaying into cold dark matter. The dilution of cold dark matter particles, attenuated with respect to the usual a(-3) scaling due to the interacting process, is characterized by a positive parameter epsilon, whereas the dark energy satisfies the equation of state p(x) = omega rho(x) (omega < 0). We carry out a joint statistical analysis involving recent observations from type Ia supernovae, baryon acoustic oscillation peak, and cosmic microwave background shift parameter to check the observational viability of the coupled quintessence scenario here proposed.

SOLITON SOLUTIONS TO SYSTEMS OF COUPLED SCHRODINGER EQUATIONS OF HAMILTONIAN TYPE

We study the existence of positive solutions of Hamiltonian-type systems of second-order elliptic PDE in the whole space. The systems depend on a small parameter and involve a potential having a global well structure. We use dual variational methods, a mountain-pass type approach and Fourier analysis to prove positive solutions exist for sufficiently small values of the parameter.

The Coupled Aerosol and Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CATT-BRAMS) - Part 2: Model sensitivity to the biomass burning

We describe an estimation technique for biomass burning emissions in South America based on a combination of remote-sensing fire products and field observations, the Brazilian Biomass Burning Emission Model (3BEM). For each fire pixel detected by remote sensing, the mass of the emitted tracer is calculated based on field observations of fire properties related to the type of vegetation burning. The burnt area is estimated from the instantaneous fire size retrieved by remote sensing, when available, or from statistical properties of the burn scars. The sources are then spatially and temporally distributed and assimilated daily by the Coupled Aerosol and Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CATT-BRAMS) in order to perform the prognosis of related tracer concentrations. Three other biomass burning inventories, including GFEDv2 and EDGAR, are simultaneously used to compare the emission strength in terms of the resultant tracer distribution. We also assess the effect of using the daily time resolution of fire emissions by including runs with monthly-averaged emissions. We evaluate the performance of the model using the different emission estimation techniques by comparing the model results with direct measurements of carbon monoxide both near-surface and airborne, as well as remote sensing derived products. The model results obtained using the 3BEM methodology of estimation introduced in this paper show relatively good agreement with the direct measurements and MOPITT data product, suggesting the reliability of the model at local to regional scales.

Strongly coupled fourth generation at the LHC

We study extensions of the standard model with a strongly coupled fourth generation. This occurs in models where electroweak symmetry breaking is triggered by the condensation of at least some of the fourth-generation fermions. With focus on the phenomenology at the LHC, we study the pair production of fourth-generation down quarks, D(4). We consider the typical masses that could be associated with a strongly coupled fermion sector, in the range (300-600) GeV. We show that the production and successive decay of these heavy quarks into final states with same-sign dileptons, trileptons, and four leptons can be easily seen above background with relatively low luminosity. On the other hand, in order to confirm the presence of a new strong interaction responsible for fourth-generation condensation, we study its contribution to D(4) pair production, and the potential to separate it from standard QCD-induced heavy quark production. We show that this separation might require large amounts of data. This is true even if it is assumed that the new interaction is mediated by a massive colored vector boson, since its strong coupling to the fourth generation renders its width of the order of its mass. We conclude that, although this class of models can be falsified at early stages of the LHC running, its confirmation would require high integrated luminosities.

New strongly coupled sector at the Tevatron and the LHC

We examine the possibility that a new strong interaction is accessible to the Tevatron and the LHC. In an effective theory approach, we consider a scenario with a new color-octet interaction with strong couplings to the top quark, as well as the presence of a strongly coupled fourth generation which could be responsible for electroweak symmetry breaking. We apply several constraints, including the ones from flavor physics. We study the phenomenology of the resulting parameter space at the Tevatron, focusing on the forward-backward asymmetry in top pair production, as well as in the production of the fourth-generation quarks. We show that if the excess in the top production asymmetry is indeed the result of this new interaction, the Tevatron could see the first hints of the strongly coupled fourth-generation quarks. Finally, we show that the LHC with root s = 7 TeV and 1 fb(-1) integrated luminosity should observe the production of fourth-generation quarks at a level at least 1 order of magnitude above the QCD prediction for the production of these states.

Spectroscopic evidence of extended states in the quantized Hall phase of weakly coupled GaAs/AlGaAs multilayers

The influence of interlayer coupling on the formation of the quantized Hall phase at the filling factor nu=2 was studied in multilayer GaAs/AlGaAs heterostructures. The disorder broadened Gaussian photoluminescence line due to localized electrons was found in the quantized Hall phase of the isolated multi-quanturn-well structure. On the other hand, the quantized Hall phase of weakly coupled multilayers emitted an unexpected asymmetrical line similar to that observed in metallic electron systems. We demonstrated that the observed asymmetry is caused by the partial population of extended electron states formed in the insulating quantized Hall phase due to spin-assisted interlayer percolation. A sharp decrease in the single-particle scattering time associated with these extended states was observed for the filling factor nu=2. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2978194]

Universal zero-bias conductance through a quantum wire side-coupled to a quantum dot

A numerical renormalization-group study of the conductance through a quantum wire containing noninteracting electrons side-coupled to a quantum dot is reported. The temperature and the dot-energy dependence of the conductance are examined in the light of a recently derived linear mapping between the temperature-dependent conductance and the universal function describing the conductance for the symmetric Anderson model of a quantum wire with an embedded quantum dot. Two conduction paths, one traversing the wire, the other a bypass through the quantum dot, are identified. A gate potential applied to the quantum wire is shown to control the current through the bypass. When the potential favors transport through the wire, the conductance in the Kondo regime rises from nearly zero at low temperatures to nearly ballistic at high temperatures. When it favors the dot, the pattern is reversed: the conductance decays from nearly ballistic to nearly zero. When comparable currents flow through the two channels, the conductance is nearly temperature independent in the Kondo regime, and Fano antiresonances in the fixed-temperature plots of the conductance as a function of the dot-energy signal interference between them. Throughout the Kondo regime and, at low temperatures, even in the mixed-valence regime, the numerical data are in excellent agreement with the universal mapping.

Simultaneous preconcentration of copper, zinc, cadmium, and nickel in water samples by cloud point extraction using 4-(2-pyridylazo)-resorcinol and their determination by inductively coupled plasma optic emission spectrometry

A procedure for simultaneous separation/preconcentration of copper. zinc, cadmium, and nickel in water samples, based on cloud point extraction (CPE) as a prior step to their determination by inductively coupled plasma optic emission spectrometry (ICP-OES), has been developed. The analytes reacted with 4-(2-pyridylazo)-resorcinol (PAR) at pH 5 to form hydrophobic chelates, which were separated and preconcentrated in a surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-I 14). The parameters affecting the extraction efficiency of the proposed method, such as sample pH, complexing agent concentration, buffer amount, surfactant concentration, temperature, kinetics of complexation reaction, and incubation time were optimized and their respective values were 5, 0.6 mmol L(-1). 0.3 mL, 0.15% (w/v), 50 degrees C, 40 min, and 10 min for 15 mL of preconcentrated solution. The method presented precision (R.S.D.) between 1.3% and 2.6% (n = 9). The concentration factors with and without dilution of the surfactant-rich phase for the analytes ranged from 9.4 to 10.1 and from 94.0 to 100.1, respectively. The limits of detection (L.O.D.) obtained for copper, zinc, cadmium, and nickel were 1.2, 1.1, 1.0. and 6.3 mu g L(-1), respectively. The accuracy of the procedure was evaluated through recovery experiments on aqueous samples. (C) 2009 Published by Elsevier B.V.