14 resultados para two-dimensional capillary electrophoresis

em Biblioteca Digital da Produção Intelectual da Universidade de São Paulo


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We investigate the interface dynamics of the two-dimensional stochastic Ising model in an external field under helicoidal boundary conditions. At sufficiently low temperatures and fields, the dynamics of the interface is described by an exactly solvable high-spin asymmetric quantum Hamiltonian that is the infinitesimal generator of the zero range process. Generally, the critical dynamics of the interface fluctuations is in the Kardar-Parisi-Zhang universality class of critical behavior. We remark that a whole family of RSOS interface models similar to the Ising interface model investigated here can be described by exactly solvable restricted high-spin quantum XXZ-type Hamiltonians. (C) 2012 Elsevier B.V. All rights reserved.

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Comprehensive two-dimensional gas chromatography (GC x GC) is a powerful technique that provides excellent separation and identification of analytes in highly complex samples with considerable increase in GC peak capacities. However, since second dimension analyses are very fast, detectors with a rapid acquisition rate are required. Over the last years, quite a number of studies have discussed the potential and limitations of the combination GC x GC with a variety of quadrupole mass spectrometers. The present research focuses on the evaluation of qMS effectiveness at a 10,000-amu/s scan speed and 20-Hz scan frequency for the identification (full scan mode acquisition-TIC) and quantification (extracted ion chromatogram) of target pesticide residues in tomato samples. The following MS parameters have been evaluated: number of data points per peak, mass spectrum quality, peak skewing, and sensitivity. The validated proposed GC x GC/qMS method presented satisfactory results in terms of repeatability (coefficient of variation lower than 15%), accuracy (84-117%), and linearity (ranging from 25 to 500 ng/g), while significant enhancement in sensitivity was observed (a factor of around 10) under scan conditions. (C) 2012 Elsevier B.V. All rights reserved.

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A thin-layer electrochemical flow cell coupled to capillary electrophoresis with contactless conductivity detection (EC-CE-(CD)-D-4) was applied for the first time to the derivatization and quantification of neutral species using aliphatic alcohols as model compounds. The simultaneous electrooxidation of four alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) to the corresponding carboxylates was carried out on a platinum working electrode in acid medium. The derivatization step required 1 min at 1.6 V vs. Ag/AgCl under stopped flow conditions, which was preceded by a 10 s activation at 0 V. The solution close to the electrode surface was then hydrodynamically injected into the capillary, and a 2.5 min electrophoretic separation was carried out. The fully automated flow system operated at a frequency of 12 analyses per hour. Simultaneous determination of the four alcohols presented detection limits of about 5 x 10(-5) mol As a practical application with a complex matrix, ethanol concentrations were determined in diluted pale lager beer and in nonalcoholic beer. No statistically significant difference was observed between the EC-CE-(CD)-D-4 and gas chromatography with flame ionization detection (GC-FID) results for these samples. The derivatization efficiency remained constant over several hours of continuous operation with lager beer samples (n = 40).

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Terbinafine hydrochloride (TerbHCl) is an allylamine derivative with fungicidal action, especially against dermatophytes. Different analytical methods have been reported for quantifying TerbHCl in different samples. These procedures require time-consuming sample preparation or expensive instrumentation. In this paper, electrochemical methods involving capillary electrophoresis with contactless conductivity detection, and amperometry associated with batch injection analysis, are described for the determination of TerbHCl in pharmaceutical products. In the capillary electrophoresis experiments, terbinafine was protonated and analyzed in the cationic form in less than 1 min. A linear range from 1.46 to 36.4 mu g mL(-1) in acetate buffer solution and a detection limit of 0.11 mu g mL(-1) were achieved. In the amperometric studies, terbinafine was oxidized at +0.85 V with high throughput (225 injection h(-1)) and good linear range (10-100 mu mol L-1). It was also possible to determine the antifungal agent using simultaneous conductometric and potentiometric titrations in the presence of 5% ethanol. The electrochemical methods were applied to the quantification of TerbHCl in different tablet samples; the results were comparable with values indicated by the manufacturer and those found using titrimetry according to the Pharmacopoeia. The electrochemical methods are simple, rapid and an appropriate alternative for quantifying this drug in real samples. (C) 2012 Elsevier B.V. All rights reserved.

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The transport properties of the two-dimensional system in HgTe-based quantum wells containing simultaneously electrons and holes of low densities are examined. The Hall resistance, as a function of perpendicular magnetic field, reveals an unconventional behavior, different from the classical N-shaped dependence typical for bipolar systems with electron-hole asymmetry. The quantum features of magnetotransport are explained by means of numerical calculation of the Landau level spectrum based on the Kane Hamiltonian. The origin of the quantum Hall plateau sigma(xy) = 0 near the charge neutrality point is attributed to special features of Landau quantization in our system.

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A metal-insulator transition in a two-dimensional semimetal based on HgTe quantum wells is discovered. The transition is induced by a magnetic field applied parallel to the plane of the quantum well. The threshold behavior of the activation energy as a function of the magnetic-field strength and an abrupt reduction of the Hall resistance at the onset of the transition suggest that the observed effect originates from the formation of an excitonic insulator.

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Nonlocal resistance is studied in a two-dimensional system with a simultaneous presence of electrons and holes in a 20 nm HgTe quantum well. A large nonlocal electric response is found near the charge neutrality point in the presence of a perpendicular magnetic field. We attribute the observed nonlocality to the edge state transport via counterpropagating chiral modes similar to the quantum spin Hall effect at a zero magnetic field and graphene near a Landau filling factor nu = 0.

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The combination of solid-phase microextraction (SPME) with comprehensive two-dimensional gas chromatography is evaluated here for fatty acid (FA) profiling of the glycerophospholipid fraction from human buccal mucosal cells. A base-catalyzed derivatization reaction selective for polar lipids such as glycerophospholipid was adopted. SPME is compared to a miniaturized liquidliquid extraction procedure for the isolation of FA methyl esters produced in the derivatization step. The limits of detection and limits of quantitation were calculated for each sample preparation method. Because of its lower values of limits of detection and quantitation, SPME was adopted. The extracted analytes were separated, detected, and quantified by comprehensive two-dimensional gas chromatography with flame ionization detection (FID). The combination of SPME and comprehensive two-dimensional gas chromatography with FID, using a selective derivatization reaction in the preliminary steps, proved to be a simple and fast procedure for FA profiling, and was successfully applied to the analysis of adult human buccal mucosal cells.

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In this study, a dynamic programming approach to deal with the unconstrained two-dimensional non-guillotine cutting problem is presented. The method extends the recently introduced recursive partitioning approach for the manufacturer's pallet loading problem. The approach involves two phases and uses bounds based on unconstrained two-staged and non-staged guillotine cutting. The method is able to find the optimal cutting pattern of a large number of pro blem instances of moderate sizes known in the literature and a counterexample for which the approach fails to find known optimal solutions was not found. For the instances that the required computer runtime is excessive, the approach is combined with simple heuristics to reduce its running time. Detailed numerical experiments show the reliability of the method. Journal of the Operational Research Society (2012) 63, 183-200. doi: 10.1057/jors.2011.6 Published online 17 August 2011

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We have performed multicanonical simulations to study the critical behavior of the two-dimensional Ising model with dipole interactions. This study concerns the thermodynamic phase transitions in the range of the interaction delta where the phase characterized by striped configurations of width h = 1 is observed. Controversial results obtained from local update algorithms have been reported for this region, including the claimed existence of a second-order phase transition line that becomes first order above a tricritical point located somewhere between delta = 0.85 and 1. Our analysis relies on the complex partition function zeros obtained with high statistics from multicanonical simulations. Finite size scaling relations for the leading partition function zeros yield critical exponents. that are clearly consistent with a single second-order phase transition line, thus excluding such a tricritical point in that region of the phase diagram. This conclusion is further supported by analysis of the specific heat and susceptibility of the orientational order parameter.

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Within the superfield approach, we discuss the two-dimensional noncommutative super-QED. Its all-order finiteness is explicitly shown. Copyright (C) EPLA, 2012

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This paper presents simple, rapid, precise and accurate stability-indicating HPLC and CE methods, which were developed and validated for the determination of nitrendipine, nimodipine and nisoldipine. These drugs are calcium channel antagonists of the 1,4-dihydropyridine type which are used in the treatment of cardiovascular diseases. Experimental results showed a good linear correlation between the area and the concentration of drugs covering a relatively large domain of concentration in all cases. The linearity of the analytical procedures was in the range of 2.0-120.0 mu g mL-1 for nitrendipine, 1.0-100.0 mu g mL(-1) for nimodipine and 100.0-600.0 mu g mL(-1) for nisoldipine, the regression determination coefficient being higher than 0.99 in all cases. The proposed methods were found to have good precision and accuracy. The chemical stability of these drugs was determined under various conditions and the methods have shown adequate separation for their enantiomers and degradation products. In addition, degradation products produced as a result of stress studies did not interfere with the detection of the drugs' enantiomers and the assays can thus be considered stability-indicating.

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In a previous work El et al. (2006) [1] exact stable oblique soliton solutions were revealed in two-dimensional nonlinear Schrodinger flow. In this work we show that single soliton solution can be expressed within the Hirota bilinear formalism. An attempt to build two-soliton solutions shows that the system is "close" to integrability provided that the angle between the solitons is small and/or we are in the hypersonic limit. (C) 2012 Elsevier B.V. All rights reserved.

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Objective To evaluate and compare the intraobserver and interobserver reliability and agreement for the biparietal diameter (BPD), abdominal circumference (AC), femur length (FL) and estimated fetal weight (EFW) obtained by two-dimensional ultrasound (2D-US) and three-dimensional ultrasound (3D-US). Methods Singleton pregnant women between 24 and 40 weeks were invited to participate in this study. They were examined using 2D-US in a blinded manner, twice by one observer, intercalated by a scan by a second observer, to determine BPD, AC and FL. In each of the three examinations, three 3D-US datasets (head, abdomen and thigh) were acquired for measurements of the same parameters. We determined EFW using Hadlock's formula. Systematic errors between 3D-US and 2D-US were examined using the paired t-test. Reliability and agreement were assessed by intraclass correlation coefficients (ICCs), limits of agreement (LoA), SD of differences and proportion of differences below arbitrary points. Results We evaluated 102 singleton pregnancies. No significant systematic error between 2D-US and 3D-US was observed. The ICC values were higher for 3D-US in both intra- and interobserver evaluations; however, only for FL was there no overlap in the 95% CI. The LoA values were wider for 2D-US, suggesting that random errors were smaller when using 3D-US. Additionally, we observed that the SD values determined from 3D-US differences were smaller than those obtained for 2D-US. Higher proportions of differences were below the arbitrarily defined cut-off points when using 3D-US. Conclusion 3D-US improved the reliability and agreement of fetal measurements and EFW compared with 2D-US.