Evaluation of Bi as internal standard to minimize matrix effects on the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru permanent modifier with co-injection of Pd/Mg(NO3)(2)

Bismuth was evaluated as an internal standard for the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru as a permanent modifier with co-injection of Pd/Mg(NO3)(2). The correlation coefficient of the graph plotted from the non-nalized absorbance signals of Bi versus Pb was r=0.989. Matrix effects were evaluated by analyzing the slope ratios between the analytical curve, and analytical curves obtained from Pb additions in red and white wine vinegar obtained from reference solutions prepared in 0.2% (v/v) HNO3, samples. The calculated ratios were around 1.04 and 1.02 for analytical curves established applying an internal standard and 1.3 and 1.5 for analvtical curves without. Analytical curves in the 2.5-15 pg L-1 Pb concentration interval were established using the ratio Pb absorbance to Bi absorbance versus analvte concentration, and typical linear correlations of r=0.999 were obtained. The proposed method was applied for direct determination of Pb in 18 commercial vinegar samples and the Pb concentration varied from 2.6 to 31 pg L-1. Results were in agreement at a 95% confidence level (paired t-test) with those obtained for digested samples. Recoveries of Pb added to vinegars varied from 96 to 108% with and from 72 to 86% without an internal standard. Two water standard reference materials diluted in vinegar sample were also analyzed and results were in agreement with certified values at a 95% confidence level. The characteristic mass was 40 pg Pb and the useful lifetime of the tube was around 1600 firings. The limit of detection was 0.3 mu g L-1 and the relative standard deviation was <= 3.8% and <= 8.3% (n = 12) for a sample containing, 10 mu L-1 Pb with and without internal standard, respectively. (C) 2007 Elsevier B.V. All rights reserved.

Determination of diclofenac in pharmaceutical preparations using a potentiometric sensor immobilized in a graphite matrix

The characteristics, performance, and application of an electrode, namely Pt| Hg|Hg-2(DCF)(2)|graphite, where DCF stands for diclofenac ion, are described. This electrode responds to diclofenac with sensitivity of (58.1 +/- 0.8) mV/decade over the range 5.0 x 10(-5) to 1.0 x 10(-2) Mol l(-1) at pH 6.5-9.0 and a detection limit of 3.2 x 10(-5) mol l(-1). The electrode is easily constructed at a relatively low cost with fast response time (within 10-30 s) and can be used for a period of 5 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for diclofenac in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used to determine diclofenac in pharmaceutical preparations by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedures. (c) 2005 Elsevier B.V. All rights reserved.

Internal standardization in graphite furnace atomic absorption spectrometry: Comparative use of As and Ge to minimize matrix effects on Se determination in milk

Arsenic and germanium have been evaluated as internal standards to minimize matrix effects on the direct determination of selenium in milk by graphite furnace atomic absorption spectrometry (GFAAS) using tubes with integrated platform, pre-treated with W together with I'd as chemical modifier. The efficiency of As and Ge as internal standards for 25 mu g L-1 Se plus 500 mu g (L)-1 As or Ge in diluted (1 + 9 v/v) milk plus 1.0% (v/v) HNO3 was evaluated by means of correlation graphs plotted from the normalized absorbance signals (n = 20) of internal standard (axis gamma) versus analyte (axis x). The equations that describe the linear regression were: A(As)= - 0.004 +/- 0.019 +/- 1.02 + 0.019 A(Se) (r=0.9967 +/- 0.005); A(Ge)= - 0.0 17 +/- 0.015 + 1.01 +/- 0.015 A(Se) (r = 0.9978 +/- 0.004). Samples and reference solutions were automatically spiked with 500 mu g L-1 Ge or As and 1.0% (v/v) HNO3 by the autosampler. For 20 mu L of aqueous standard solutions, analytical curves in the 5.00-40.0 mu g L-1 Se range were established using the ratio of Se absorbance to internal standard absorbance (A(Se)A(IS)) versus analyte concentration, and good linear correlations were obtained. The characteristic mass was 40 pg Se. Limits of detection were 0.55 and 0.40 mu g L-1 with As and Ge as the internal standard, respectively. Relative standard deviations (RSD) for a sample containing 25 mu g L-1 Se were 1.2% and 1.0% (n = 12) using As and Ge, respectively. The RSD without internal standardization was about 6%. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values were in the 99-105% range with IS and in the 70-80% range without IS. Using Ge as the internal standard, results of analysis of standard reference materials were in agreement with certified values at a 95% confidence level. The selenium concentration for 10 analyzed milk samples varied from 5.0 to 20 mu g L-1. (c) 2005 Elsevier B.V. All rights reserved.

Characterization of gallotannins from Astronium species by flow injection analysis-electrospray ionization-ion trap-tandem mass spectrometry and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Analytical optimization of spread and change of exponential decay of generalized Wannier functions in one dimension

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estimation of variances of the effects of incomplete diallels using a matrix approach

A matrix approach is described for assessing the variance of effects in incomplete diallels designs. The method is illustrated by reference to simulated complete and incomplete diallels using different combinations of constraints, average degree of dominance and, for the incomplete diallel, number of hybrids. Our results showed that caution should be taken in working with incomplete diallels under conditions of overdominance because there were changes in the rank of the genotypes when the excluded hybrid had parents with a low frequency of the favorable allele (i.e. the allele which increases expression of a character). The expression described in this paper is a rapid and safe approach to estimate variances and covariances of the effects of contrasts of incomplete diallels. Copyright by the Brazilian Society of Genetics.

A novel potentiometric naproxenate ion sensor immobilized in a graphite matrix for determination of naproxen in pharmaceuticals

The characteristics, performance, and application of an electrode, namely, Pt|Hg|Hg 2(NAP) 2| Graphite, where NAP stands for naproxenate ion, are described. This electrode responds to NAP with sensivity of (58.1± 0.9) mV decade -1 over the range 5.0 × 10 -5 - 1.0 × 10 -2 mol L -1 at pH 6.0-9.0 and a detection limit of 3.9 × 10 -5 mol L -1. The electrode is easily constructed at a relatively low cost with fast response time (within 10-35 s) and can be used for a period of 6 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for naproxen in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used for the direct assay of naproxen in commercial tablets by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedure. ©2006 Sociedade Brasileira de Química.

Representation of transmission lines in modal domain using analytical transformation matrices

The phases of a transmission line are tightly coupled due to mutual impedances and admittances of the line. One way to accomplish the calculations of currents and voltages in multi-phase lines consists in representing them in modal domain, where its n coupled phases are represented by their n propagation modes. The separation line in their modes of propagation is through the use of a modal transformation matrix whose columns are eigenvectors associated with the parameters of the line. Usually, this matrix is achieved through numerical methods which does not allow the achievement of an analytical model for line developed directly in the phases domain. This work will show the modal transformation matrix of a hypothetical two-phase obtained with numerical and analytical procedures. It will be shown currents and voltage s at terminals of the line taking into account the use of modal transformation matrices obtained by using numerical and analytical procedures. © 2011 IEEE.

Matrix effect on butyltin analysis of sediments and fish tissues by GC-PFPD

Butyltin (BTs) quantification in environmental matrices can be affected by interfering species found primarily in complex matrices,such as sediment and biota tissues. This study investigated matrix effects in analytical procedures for butyltin (TBT,DBT and MBT) quantification and speciation in sediments and in two fish tissues (gill and liver) by gas chromatography with pulsed flame photometric detection (GC-PFPD) analysis. Unlike sediment samples,tissues exhibited a significant matrix effect,thus,the quantification should be made by curve over matrix to avoid quantification errors and loss of analytical accuracy. © 2013 Sociedade Brasileira de Química.

Matrix Effects on Water Analysis for Alkylphenols Using Solid Phase Extraction Gas Chromatography-Mass Spectrometry

Gas chromatography with mass spectrometry is frequently used for the quantification of many classes of substances, including alkylphenols. Alkylphenol polyethoxylates are nonionic surfactants used in a wide variety of industrial and consumer applications. Alkylphenol polyethoxylates can degrade to alkylphenols, which are endocrine disruptors. In analytical validation procedures, the most common parameters studied are the detection and quantification limits, linearity, and recovery; however, the matrix effects are sometimes neglected. Although some investigators have evaluated matrix effects, there is no consensus on how to evaluate them during method validation. In this study, the matrix effects of alkylphenol polyethoxylates (nonylphenol monoethoxylate, nonylphenol diethoxylate, octylphenol monoethoxylate, octylphenol diethoxylate) and alkylphenols (nonylphenol and octylphenol) were studied using solid phase extraction and gas chromatography-mass spectrometry analysis. For alkylphenol polyethoxylates, the matrix effects ranged from 16 to 4692%, whereas for alkylphenols (nonylphenol and octylphenol), the effects were insignificant. Therefore, constructing an analytical curve in the matrix for alkylphenol polyethoxylates is essential. © 2013 Copyright Taylor and Francis Group, LLC.

New voltammetry-based analytical method for indirect determination of procymidone in brazilian apples

Procymidone, a potentially carcinogenic and mutagenic pesticide, can contribute to environmental and human contamination when applied to apple crops. In this work, we propose a reliable and sensitive method to determine procymidone in Brazilian apples. The method involves differential pulse (DPV) and square-wave voltammetry (SWV) techniques on a glassy carbon electrode. In a supporting electrolyte solution of 0.5 mol L−1 NaOH, procymidone undergoes an irreversible one-electron oxidation at +1.42 V by cyclic voltammetric vs. Ag|AgCl, KCl 3 M reference electrode. The proposed DPV and SWV methods have a good linear response in the 8.00–20.0 mg L−1 range, with limits of detection (LOD) of 0.678 and 0.228 mg L−1, respectively, in the absence of the matrix. We obtained improved LOD (0.097 mg L−1) in the presence of apple matrix and the supporting electrolyte solution. We used three commercial apple samples to evaluate recovery, and we achieved recovery percentages ranging from 94.6 to 110 % for procymidone determinations. We also tested the proposed voltammetric method for reproducibility, repeatability, and potential interferents, and the results were satisfactory for electroanalytical purposes.

Validation of analytical methodology for quantification of cefazolin sodium pharmaceutical dosage form by high performance liquid chromatography to be applied for quality control in pharmaceutical industry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Physical and chemical matrix effects in soil carbon quantification using laser-induced breakdown spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Validation of analytical methodology for quantification of cefazolin sodium by liquid chromatography

A reversed-phase high performance liquid chromatography method was validated for the determination of cefazolin sodium in lyophilized powder for solution for injection to be applied for quality control in pharmaceutical industry. The liquid chromatography method was conducted on a Zorbax Eclipse Plus C18 column (250 x 4.6 mm, 5 μm), maintained at room temperature. The mobile phase consisted of purified water: acetonitrile (60: 40 v/v), adjusted to pH 8 with triethylamine. The flow rate was of 0.5 mL min-1 and effluents were monitored at 270 nm. The retention time for cefazolin sodium was 3.6 min. The method proved to be linear (r2 =0.9999) over the concentration range of 30-80 µg mL-1. The selectivity of the method was proven through degradation studies. The method demonstrated satisfactory results for precision, accuracy, limits of detection and quantitation. The robustness of this method was evaluated using the Plackett–Burman fractional factorial experimental design with a matrix of 15 experiments and the statistical treatment proposed by Youden and Steiner. Finally, the proposed method could be also an advantageous option for the analysis of cefazolin sodium, contributing to improve the quality control and to assure the therapeutic efficacy

Structure of trajectories of complex-matrix eigenvalues in the Hermitian-non-Hermitian transition

The statistical properties of trajectories of eigenvalues of Gaussian complex matrices whose Hermitian condition is progressively broken are investigated. It is shown how the ordering on the real axis of the real eigenvalues is reflected in the structure of the trajectories and also in the final distribution of the eigenvalues in the complex plane.