Desenvolvimento de colunas cromatográficas de meios de acesso restrito proteína-imobilizada e suas avaliações para análise de fármacos com injeção direta de plasma humano

A series of bovine serum albumin-immobilized supports have been prepared and used as restricted access media (RAM) columns. Restricted-access supports combine size-exclusion of proteins and other high-molar-mass matrix components with the simultaneous enrichment of low-molar mass analytes. These characteristics were chromatographically evaluated for the columns. The RAM-BSA (Bovine Serum Albumin) columns showed excellent performance for exclusion of human plasma protein with good retention capacity for a series of acidic, basic, and neutral drugs.

Utilização de técnicas eletroanalíticas na determinação de pesticidas em alimentos

The aim of this work is to discuss selected applications of electroanalytical techniques for the detection of pesticides in foods and beverages, published in the last ten years. The applications involved different working electrodes for the electroanalytical determination of pesticides, namely amperometric biosensors, cholinesterase-based biosensors, polymer-modified electrodes, ultramicroelectrodes and hanging mercury drop electrodes. They were used for several voltammetric and amperometric techniques in different analytical procedures for the detection and quantification of different classes of pesticides in different food matrices.

Espectrofotometria derivativa: uma estratégia simples para a determinação simultânea de corantes em alimentos

A very simple spectrophotometric method is described for resolving binary mixture of the food colorants Sunset Yellow (INS 110) and Tartrazine Yellow (INS 102) by using the first derivative spectra with measurements at zero-crossing wavelengths. Before the spectrophotometric measurements, the dyes were sorbed onto polyurethane foam and recovered in N,N-dimethilformamide. Commercial food products (gelatine and juice powder) were analysed by using the proposed method and the HPLC technique. The results are in very good agreement and the differences between the methods is not statistically important. Therefore, the first-order derivative spectrophotometric method is accurate, precise, reliable and could be applied to the routine analysis of food samples.

Metodologias analíticas para determinação das fumonisinas em milho e alimentos à base de milho

Fumonisins are mycotoxins occurring worldwide, mainly in maize and maize-based food products, which could affect animal and human health. This paper reviews analytical methodologies for the determination of these fungal toxins in foods. It includes extraction, cleanup, derivatization procedures, detection, quantification, and confirmation procedures. Initial attempts at gas chromatographic methods and thin layer chromatography were supplanted by liquid chromatographic methods, mainly performed with fluorometric detection, or mass spectrometry detection, enabling the analysis of polar and thermolabile chemicals without chemical derivatization, which results in lower limits of detection. Alternative methods, such as enzyme linked immunosorbent assay or zone capillary zone electrophoresis, are also described.

Construção de amostrador passivo de baixo custo para determinação de dióxido de nitrogênio

A new passive sampling system for monitoring NO2 in air has been developed to measure gas concentrations in indoor and outdoor air. The sampler is inexpensive, and easy to construct and operate. Nitrogen dioxide forms a derivative after reaction with a filter coated with triethanolamine and ethyleneglycol. The nitrogen dioxide derivative is extracted from the filter, and the concentration is determined by colorimetry. To test the sampler for measuring ambient level nitrogen dioxide, measurements were carried out inside homes and in a range of workplace environments.

Determinação da origem biossintética de ácido acético através da técnica "Site Specific Natural Isotopic Fractionation Studied by Nuclear Magnetic Resonance (SNIF-NMR)"

The main purpose of this work is to describe the use of the technique Site-Specific Natural Isotopic Fractionation of hydrogen (SNIF-NMR), using ²H and ¹H NMR spectroscopy, to investigate the biosynthetic origin of acetic acid in commercial samples of Brazilian vinegar. This method is based on the deuterium to hydrogen ratio at a specific position (methyl group) of acetic acid obtained by fermentation, through different biosynthetic mechanisms, which result in different isotopic ratios. We measured the isotopic ratio of vinegars obtained through C3, C4, and CAM biosynthetic mechanisms, blends of C3 and C4 (agrins) and synthetic acetic acid.

Determinação de hidrocarbonetos voláteis e semi-voláteis na atmosfera

This paper focuses: (i) the development of a measurement technique for the determination of atmospheric C2-C6 hydrocarbons with sampling in canisters and analysis by gas chromatography/flame ionisation detector (GC/FID), (ii) the improvement of an existent adsorption-sampling technique with Tenax TA tubes for the determination of C6-C11 hydrocarbons and analysis by GC/FID after thermal desorption and cryogenic concentration, (iii) the identification of compounds present in ambient air by gas chromatography/mass spectrometry (GC/MS) for both canister and Tenax samples, (iv) a program of interlaboratorial comparison for quality control of C2-C11 analyses, and (v) the seasonal characterisation of ambient air C2-C11 hydrocarbons.

Determinação de resíduos de cloranfenicol em amostras de leite e mel industrializados utilizando a técnica de espectrometria de massas em "tandem" (CLAE-EM/EM)

The present work shows a method for the determination of chloramphenicol (CAP) antibiotic in milk, powder milk and honey. The solid phase extraction and liquid-liquid extraction were applied as a clean-up and pre-concentration strategies followed by LC-ESI/MS/MS analysis. The recovery was studied for different fortification levels from 0.05 to 1.00 µg L-1 in milk, showing values between 91 101% and RSD bellow 8.0%, while honey was spiked with a concentration of 0.20 µg kg-1 yelding a mean recovery of 83% and RSD of 6.5%. The quantification transition 321>152 showed a LOD of 0.52 ng kg-1 and LOQ of 1.85 ng kg-1.

Titulação potenciométrica aplicada na determinação de ácidos graxos livres de óleos e gorduras comestíveis

Free fatty acids are a measure of evaluating fats and oils, submitted to abusive conditions, besides being a quality characteristic of edible vegetable oils. The official method of determination (AOCS Ca 5a-40, 2004) is based on titration, using phenolphthalein as an indicator. For crude and degummed oils, the titration end point is difficult to be observed due to the high level of pigments, resulting in dark solutions. In this case and others, such as self-life studies, in which sample quantities are limited, potentiometric titration may be a very good alternative.

Determinação do coeficiente de distribuição (Kd) de benzo(a)pireno em solo por isotermas de sorção

Leaking of diesel oil from gas stations is frequent in Brazil. The presence of polycyclic aromatic hydrocarbons (PAHs), which are highly toxic is an indication of contamination by heavy hydrocarbons from diesel oil. Here were present the determination of the distribution coefficient (Kd) of benzo(a)pyrene (the most carcinogenic of the PAHs) in tropical soils using the sorption isotherm model. The sorption curves acquired for benzo(a)pyrene were of the S-type, probably due to the water/methanol experimental conditions. The sorption curves allowed calculation of the distribution coefficient (Kd). The experimental Kd values were lower than those calculated from literature Koc values (partition coefficient normalized by organic carbon), due mainly to the cosolvency effect and the percentage of organic matter and clay in soil.

Eletroanálise de derivados acetaldeído com hidrazina e determinação em amostras de álcool combustível por voltametria de onda quadrada

A square wave voltammetric method is described for the determination of acetaldehyde using the derivatization reaction with hydrazine sulphate, based on the reduction of hydrazone generated as a product that exhibits a single well-defined peak at -1.19V in acetate buffer at pH 5. Calibration graphs were obtained from 1.0 x 10-6 mol L-1 to 10 x 10-6 mol L-1 of acetaldehyde, using a reaction time of 8 min and a hidrazine concentration of 0.02 mol L-1. The detection limit was 2.38 x 10-7 mol L-1. The method was applied satisfactorily to the determination of total aldehyde in fuel ethanol samples without any pre-treatment.

Determinação das propriedades catalíticas em meio aquoso e orgânico da lipase de Candida rugosa imobilizada em celulignina quimicamente modificada por carbonildiimidazol

Microbial lipase from Candida rugosa was immobilized by covalent binding on wood cellulignin (Eucaliptus grandis) chemically modified with carbonyldiimidazole. The immobilized system was fully evaluated in aqueous (olive oil hydrolysis) and organic (ester synthesis) media. A comparative study between free and immobilized lipase was carried out in terms of pH, temperature and thermal stability. A higher pH value (8.0) was found optimal for the immobilized lipase. The optimal reaction temperature shifted from 37 °C for the free lipase to 45 °C for the immobilized lipase. The pattern of heat stability indicated that the immobilization process tends to stabilize the enzyme. Kinetics tests at 37 °C following the hydrolysis of olive oil obeyed the Michaelis-Menten rate equation. Values for Km = 924.9 mM and Vmax = 198.3 U/mg were lower than for free lipase, suggesting that the affinity towards the substrate changed and the activity of the immobilized lipase decreased during the course of immobilization. The immobilized derivative was also tested in the ester synthesis from several alcohols and carboxylic acids.

Determinação espectrofotométrica simultânea de cobre e ferro em álcool etílico combustível com reagentes derivados da ferroína

In the present work three ferroin reagents were studied for the simultaneous spectrophotometric determination of iron and copper: 1,10-phenanthroline, 2,2'-bipyridine and 2,4,6-tri(2-pyridyl)-1,3,5-triazine. Effect of pH, conditions, order reagent addition, interferences, amount of reagents, lineal range, sensitivity and stability of each system were compared. The 2,4,6-tri(2-pyridyl)-1,3,5-triazine can be used for determination of iron in the presence of copper with a detection limit of 5 µg L-1 and coefficient of variation of 2.0%; However it was not possible to determine directly copper in the presence of iron with this reagent. 1,10-phenanthroline can be used for simultaneous determination of the metallic ions with detection limits of 7 and 8 mg L-1 and coefficients of variation of 1.8 and 2.3% in the determination of iron and copper, respectively. The results showed also that 2,2'-bipyridine can be used for simultaneous determination of the metallic ions with detection limits of 11 and 32 µg L-1 and coefficients of variation of 1.9 and 2.5% in the determination of iron and copper, respectively. The reagents were used for spectrophotometric determination of iron and copper in ethanol fuel.

Uso de frascos de polipropileno descartáveis no pré-tratamento de amostras de água para determinação de chumbo, cobre e mercúrio por voltametria de onda quadrada

In this work a simple and versatile procedure is described for treating water samples using small polypropylene (PP) vials (4 mL) for determining heavy metals by square wave voltammetry (SWV). This procedure involves treatment with nitric acid (0.2 mol L-1) and boiling in a water-bath (~ 100 ºC). This process is completed after one hour and allows the pretreatment of several samples simultaneously. The accuracy was estimated using addition/recovery studies and certified water sample analysis, yielding an agreement near to 100%.

Determinação de nitrato e nitrito em chás de peles de pescados empregados para tratamento de asma brônquica na região sul do Rio Grande do Sul

The objective of this paper was to determine nitrate and nitrite anions in toasted fish skin tea, which the population of southern Rio Grande do Sul believes to have pharmacological properties for trating asthma. Two methods were compared, an official and one described by Guozhen et al., that has the advantage of not needing reduction of nitrate to nitrite on a Cd column. The samples were the skin of the fish species Balistes capriscus (peixe porco) and Menticirrhus littoralis (papa-terra), both crude and toasted, as traditionally used. The method of Guozhen et al. was used due to its performance (detection limit 0.005 µmol/L NO3- and 0.02 µmol/L - NO2- and mean recuperation of 100 and 97% respectively for each anion) and results similar to those of the official methods under conditions used by the population, the estimated daily intake, of the teas is equivalent to 0.03 to 0.05 mg of nitrate and 0.007 to 0.014 mg of nitrite. These values are in accord with safety recommendations and don't represent a health risk.