Development of an on-line preconcentration system for zinc determination in biological samples

An on-line preconcentration system for zinc determination in 24-h urine, blood plasma and erythrocyte matrices by flame atomic absorption spectrometry (FAAS) was used. This procedure was based on adsorption of Zn(II) ions onto a minicolumn filled with silica gel, chemically modified with niobium(V) oxide (Nb₂O₅-SiO₂). The determination of the optimum conditions for Zn(II) preconcentration was done using two-level full factorial and Doehlert designs. In the optimization procedure, four variables (sample pH, eluent concentration, sample flow rate and eluent flow rate) were investigated. The results obtained from the full factorial design demonstrated that the sample pH and sample flow rate variables, and their interactions, were statistically significant. A Doehlert matrix was used in order to determine the optimum conditions for the sample pH and sample flow rate. The optimized conditions for sample pH and flow rate sampling were 6.6 and 7.1 ml min⁻¹, respectively, to obtain the maximum Zn(II) preconcentration and determination in the biological samples studied. Parameters of analytical curve, precision, effect of other ions in the proposed system and accuracy were achieved to assess the proposed method. The accuracy was confirmed by analysis of certified reference materials (urine Seronorm™ Trace Elements) and recovery tests in blood plasma and erythrocyte samples. Detection limit (3σ/S) of 0.77 μg l⁻¹, precision (calculated as relative standard deviation) of 1.5% for Zn(II) concentration of 10 μg l⁻¹ (n = 7) and a sampling frequency of 27 samples/h were obtained from the proposed system.     

Electrochemical Characterization of CoHP–Si Incorporated into a Carbon Paste Electrode

Reduction of dioxygen at a carbon paste electrode (CPE) modified with cobalt hematoporphyrin complex immobilized on silica gel (CoHP–Si) was studied by cyclic voltammetry and rotating disk electrode. In 0.5molL^–1 KCl solution, the supported complex showed significant catalytic activity towards four-electron reduction of O₂ to H₂O at a relatively high pH (5.4). The reduction of dioxygen proceeds at a more negative potential (–0.375V) than the redox reaction Co^III/Co^II (0.464V), indicating that the mechanism does not involve the complex as an electron transfer mediator. Catalytic activity of CoHP–Si towards reduction of H₂O₂ was tested, but no activity was observed.Received October 26, 2002; accepted March 10, 2003 Published online July 16, 2003     

Comparison between ordinary least squares regression and weighted least squares regression in the calibration of metals present in human milk determined by ICP-OES

In this study we compared the use of ordinary least squares and weighted least squares in the calibration of the method for analyzing essential and toxic metals present in human milk by ICP-OES, in order to avoid systematic errors in the measurements used. Human milk samples were provided by maternity clinic Odete Valadares and digested by means of a high-performance microwave (MW) oven. Evaluation of plasma short and long-term stability was made using a solution of digested milk (1:50) with 2.0 mg L⁻¹ Mg in HNO₃ 2% (v/v). The detection power resulted to be at or below the μg L⁻¹ level, whilst the precision expressed as relative standard deviation R.S.D. was almost always equal to or better than 3.3%. Certified reference material Infant Formula (NIST SRM 1846) was used to assess the accuracy of the proposed method, which proved to be accurate and precise. Recovery rates were in the range of 83-117%. Aqueous calibration was carried out for each element under study.     

Palladium (II) Assisted Preparation of Methoxyarylbenzoquinones

The reaction of 2-methoxy-1,4-benzoquinone with methoxyphenolic derivative compounds obtained from wood tar constituents, assisted by palladium (II) acetate in acetic acid, allowed the preparation of five novel methoxyaryl-substituted 1,4-benzoquinones, as well as four structural isomer mixtures.     

Synthesis of 2‐Aryl‐ and 2‐Heteroaryl‐3,5‐dimethoxy‐1,4‐benzoquinones Involving Pd‐Catalyzed Cross‐Coupling of (2,3,4,6‐Tetramethoxyphenyl)boronic Acid

A series of 2‐aryl‐ and 2‐heteroaryl‐substituted 3,5‐dimethoxy‐1,4‐benzoquinones (compounds 27 – 36 ) have been synthesized by cross‐coupling of (2,3,4,6‐tetramethoxyphenyl)boronic acid ( 2 ) with aromatic bromides or iodides in the presence of [Pd⁰(Ph₃)₄] and Na₂CO₃, followed by AgO‐promoted oxidation of the resulting biaryl compounds 17 – 26 .     

Validated HPLC method for the standardization of Phyllanthus niruri (herb and commercial extracts) using corilagin as a phytochemical marker

Phyllanthus niruri L., commonly known in Brazil as ‘quebra‐pedra’, has long been used in the treatment of diverse diseases and especially urolithiasis. The therapeutic effects of P. niruri are attributed to various compounds present in the plant, including the hydrolysable tannin corilagin. In the present study, high‐performance liquid chromatography (HPLC‐/PAD) profiles of leaves and commercial extracts of P. niruri were examined and three compounds, found to be present in all of the samples studied, were isolated by open column chromatography over C₁₈ silica gel followed by preparative HPLC. These compounds were identified by nuclear magnetic resonance as corilagin, rutin and ethyl 3,4,5‐trihydroxybenzoate. Corilagin, which has been proposed as a phytochemical marker for P. niruri, was employed as an external standard in the development and validation of a rapid and efficient qualitative and quantitative HPLC assay for the analyte. The method may be applied in the standardization of herbs and phytomedicines commercialized in Brazil as quebra‐pedra. Copyright © 2009 John Wiley & Sons, Ltd.     

A rapid and automated low resolution NMR method to analyze oil quality in intact oilseeds

Oilseeds with modified fatty acid profiles have been the genetic alternative for high quality vegetable oil for food and biodiesel applications. They can provide stable, functional oils for the food industry, without the hydrogenation process that produces trans-fatty acid, which has been linked to cardiovascular disease. High yield and high quality oilseeds are also necessary for the success of biodiesel programs, as polyunsatured or saturated fatty acid oil produces biofuel with undesirable properties. In this paper, a rapid and automated low resolution NMR method to select intact oilseeds with a modified fatty acid profile is introduced, based on ¹H transverse relaxation time (T₂). The T₂ weighted NMR signal, obtained by a CPMG pulse sequence and processed by chemometric methods was able to determine the oil quality in intact seeds by its fatty composition, cetane number, iodine value and kinematic viscosity with a correlation coefficient r > 0.9. The automated system has the potential to analyze more than 1000 samples per hour and is a powerful tool to speed up the selection of high quality oilseeds for food and biodiesel applications.