Volume 73, Nº 5 (2018)

The interfacial distribution of a number of organic photometric reagents in a water‒potassium bis(alkylpolyoxyethylene)phosphate (oxyphos B)‒ammonium sulphate splitting system is studied. It is found that alizarin complexone, 1-(2-pyridylazo)-2-naphthol-2 (PAN), bromothymol blue, rhodamine 6G, pyrogallol red, morin, fuchsine, malachite green, bromothymol blue, pyrocatechol violet (PCV), chromazurol S, and aluminon are extracted with partition coefficients higher than 100. A possibility of the extraction‒photometric determination of gallium with PCV and cobalt with PAN is shown. The proposed procedures do not require the use of fire-hazardous, volatile, and toxic organic solvents.

A simple, rapid, selective, sensitive and reliable extractive spectrophotometric method was developed for the determination of ruthenium(III) using 2-nitrobenzaldehyde thiocarbohydrazone (2-NBATCH) as a chromogenic chelating ligand. The ruthenium(III)‒2-NBATCH complex is formed in aqueous acetic acid media (0.7 M) containing an organic solvent after 5 min heating on a water bath. The red colored complex is extracted into 1,2-dichloroethane and absorbance is measured at 445 nm against reagent blank. The Beer’s law is obeyed within 1‒6 g/mL of ruthenium(III), the optimum concentration range was 2‒5 g/mL of ruthenium(III) evaluated by Ringbom’s plot. Molar absorptivity and Sandell’s sensitivity of complex were 1.41 × 10⁴ L/mol/cm and 0.0075 μg/cm², respectively. The stoichiometry of complex was 1: 3 established from Job’s method of continuous variation, molar ratio method and logarithmic slope method. The proposed method was applied for determination of ruthenium(III) in binary and ternary, synthetic mixtures corresponding to fission product elements alloy and ruthenium(III) catalysts.

Three methods, two spectrophotometric and one titrimetric, which are simple, easy to perform and cost-effective, are presented for the determination of flutamide, an anti-cancer drug. In the first spectrophotometric method (method A), absorbance of flutamide solution in methanol was measured at 290 nm. Measurement of absorbance of reduced flutamide (RFAD) in HCl at 245 nm serves as the basis of the second spectrophotometric method (method B). RFAD, in strong HCl medium was titrated vs standard sodium nitrite, determining the end-point potentiometrically (method C). Experimental variables influencing assays were studied and optimized. Beer’s law was obeyed over concentration ranges: 2.5–25.0 and 1.0–9.0 μg/mL for method A and method B, respectively, with molar absorptivity values of 1.0 × 10⁴ and 2.4 × 10⁴ L/(mol cm). Calculated limits of detection and quantification were 0.18 and 0.54 μg/mL (method A) and 0.16 and 0.18 μg/mL (method B). Titration reaction followed a 1: 1 stoichiometry and the method is applicable to 4‒30 mg RFAD. Repeatability, reproducibility and accuracy of the methods were satisfactory. The methods were also validated for selectivity, robustness and ruggedness. The developed methods were applied to the determination of active ingredient in tablets, and the results agreed well with the label claim and those of a reference method. Accuracy was also assessed by recovery test via standard–addition procedure. The drug was subjected to different stress conditions, such as acid and base hydrolysis, oxidation and thermolysis and analyzed subsequently by method A, as a part of stress testing. Results indicated that the drug is slightly vulnerable to all stress-conditions studied.

The presented study investigates the application of MnO₂/3MgO nanocomposite, as a new sorbent for solid phase extraction and determination of trace amounts of Pb²⁺ and Cu²⁺ from various samples using flame atomic absorption spectrometry. After extraction, the analytes were desorbed using 0.01 M ethylenediaminetetraacetic acid. The effects of various parameters were studied and optimized. Under optimized experimental conditions the linear dynamic ranges for Cu²⁺ and Pb²⁺ were 10‒900 and 30‒900 μg/L, respectively, with a preconcentration factor of 20. The detection limits of Cu²⁺ and Pb²⁺ were 4 and 11 μg/L, respectively, and relative standard deviations for eight determinations of 100 μg/L were 3.6 and 3.8% for Cu²⁺ and Pb²⁺, respectively. The method was successfully applied for determination of copper and lead in mushrooms, rice, tap water and refinery wastewater with good spike recoveries ranging between 95‒106%.

The distribution of 166 pesticides of various classes (amides, dinitroanilines, pyrethroids, thiocarbamates, triazines, etc.) was studied at 20 ± 1°C in multiple extraction systems. The distribution constants (P) of pesticides between hexane and a polar phase are calculated. Based on the distribution constants of pesticides, a possibility of using distribution chromatography for their identification was considered. It is demonstrated on an example of pesticides with similar retention times that the hexane–water extraction system is most selective and universal for the identification of most compounds by gas and liquid chromatography. Using this system, logarithms of distribution constants of the substances under consideration are maximally differentiated and ranged from–1.32 to 8.0. Such a range makes it possible, with an acceptable volume ratio of the hexane and water phases (up to 1: 500), to achieve a significant decrease in the peak area of the pesticide in hexane when it is washed with water in accordance with its P value up to logP = 3.0. In the case of more hydrophobic pesticides, extraction systems of hexane–ethylene glycol, hexane–acetonitrile, and hexane–mixtures of acetonitrile with water and ethylene glycol can be used.

A new sensor was developed using a screen-printed carbon electrode modified with single-walled carbon nanotubes (SWCNTs) and Prussian blue (PB) coated with chitosan. The modified electrode allowed the oxidation and reduction of rutin at 0.25 and 0.096 V, respectively, with a ΔE of 0.154 V. Furthermore, the peak currents increase nearly 100% compared with the electrode without modification. The process was more reversible compared with the electrode modified with only SWCNTs or PB. Cyclic voltammetry was used to characterize the modified electrode surface. The quantification of rutin was more sensitive with adsorptive stripping voltammetry than with anodic stripping voltammetry. Adsorption potential, adsorption time and pH were optimized based on the oxidation of rutin: E_ads =–0.10 V, t_ads = 60 s, pH 3.0. The detection limit (3σ/b) was 0.01 μM and the relative standard derivation was 3%. The new sensor was used in the quantification of rutin in black tea, coffee and synthetic drink of tea with satisfactory results.