Temperature-controlled liquid-liquid microextraction combined with high-performance liquid chromatography for the simultaneous determination of diazinon and fenitrothion in water and fruit juice samples.

A simple, environmentally benign, and rapid method based on temperature-controlled liquid-liquid microextraction using a deep eutectic solvent was developed for the simultaneous extraction/preconcentration of diazinon and fenitrothion. The method involved the addition of deep eutectic solvent to the aqueous sample followed by heating the mixture in a 75°C water bath until the solvent was completely dissolved in the aqueous phase. Then, the resultant solution was cooled in an ice bath and a cloudy solution was formed. Afterward, the mixture was centrifuged and the enriched deep eutectic solvent phase was analyzed by high-performance liquid chromatography with ultraviolet detection for quantification of the analytes. The factors affecting the extraction efficiency were optimized. Under the optimized extraction conditions, the limits of detection for diazinon and fenitrothion were 0.3 and 0.15 µg/L, respectively. The calibration curves for diazinon and fenitrothion exhibited linearity in the concentration range of 1-100 and 0.5-100 µg/L, respectively. The relative standard deviations for five replicate measurements at 10.0 µg/L level of analytes were less than 2.8 and 4.5% for intra- and interday assays, respectively. The developed method was successfully applied to the determination of diazinon and fenitrothion in water and fruit juice samples.

Chemometric-assisted kinetic-spectrophotometric method for simultaneous determination of ascorbic acid, uric acid, and dopamine.

A chemometric-assisted kinetic spectrophotometric method has been developed for simultaneous determination of ascorbic acid (AA), uric acid (UA), and dopamine (DA). This method relies on the difference in the kinetic rates of the reactions of analytes with a common oxidizing agent, tris(1,10-phenanthroline) and iron(III) complex (ferritin, [Fe(phen)(3)](3+)) at pH 4.4. The changes in absorbance were monitored spectrophotometrically. The data obtained from the experiments were processed by chemometric methods of artificial neural network (ANN) and partial least squares (PLS). Acceptable techniques of prediction set, randomization t test, cross-validation, and Y randomization were applied for the selection of the best chemometric method. The results showed that feedforward artificial neural network (FFANN) is more efficient than the other chemometric methods. The parameters affecting the experimental conditions were optimized, and it was found that under optimal conditions Beer's law is followed in the concentration ranges of 4.3-74.1, 4.3-78.3, and 2.0-33.0 µM for AA, UA, and DA, respectively. The proposed method was successfully applied to the determination of analytes in serum and urine samples.

Development of a novel method for determination of mercury based on its inhibitory effect on horseradish peroxidase activity followed by monitoring the surface plasmon resonance peak of gold nanoparticles.

A highly sensitive and simple indirect spectrophotometric method has been developed for the determination of trace amounts of inorganic mercury (Hg(2+)) in aqueous media. The method is based on the inhibitory effect of Hg(2+) on the activity of horseradish peroxidase (HRP) in the oxidation of ascorbic acid by hydrogen peroxide followed by the reduction of Au(3+) to Au-NPs by unreacted ascorbic acid and the measurement of the absorbance of localized surface plasmon resonance (LSPR) peak of gold nanoparticles (at 530 nm) which is directly proportional to the concentration of Hg(2+). Under the optimum conditions, the calibration curve was linear in the concentration range of 1-220 ng mL(-1). Limits of detection (LOD) and quantification (LOQ) were 0.2 and 0.7 ng mL(-1), respectively and the relative standard deviation at 100 ng mL(-1) level of Hg(2+) was 2.6%. The method was successfully applied to the determination of mercury in different water samples.

Spectrophotometric determination of iron species using a combination of artificial neural networks and dispersive liquid-liquid microextraction based on solidification of floating organic drop.

A dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) and artificial neural networks method was developed for the simultaneous separation/preconcentration and speciation of iron in water samples. In this method, an appropriate mixture of ethanol (as the disperser solvent) and 1-undecanol (as the extracting solvent) containing appropriate amount of 2-thenoyltrifluoroacetone (TTA) (as the complexing agent) was injected rapidly into the water sample containing iron (II) and iron (III) species. At this step, the iron species interacted with the TTA and extracted into the 1-undecanol. After the phase separation, the absorbance of the extracted irons was measured in the wavelength region of 450-600 nm. The artificial neural networks were then applied for simultaneous determination of individual iron species. Under optimum conditions, the calibration graphs were linear in the range of 95-1070 µg L(-1) and 31-350 µg L(-1) with detection limits of 25 and 8 µg L(-1) for iron (II) and iron (III), respectively. The relative standard deviations (R.S.D., n=6) were lower than 4.2%. The enhancement factor of 162 and 125 were obtained for Fe(3+) and Fe(2+) ions, respectively. The procedure was applied to power plant drum water and several potable water samples; and accuracy was assessed through the recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry.

Speciation and determination of ultra trace amounts of chromium by solidified floating organic drop microextraction (SFODME) and graphite furnace atomic absorption spectrometry.

Solidified floating organic drop microextraction (SFODME) method in combination with graphite furnace atomic absorption spectrometry (GFAAS) has been used for the determination of chromium species in water and urine samples. 1-undecanol containing 2-thenoyltrifluoroacetone (TTA) was used as a selective chelating agent for the extraction of Cr(III). The total Cr was determined after the reduction of Cr(VI) to Cr(III) with hydroxylamine. The concentration of Cr(VI) was determined from the difference between the concentration of total chromium and the Cr(III). Several variables such as the sample pH, concentration of TTA, salt concentration, extraction time and the sample volume were investigated in detail. Under the optimum conditions, the limit of detection of the proposed method was 0.006 µg l(-1) for Cr(III) and the relative standard deviation for six replicate determinations at 0.1 µg l(-1) Cr(III) was 5.1%. The proposed method was successfully applied for the determination of chromium species in tap water, well water, mineral water, and urine samples.