Vol 71, No 8 (2016)

We describe three types of automatic software for the chemometric processing of spectrometric data. The software was developed in the MATLAB working environment and includes data import, mathematical preprocessing, chemometric analysis, and generation of a report file. The software is designed to solve problems regarding identification of some components of multicomponent mixtures, determination of compounds with overlapping signals, and differentiation of samples by their spectral responses. To test the software, we present examples of spectrometric analyses of coffee, fruit juices, and alcoholic beverages using chemometric methods of independent component analysis (ICA) and partial least squares–discriminant analysis (PLS–DA). In particular, we simulated electronic absorption spectra for the identification of three artificial colors (E110, E102, and E122) in alcoholic beverages, NMR spectra for the simultaneous determination of five components (acetic acid, γ-aminobutyric acid, arginine, acetaldehyde, and proline) in orange juice without using reference standards, and NMR spectra of coffee samples to determine its varietal authenticity (Arabica or Robusta). The duration of automatic chemometric processing did not exceed 1 min per sample. The developed software can be optimized for other matrices and/or brands of spectrometers.

Using emulsion dispersive liquid–liquid microextraction preconcentration and injection of a large volume of an extract (10 μL), the limits of chromatographic–mass spectrometric detection of o-phthalic acid esters in water have been attained at the level 4 × 10^–6–1 × 10^–5 mg/L. The main source of the systemic error of the determination of impurities was found to be the release of o-phthalates from microparticles of chromatographic septum to the carrier gas. The extractant (n-octane) was purified by Rayleigh distillation. The independence of the concentration coefficient of the studied o-phthalates of concentration in the range (0.4–30) × 10^–4 mg/L has been demonstrated. The relative expanded uncertainty of the determination of o-phthalates has been calculated and equals 12–39%.

A simple approach for studying and identifying matrix effect is described. This method for the determination of matrix effect combines the advantages of two most popular traditional methods while eliminating their disadvantages. A postcolumn infusion system was used to observe the MS signal alterations of synthetic cannabinoids: UR-144, XLR-11 and STS-135. Protein precipitation, liquid–liquid extraction and solid phase extraction sample preparation methods were tested. The results of the experiments showed that the discussed method of matrix effect estimation can have practical application in the development of analytical methods. The comparison of the normalized matrix effect profiles can be done even for data obtained over time. Obtained results also indicated that matrix effect was highly dependent on sample preparation. Although similar structure, significant differences were observed for different synthetic cannabinoids.

A sensitive and convenient method for sphingomyelin determination was developed based on thinlayer chromatography (TLC) and image-processing analysis. The mobile phase composition, detection and quantification conditions were systematically investigated through several trials. The molybdenum blue reaction allowed specific detection of the phospholipid with a high sensitivity and a wide linear range. Digital images of TLC plate chromatograms were captured with flatbed scanner and converted into peak chromatograms using TLSee® software and quantitative analysis was conducted. The linearity, sensitivity, accuracy and precision of the system were evaluated. The limits of detection and quantification were 0.5 and 1.7 μg/spot, respectively. Separation of the mixture consisting of sphingomyelin, phosphatidylcholine, and phosphatidylethanolamine was also carried out.

Two methods are considered for the direct determination of trace amounts of As(III) and As(V) in solutions by stripping voltammetry (SVA) using an ensemble of gold microelectrodes (Au-MEA) previously developed by the authors of this paper. In both methods, analyzing a mixture of As(III) and As(V), analysts first record an SVA signal of As(III) in a supporting Na₂SO₃ electrolyte. To record an analytical SVA signal of As(V), in the first method one should use the reduction of As(V) to As(III) on the surface of an Au-MEA catalyzed by the system Mn(II)/Mn(0) and followed by the formation of As(0) and its anode dissolution. In the second method, the photoreduction of As(V) to As(III) in a Na₂SO₃ solution is conducted under UV irradiation followed by the reduction of As(III) to As(0) and its electrooxidation on Au-MEA. The two methods are compared taking into account their performance characteristics and interfering ions. To improve the reliability of the results of analysis at an insignificant increase in its cost, we propose the consecutive use of both methods. The procedures are simple and rapid, do not require the removal of dissolved oxygen or toxic reactants, and can be used for the analysis of aqueous solutions at the place of sampling. The results of analyses of real objects, snow, river water, and process solutions are presented.

Levofloxacin is a bacteriostatic L-isomer of ofloxacin. This drug is a third generation fluoroquinolone. Its activity strongly depends on its concentration and the AUC/MIC ratio is the best indication of drug exposure. A simple, specific and fast HPLC method with fluorescence detection for assay of levofloxacin level in human plasma was developed. The separation was performed on a reversed phase column. The mobile phase contained 0.4% solution of triethylamine. The regression equation was linear within the concentration range 0.15–30.0 mg/L. The validation parameters i.e. accuracy, precision and stability did not exceed 10%. High recovery was observed. The developed method fulfils the validation parameters. Due to the short time of analysis it may be applied to biomedical analysis.

A comparative study of the efficiency of procedures for the determination of the biomarkers of organophosphorus agents (OPAs) in blood plasma was performed. It was found that the gas chromatography–mass spectrometry determination of OPAs reactivated from the composition of protein adducts is a rapid method for the detection of exposure to OPAs. The liquid chromatography–mass spectrometry determination of phosphonylated butyrylcholinesterase and albumin fragments modified with OPA residues provides an opportunity to perform more sensitive and retrospective analysis. The tyrosine adducts of OPAs with serum albumin and other blood plasma proteins are not prone to dealkylation in the course of aging; in the series of the test markers, they possess the greatest diagnostic value because they make it possible to determine the precise structure a toxic agent after the longest time interval after exposure. The tentative limit of detection of OPA markers varies from 0.1 to 1.0 ng/mL.