


Vol 79, No 7 (2024)
Articles
Artificial modified nucleotides for the electrochemical detection of nucleic acid amplification products



A voltammetric sensor based on carbon fiber paper modified with shungite and copper formazanate for the determination of lidocaine
Abstract
A highly sensitive sensor based on carbon fiber paper modified with a shungite–copper formazanate composite is presented for the voltammetric determination of lidocaine. The synthesized organometallic complex, composite, and modified electrode are characterized by infrared spectroscopy, high-resolution mass spectrometry, elemental analysis, scanning electron microscopy, and cyclic and linear sweep voltammetry. The twofold increase in the current of the lidocaine oxidation peak on the modified electrode compared to the unmodified one is associated with the sensitizing effect of the composite modifier, which is due to an increase in the electroactive area and the number of lidocaine binding sites on the electrode surface. The sensor exhibits a wide dynamic range from 2 to 2120 µM with a low limit of detection of 0.18 µM lidocaine and high sensitivity of 0.755 µA/V µM. The interelectrode and intraelectrode repeatability of the analytical signal do not exceed 3.5%. The sensor response is stable within three weeks. The developed sensor was used for the determination of lidocaine in pharmaceuticals. The results of an analysis of real samples demonstrated good reproducibility (RSD ≤ 5.5%) and recovery (98–102%).



Electrochemical immunosensors based on gold nanoparticles for the determination of ovalbumin in immunobiological preparations
Abstract
A sandwich-type voltammetric immunosensor based on conjugates of gold nanoparticles (AuNP) with specific immunoglobulins (IgG) against ovalbumin (IgG@AuNP) is developed for the determination of ovalbumin in some immunobiological preparations. The IgG@AuNP conjugate is synthesized by passive adsorption. A carbon-containing planar printed electrode modified by laser reduced graphene oxide is used as a substrate electrode for immobilizing the receptor layer of specific immunoglobulins. A possibility of the catalytic reduction of silver nitrate with a mixture of reducing agents, citric acid and metol, is considered in order to enhance the signal of AuNP. Conditions for the voltammetric recording of the electrochemical signal of silver on an immunosensor, which has been successfully tested in determining ovalbumin residues in some immunobiological drugs, are selected. Enzyme-linked immunosorbent assay is used as a reference method.



A sensitive electrochemical sensor based on an organomodified glassy carbon electrode for monitoring the release of amikacin from biodegradable coatings of bone implants
Abstract
The high catalytic activity of arenediazonium, along with the ability of gold ions to form specific bonds with amikacin, has been used in the fabrication of an electrochemical sensor based on a glassy carbon electrode modified with a gold solution and arenediazonium tosylate (Ar/GGCE) for the detection and quantification of amikacin upon its release from implants. Atomic force microscopy, cyclic voltammetry, and square-wave voltammetry were used to demonstrate that the use of a gold solution and arenediazonium tosylate for the surface modification of a glassy carbon electrode significantly enhances the electrode characteristics. The determination of amikacin was achieved using square wave voltammetry, which enabled the detection of amikacin at the Ar/GGCE in the concentration range 0.2–60 μM and ensured a limit of detection of 0.058 μM for amikacin released from implants.



Electrochemical analysis of the interaction between DNA and abiraterone D4A metabolite
Abstract
The electroanalytical characteristics of double-stranded DNA (dsDNA) and the complex of dsDNA with the anticancer drug metabolite, abiraterone D4A, in the concentration range of 25–200 μM were investigated using differential pulse voltammetry. The effect of D4A on dsDNA was detected by changes in the intensity of the electrochemical oxidation of the heterocyclic bases guanine, adenine, and thymine. This investigation used screen-printed electrodes modified with carbon nanotubes. Binding constants (Kb) for guanine, adenine, and thymine in the dsDNA/D4A complexes were calculated to be 1.1 × 104, 5.5 × 103, and 2.5 × 103 M–1, respectively. The DNA-mediated electrochemical coefficients of the toxic effect were calculated as the ratio of the signal intensities of guanine and adenine in the presence of D4A compared to those without the drug (T, %). Based on an analysis of electrochemical parameters and binding constant values, an assumption was made regarding the mechanism of the interaction between D4A and DNA, predominantly through electrostatic interactions and the formation of hydrogen bonds with the minor groove. Conclusions about the mechanism of the interaction of the abiraterone D4A metabolite with the dsDNA minor groove, obtained by electrochemical methods, were supported by the molecular simulation of the DNA/D4A complex.



Oxythermography for exploring the thermal stability of polymer materials: a novel analytical approach
Abstract
The control of oxygen and carbon dioxide concentrations in an airflow released from a reactor, in which a sample is heated, can be used to investigate the thermal stability of polymer materials. This approach, known as oxithermography, involves analyzing experimental data (oxithermograms), representing the variation in oxygen concentration decrease and carbon dioxide appearance in an airflow with changing temperature conditions. This method allows for monitoring the effect of fillers introduced into polymer compositions on their thermal stability. The application of oxithermography to studying oxidative thermostability is demonstrated using pure polypropylene and polypropylene with titanium dioxide admixtures as examples.



Valery Nikolaevich Maistrenko: life in science



Application of effervescent tablets based on magnetic charcoal for the preconcentration and determination of dichlorophenoxycarboxylic acids and their metabolites by gas chromatography–mass spectrometry in soils and natural waters
Abstract
A method for obtaining effervescent tablets, consisting of magnetic carbon, tartaric acid, sodium carbonate and sodium bicarbonate, and their use for the adsorption of dichlorophenoxycarboxylic acids (DCPA)—2,4-dichlorophenoxyacetic, 2,4-dichlorophenoxypropionic and 2,4-dichlorophenoxybutyric acids and their metabolites—2,4-dichlorophenol and 4-chlorophenol is proposed. The tablets are immersed in an analyzed solution with a neutral reaction medium. To analyze soils, extraction with an alkali solution followed by the neutralization of the extract is carried out. After CO2 separation is completed, the sorbent is removed with a neodymium magnet and the analytes are desorbed with acetone. The acetone extract is evaporated under a stream of nitrogen, and the concentrate is analyzed by gas chromatography–mass spectrometry. The method was tested on model systems—samples of river water and typical chernozem, which were artificially contaminated with DCPA and chlorophenols (CP). In analyzing river waters, the limits of determination for DCPA are 0.7–0.9 μg/L, for CP—40 ng/L. In soils, the limit of detection is 3–4 and 0.1 μg/kg for DCPA and CP, respectively.



Detecting trace amounts of peroxides and ammonium nitrate in fingerprints by ion mobility spectrometry
Abstract
The effect of the sweat and grease deposits (SGD) from fingerprints on the detection efficiency of trace amounts of explosive substances—triacetone triperoxide (TATP), hexamethylene triperoxide diamine (HMTD), and ammonium nitrate (AN) by ion mobility spectrometry in air at atmospheric pressure was investigated. Among the main components of SGD, urea is identified as a positive mode influencer, while lactic acid (LA) affects in a negative mode. The presence of urea or SGD in the sample does not significantly affect the detection of TATP in the positive mode but decreases the efficiency of HMTD ion formation and leads to the appearance of adduct cations of HMTD and urea. The presence of lactic acid or SGD slightly decreases the efficiency of ammonium nitrate ion formation in the negative mode and significantly alters the qualitative composition of HMTD ions, leading to the appearance of HMTD and LA adduct anions. In the absence of any impurities in the sample, the best reduced limit of detection (signal-to-noise ratio = 3σ), estimated at 30–50 pg, was observed for HMTD. The lifetime of HMTD, TATP, and AN traces on aluminum foil under laboratory conditions was determined to be 1, 3, and 12 h for samples with masses of mHMTD 1 × 10–9, 2 × 10–9, and 1 × 10–8 g and surface densities ds of 0.008, 0.016, and 0.08 μg/cm2, respectively; 102 and 103 s for mTATP 1 × 10–5 and 1 × 10–4 g and ds of 80 and 800 μg/cm2, respectively; 12 and 25 h for mAN 3 × 10–8 and 5 × 10–8 g and ds of 0.24 and 0.4 μg/cm2, respectively.



Comparison of methods for rapid assessment of selectivity and efficiency of the analytical signal of fluorescent phases of different natures
Abstract
The paper presents the results of assessing the sorption and fluorescence properties of compounds from the azolotriazine class and phases based on cadmium sulfide quantum dots in the presence of volatile organic compounds (biomarkers of the state of living systems). The sorption properties of phases based on organic dyes and encapsulated semiconductors in relation to vapors of alcohols, ketones, amines, acids, ammonia, and aldehydes were studied using direct high-sensitivity quartz crystal microgravimetry. Spectral properties and their changes in the presence of analyte vapors were studied using various spectroscopic methods (absorption, photoluminescence). The results of these studies and the possibility of optimizing this stage were compared. It is proposed to evaluate the consistency of methods for predicting changes in fluorescence properties in test systems for volatile organic compounds using Kendall’s W concordance coefficient. It was found that the highest concordance coefficient (W = 0.89) was obtained with the methods of spectrofluorimetry and direct vapor microgravimetry when sorption occurs on phases—potential fillers for test systems. The correlation of results obtained by different fluorescence methods (visual plate test systems and fluorimetry of phases on paper substrates) is 0.80, which confirms a high degree of consistency in assessing the interaction between analytes and organic, combined fluorochromes. It was established that methods similar in the nature of their analytical response are not better aligned with each other than with the method of direct vapor microgravimetry on microphases of fluorimetric reagents of different natures (CdS/chitosan quantum dots, organic compounds of the azolotriazine class, mixed phases). This, in turn, allows for the selection of simpler, more accessible, and rapid methods and tools for analysis during routine experiments.



Optimization of conditions for the determination of low concentrations of chlorate ions in alkali metal chloride solutions by capillary electrophoresis
Abstract
The separation of chloride and chlorate ions in the case of a significant excess of chloride ions in a sample is studied by capillary electrophoresis. It is found that under standard separation conditions using a chromate background electrolyte, the signal-to-noise ratio for the chlorate ion peak at c(ClO3–) = 0.1 mM sharply decreases at the concentration ratio c(Cl–)/c(ClO3–) > 100. A number of approaches are considered to eliminate this phenomenon. The most effective approach was to introduce a solution containing acetate ions into the capillary after the sample zone to create conditions for transient isotachophoresis. Optimal parameters for the electrophoretic separation of chloride and chlorate ions are selected at a chloride ion content of 35 mM in the sample. The limit of detection is 0.01 mM chlorate ions (0.03–0.06% based on the mass of dry potassium, sodium, or lithium chlorides). The calibration curve is linear in the range of 0.01–1 mM ClO3–. The selected conditions allow the determination of chlorate ions at a molar ratio of chloride to chlorate ions of 35–3500. The stacking efficiency factors are 10–70. Perchlorate ions do not interfere with the determination of chlorate ions at the concentrations of both ions of 0.1 mM or lower. The procedure is tested by analysis of table salt.


