


Volume 80, Nº 5 (2025)
REVIEWS
Explosive detectors: state of the art
Resumo
The review justifies the list of explosives and their components (E&Cs) to be controlled. Typical objects of detection by instrumental methods of chemical analysis are described – trace amounts of E&Cs on various surfaces or their vapours in the air as indications of the presence of explosive devices or explosive charges. On the basis of these descriptions, requirements for the E&Cs detection equipment to be used are formulated. Analytical and operational characteristics of devices based on standoff laser spectroscopy methods, as well as devices based on sample selection, preparation and analysis by ion mobility spectrometry, colourimetry using reagents for colour reactions, mass spectrometry, high-speed gas chromatography, chromatography-mass spectrometry, high-performance liquid chromatography, sensor methods (optical (chemical), electrical, electrochemical) have been evaluated and compared at the qualitative level. The main directions of development of instrumental analytical technologies for E&Cs detection are listed.



ORIGINAL ARTICLES
Identification and adulteration of salmoninae caviar by PCR, IR spectroscopy and digital colourometry
Resumo
The possibility to identify and establish adulteration of salmon fish eggs in a simple and accessible way using PCR, Fourier transform infrared spectroscopy, digital colourometry and chemometric processing of analysis results has been shown. The PCR method was used to determine the species affiliation of Salmoninae caviar. Absence of Salmoninae DNA in the samples of caviar, as well as the presence of DNA of other fish, indicated the adulteration of caviar products. Fourier transform infrared spectroscopy in the near and middle regions allowed to distinguish between natural and imitated caviar after processing of diffuse reflectance spectra by principal component and hierarchical cluster analysis methods. The above methods were combined with a simpler and cheaper colourometric method of analysis. Handmade devices with LEDs emitting light in the UV and IR ranges were used. The analytical signal was recorded using smartphones via specialised applications. Chemometric processing of the spectral characteristics of the samples made it possible to distinguish natural caviar from imitated and structured caviar: in the principal component method and hierarchical cluster analysis, points from the analyzed samples were located in different quadrants and clusters.



Influence of non-ionogenic pav on the intensity of metal lines in drop-spark discharge spectra
Resumo
Multiple amplification of metal lines in the emission spectrum of drop-spark discharge was found when non-ionogenic surfactants are introduced into the sample. The effect occurs at the content of Triton X-100 more than 1 % and persists up to 35 wt.% The degree of enhancement depends on the concentration of the background electrolyte, reaching two orders of magnitude for highly dilute acids (e.g., 10 mM HCl). In the presence of 1.5 wt.% Triton X-100, an order of magnitude decrease in the detection limits of Cu, Cs, Mg, Li and Pb is observed.



Improvement of selectivity and sensitivity of tetracycline antibiotics analysis based on ESI-MS method with monoquadrupole mass analyser
Resumo
Methodological approaches that can be applied to improve the metrological characteristics of a monoquadrupole mass analyser for the study of residual content of small organic substances in aqueous media on the example of tetracycline antibiotics are described. To improve the selectivity of the analysis it is suggested to use optimal parameters of electron optics in the source (voltage at the fragmentor) in order to achieve high yield of ion-products. It is shown that the sensitivity of the analysis can be improved by summing the signals of all formed ion-products.



Development and validation of an immunochromatographic test system for the determination of okadaic acid in seafood
Resumo
Okadaic acid (OA) and its derivatives, dinophysistoxins, belong to the group of diarrhoeal toxins (DSP-toxins) produced by toxin-producing dinoflagellates. When algae are ingested by molluscs, DSP-toxins concentrate in the fatty tissue of the animals and can lead to acute poisoning in humans if consumed. We have developed a simple, sensitive and specific test system for the detection and semi-quantitative rapid determination of OA and its derivatives in shellfish, based on a direct competitive immunochromatographic assay. The test strips have three immunoreagent binding lines – test line, control line and internal comparison line, the staining intensity of which does not depend on the concentration of OA in the solution and is comparable to the staining intensity of the test line. When DSP toxins are present in the sample, the staining intensity of the test line decreases relative to the reference line, which allows detection of the presence of toxins in the samples. Sample preparation includes extraction of mollusk tissue homogenates with methanol followed by dilution of the extract with the solution for analysis. The test strips are manufactured in a “dip-stick” format and the analysis procedure involves dipping part of the test strip into the sample for a few seconds with results processed after 30 min. The total duration of the analysis including sample preparation is about 1 h. The test system allows reliable detection and semi-quantitative determination of OA in various shellfish (oysters, mussels, vongole, Buccinidae, scallops) with the toxin content not more than 40 ng/g (visual method of results registration) and not more than 10 ng/g (instrumental method of results registration), which is significantly lower than the maximum permissible concentration for OA established by the World Health Organisation and Rospotrebnadzor (160 ng/g). In addition to OA, the test system is able to detect its derivatives, dinophysistoxin-1 and dinophysistoxin-2, in molluscs. The developed immunochromatographic test system can be used for monitoring the content of OA-group toxins in molluscs inhabiting Russia.



Development of an algorithm for processing “electronic nose” data on piezosensors when analyzing blood samples without sample preparation: a pilot study
Resumo
The first results of blood analysis of patients of different profile departments without sample preparation using portable “electronic nose” on piezosensors are presented. During half a year on the basis of the clinical laboratory of the regional hospital the blood of patients was analyzed in parallel by traditional and sensor methods. The influence of conditions (room temperature, repetition rate, nature of modifiers of piezosensor electrodes) on the repeatability of sensor array signals was considered. Effective approaches and algorithms for processing multidimensional data of the piezosensor array for detection of the profile of volatile compounds (VOCs) of blood of small volume (not more than 0.5 ml) are proposed. The use of type II distilled water samples is effective as an internal standard when analyzing blood samples without sample preparation in a laboratory setting. Blood samples from 250 patients were analyzed. It was found that the set of piezosensors reliably distinguishes samples with pronounced pathologies of inflammation, oncology, serious problems in kidney function, the highest level of stress (surgery; traffic accident with injuries incompatible with life; burns). Other pathologies are also recorded with the proposed parameter, but its value depends on the individual state of the patient, the presence of comorbidities, the achievement of compensation, the degree of severity of negative processes on admission (for example, type 2 diabetes mellitus). The difference of VOC profiles for samples with different significant pathologies with component-by-component analysis is the subject of the next communication. The method of blood volatile compounds detection (measurement mode, repetition rate) is optimized and simple efficient algorithms for sensor data array processing are proposed.



Inverse multivariate graduations as a means of separate determination of similar analytes from the spectrum of a non-additive light absorption mixture
Resumo
Multivariate graduations are used in spectrophotometric analysis for the determination of a number of analytes in multicomponent solutions. These graduations relate generalized signals measured at multiple wavelengths to analyte concentrations. The purpose of this work is to test the applicability of inverse multivariate graduations (OMG) for the separate determination of analytes of the same type when their light absorption is non-additive. The objects of analysis were model aqueous solutions simultaneously containing Cu(II), Co(II), Ni(II), Zn(II), Pb(II) and an excess of the photometric reagent 4-(2-pyridylazo) resorcinol. In such solutions, statistically significant deviations from light absorption additivity were observed, probably caused by a shift in the complexation equilibrium. The initial data for the construction of OMGs were spectra of model mixtures from the training sample. The number of analytical wavelengths (m) and the number of mixtures in the training sample (n) were varied during the experiment. Metal concentrations in the mixtures from the test sample were calculated separately by multiple linear regression using different spectral intervals and different OMGs. The best results were obtained at m = 16 and n = 30. The errors of determination of Co, Ni and Zn in single mixtures do not exceed 25 oz.% (modulo), and the generalized errors (RMSEP) were 10-15 oz.%. The errors of copper and lead determination were characterized by much higher values. The experiment showed that OMG can be used to separately determine components of mixtures with similar but not additive spectra. However, the volume of initial data in this case should be much larger than in the assessment of the total content of the same analytes, the accuracy of the results will be lower, and the possibility of correct determination of all analytes is not guaranteed.


