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Vol 80, No 2 (2025)
REVIEWS
Methods for the Determination of Toxins and Biologically Active Components of Higher Fungi
Abstract
Toxic mushrooms can be categorized into different groups depending on their constituents: cyclopeptides, hyromitrin, muscarine, isoxazoles (muscimol, ibotenic acid), orellanin, psilocybin and gastrointestinal irritants. Mushrooms containing cyclopeptides are the most toxic species worldwide and are responsible for 90–95% of human deaths. Rapid and accurate identification of toxins in mushrooms and biological samples is critical for the diagnosis and treatment of mushroom poisoning. Methods for toxin identification are essential to ensure timely treatment. This review presents an analysis of the scientific literature on the determination of mushroom toxins in mushroom and biological samples. Particular attention is paid to chromatographic methods, in particular high-performance liquid chromatography coupled with mass spectrometry.
113-124
Mass Spectrometry as a Tool to Ensure Food Safety: Practical Aspects of Application on The Example of the Work of FGBU “VGNKI”
Abstract
When ensuring the safety of food products, the list of regulated contaminants is very extensive: pharmaceuticals (antibiotics, non-steroidal anti-inflammatory drugs, coccidiostatics, thyreostatics, β-adrenostimulants, antihelminthic agents, etc.), pesticides, toxic elements, hormones, polychlorinated biphenyls, dioxins, natural toxins (zoo-, phyto- and mycotoxins, toxins of bacterial bacteria, etc.). ), pesticides, toxic elements, hormones, polychlorinated biphenyls, dioxins, natural toxins (zoo-, phyto- and mycotoxins, toxins of bacterial origin, biogenic amines), etc. The main means of determining the contaminants in food raw materials and food products when establishing compliance of their content with hygienic standards is laboratory control. Mass spectrometry has been the most effective tool of laboratory control both in Russia and abroad for more than 20 years. The review considers the methods developed by Federal State Budgetary Institution “The Russian State Center for Animal Feed and Drug Standardization and Quality” (FGBU “VGNKI”) using mass spectrometry, which are of the greatest interest from the point of view of implementation of food safety monitoring in the Russian Federation, as well as promising directions of research work taking into account the main problems and achievements in the field of mass spectrometry.
125-139
ORIGINAL ARTICLES
Approaches to Sample Preparation of Complex Biological Matrices for the Forensic Chemical Determination of Carfentanil
Abstract
Two sample preparation procedures (liquid extraction into nonpolar solvent and solid-phase extraction) of cadaver biological tissues altered by putrefaction are compared. The work is devoted to the creation of a rapid and simple sample preparation method for the determination of carfentanil in putrefactive tissue samples. GC-MS analysis was performed on an Agilent 7820/5975 Maestro mass-selective chromatograph (Rxi-5ms, Restek). A three-quadrupole mass spectrometric detector (LC-MS/MS Shimadzu 8050) was used for HPLC-MS/MS analysis. Chromatographic separation was carried out on a column with reversed-phase sorbent Phenomenex Kinetex C18. Liver homogenates were chosen as the object of study, and alternatively, lysis products obtained by freezing/thawing of liver tissue samples. Sample preparation of homogenates was carried out by heptane liquid extraction and solid-phase extraction methods. Comparison of the results showed that liquids containing lysis products are the optimal choice for fast and efficient sample preparation. The analytical signal of target substances is 1.5-2 times higher than the signal obtained in the study of tissue homogenates using both solid-phase and liquid-phase extraction.
140-148
Approach to Optimization of Mass Spectrometric Detection Parameters for Identification of Ultra-Small Amounts of Highly Toxic Substances
Abstract
The procedure of optimization of the following parameters is described: scanning speed, duration of registration of selective transitions (dwell time), duration of delay in transition from one selective transition to another (pause time). A chromatograph for HPLC with a three-quadrupole mass spectrometric detector (LC-MS/MS Shimadzu 8050) was used. Chromatographic separation was carried out on a column with reversed-phase sorbent Phenomenex Kinetex C18. As mobile phase A was used 0.1 % solution of formic acid in water with addition of 10 mM/L ammonium formate, as mobile phase B – 0.1 % solution of formic acid in methanol with addition of 10 mmol/L ammonium formate. The optimal parameters for confirmatory methods were established: duration of registration of selective transitions – not less than 10 ms, duration of delay in transition from one selective transition to another – 1 ms, scanning speed – from 1000 to 5000 scans per second. This technique has been successfully applied in routine chemical and toxicological studies of urine samples with low content of various narcotic and medicinal substances.
149-160
Methods for the Detection of Muscarinic, Muscimol and Ibotenic Acid in Fungi and Biological Matrices Using the HPLC-MS/MS Method
Abstract
An algorithm for two-step detection of muscarinic, ibotenic acid and muscimol in urine samples is described. A two-step method for the detection of muscarinic, muscimol and ibotenic acid in data-dependent MRM analysis mode with simultaneous registration of complete mass spectra of the target substances was developed. Detection of analytes was carried out by HPLC with a three-quadrupole mass spectrometric detector (LC-MS/MS Shimadzu 8050). Chromatographic separation was performed on a column with reversed-phase sorbent Phenomenex Kinetex C18. At the first stage, muscarine was detected in a diluted urine sample; at the second stage, muscimol and ibotenic acid were detected using the bimolecular dansylation method. The method was successfully applied in practice for routine chemical-toxicological studies of urine samples of patients delivered with suspected mushroom poisoning.
161-173
Simultaneous Determination of Avilamycin and Nosigeptide Marker Residues in Chicken Meat by the HPLC-MS/MS Method
Abstract
Multicomponent residue analysis of veterinary drugs by HPLC-MS/MS is relevant for food safety. A significant problem is the determination of veterinary drugs whose molecules are large in size. Electrospray ionization of such molecules is difficult, and it is difficult to achieve the required sensitivity by classical separation from the matrix with subsequent detection. Such drugs include avilamycin and nosiheptide. To solve this problem, it is possible to fragment the molecules into smaller and easily detectable residues by hydrolysis, which in turn raises the problem of optimizing the conditions of such preparation, as well as assessing the uniqueness of the selected marker. The possibility of simultaneous determination of avilamycin and nosiheptide in chicken meat by their alkaline hydrolysis to the markers dichloroisoverninic acid and 4-hydroxymethyl-3-methylindole-2-carboxylic acid, respectively, has been demonstrated. The conditions of extraction, hydrolysis and methods of further purification were studied. Under the selected conditions, analyte recovery was >85% and satisfactory reproducibility was achieved (sr ≤ 0.15). The detection limits were 5 µg/kg. The developed method is highly selective, rapid, easy to perform, inexpensive and has good analytical performance.
174-182
Determination of Short-Chain Fatty Acids in Serum as Biomarkers of Renal Dysfunction
Abstract
Short-chain fatty acids (SCFAs) produced by the gut microbiota play an important role in maintaining the immune status of the body. Chronic kidney disease is associated with decreased microbial diversity in the gut and impaired production of SCFAs. In chronic kidney disease, the level of SCFAs in circulating blood decreases; therefore, the development of highly sensitive methods is required for the determination of SCFAs in serum. We have developed a technique for the determination of SCFAs in serum and tested it in a comparative study of serum samples from healthy volunteers and patients with diagnosed chronic kidney disease. The determination of SCFAs (acetic, propionic, oily, valerian, caproic, isobutyric and isovalerian) in blood serum was performed by gas chromatography-mass spectrometry (GC-MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS). The limits of determination of the investigated SCFAs by GC-MS method are in the range of 0.05–0.09 µg/mL, by GC-MS/MS method – 0.002–0.007 µg/mL. We showed that in blood serum samples of patients with chronic kidney disease the concentrations of all investigated SCFAs are reduced in comparison with the control group and lie below the limits of detection by GC-MS method.
183-188
One-Time Definition of Biologically Active Components of Rhodiola rosea in Extracts of Plant Sources by HILIC-MS/MS Method
Abstract
A simple, rapid and highly sensitive method for the simultaneous determination of the main components of Rhodiola rosea (rosin, salidroside, rosarin, and rosavin) in a wide range of concentrations by hydrophilic chromatography-tandem mass spectrometry has been developed. The conditions for extraction (type and composition of extractant, extraction time) of the main components from Rhodiola rosea root samples, chromatographic separation and detection of these compounds were selected, and the metrological characteristics of the proposed approach were evaluated. The detection limits were 250, 2.4, 2.3, and 5.4 ng/mL, and the linear ranges of detectable concentrations are 1–100, 0.01–10, 0.01–10, and 0.01–100 µg/mL for rosin, salidroside, rosarin, and rosavin, respectively. The developed approach is tested in the analysis of real samples of pharmaceuticals and plant raw materials.
189-200
Detection of Metabolites of the New Synthetic Cannabinoid MDMB-4en-PINACA in Human Urine by Liquid and Gas Chromato-Mass Spectrometry Methods
Abstract
MDMB-4en-PINACA belongs to the new synthetic psychoactive compounds that have been distributed in Russia since at least 2020 and is highly active against the human cannabinoid receptor CB1. Its distinctive feature is the presence of an N-pentene residue, which is rare for this group of compounds. The significant hydrophobicity of MDMB-4en-PINACA, like most other synthetic cannabimimetics on the world market, results in almost complete biotransformation of the parent compound and very low levels in urine. Hence the need to identify its metabolites, the detection of which would indicate the use of MDMB-4en-PINACA. To solve this problem we used gas and liquid chromatography-mass spectrometry methods, including high-performance chromatography-mass spectrometry with a quadrupole time-of-flight detector and a three-dimensional ion trap detector equipped with an electrospray ionization source. A number of putative metabolites of MDMB-4en-PINACA in human urine were identified as products of hydrolysis, mono- and dihydroxylation, reduction, dihydrodiol formation, carboxylation, carboxylation with elimination of methylene group, N-dealkylation and combinations of these processes. A number of metabolites were found in the form of glucuronides. The obtained results are in good agreement with literature data. For routine chemical-toxicological and forensic chemical analysis of urine by gas chromatography-mass spectrometry is optimal to search for products of hydrolysis, dihydroxylation and dihydrodiol formation, while when using liquid chromatography-mass spectrometry is also recommended detection of glucuronides of hydrolysis products and dihydrodiol formation.
201-216
Identification and Authentication of Vegetable Oils by Digital Colorometry and IR Spectroscopy Methods
Abstract
The possibility of a simple and accessible method of identification and authentication of edible vegetable oils using methods of digital colorometry, Fourier transform infrared spectroscopy in the near and middle spectral regions and chemometric processing of the analysis results is shown. Identification by species of oils (mustard, linseed, corn, olive and sunflower), authentication (authenticity and adulteration) was carried out by the intrinsic coloring of vegetable oils and fluorescence when the samples were irradiated with monochromatic light in the UV, visible and infrared regions. (365, 390, 470, 565, 700, 850, 880, 940 nm and 400–10 000 cm–1). A device and method for measuring colorometric parameters using a smartphone and data processing using RGBer, PhotoMetrix PRO®, XLSTAT, and The Unscrambler X specialized software are proposed. Application of chemometric analysis allowed to establish the authenticity of vegetable oils and to reveal the facts of adulteration by diluting expensive oils with cheaper ones.
217-225
Principle of complex graduation of a portable gas chromatograph with a photoionization detector for geochemical prospecting of hydrocarbon deposits
Abstract
The results of formation of the calibration concentration of equilibrium vapor of toluene in the field conditions by the method of single extraction under static conditions are presented. The method of current adjustment of calibration of gas chromatograph is substantiated taking into account instability of light flux of electrodeless vacuum ultraviolet lamp of photoionization detector.
226-232