![QUANTUM CHEMICAL MODELING OF THE STRUCTURE OF THE PSEUDOMOLECULAR ION [M+H]+ T-2 TOXIN](/upload/84d3a89c18d437fa8a9ddc6bbecb2e79/issues/cover/e77180c0aa4b67abc73ddef4c1030512.jpeg)
QUANTUM CHEMICAL MODELING OF THE STRUCTURE OF THE PSEUDOMOLECULAR ION [M+H]+ T-2 TOXIN
Rubrics: 1. CHEMISTRY
Authors:
1.
Federal'nyy centr toksikologicheskoy, radiacionnoy i biologicheskoy bezopasnosti
2.
Federal'nyy centr toksikologicheskoy, radiacionnoy i biologicheskoy bezopasnosti
3.
Federal'nyy centr toksikologicheskoy, radiacionnoy i biologicheskoy bezopasnosti
4.
Federal'nyy centr toksikologicheskoy, radiacionnoy i biologicheskoy bezopasnosti
Type:
Article
Pages:
from 15
to 19
Status:
Published
Received:
24.12.2025
Accepted:
25.12.2025
Published:
25.12.2025
Language:
Russian
Keywords:
T-2 TOXIN, QUANTUM CHEMICAL CALCULATIONS, MASS SPECTROMETRY
Abstract (English):
Mycotoxins are secondary metabolites of microscopic molds. One of the important families of mycotoxins, from the point of view of monitoring their content in feed and food raw materials, are trichothecins. Mass spectrometric methods for the qualitative and quantitative determination of mycotoxins are the most sensitive and make it possible to cover a wide range of analytes. However, when developing such techniques, researchers pay little attention to studying the structural features of ionization and fragmentation of mycotoxin molecules. This knowledge can further help in the improvement of new techniques being created. Using the example of T-2 toxin, one of the most toxic and frequently detected representatives of trichothecenes, model theoretical studies of some processes occurring in a mass spectrometer have been conducted. Quantum-chemically, within the framework of the density functional theory (PBE/def2-TZVP), the patterns of geometry changes during protonation of various donor centers of the T-2 toxin molecule are considered. In total, 10 protonation centers were considered, necessary to understand the structure of the pseudomolecular ion [M+H]+ formed in the electrospray ionization source of the mass spectrometer. The most energetically advantageous direction of protonation was the interaction of the hydrogen ion with the free alcohol group of the molecule. In this case, the hydrogen ion also interacts with the carbonyl oxygen of the neighboring acetyl group. The results obtained can also explain some directions of pseudomolecular ion fragmentation in the mass spectrometer, which are in good agreement with the literature data. As a result of optimization of the geometry of the most energetically favorable geometry of the [M+H]+ ion, the C-O bond of the alcohol group is elongated, which can lead to the cleavage of the water molecule and the ester C-O bonds of the isovaleryl substituent.
Mycotoxins are secondary metabolites of microscopic molds. One of the important families of mycotoxins, from the point of view of monitoring their content in feed and food raw materials, are trichothecins. Mass spectrometric methods for the qualitative and quantitative determination of mycotoxins are the most sensitive and make it possible to cover a wide range of analytes. However, when developing such techniques, researchers pay little attention to studying the structural features of ionization and fragmentation of mycotoxin molecules. This knowledge can further help in the improvement of new techniques being created. Using the example of T-2 toxin, one of the most toxic and frequently detected representatives of trichothecenes, model theoretical studies of some processes occurring in a mass spectrometer have been conducted. Quantum-chemically, within the framework of the density functional theory (PBE/def2-TZVP), the patterns of geometry changes during protonation of various donor centers of the T-2 toxin molecule are considered. In total, 10 protonation centers were considered, necessary to understand the structure of the pseudomolecular ion [M+H]+ formed in the electrospray ionization source of the mass spectrometer. The most energetically advantageous direction of protonation was the interaction of the hydrogen ion with the free alcohol group of the molecule. In this case, the hydrogen ion also interacts with the carbonyl oxygen of the neighboring acetyl group. The results obtained can also explain some directions of pseudomolecular ion fragmentation in the mass spectrometer, which are in good agreement with the literature data. As a result of optimization of the geometry of the most energetically favorable geometry of the [M+H]+ ion, the C-O bond of the alcohol group is elongated, which can lead to the cleavage of the water molecule and the ester C-O bonds of the isovaleryl substituent.
Keywords:
T-2 TOXIN, QUANTUM CHEMICAL CALCULATIONS, MASS SPECTROMETRY
T-2 TOXIN, QUANTUM CHEMICAL CALCULATIONS, MASS SPECTROMETRY
