Bulhakova A.I. Ionization, fragmentation and excitation of glutamine, glutamic acid and valine molecules by electron impact. – Qualifying scientific work as a manuscript.
Thesis is submitted to acquire the scientific degree of Doctor of Philosophy in the specialty 104 “Physics and astronomy”. – Institute of Electron Physics NAS Ukraine, Uzhhorod, 2022.
The work is devoted to complex mass spectrometric and optical spectroscopic studies of the amino acid molecules glutamine (С5Н10N2O3), glutamic acid (С5Н9NO4), and valine (C5H11NO2), both unirradiated and irradiated.
The introduction substantiates the relevance of the chosen topic of the dissertation, indicates the purpose, tasks, subject and object of research. The practical significance and scientific novelty of the obtained results are outlined.
The first chapter "Ionization, fragmentation and excitation of molecules by electron impact" presents an overview and analysis of methods of ionization, fragmentation and dissociation of molecules, as well as excitation of molecules by electron impact.
In the second chapter "Experimental equipment and research methods" the experimental setup with the monopole mass spectrometer МХ7304А and the general scheme of the experiment are considered. The installation for the study of the optical spectra of the emission of pairs of molecules is presented and described, as well as the installation for the irradiation of molecules with high-energy microtron M-30 electrons.
The third chapter " Fragmentation and ionization of glutamine, glutamic acid and valine molecules by electron impact" is devoted directly to the description of mass spectrometric studies of the yield of positive ions in the gas phase, formed as a result of dissociative ionization of glutamine, glutamic acid, and valine molecules by electron impact. The peculiarities of the processes of the formation of fragment ions of these molecules were analyzed in detail, and the dynamics of the release of fragment ions in the range of temperatures of evaporation of the original substance 290-460 K. The results of measuring the energy dependences of the complete ionization cross sections of glutamine, glutamic acid and valine molecules were described. The ionization energy of glutamine molecules (EIE = 8,64 ± 0,25 eV), glutamic acid (EIE = 8,86 ± 0,25 eV), and valine (8.72 ± 0.22 eV) was determined.
The results of experimental studies were compared with theoretical ab initio calculations of the ionization potentials of glutamic acid and glutamine molecules in the adiabatic approximation and by the binding energies of HOMO and LUMO orbitals of neutral molecules, as well as with the calculated total cross sections of one-electron ionization of both molecules by electron impact in Binary-Encounter-Bethe model and Gryzinsky's formula. It is shown that the calculated cross sections agree well with the obtained experimental data.
The fourth chapter "Excitation of valine and glutamine molecules by electron impact" describes the cycle of conducted experimental studies of processes of electron excitation of valine and glutamine molecules in the gas phase. The optical excitation functions of the most intense emissions (spectral lines and bands) of radiation were measured. It was found that the energy thresholds for all types of emissions are within 10-11 eV, which is associated with the fragmentation of the valine molecule. It was established that due to the dissociation of glutamine molecules, molecular emissions of the OH radical and some other molecular fragments are most efficiently formed, and spectral lines of excited hydrogen atoms are also recorded. It was found that the energetic excitation thresholds of molecular emissions are within 10-12 eV, while for atomic lines of hydrogen – within 13-15 eV.
For the first time, the process of electronic excitation of glutamine molecules in the gas phase before and after irradiation of samples (with electrons with an energy of 11,5 MeV electrons) on the M-30 microtron with doses of 10 kGy was investigated by the method of optical spectroscopy. For the most intense emission lines of molecular fragments, located in the energy range of 4.4-11.8 eV, their thresholds and energy dependences of the excitation efficiency in the range of electron energies up to 30 eV were determined. Processes and channels responsible for radiation have been identified. It was established that the difference in the characteristic features of the optical excitation functions of irradiated glutamine can be associated with the presence of metastable states in it, which are absent in the non-irradiated sample.
The role of radiation in the formation of metastable molecular structures, which determine the features of the optical and mass spectra of irradiated glutamine samples, was studied. It has been established that the choice of the energy range of the scanning electron beam is important for the diagnosis of radiation damage to amino acids.
