Resonant electron capture by 5-Br-2'-deoxyuridine.

The results of the study of resonant electron capture by molecules of 5-Br-2'-deoxyuridine (BrdUrd) over the range of electron energies from near zero to 14 eV are described. In the thermal energy range, long-lived molecular negative ions, unstable with respect to autoneutralization and dehalogenation, have been registered. Examination of the kinetics of these decay processes led us to the conclusion that the most probable structure for molecular negative ions is that with an extended C-Br bond, which was predicted earlier using quantum-chemical calculations. Estimates have shown that the BrdUrd molecule owns a significant electronic affinity of 0.93-1.38 eV. The most intense fragmentation channel leads to the abundant formation of Br- ions. The dissociative electron attachment cross section for Br- ions formation was estimated to amount to no less than 1.65 × 10-15 cm2, indirectly implying a fairly intense formation of complementary highly reactive deoxyuridine-5-yl particles. These particles are known to be responsible for the radiosensitizing properties of BrdUrd.

Resonant electron capture by aspartame and aspartic acid molecules.

RATIONALE: The processes for dissociative electron capture are the key mechanisms for decomposition of biomolecules, proteins in particular, under interaction with low-energy electrons. Molecules of aspartic acid and aspartame, i.e. modified dipeptides, were studied herein to define the impact of the side functional groups on peptide chain decomposition in resonant electron-molecular reactions. METHODS: The processes of formation and decomposition of negative ions of both aspartame and aspartic acid were studied by mass spectrometry of negative ions under resonant electron capture. The obtained mass spectra were interpreted under thermochemical analysis by quantum chemical calculations. RESULTS: Main channels of negative molecular ions fragmentation were found and characteristic fragment ions were identified. CONCLUSIONS: The СООН fragment of the side chain in aspartic acid is shown to play a key role like the carboxyl group in amino acids and aliphatic oligopeptides. Copyright © 2016 John Wiley & Sons, Ltd.

Study of fragmentation pathways of metastable negative ions in aliphatic dipeptides using the statistical theory.

RATIONALE: Dipeptide molecules are good model systems for investigation of resonant reactions of low-energy electrons with proteins. The present work is devoted to the study of the processes of formation and fragmentation of negative ions in aliphatic dipeptides glycyl-glycine and glycyl-alanine. The metastable decays of negative ions were detected in these objects, and have been investigated with the aim of clarification of the mechanisms of fragmentation. METHODS: The effective yield curves for negative ions as functions of electron energy were obtained using a magnetic sector mass spectrometer rebuilt for generation and detection of negative ions. For analysis of the observed metastable decays statistical and thermochemical approaches have been used. RESULTS: The ions structures, the enthalpies of formation of neutral and charged particles, and the rate constants of dissociative reactions have been found. CONCLUSIONS: Comparison of the experimental results with theoretical data leads to the conclusion that metastable ion decay proceeds with minimal structural changes avoiding complicated rearrangements and isomerization processes.

Dissociative electron attachment to glycyl-glycine, glycyl-alanine and alanyl-alanine.

The processes of negative ions formation of dipeptides glycyl-glycine, glycyl-alanine and alanyl-alanine in the conditions of resonant electron capture have been studied with a help of negative ions mass spectrometry. Using a thermochemical approach, the main channels of fragment negative ions formation were found and the structure of the ions were established. The isobaric ions have been identified by the experiments with high mass resolution. The cross sections of fragment ions formation were measured. The metastable fragmentation of [M-H](-) and [M-COOH](-) ions in the energy range 4.5-7.5 eV have been found.