The phototransformation of sulfaguanidine in water under ultraviolet (UV) radiation was studied experimentally and theoretically. Absorption, fluorescence and fluorescence excitation spectra of the studied substance before and after irradiation were obtained. Under the influence of KrCl excylamp radiation, stained photoproducts were formed. Quantum-chemical analysis of the orbital nature and localization of electronic transitions of complexes of photoproducts with water 1 : 3 reveals great similarity with the spectrum of the complex of the parent compound. The energy of electronic transitions of primary photoproducts decreases that is there is a low-energy shift of transitions S0→S1(ππ) and S0→S3(ππ) of the original molecule to long-wave region of spectrum (260-315 nm) and decrease of intensity of transition S0→S3(ππ) of sulfaguanidine coplex. In the process of irradiation under the action of KrCl excylamp, the transformation of sulfaguanidine, its primary photoproducts and their subsequent interaction with each other and the solvent occur, which leads to the appearance of a colored photoproduct absorbing at λmax = 560 nm.
The absorption and fluorescence spectra of sulfaguanidine, its complexes with hydrogen bonds, and doubly charged cationic forms have been studied experimentally and theoretically. The orbital nature of electronically excited states is established and a theoretical interpretation of the absorption and fluorescence spectra is given. It was shown that the main reason for the anomalously large Stokes shift of fluorescence is the rearrangement of the benzoid structure of the phenyl fragment of sulfaguanidine into a quasi-quinoid one. The influence of the formation of hydrogen bonds and the addition of a proton on the amount of charge transfer between weakly bound fragments of the molecule has been established
The absorption spectra of chloramphenicol aqueous solution were obtained experimentally. The absorption spectra of chloramphenicol isomers and the effect on the spectra of the formation of H-bonded complexes were calculated and interpreted using quantum chemistry methods. Calculation results showed that the absorption spectrum of chloramphenicol by position of bands and their nature is largely determined by the nitrobenzene fragment with little participation of propanol and dichloroacetamide fragments of chloramphenicol. The proton acceptor properties of individual chloramphenicol fragments and the effect of the formation of H-bonded complexes on them have been analyzed.
The results of measuring the luminescence of ambient air and solutions of an organic compound during their irradiation with a high-current pulsed electron beam with an average energy of Ee=170 keV and a duration of 2 ns, generated by the RADAN-303 accelerator, are presented. It is shown that, under such exposure, the transformation of dissolved bisphenol A occurs, which is accompanied by an increase in the absorption coefficient of the solution in the wavelength range of more than 300 nm and, as a consequence, a decrease in the intensity of air luminescence bands with an increase in the number of irradiation pulses. The results showed the degradation of the BPA solution to complete decomposition under the action of an electron beam treatment.
The spectral luminescent properties and photolysis of the ionic forms (neutral, cationic and anionic) of bisphenol A have been studied experimentally and by methods of quantum chemistry. Calculations and experiment have shown that, in comparison with a neutral form, no new absorption bands appear in the absorption spectra of ionic form in the range 200–600 nm. The polar solvent (water) shifts the absorption spectrum bands of ionic forms towards low energies. In this case, the shift of the absorption spectrum of the cation is insignificant, and the shift of the anion is significant with an increase in the intensity of the absorption bands. The low quantum yield of fluorescence of ionic form is explained by the prevalence of the efficiency of singlet-triplet conversion over the efficiency of the radiation channel of decay of the fluorescent state. The low quantum yield of fluorescence of the anionic form is due not only to the effective singlet-triplet conversion, but also to the low efficiency of the radiative decay of the fluorescent state of the anion caused by a change in its orbital nature. Calculations have shown that the potential curves of the excited states of bisphenol A and its ionic forms have a significant potential barrier to photolysis. The increase in the efficiency of the process of photodissociation of the bisphenol A anion is caused by a noticeable decrease in the potential barrier and an increase in the overlap of the absorption spectra of the bisphenol A anion and solar radiation.