ABSTRACT
Genistein isoflavone is shown to exist in two different conformations which are the 90 degrees completely twisted geometry and the 50 degrees less twisted one. Specific interactions with the solvent cage as well as self-association processes seem shifting the isoflavone from the perpendicular conformation towards the less twisted one. The theoretical simulation, using analytical atom-atom pair potential, predicts a self-dimer in a slipped non-sandwich, face to river, perpendicular structure. From the UV-visible photophysics investigations it is revealed that monomeric species cannot exist alone even at very low solute concentration (approximately 10(-6) M), the self-association process occurs already in this concentration range.
Subject(s)
Genistein/chemistry , Phytoestrogens/chemistry , Computer Simulation , Dimerization , Models, Molecular , Molecular Structure , Solvents/chemistry , Spectrophotometry , Spectrophotometry, UltravioletABSTRACT
Room temperature UV-vis absorption spectra of the tautomeric system 3,5-dithio-2,7-dimethyl-[1,2,4]-triazepine in solution, in acetonitrile (CH3CN), are measured at different water volume percentages. The comparison of the obtained measures to the calculated allowed absorption transitions, using ZINDO/S package, reveals the coexistence of all the tautomeric forms in aprotic polar solution with a high dominance of the dithione form. The solute-water hydrogen bond, which seems to be of 1:n-type, favours the dithiol and monothiol conformers to the detriment of the dithione one. Further experimental investigations lead to the result that standing at ambient Laboratory conditions in the dark favours the dithione tautomeric isomer, while standing at indirect sunlight shifts the tautomeric equilibrium away from this species.
