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The low volatility and thermal instability made the photoelectron (PE), electron transmission (ET), and dissociative electron attachment (DEA) spectroscopy measurements on curcumin (a potent chemopreventive agent) unsuccessful. The filled and empty electronic structure of curcumin was therefore investigated by exploiting the PES, ETS, and DEAS results for representative fragment molecules and suitable quantum-mechanical calculations. On this basis, a reliable pattern of the vertical ionization energies and electron attachment energies of curcumin was proposed. The frontier molecular orbitals (MOs) are characterized by sizable interaction between the two phenol rings transmitted through the dicarbonyl chain and associated with a remarkably low ionization energy and a negative electron attachment energy (i.e., a largely positive electron affinity), diagnostic of a stable anion state not observable in ETS. The lowest energy electronic transitions of half-curcumin and curcumin and their color change by alkalization were interpreted with time-dependent density functional theory (DFT) calculations. For curcumin, it is shown that loss of a phenolic proton occurs in alkaline ethanolic solution. [ABSTRACT FROM AUTHOR]

The conformational preferences of capsaicin were investigated by using the hybrid meta density functional theory (DFT) method MPWB1K. Its flexible, pendant side chain allows for a multitude of conformations only slightly different in energy. The distinctive vibrational features of the most stable conformers were characterized. To elucidate the most favorable reaction sites of capsaicin for radical scavenging, various homolytic bond-dissociation energies were also calculated. Of the possible radical intermediates, the allyl and benzyl radicals are energetically preferred. The filled and empty electronic structures of capsaicin were investigated by exploiting the photoelectron and electron-transmission spectra also of reference molecules and suitable quantum-mechanical calculations. On this basis, a reliable pattern of the vertical ionization energies and electron-attachment energies of capsaicin was proposed. The frontier π molecular orbitals are concentrated over the vanillyl moiety, with a modest influence of the amidic−aliphatic chain. The (negative) first vertical electron affinity is predicted to be similar to that of benzene. The absorption spectrum of capsaicin and its change by conversion into a phenolic deprotonated anion (modest bathochromic displacement) or a phenoxyl neutral radical (from colorless to red) were interpreted with time-dependent DFT calculations. ESR measurements following chemical or electrochemical reduction of capsaicin did not lead to detection of the corresponding radical anion. The spectra show fragmentation of the original molecule and formation of a variety of radical species which are believed to have a semiquinonic structure. [ABSTRACT FROM AUTHOR]