Aggregation state and pKa values of (E)-resveratrol as determined by fluorescence spectroscopy and UV-visible absorption

Whether or not (E)-resveratrol can be used as a functional ingredient in foods depends on its structure at different concentrations and pH values. For this reason, the aggregation state of (E)-resveratrol at acidic and basic pH is investigated here for the first time. The data show that (E)-resveratrol forms aggregates above a certain critical concentration, and this concentration is lower at acid (12.5 microM at pH 5.5) than at basic pH values (37 microM at pH 10.5). Moreover, although several papers have focused on the effect of the protonation state of (E)-resveratrol on its biological activity, different data concerning the acidic dissociation constants of this natural antioxidant have been reported in the literature. The present paper shows a way of determining the acidic dissociation constants (pKa1 = 8.8, pKa2 = 9.8, pKa3 = 11.4) of (E)-resveratrol in aqueous medium using both absorbance and fluorescence spectroscopy. Furthermore, the spectroscopic study of (E)-resveratrol under different ionization states corresponding to the deprotonation of the hydroxyl groups present in the molecule shows significant differences among the absorbance, excitation, and emission spectra of (E)-resveratrol that have not previously been reported.