Xanthones as antioxidants: a theoretical study on the thermodynamics and kinetics of the single electron transfer mechanism

Abstract

Mangosteen (Garcinia mangostana) is considered the queen of the tropical fruits. It has a dark red pericarp that is rich in bioactive compounds including xanthones, which have been classified as very good antioxidants from several experimental results. In this work, the antioxidant properties of twenty xanthones isolated from the pericarp of Garcinia mangostana are studied considering the single electron transfer mechanism (SET). According to their most acidic pK(a) value, under physiological conditions the monoanionic form is present in significant amounts. For this reason, eight deprotonated xanthones are also considered in this study. Quantum chemical calculations were performed in order to assess their free radical scavenging capacity in terms of vertical ionization energies and vertical electron affinities. With these two chemical descriptors it is possible to construct a map that allows a straightforward comparison of the electron transfer viability between any pair of reactants. Such a map for the studied xanthones and the free radicals ˙OH and O(2)˙(-), in aqueous solution, indicates that xanthones can either donate or accept electrons in order to deactivate free radicals. A new relationship between the ionization potential and the electron affinity is proposed to predict the thermochemical viability of the SET processes. The electron transfer reactions between xanthones and ˙OH or O(2)˙(-) are endergonic and, therefore, thermodynamically unfeasible. However, the reaction of deprotonated xanthones with ˙OH is exergonic. Thus, the deprotonated xanthones are more reactive than the neutral species through the SET mechanism. The monoanions of xanthones, which are present under physiological conditions were found to react with ˙OH at diffusion-limited rates.