Kinetic model for the antiradical activity of the isolated p-catechol group in flavanone type structures using the free stable radical 2,2-diphenyl-1-picrylhydrazyl as the antiradical probe.

The time evolution of 2,2-diphenyl-1-picrylhydrazyl radical (DPPH*) concentration in four solvents (methanol, ethanol, propanol, and acetonitrile) during its reduction by three flavanones containing an isolated p-catechol group (taxifolin, eriodyctiol, and fustin) as well as the time evolution of the mass spectra of the reaction mixture has been determined by spectrophotometry and liquid mass spectrometry, respectively. In alcoholic solvents the reduction curves consisted of an initial short but fast kinetics step followed by a longer slow kinetics step; in contrast, in acetonitrile the reduction curves completely lacked the slow kinetics step. From the results, a kinetic model for the reaction of reduction of the DPPH* by the isolated p-catechol group in flavanone type structures is proposed. According to this model, the p-catechol group rapidly transfers two hydrogen atoms to DPPH*, through a fast rate constant k1, yielding the corresponding o-quinone. Then, the intermediate o-quinone forms an adduct with the alcoholic solvent, through a slow rate constant k2, and regenerates the p-catechol group. The regenerated p-catechol group reduces additional DPPH* through a fast rate constant k3, yielding the corresponding o-quinone, which can form a new adduct with the solvent to regenerate the p-catechol group, and so on. From the kinetics model, two explicit kinetics equations have been derived that fit very well the experimental data points acquired from all assayed compounds in all of the experiments carried out, thus allowing an accurate determination of the corresponding rate and stoichiometric constants.