A Continuous Visible Light Spectrophotometric Approach To Accurately Determine the Reactivity of Radical-Trapping Antioxidants.

Abstract

Inhibited autoxidations-monitored either by O2 consumption or hydroperoxide formation-are the most reliable way to obtain kinetic and stoichiometric information on the activity of radical-trapping antioxidants (RTAs). While many comparatively simple "antioxidant assays" (e.g., the DPPH assay) have supplanted these in popularity, they are generally very poor substitutes since they often do not employ peroxyl radicals as the oxidant and do not account for both the kinetics and stoichiometry of the radical-trapping reaction(s). In an effort to make inhibited autoxidations as simple as the most popular "antioxidant assays", we have developed a spectrophotometric approach for monitoring reaction progress in inhibited autoxidations. The approach employs easily prepared 1-phenylbutadiene-conjugated or styrene-conjugated BODIPY chromophores (PBD-BODIPY or STY-BODIPY, respectively) as signal carriers that co-autoxidize along with a hydrocarbon substrate. We show that inhibition rate constants (kinh) are accurately determined for a range of phenolic and diarylamine RTAs using this approach and that mechanistic experiments, such as kinetic isotope effects and kinetic solvent effects, are equally easily carried out. Moreover, synergistic interactions between RTAs, as well as the unconventional activity of diarylamine RTAs, are captured using this methodology. Lastly, we show that the approach can be employed for monitoring reactions in aqueous solution.