An experimental and theoretical study of the reactivity of selected catecholamines and their precursors towards ascorbyl radical

Abstract

Ascorbyl radical is often used as a biomarker of oxidative stress in human organism. It is a product of the antioxidant activity of ascorbic acid and it is not expected to react further with biologically important molecules. For the first time, the reactivity of catecholamines and their precursors was investigated theoretically and experimentally towards ascorbyl radical and the main structural parameters governing activity were analyzed. It was shown that catechol moiety plays an important role, which classifies norepinephrine and 3,4-dihydroxyphenylacetic acid as the most reactive when compared to homovanillic acid, vanillylmandelic acid, and octopamine. DFT methods have been employed to determine the most probable mechanism of the reaction. Based on the change in reaction enthalpy it was concluded that Hydrogen Atom Transfer (HAT) is a preferred mechanism both in water and pentyl ethanoate. The stabilization interactions in ascorbic acid, its anion and radical are carefully analyzed in order to understand the preferability of the mentioned mechanism. The stability of the ascorbyl radical is explained in detail. The results prove that ascorbyl radical is not just a product of antioxidant activity, but also a potentially harmful species in an organism.