Mechanistic and Kinetic Study on the Reactions of Coumaric Acids with Reactive Oxygen Species: A DFT Approach

The mechanism and kinetics of reactions between coumaric acids and a series of reactive oxygen species (•OX) was studied through the density functional theory (DFT). H atom abstraction from −OH and −COOH groups and addition to the nonaromatic double bond were the most representative reaction pathways chosen for which free energy barriers and rate constants were calculated within the transition state theory (TST) framework. From these calculations, it was estimated that •OH > •OCH3 > •OOH > •OOCH3 is the order of reactivity of •OX with any coumaric acid. The highest rate constant was estimated for p-coumaric acid + •OH reaction, whereas the rest of the •OX species are more reactive with o-coumaric acid. On the basis of the calculated rate constants, H abstraction from a −OH group should be the main mechanism for the reactions involving •OCH3, •OOH, and •OOCH3 radicals. Nevertheless, the addition mechanism, which sometimes is not considered in theoretical studies on reactions of phenolic compounds with electrophilic species, could play a relevant role in the global mechanism of coumaric acid + •OH reactions.