Oxidative Damage in Aliphatic Amino Acids and Di- and Tripeptides by the Environmental Free Radical Oxidant NO3 center dot: The Role of the Amide Bond Revealed by Kinetic and Computational Studies

Abstract

Kinetic and computational data reveal a complex behavior of the important environmental free radical oxidant NO3• in its reactions with aliphatic amino acids and di- and tripeptides, suggesting that attack at the amide N-H bond in the peptide backbone is a highly viable pathway, which proceeds through a proton-coupled electron transfer (PCET) mechanism with a rate coefficient of about 1 × 106 M-1 s-1 in acetonitrile. Similar rate coefficients were determined for hydrogen abstraction from the α-carbon and from tertiary C-H bonds in the side chain. The obtained rate coefficients for the reaction of NO3• with aliphatic di- and tripeptides suggest that attack occurs at all of these sites in each..