Physical Sciences and Mathematics Commons^™

Synthesis Of N-Acetyl And C-Tert-Butyl Natural Amino Acid Substrates That Mimic Residues Of Polypeptides And Their Reactivity With [Feiv(O)(N4py)]2+: Kinetic And Mechanistic Investigations, Ashley Ann Campanali

Wayne State University Dissertations

This dissertation is divided into two chapters, the first chapter includes an introduction to reactive oxygen species and their reactions with proteins. The introduction also covers metal-based oxidants, including both heme and non-heme enzymes that activate dioxygen as well as complexes that mimic these enzymes. The work discussed in chapter one concerns the synthesis of amino acid substrates that mimic amino acid residues. Substrates synthesized were derived from Gln, Asn, Ile, Cys and Tyr. Once synthesized, these substrates were reacted with [FeIV(O)(N4Py)]2+ under pseudo-first order conditions. The mechanisms for the reactions of the most reactive substrates were investigated. Electron-transfer proton-transfer …