Peroxide Reaction Mechanisms

Vanderbilt University, Nashville TN

Investigators

Abstract

With the support of the Organic and Macromolecular Chemistry Program, Professor Ned Porter, of the Department of Chemistry at Vanderbilt University, is studying the mechanism of peroxidation reactions of organic compounds and the chemistry of organic peroxides. New methods for the analysis of peroxides (silver coordination ion spray mass spectrometry coupled to HPLC), coupled with parallel computational analyses, have led to the investigation of dioxiranes, energetically accessible from peroxy acids and their conjugate bases. A new class of compounds, pyri(mi)dinols, will be prepared and studied for their antioxidant properties. New azo compounds that serve as radical initiators will permit the evaluation of these compounds as antioxidants in human low density liposomes. Theory and experiment will together be used to target the development of compounds which will convert a lipid soluble peroxyl radical into a water soluble superoxide radical, thereby acting as agents for the "export" of a free radical chain from an organic lipophilic aggregate into water. Many organic compounds react with molecular oxygen to give peroxide products, a process that has both commercial importance and relevance to human health. Professor Ned Porter, of the Department of Chemistry at Vanderbilt University, is supported by the Organic and Macromolecular Chemistry Program for his study of the mechanism of the chemistry of this process, called autoxidation or peroxidation, and the chemistry of peroxide compounds. His studies also address the inhibition of autoxidation and the study of new antioxidants. Through a combination of calculational and experimental studies, Professor Porter is developing new compounds of potential activity as antioxidants and as agents for the transferral of oxidant activity from the cell membrane, where it causes cellular damage, to water, where the activity may be discharged without causing damage.