ABSTRACT

This chapter highlights some key facts necessary to understand the radical reactions of dioxygen and reactive oxygen species (ROS). It focuses on the chemical aspects of ROS rather than the biochemical and biomedical aspects, which have been covered extensively elsewhere. A treatment of the fundamental chemistry should provide a framework for a better understanding of ROS. Dioxygen metabolism provides nature with a paradoxical dilemma. The chapter discusses that the biological catalysts of dioxygen metabolism must use one-electron processes to overcome the singlet-triplet problem. It provides a chemical and mechanistic perspective to aid in thinking about ROS chemistry by the chemical facts and analysis. Autoxidation is the oxidation of carbon-hydrogen bonds in organic molecules by dioxygen. Autoxidation causes considerable degradation in biological systems and in anything that contains oxidizable carbon-hydrogen bonds, i.e., in almost all things made of organic compounds.