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Free Radicals in Biology and Medicine$
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Barry Halliwell and John M. C. Gutteridge

Print publication date: 2015

Print ISBN-13: 9780198717478

Published to Oxford Scholarship Online: October 2015

DOI: 10.1093/acprof:oso/9780198717478.001.0001

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Redox chemistry: the essentials

Redox chemistry: the essentials

(p.30) Chapter 2 Redox chemistry: the essentials
Free Radicals in Biology and Medicine

Barry Halliwell

John M.C. Gutteridge

Oxford University Press

This chapter explains the basic chemistry of free radicals and other reactive species (RS), beginning with the concepts of thermodynamically possible reactions, reaction rate, rate constants, activation energy, and reduction potential. The different radical and non-radical RS encountered in biology are described, and how thermodynamics and reduction potentials can be used to predict their reactions. Pulse radiolysis and stopped flow are described as methods to study reaction rates and mechanism. The chapter goes on to explain the methods of laboratory synthesis, properties, and reactions of the major RS, including hydroxyl radical (OH), superoxide ( (O2•−)), carbonate, thiyl and oxysulphur radicals, peroxyl and alkoxyl radicals, singlet O2 (e.g. its production by photosensitization and how this relates to human diseases such as the porphyrias, and how it can be used to treat cancer), nitric oxide, hydrogen peroxide (how its properties explain its importance as a signalling molecule in vivo), hypochlorous acid, peroxynitrite (leading to nitration of biomolecules), nitrosoperoxycarbonate, peroxomonocarbonate, nitrogen dioxide, and ozone. The properties of O2•− (selectively reactive with a few molecules, such as nitric oxide and [Fe-S] clusters in enzymes) and OH (which reacts with everything) are given special attention because of their key roles in biology. The chapter also describes the chemistry of transition metals (especially iron, copper, zinc, and manganese) and how this relates to Fenton-type reactions that produce OH and possibly other reactive species. The ways in which metal ion chelators can affect OH production by Fenton chemistry are described in relation to their biological effects.

Keywords:   Fenton chemistry, hydrogen peroxide, hydroxyl radical, nitric oxide, ozone, peroxynitrite, pulse radiolysis, reduction potential, singlet O2, superoxide

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