Control of the generation and reactions of free radicals in biological systems by kinetic and thermodynamic factors.

Quantifiable redox properties are useful predictors of substrate reactivity in enzyme-catalysed redox reactions of e.g. nitroreductases or peroxidases. Redox properties may also control the rates of electron-transfer reactions between radical products of reduction and oxidation, and endogenous oxidants and reductants respectively. However, in numerous instances prototropic properties of substrate or radical may have profound kinetic consequences, protonation of radicals frequently slowing down electron-transfer reactions. Further, reactions which are thermodynamically extremely unfavourable may still proceed if radical products are removed from the pre-equilibrium efficiently. Thus kinetic considerations often outweigh the purely thermodynamic viewpoint.