Hemoproteins free radical mechanism

A quarter of a century has passed since the first contribution on catalase to The Enzymes Enzyme substrate compounds Mechanism of action of hydroperoxidases (I). In this perspective, we can identify a sequence of steps in the development of ideas on the mechanism of enzymic action and the nature of enzyme-substrate compounds. The identification of these compounds and the approach to enzymic reactions at concentrations stoichiometric with the substrate caused a principal transition of viewpoint on hemoprotein catalysis from free radical mechanisms (2) unrelated to an active center toward the acceptance of catalysis occurring at the iron atom of the porphyrin (S-5). The latter concept followed natu-... 

The Applicability of These Free Radical Mechanisms in the Hemoprotein Reactions. 415... 

Many experimental studies now support a free radical mechanism for these reactions of ionic iron, and it is the main theme of the report to examine the data on the hemoprotein reactions to see whether similar reaction mechanisms are first of all possible and if so whether there is evidence that the reactions do proceed in this way. 

The evidence for the free radical mechanisms of the reaction between ferrous and ferric ions and hydrogen peroxide is fully discussed in the article by J. H. Baxendale in this volume, and it is necessary here only to summarize and comment on those features especially relevant to hemoprotein reactions. This evidence is essentially indirect. Experiment shows very reactive intermediates to be present and extensive kinetic studies reveal competition reactions for these intermediates in that the overall order of the reaction is found to depend on the reactant concentrations. A free radical mechanism is adopted because it accounts for the chemical reactivity of the system in the oxidation of substrates (Fenton s reaction) and the initiation of the polymerization of vinyl compounds (Baxendale, Evans, and Park, 84) and it provides a set of reactions which largely account for the observed kinetics. The set of reactions which fit best the most recent experimental data is that proposed by Barb, Baxendale, George, and Hargrave (83) ... 

In the absence of direct proof of a valency change or free radical intermediates participating, it is valuable to survey the data on the reactions of ionic iron in similar systems and then examine the possibility of similar mechanisms occurring in hemoprotein reactions. 

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