Oxidation of metal ions

Measurements of absolute rate constants for the reduction and oxidation of metal ions by e, H- and OH- has been a prominent achievement of the technique of pulse radiolysis. This subject is too broad to be included in this review and is to be dealt with later in the series. A key reference is given, however, to help cover the interim period. 

Michael Anbar For two years I have been interested in the redox changes in ligands owing to the oxidation of metal ions. Since I could not find a review of the developments in this field, I decided to systematize the available material on this type of reaction myself. 

It is usually believed that NO inhibits enzymes by reacting with heme or nonheme iron or copper or via the S-nitrosilation or oxidation of sulfhydryl groups, although precise mechanisms are not always evident. By the use of ESR spectroscopy, Ichimori et al. [76] has showed that NO reacts with the sulfur atom coordinated to the xanthine oxidase molybdenum center, converting xanthine oxidase into a desulfo-type enzyme. Similarly, Sommer et al. [79] proposed that nitric oxide and superoxide inhibited calcineurin, one of the major serine and threonine phosphatases, by oxidation of metal ions or thiols. 

The electrochemical oxidation of metal ions (e.g., Ag+ - Ag2+) for the catalytic oxidation of organic compounds has been practiced on a small scale.24 The feasibility of recycling Cr3+ produced from Cr6+ in the Marker degradation of diosgenin acetate is outlined in Chapter 11. 

The oxidation of metallic ions in aqueous solutions by X-rays has been studied extensively.17 In these and other reactions it is necessary to remove dissolved air and other impurities from the water in order to study the primary reaction. Fricke18 found that even after chemical purification and passage of the water vapor... 

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