Autoxidation biological role

Misra, H.P. and Fridovich, I. (1972). The role of superoxide anion in the autoxidation of epinephrine and a simple assay for superoxide dismutase. Journal of Biological Chemistry 247 3170-3175. 

Metal ions play an important role as catalysts in many autoxidation reactions and have been considered instrumental in regulating natural as well as industrial processes. In these reactive systems, in particular when the reactions occur under environmental or in vivo biochemical conditions, the metal ions are involved in complicated interactions with the substrate(s) and dioxygen, and the properties of the actual matrix as well as the transport processes also have a pronounced impact on the overall reactions. In most cases, handling and analyzing such a complexity is beyond the capacity of currently available experimental, computational and theoretical methods, and researchers in this field are obliged to use simplified sub-systems to mimic the complex phenomena. When the simplified conditions are properly chosen, these studies provide surprisingly accurate predictions for the real systems. In this paper we review the results obtained in kinetic and mechanistic studies on the model systems, but we do not discuss their broad biological or environmental implications. 

This review is concerned with the quantitative aspects of metal-catalysed oxyradical reactions. As such one will find discussions of structures of metal complexes, rate constants and reduction potentials, not unlike our review of 1985 [34], Two areas related to the role of transition metals in radical chemistry and biology have been reviewed recently these are the metal-ion-catalysed oxidation of proteins [35] and the role of iron in oxygen-mediated toxicities [36]. These topics will not be discussed in detail in this review. Related to this work is a review on the role of transition metals in autoxidation reactions [37]. Additional information can be obtained from Afanas ev s two volumes on superoxide [38,39], This subject is also treated in a more general and less quantitative manner by Halliwell and Gutteridge [40],... 

Radical reactions may play an important role in the biological chemistry of phosphines. As discussed in Sects. 4.1 and 4.2, under certain conditions phosphines can react with dialkyl peroxides, disulphides and thiols by radical pathways rather than ionic mechanism. The autoxidation of phosphines also appears to involve a radical mechanism. For all of these examples the intermediate species is a phosphoranyl radical R4P which contains... 

Thiobarbituric acid (HjTBA) just like its oxa analog, barbituric acid (HjBA), has an important role in biological and medicinal chemistry. Owing to its reactivity with carbonyl compounds (aldehydes/ketones) HgTBA is widely used to determine the extent of the autoxidative spoilage of fats and oils, commonly known as TEA assay [113]. 

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