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  • Title: Mechanistic aspects of the Fenton reaction under conditions approximated to the extracellular fluid.
    Author: Freinbichler W, Tipton KF, Corte LD, Linert W.
    Journal: J Inorg Biochem; 2009 Jan; 103(1):28-34. PubMed ID: 18848726.
    Abstract:
    The Fenton reaction was investigated, in a medium approximating to that of the extracellular fluid (ECF), by rapid-mixing stopped flow experiments and HPLC analysis using sodium terephthalate (TA(2-)). The reactive intermediate of the Fenton reaction hydroxylates the essentially nonfluorescent, TA(2-) to the brilliant fluorophor 2-hydroxy-terephthalate (OH-TA), which allows the Fenton reaction to be monitored in stopped-flow experiments. There was no artefactual quenching of the fluorescence by substances present in the Fenton-reaction mixture or in the artificial cerebrospinal fluid (aCSF) that might have influenced OH-TA quantification. A mathematical model based on kinetic considerations was developed. This explains the observed independence of the OH-TA concentration on the amount of TA(2-) present in aCSF as well as its dependence on TA(2-) concentration in potassium acetate buffer. A mechanism based on this model, involving complex formation between Fe(II), TA(2-) and H(2)O(2), followed by an intra-molecular hydroxylation accompanied by an intra-molecular electron transfer was developed. The results are consistent with a reactive intermediate, which causes oxidative stress in vivo, not being a free hydroxyl radical, but a ferryl species or a "crypto" radical. The biological implications of these results are discussed.
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