Sutton H C, Vile G F, Winterbourn C C
Arch Biochem Biophys. 1987 Aug 1;256(2):462-71. doi: 10.1016/0003-9861(87)90603-5.
Micromolar concentrations of nonchelated ferrous sulfate catalyze a reaction between H2O2 and radiolytically generated paraquat radicals, causing the concurrent oxidation of deoxyribose to thiobarbituric acid reactive products. The oxidation yield per paraquat radical increases with increasing concentration of deoxyribose, and decreases as the instantaneous or steady-state concentration of paraquat radicals is increased, thus explaining previous anomalies in which oxidation was not observed at high paraquat radical concentrations. The process is not mediated by OH. (which gives different products) but is attributed to an oxidizing intermediate resulting from the two electron oxidation of Fe2+ to a peroxo complex, or a derivative of tetravalent iron. Similar but less pronounced concentration dependences occur in the corresponding oxidation of formate or of deoxyribose catalyzed by Fe(EDTA), where at pH 7.3 90% of the pathway is attributed to one electron oxidation of the Fe2+(EDTA) by H2O2, producing OH., while two electron oxidation accounts for the remaining 10%.
微摩尔浓度的非螯合硫酸亚铁催化过氧化氢与辐射产生的百草枯自由基之间的反应，导致脱氧核糖同时氧化为硫代巴比妥酸反应产物。每个百草枯自由基的氧化产率随着脱氧核糖浓度的增加而增加，并随着百草枯自由基的瞬时或稳态浓度的增加而降低，从而解释了之前在高百草枯自由基浓度下未观察到氧化的异常现象。该过程不是由OH·（会产生不同产物）介导的，而是归因于Fe2+双电子氧化为过氧络合物或四价铁衍生物产生的氧化中间体。在Fe(EDTA)催化的甲酸盐或脱氧核糖的相应氧化中也出现了类似但不太明显的浓度依赖性，在pH 7.3时，90%的反应途径归因于H2O2对Fe2+(EDTA)的单电子氧化，产生OH·，而双电子氧化占其余10%。
