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Here is an extract on one of my prior discussion of Fenton-type reactions proceeding from in situ formed H2O2, to quote:
"Well, let's start with some possible Fenton based reactions creating the hydroxyl radicals, .OH and the superoxide anion, .O2- . As a reference, see,
for example, "Generation of Hydroxyl Radicals from Dissolved Transition Metals in Surrogate Lung Fluid Solutions" by Edgar Vidrio, et al at http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2626252/ . Cited reactions :
Cu(l)/Fe(II) + O2(aq) → Cu(ll)/Fe(III) + .O2-
As an alternate reference for the above reaction (which I have personally performed on Cuprous citrate using an air pump from an old fish tank), see
for example, https://books.google.com/books?id=WjReuSXxl4YC&pg=PA17&a...
The reaction chain continues as:
Cu(l)/Fe(II) + .O2- +2 H+ → Cu(ll)/Fe(III) + HOOH
Cu(l)/Fe(II) + HOOH → Cu(ll)/Fe(III) + .OH + OH-
Net of the last three reactions:
3 Cu(l)/Fe(II) + O2(aq) +2 H+ → 3 Cu(ll)/Fe(III) + .OH + OH-
And, in the presence of sunlight (or a reductant like Citric or Ascorbic acid), a cyclic reaction could ensue in the case of sunlight:
Cu(ll)/Fe(lll) (aq) + hv → Cu(l)/Fe(ll) (aq) + HO• + H+ "
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[Edited on 11-11-2017 by AJKOER][/rquote]
An added quote from the Vidrio's work detailing the limited recycling ability of citrate (and ascorbate):
“Similar reactions can occur with Cu, Cr and Ni. Furthermore, biological chelators and reductants can greatly enhance the production of ROS (Burkitt
et al., 1991; Engelmann et al., 2003; Wenk et al., 2001). For example, in the presence of ascorbate (Asc), a biological reductant, the oxidized form
of the transition metal produced by the Fenton reaction can be reactivated (R2 and R3), thus allowing additional ROS to be produced.
Fe(III) + Ascn → Fe(II) + Ascn+1 (R2)
Cu(II) + Ascn → Cu(I) + Ascn+1 (R3) “
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[Edited on 7-10-2018 by AJKOER] |