PMID: 6978296Dec 1, 1981Paper

Tl2+ and Ag2+ metal-ion-induced oxidation of methionine in aqueous solution. A pulse radiolysis study

International Journal of Radiation Biology and Related Studies in Physics, Chemistry, and Medicine
K O Hiller, K D Asmus

Abstract

Oxidation of methionine by Tl2+ and Ag2+ occurs with bimolecular rate constants of 2.5 x 10(9) and 3.3 x 10(8) mol-1 ls-1, respectively, and lead to sulphur-centred radical cations as primary intermediates. The overall mechanism is in principle the same as for OH. and X2.- (X = halide) induced oxidations with however one significant difference. Thus no oxidation of the amino group by S+. including subsequent decarboxylation is observed for methionine in its zwitterionic form while this readily occurs in the OH. and X2.- initiated mechanism. The reason is suggested to be complexing of the amino function by the metal ions which effectively lowers the reduction potential of the amino group. The sulphur-centred radical cation rather decays by a mostly first-order deprotonation process to yield CH2-S-CH2 approximately and CH3-S-CH approximately radicals of methionine. They absorb with lambda max = 290 mm and epsilon = 3000 +/- 600 mol-1 l cm-1, and exhibit reducing properties.

Citations

Sep 7, 2016·Free Radical Research·Sebastian Barata-VallejoChryssostomos Chatgilialoglu
Aug 20, 2020·The Journal of Physical Chemistry. B·Piotr FilipiakBronislaw Marciniak
Dec 17, 2009·The Journal of Physical Chemistry. a·Pawel B WisniowskiKrzysztof Bobrowski
Jan 26, 2013·The Journal of Physical Chemistry. B·Piotr FilipiakBronislaw Marciniak
Aug 12, 2016·The Journal of Physical Chemistry. B·Piotr FilipiakBronislaw Marciniak

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