The reaction of methionine with hydroxyl radical: reactive intermediates and methanethiol production
- 393 Downloads
The mechanisms of reaction of methionine with hydroxyl radical are not fully understood. Here, we unequivocally show using electron paramagnetic resonance spin-trapping spectroscopy and GC–FID and GC–MS, the presence of specific carbon-, nitrogen- and sulfur-centered radicals as intermediates of this reaction, as well as the liberation of methanethiol as a gaseous end product. Taking into account the many roles that methionine has in eco- and biosystems, our results may elucidate redox chemistry of this amino acid and processes that methionine is involved in.
KeywordsMethionine Hydroxyl radical EPR GC Free radical Methanethiol
This work was supported by the Ministry of Science of the Republic of Serbia, Grant numbers 173014 and 173017. We are thankful to Mladen Simonović at the Institute of General and Physical Chemistry, University of Belgrade for technical help.
Conflict of interest
The authors declare that they have no conflict of interest.
- Campolo J, De Chiara B, Caruso R, De Maria R, Sedda V, Dellanoce C, Parolini M, Cighetti G, Penco S, Baudo F, Parodi O (2006) Methionine challenge paradoxically induces a greater activation of the antioxidant defence in subjects with hyper- vs. normohomocysteinemia. Free Radic Res 40:929–935PubMedCrossRefGoogle Scholar
- Halliwell B, Gutteridge JMC (2007) Free radicals in biology and medicine. Clarendon, OxfordGoogle Scholar
- Hawkins CL, Davies M (2002) Comparison of 5, 5-dimethyl-1-pyrroline-n-oxide (DMPO) and a new cyclic nitrone spin trap—5-tert-butoxycarbonyl-5-methyl-1-pyrroline-noxide (BMPO) for the trapping of nitrogen-centred radicals. J Curr Top Biophys 26:137–144Google Scholar
- Higgins MI, Mams G, Chen YC, Erdal Z, Forbes RH Jr, Glindemann D, Hargreaves JR, Ewen D, Murthy SN, Novak JT, Witherspoon J (2008) Role of protein, amino acids, and enzyme activity on odor production from anaerobically digested and dewatered biosolids. Water Environ Res 80:127–135PubMedCrossRefGoogle Scholar
- Kell DB (2010) Towards a unifying, systems biology understanding of large-scale cellular death and destruction caused by poorly liganded iron: Parkinson’s, Huntington’s, Alzheimer’s, prions, bactericides, chemical toxicology and others as examples. Arch Toxicol 84:825–889PubMedCrossRefGoogle Scholar
- Miller RA, Buehner G, Chang Y, Harper JM, Sigler R, Smith-Wheelock M (2005) Methionine-deficient diet extends mouse lifespan, slows immune and lens aging, alters glucose, T4, IGF-I and insulin levels, and increases hepatocyte MIF levels and stress resistance. Aging Cell 4:119–125PubMedCrossRefGoogle Scholar
- Taniguchi H, Takagi H, Hatano HJ (1972) Free-radical intermediates in the reaction of the hydroxyl radical with dialkyl sulfoxides. Phys Chem 76:136–138Google Scholar