title: Complex-formation and reduction of ferric iron by 2-oxo-4-thiomethylbutyric acid, and the production of hydroxyl radicals.
abstract: 2-Oxo-4-thiomethylbutyric acid (OMBA) is a widely used oxygen-radical-scavenging agent and has been used for the detection of .OH-like species in a variety of systems. This scavenger reacts with other radicals and is therefore not specific for .OH. Since iron is required in most systems for the generation of OH-like species, studies were carried out to investigate the possible interaction of OMBA with iron. Fe3+ reacted with OMBA to produce complexes that gave rise to discrete spectra. Intense purple complexes, with broad absorbance maxima of 525-550 nm, were found at OMBA/Fe3+ ratios of up to 1:1, whereas red complexes with a prominent shoulder between 440 and 480 nm were found at higher OMBA/Fe3+ ratios. OMBA caused reduction of ferric iron to the ferrous state, as detected with 2,2'-bipyridyl as the indicator. This reduction occurs in the dark, can be photo-accelerated especially by light with wavelengths near the absorbance maximum of the respective complexes, and is increased as the OMBA/Fe3+ ratio is elevated. The presence of phosphate buffer quenches the purple and red ferric-ion-OMBA complexes and lowers the rate of reduction of Fe3+ by OMBA about 10-fold. The resulting ferrous-ion-OMBA-phosphate complex is very stable against autoxidation. Both the ferrous-ion-OMBA and ferric-ion-OMBA complexes reacted with H2O2, with the subsequent production of ethylene gas from OMBA. The interaction with H2O2 resulted in discrete spectral changes of both the ferrous-ion-OMBA and ferric-ion-OMBA complexes. The ferrous-ion-OMBA/H2O2 or ferric-ion-OMBA/H2O2 system appeared to produce .OH free radicals via a Fenton-type of reaction since ethylene production was inhibited by competitive OH scavengers. Ferrous-ion-OMBA complex reacted with H2O2 not only to produce ethylene from the OMBA, but also to promote the oxidation of another scavenger, ethanol. The ability of OMBA to chelate iron, to promote reduction of ferric iron and to react with H2O2 to produce potent oxidizing radicals may play a role in the lack of specificity of OMBA as a scavenger of oxygen radicals.
mesh_terms: D000431:Ethanol / Q000494:pharmacology; D005290:Ferric Compounds / Q000378:metabolism*; D005609:Free Radicals; D006861:Hydrogen Peroxide / Q000378:metabolism; D006878:Hydroxides / Q000378:metabolism; D007501:Iron / Q000378:metabolism*; D046911:Macromolecular Substances; D008715:Methionine / Q000031:analogs & derivatives* / Q000378:metabolism; D009942:Organometallic Compounds / Q000378:metabolism*; D010084:Oxidation-Reduction; D010710:Phosphates; D010775:Photic Stimulation; D013053:Spectrophotometry
chemical_list: D005290:Ferric Compounds; D005609:Free Radicals; D006878:Hydroxides; D046911:Macromolecular Substances; D009942:Organometallic Compounds; D010710:Phosphates; D000431:Ethanol; C014632:2-keto-4-methylthiobutyric acid; D008715:Methionine; D006861:Hydrogen Peroxide; D007501:Iron