Direct detection of peroxyl radicals formed in the reactions of metmyoglobin and methaemoglobin with t-butyl hydroperoxide. 1989

M J Davies
Department of Chemistry, University of York, Heslington, U.K.

The reaction of metmyoglobin and methaemoglobin with t-butyl hydroperoxide has been investigated using stopped-flow e.s.r. spectroscopy. The major species observed immediately after mixing has been identified as the basis of its g value (2.014) and line width as being due to a peroxyl radical. The detection of this species under anaerobic conditions suggests that this species is the t-butyl peroxyl radical rather than a secondary species. The immediate observation of this species on mixing suggests that this species is arising via a reaction involving the intact haem moiety rather than via 'free iron' produced via oxidative damage. Detection of a second, oxygen-dependent, species, which is formed at a slower rate, in the metmyoglobin reaction suggests that the initial peroxyl radical subsequently reacts with the protein to give a protein-derived radical.

UI MeSH Term Description Entries
D008706 Methemoglobin Ferrihemoglobin
D008786 Metmyoglobin Myoglobin which is in the oxidized ferric or hemin form. The oxidation causes a change in color from red to brown. Ferrimyoglobin
D010545 Peroxides A group of compounds that contain a bivalent O-O group, i.e., the oxygen atoms are univalent. They can either be inorganic or organic in nature. Such compounds release atomic (nascent) oxygen readily. Thus they are strong oxidizing agents and fire hazards when in contact with combustible materials, especially under high-temperature conditions. The chief industrial uses of peroxides are as oxidizing agents, bleaching agents, and initiators of polymerization. (From Hawley's Condensed Chemical Dictionary, 11th ed) Peroxide
D011190 Potassium Cyanide A highly poisonous compound that is an inhibitor of many metabolic processes, but has been shown to be an especially potent inhibitor of heme enzymes and hemeproteins. It is used in many industrial processes. Potassium Cyanide (K(14)CN),Potassium Cyanide (K(C(15)N)),Cyanide, Potassium
D002621 Chemistry A basic science concerned with the composition, structure, and properties of matter; and the reactions that occur between substances and the associated energy exchange.
D004578 Electron Spin Resonance Spectroscopy A technique applicable to the wide variety of substances which exhibit paramagnetism because of the magnetic moments of unpaired electrons. The spectra are useful for detection and identification, for determination of electron structure, for study of interactions between molecules, and for measurement of nuclear spins and moments. (From McGraw-Hill Encyclopedia of Science and Technology, 7th edition) Electron nuclear double resonance (ENDOR) spectroscopy is a variant of the technique which can give enhanced resolution. Electron spin resonance analysis can now be used in vivo, including imaging applications such as MAGNETIC RESONANCE IMAGING. ENDOR,Electron Nuclear Double Resonance,Electron Paramagnetic Resonance,Paramagnetic Resonance,Electron Spin Resonance,Paramagnetic Resonance, Electron,Resonance, Electron Paramagnetic,Resonance, Electron Spin,Resonance, Paramagnetic
D006418 Heme The color-furnishing portion of hemoglobin. It is found free in tissues and as the prosthetic group in many hemeproteins. Ferroprotoporphyrin,Protoheme,Haem,Heme b,Protoheme IX
D006420 Hemeproteins Proteins that contain an iron-porphyrin, or heme, prosthetic group resembling that of hemoglobin. (From Lehninger, Principles of Biochemistry, 1982, p480) Hemeprotein,Heme Protein,Heme Proteins,Protein, Heme,Proteins, Heme
D055598 Chemical Phenomena The composition, structure, conformation, and properties of atoms and molecules, and their reaction and interaction processes. Chemical Concepts,Chemical Processes,Physical Chemistry Concepts,Physical Chemistry Processes,Physicochemical Concepts,Physicochemical Phenomena,Physicochemical Processes,Chemical Phenomenon,Chemical Process,Physical Chemistry Phenomena,Physical Chemistry Process,Physicochemical Phenomenon,Physicochemical Process,Chemical Concept,Chemistry Process, Physical,Chemistry Processes, Physical,Concept, Chemical,Concept, Physical Chemistry,Concept, Physicochemical,Concepts, Chemical,Concepts, Physical Chemistry,Concepts, Physicochemical,Phenomena, Chemical,Phenomena, Physical Chemistry,Phenomena, Physicochemical,Phenomenon, Chemical,Phenomenon, Physicochemical,Physical Chemistry Concept,Physicochemical Concept,Process, Chemical,Process, Physical Chemistry,Process, Physicochemical,Processes, Chemical,Processes, Physical Chemistry,Processes, Physicochemical
D020122 tert-Butylhydroperoxide A direct-acting oxidative stress-inducing agent used to examine the effects of oxidant stress on Ca(2+)-dependent signal transduction in vascular endothelial cells. It is also used as a catalyst in polymerization reactions and to introduce peroxy groups into organic molecules. t-Butyl Hydroperoxide,tert-Butyl Hydroperoxide,t-Butylhydroperoxide,tertiary-Butylhydroperoxide,Hydroperoxide, t-Butyl,Hydroperoxide, tert-Butyl,t Butyl Hydroperoxide,t Butylhydroperoxide,tert Butyl Hydroperoxide,tert Butylhydroperoxide,tertiary Butylhydroperoxide

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