title: Reactivity of ubiquinone and ubiquinol with superoxide and the hydroperoxyl radical: implications for in vivo antioxidant activity.
abstract: Endogenous ubiquinones (UQ) such as coenzyme Q(10) are essential electron carriers in the mitochondrial respiratory chain, and the reduced ubiquinol form (UQH(2)) is a chain-breaking antioxidant, decreasing oxidative damage caused by lipid peroxidation within mitochondria. Consequently, exogenous UQ are used as therapies to decrease mitochondrial oxidative damage. The proximal radical produced during mitochondrial oxidative stress is superoxide (O(2)(.-)) and the reaction between UQ and O(2)(.-) to form the ubisemiquinone radical anion (UQ(.-)) may also be important for the scavenging of O(2)(.-) by exogenous UQ. The situation in vivo is that many UQ are predominantly located in the hydrophobic membrane core, from which O(2)(.-) will be excluded but its conjugate acid, HOO(.), can enter. The reactivity of UQ or UQH(2) with HOO(.) has not been reported previously. Here a pulse radiolysis study on the reactions between UQ/UQH(2) and O(2)(.-)/HOO(.) in water and in solvent systems mimicking the surface and core of biological membranes has been undertaken. O(2)(.-) reacts very rapidly with UQ, suggesting that this may contribute to the scavenging of O(2)(.-) in vivo. In contrast, UQH(2) reacts relatively slowly with HOO(.), but rapidly with other oxygen- and carbon-centered radicals, indicating that the antioxidant role of UQH(2) is mainly in preventing lipid peroxidation.
authors.affiliation: Department of Chemistry, The University of Auckland, New Zealand.
authors.forename: Andrej
authors.initials: A
authors.lastname: Maroz
authors.forename: Robert F
authors.initials: RF
authors.lastname: Anderson
authors.forename: Robin A J
authors.initials: RA
authors.lastname: Smith
authors.forename: Michael P
authors.initials: MP
authors.lastname: Murphy
mesh_terms: D000975:Antioxidants / Q000737:chemistry*; D019610:Cytoprotection; D004579:Electron Transport / Q000502:physiology; D006861:Hydrogen Peroxide / Q000737:chemistry*; D015227:Lipid Peroxidation; D008928:Mitochondria / Q000502:physiology; D051336:Mitochondrial Membranes / Q000737:chemistry; D008956:Models, Chemical; D018384:Oxidative Stress; D011675:Pulse Radiolysis; D013481:Superoxides / Q000737:chemistry*; D014451:Ubiquinone / Q000031:analogs & derivatives* / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D000975:Antioxidants; D014867:Water; D013481:Superoxides; D014451:Ubiquinone; D006861:Hydrogen Peroxide; C003741:ubiquinol