Antioxidant properties of natural and synthetic chromanol derivatives: study by fast kinetics and electron spin resonance spectroscopy.
[structure: see text] Chromanol-type compounds act as antioxidants in biological systems by reduction of oxygen-centered radicals. Their efficiency is determined by the reaction rate constants for the primary antioxidative reaction as well as for disproportionation and recycling reactions of the antioxidant-derived radicals. We studied the reaction kinetics of three novel chromanols: cis- and trans-oxachromanol and the dimeric twin-chromanol, as well as ubichromanol and ubichromenol, in comparison to alpha-tocopherol and pentamethylchromanol. The antioxidant-derived radicals were identified by optical and electron spin resonance spectroscopy (ESR). The kinetics of the primary antioxidative reaction and the disproportionation of the chromanoxyl radicals were assessed by stopped-flow photometry in different organic solvents to simulate the different polarities associated with biomembranes. Furthermore, the reduction of the chromanoxyl radicals by ubiquinol and ascorbate was measured after laser-induced one-electron chromanol oxidation in ethanol and in a micellar system, respectively. The rate constants showed that twin-chromanol had better radical scavenging properties than alpha-tocopherol and a significantly slower disproportionation rate of its corresponding chromanoxyl radical. In addition, the radical derived from twin-chromanol is reduced by ubiquinol and ascorbate at a faster rate than the tocopheroxyl radical. Finally, twin-chromanol can deliver twice as many reducing equivalents, which makes this compound a promising new candidate as artificial antioxidant in biological systems.
Gregor
Wolfgang
W
Research Institute for Pharmacology and Toxicology of Oxygen Radicals, University of Veterinary Medicine Vienna, Vienna, Austria.
Grabner
Gottfried
G
Adelwöhrer
Christian
C
Rosenau
Thomas
T
Gille
Lars
L
D000975:Antioxidants / Q000737:chemistry* / Q000494:pharmacology*; D002839:Chromans / Q000737:chemistry* / Q000494:pharmacology*; D004578:Electron Spin Resonance Spectroscopy; D007700:Kinetics; D015394:Molecular Structure; D010084:Oxidation-Reduction; D024502:alpha-Tocopherol / Q000737:chemistry / Q000494:pharmacology
D000975:Antioxidants; D002839:Chromans; C003740:ubichromenol; C029141:2,2,5,7,8-pentamethyl-1-hydroxychroman; D024502:alpha-Tocopherol