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Increased understanding of the role of mitochondria under physiological and pathological conditions parallels increased exploration of synthetic and natural compounds able to mimic MnSOD — endogenous mitochondrial antioxidant defense essential for the existence of virtually all aerobic organisms from bacteria to humans. This review describes most successful mitochondrially-targeted redox-active compounds, Mn porphyrins and MitoQ₁₀ in detail, and briefly addresses several other compounds that are either catalysts of O₂⁻ dismutation, or its non-catalytic scavengers, and that reportedly attenuate mitochondrial dysfunction. While not a true catalyst (SOD mimic) of O₂⁻ dismutation, MitoQ₁₀ oxidizes O₂⁻ to O₂ with a high rate constant. In vivo it is readily reduced to quinol, MitoQH₂, which in turn reduces ONOO⁻ to NO₂, producing semiquinone radical that subsequently dismutes to MitoQ₁₀ and MitoQH₂ …