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Reaction of chromium(VI) with glutathione or with hydrogen peroxide: identification of reactive intermediates and their role in chromium(VI)-induced DNA damage.

机译:六价铬与谷胱甘肽或过氧化氢的反应:鉴定活性中间体及其在六价铬诱导的DNA损伤中的作用。

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摘要

The types of reactive intermediates generated upon reduction of chromium(VI) by glutathione or hydrogen peroxide and the resulting DNA damage have been determined. In vitro, reaction of chromium(VI) with glutathione led to formation of two chromium(V) complexes and the glutathione thiyl radical. When chromium(VI) was reacted with DNA in the presence of glutathione, chromium-DNA adducts were obtained, with no DNA strand breakage. The level of chromium-DNA adduct formation correlated with chromium(V) formation. Reaction of chromium(VI) with hydrogen peroxide led to formation of hydroxyl radical. No chromium(V) was detectable at 24 degrees C (297 K); however, low levels of the tetraperoxochromium(V) complex were detected at 77 K. Reaction of chromium(VI) with DNA in the presence of hydrogen peroxide produced significant DNA strand breakage and the 8-hydroxydeoxyguanosine adduct, whose formation correlated with hydroxyl radical production. No significant chromium-DNA adduct formation was detected. Thus, the nature of chromium(VI)-induced DNA damage appears to be dependent on the reactive intermediates, i.e. chromium(V) or hydroxyl radical, produced during the reduction of chromium(VI).
机译:已经确定了由谷胱甘肽或过氧化氢还原铬(VI)时产生的反应性中间体的类型以及对DNA的破坏。在体外,铬(VI)与谷胱甘肽的反应导致形成两个铬(V)配合物和谷胱甘肽硫基自由基。当在谷胱甘肽存在下铬(VI)与DNA反应时,获得的铬-DNA加合物没有DNA链断裂。铬-DNA加合物形成的水平与铬(V)的形成相关。铬(VI)与过氧化氢反应导致羟基自由基的形成。在24°C(297 K)下没有检测到铬(V);然而,在77 K时检测到低水平的过氧化铬(V)络合物。在过氧化氢存在下铬(VI)与DNA的反应产生了显着的DNA链断裂和8-羟基脱氧鸟苷加合物,其形成与羟基自由基的产生相关。未检测到明显的铬-DNA加合物形成。因此,铬(VI)诱导的DNA损伤的性质似乎取决于在铬(VI)还原过程中产生的反应性中间体,即铬(V)或羟基自由基。

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