Characterization of 4-oxo-2-nonenal as a novel product of lipid peroxidation
Characterization of 4-oxo-2-nonenal as a novel product of lipid peroxidation
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DOI：
10.1021/tx000101a
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发表时间：
2000-08-01
影响因子：
4.1
通讯作者：
Blair, IA
中科院分区：
文献类型：
--
作者：
Lee, SH;Blair, IA
Fe-II介导的13-[S-（Z，E）]-9，11-氢过氧十八碳二烯酸（氢过氧亚油酸）的分解导致三种α，β-不饱和醛的形成。在低Fe-II浓度下或在加入Fe-II后的早期时间点，观察到两种主要产物。极性最小的产物具有与4-氧代-2-壬烯醛相同的色谱性质。用盐酸羟胺将该产物转化为其双肟衍生物，得到两种顺式和两种反式肟异构体，其色谱和质谱性质与衍生自真实标准品4-氧代-2-壬烯醛的产物的性质相同。这首次证实4-氧代-2-壬烯醛是Fe-II介导的脂质氢过氧化物分解的主要产物，极性更强的产物具有与4-氢过氧基-2-壬烯醛类似的色谱性质。其顺式和反式肟异构体的LC/MS分析证实了这种结构归属，因此，4-氢过氧基-2-壬烯醛是以前未认识到的脂质氢过氧化物分解的主要产物。在高Fe-II浓度和较长的孵育时间，第三个更极性的产品，观察到与4-羟基-2-壬烯醛的色谱特性相同。顺式和反式肟异构体的色谱和质谱性质与源自4-羟基-2-壬烯醛的真实标准品的产物的性质相同。似乎最初形成4-氢过氧基-2-壬烯醛，然后在高Fe-II浓度存在下或通过在低Fe-II浓度存在下延长孵育将其转化为4-羟基-2-壬烯醛。可以想象，一些4-氢过氧基-2-壬烯醛也转化为4-氧代-2-壬烯醛。然而，我们不能排除它也是由13-[S-（Z，E）]-9，11-氢过氧十八碳二烯酸的重排产物通过协同机制形成的可能性。
Fe-II-mediated decomposition of 13-[S-(Z,E)]-9,11-hydroperoxyoctadecadienoic (hydroperoxylinoleic) acid resulted in the formation of three alpha,beta-unsaturated aldehydes. At low Fe-II concentrations or at early time points after the addition of Fe-II, two major products were observed. The least polar product had chromatographic properties that were identical with those of 4-oxo-2-nonenal. Conversion of this product to its bis-oxime derivative with hydroxylamine hydrochloride resulted in two syn- and two anti-oxime isomers that had chromatographic and mass spectral properties identical with the properties of products derived from an authentic standard of 4-oxo-2-nonenal, This confirmed for the first time that 4-oxo-2-nonenal is a major product of the Fe-II-mediated breakdown of lipid hydroperoxides, The more polar product had chromatographic properties that were similar to those of 4-hydroperoxy-2-nonenal. LC/MS analysis of its syn- and anti-oxime isomers confirmed this structural assignment, Thus, 4-hydroperoxy-2-nonenal is a previously unrecognized major product of lipid hydroperoxide decomposition. At high Fe-II concentrations and at longer incubation times, a third more polar product was observed with chromatographic properties that were identical to those of 4-hydroxy-2-nonenal. The syn- and anti-oxime isomers had chromatographic and mass spectral properties identical with the properties of products derived from an authentic standard of 4-hydroxy-2-nonenal. It appears that 4-hydroperoxy-2-nonenal is formed initially and that it is then converted to 4-hydroxy-2-nonenal in the presence of high Fe-II concentrations or by extended incubations in the presence of low Fe-II concentrations. It is conceivable that some of the 4-hydroperoxy-2-nonenal is also converted to 4-oxo-2-nonenal. However, we cannot rule out the possibility that it is also formed by a concerted mechanism from a rearrangement product of 13-[S-(Z,E)]-9,11-hydroperoxyoctadecadienoic acid.