Isomer distribution of hydroxyoctadecadienoates (HODE) and hydroxyeicosatetraenoates (HETE) produced in the plasma oxidation mediated by peroxyl radical, peroxynitrite, hypochlorite, 15-lipoxygenase, and singlet oxygen.
Isomer distribution of hydroxyoctadecadienoates (HODE) and hydroxyeicosatetraenoates (HETE) produced in the plasma oxidation mediated by peroxyl radical, peroxynitrite, hypochlorite, 15-lipoxygenase, and singlet oxygen.
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DOI：
10.1016/j.abb.2017.10.023
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发表时间：
2017-12
影响因子：
3.9
通讯作者：
A. Umeno;M. Morita;Y. Yoshida;Y. Naito;E. Niki
中科院分区：
文献类型：
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作者：
A. Umeno;M. Morita;Y. Yoshida;Y. Naito;E. Niki
游离和酯形式的不饱和脂肪酸和胆固醇在体内被多种氧化剂氧化，产生不同的产物。有些脂质氧化是由酶介导的，选择性地产生特定的产物，而另一些则是随机进行的，产生许多种区域异构体和立体异构体的混合物。抗氧化剂对抗脂质氧化的功效取决于氧化剂的性质，因此氧化剂的鉴定对于理解脂质氧化和抗氧化剂在体内的作用和影响是重要的。在本研究中，氢（佩罗）氧基十八碳二烯酸酯（H（p）ODEs）和氢（佩罗）氧基二十碳四烯酸酯（H（p）ETEs），最丰富的脂质氧化产物中发现的血浆中，产生的过氧自由基，过氧亚硝酸盐，次氯酸盐，15-脂氧合酶，单线态氧氧化的异构体分布进行了检查。结果表明，9-和13-（E，E）-HODE，13（S）-（Z，E）-HODE和10-和12-（Z，E）-HODE分别是自由基，15-脂氧合酶和单线态氧的特异性脂质氧化产物。过氧亚硝酸根产生的HODE的异构体分布与过氧自由基相似，表明过氧亚硝酸根介导的脂质氧化是通过自由基机制进行的。次氯酸盐产生的HODE和HETE非常少。HODE可能是比HETE更好的生物标志物，因为亚油酸酯的氧化机制比花生四烯酸酯更简单，并且所有HODE异构体都可以更容易地定量。这些产品可用作特异性生物标志物，用于识别负责任的氧化剂，并用于评估氧化剂特异性脂质氧化水平和抗氧化剂在体内的作用。
Free and ester forms of unsaturated fatty acids and cholesterol are oxidized in vivo by multiple oxidants to give diverse products. Some lipid oxidation is mediated by enzymes to selectively give specific products, while others proceed randomly to produce mixtures of many kinds of regioisomers and stereoisomers. The efficacy of antioxidants against lipid oxidation depends on the nature of the oxidants and therefore the identification of oxidant is important for understanding the roles and effects of lipid oxidation and antioxidants in vivo. In the present study, the isomer distribution of hydro(pero)xyoctadecadienoates (H(p)ODEs) and hydro(pero)xyeicosatetraenoates (H(p)ETEs), the most abundant lipid oxidation products found in human plasma, produced in the oxidation of plasma by peroxyl radicals, peroxynitrite, hypochlorite, 15-lipoxygenase, and singlet oxygen were examined. It was shown that 9- and 13-(E,E)-HODEs, 13(S)-(Z,E)-HODE, and 10- and 12-(Z,E)-HODEs were specific lipid oxidation products by free radical, 15-lipoxygenase, and singlet oxygen, respectively. The isomer distribution of HODEs produced by peroxynitrite was similar to that by peroxyl radical, suggesting that the peroxynitrite mediated lipid oxidation proceeds by free radical mechanisms. The production of HODEs and HETEs by hypochlorite was very small. HODEs may be a better biomarker than HETEs since linoleates are oxidized by simpler mechanisms than arachidonates and all the HODEs isomers can be quantified more easily. These products may be used as specific biomarkers for the identification of responsible oxidants and for the assessment of oxidant-specific lipid oxidation levels and effects of antioxidants in vivo.