Nitration of unsaturated fatty acids is a (patho)physiologically important pathway of lipid modification induced by nitric oxide-derived species. We report herein on the unexpected chain rearrangement undergone by (13S,9Z,11E)-13-hydroxyoctadeca-9,11-dienoic acid (1), a linoleic acid metabolite, when exposed to nitrating agents of biological relevance. At pH 7.4 and at room temperature, reaction of 1 with peroxynitrite (ONOO-) as well as Fe2+-EDTA/H2O2/NO2- and horseradish peroxidase/H2O2/NO2- led to the formation of two nitration products, which could be isolated as the methyl esters and were identified as diastereoisomeric methyl (12S)-10,11-epoxy-12-hydroxy-9-nitromethylheptadecanoates by extensive 1H, 13C, 15N NMR and MS analysis.

中文翻译：

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亚油酸代谢物13-羟基十八碳二烯酸的仿生硝化：新型链重排的环氧硝基衍生物的分离和光谱表征。

不饱和脂肪酸的硝化是一氧化氮衍生物种引起的脂质修饰的（病理）生理重要途径。我们在这里报道了当暴露于具有生物相关性的硝化剂时，（13S，9Z，11E）-13-羟基十八烷基-9,11-二烯酸（1），一种亚油酸代谢产物发生的意外的链重排。在pH 7.4和室温下，1与过氧亚硝酸盐（ONOO-）以及Fe2 + -EDTA / H2O2 / NO2-和辣根过氧化物酶/ H2O2 / NO2-的反应导致形成两个硝化产物，可以将其分离为通过大量的1H，13C，15N NMR和MS分析，将其鉴定为非对映异构体甲基（12S）-10,11-环氧-12-羟基-9-硝基甲基庚二酸酯。