Autooxidation of docosahexaenoic acid: analysis of ten isomers of hydroxydocosahexaenoate.
Autooxidation of docosahexaenoic acid: analysis of ten isomers of hydroxydocosahexaenoate.
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发表时间：
1984-05
影响因子：
6.5
通讯作者：
M. Vanrollins;R. Murphy
中科院分区：
文献类型：
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作者：
M. Vanrollins;R. Murphy
二十二碳六烯酸，一种n-3必需脂肪酸，最近被证明是由血小板，嗜碱性粒细胞和肝微粒体酶转化为含有烯丙基羟基共轭二烯的代谢产物。为了帮助鉴定这些代谢物，通过二十二碳六烯酸的自氧化制备标准品。通过反相和正相高效液相色谱（HPLC）分离后，用毛细管气相色谱、紫外光谱和质谱鉴定了二十二碳六烯酸的10个羟基异构体。根据这些研究和报告的亚油酸、亚麻酸和花生四烯酸衍生的类似代谢物的洗脱顺序，两种基本HPLC洗脱模式变得明显。在反相色谱条件下，反式双键与羧基的距离是确定洗脱顺序的关键参数。在反丁烯二酸色谱条件下，羟基与甲氧羰基的距离似乎决定了洗脱顺序。羟基酸的反相和正相HPLC之间选择性的显著差异为鉴别内源性代谢物提供了有用的关键信息。
Docosahexaenoic acid, an n-3 essential fatty acid, was recently shown to be enzymically converted by platelets, basophils, and liver microsomes into metabolites containing conjugated dienes with allylic hydroxyl groups. To help identify these metabolites, standards were prepared by autooxidation of docosahexaenoic acid. After isolation by reverse phase and normal phase high performance chromatography (HPLC), ten hydroxy isomers of docosahexaenoic acid were identified by capillary gas-liquid chromatography, ultraviolet spectroscopy, and mass spectrometry. From these studies and reported elution orders for similar metabolites derived from linoleic, linolenic, and arachidonic acids, two basic HPLC elution patterns became apparent. Under reverse phase chromatography conditions, the distance of the trans-double bond from the carboxyl group was the critical parameter in determining the elution order. Under silicic acid chromatography conditions, the distance of the hydroxyl from the carbomethoxy group seemed to determine the elution order. The dramatic difference in selectivity between reverse and normal phase HPLC of the hydroxy acids provides critical information useful for identifying endogenous metabolites.