Unexpected products of the hypochlorous acid-induced oxidation of oleic acid: A study using high performance thin-layer chromatography-electrospray ionization mass spectrometry.
Unexpected products of the hypochlorous acid-induced oxidation of oleic acid: A study using high performance thin-layer chromatography-electrospray ionization mass spectrometry.
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DOI：
10.1016/j.chroma.2015.11.059
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发表时间：
2016-03
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通讯作者：
J. Schröter;Hans Griesinger;Eyla Reuÿ;M. Schulz;T. Riemer;Rosmarie Süÿ;J. Schiller;B. Fuchs
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文献类型：
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作者：
J. Schröter;Hans Griesinger;Eyla Reuÿ;M. Schulz;T. Riemer;Rosmarie Süÿ;J. Schiller;B. Fuchs
活性氧（ROS）在炎症性疾病的发病机制中起着重要的生理作用。在炎症条件下，髓过氧化物酶产生次氯酸（HOCl），其在氯代醇的形成下添加到（磷酸）脂质的脂肪酰基残基的双键。如果ROS产生超过一定程度，这可能导致许多炎症性疾病的发展，如动脉粥样硬化或关节炎。使用油酸作为最简单的不饱和脂肪酸，它只包含一个单一的双键，作为一个模型系统，我们研究了所有的产品，包括氯代醇后，其与HOCl反应，通过薄层色谱和电喷雾电离质谱相结合。与普遍接受的不同，油酸和HOCl的反应不仅导致氯代醇（异构体）的形成，而且更为复杂：还有相当数量的二聚体和（在较小程度上）三聚体产物，可归因于异构体醚和酯。将油酸氯化后的产物与1-棕榈酰-2-油酰-sn-磷脂酰胆碱（POPC）和HOCl的反应产物进行了比较。将讨论获得不同产物的原因，并强调羧酸的参与。
Reactive oxygen species (ROS) play important physiological roles and are of particular relevance in the pathogenesis of inflammatory diseases. At inflammatory conditions, the enzyme myeloperoxidase generates hypochlorous acid (HOCl) which adds to the double bonds of fatty acyl residues of (phospho)lipids under the formation of chlorohydrins. This may lead to the development of many inflammatory diseases, such as atherosclerosis or arthritis, if the ROS generation exceeds a certain extent. Using oleic acid as the simplest unsaturated fatty acid which contains just a single double bond, as a model system, we investigated all products ⿿ including the chlorohydrin ⿿ after its reaction with HOCl by a combination of thin-layer chromatography and electrospray ionization mass spectrometry. Unlike the general acceptance, the reaction of oleic acid and HOCl leads not exclusively to the formation of chlorohydrin (isomers) but is much more complex: there are also considerable amounts of dimeric and (to a minor extent) trimeric products which can be assigned to isomeric ethers and esters. The obtained products after oleic acid chlorination were also compared with the reaction products of 1-palmitoyl-2-oleoyl-sn-phosphatidylcholine (POPC) and HOCl. The reasons why different products are obtained will be discussed and the involvement of the carboxylic acid emphasized.