CHLOROHYDRIN FORMATION FROM UNSATURATED FATTY-ACIDS REACTED WITH HYPOCHLOROUS ACID
CHLOROHYDRIN FORMATION FROM UNSATURATED FATTY-ACIDS REACTED WITH HYPOCHLOROUS ACID
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DOI：
10.1016/0003-9861(92)90609-z
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发表时间：
1992-08-01
影响因子：
3.9
通讯作者：
KUYPERS, FA
中科院分区：
文献类型：
--
作者：
WINTERBOURN, CC;VANDENBERG, JJM;KUYPERS, FA
受刺激的中性粒细胞通过髓过氧化物酶催化的过氧化氢与氯化物的反应产生次氯酸（HOCl）。研究了HOCl与油酸、亚油酸和花生四烯酸的反应。通过甲基化和三甲基硅烷化衍生物的气相色谱-质谱法鉴定产物。油酸以接近化学计量的产率转化为两种9，10-氯醇异构体。亚油酸，在低HOCl：脂肪酸的比例，主要产生了四种可能的单氯代醇异构体的混合物。还形成了双氯代醇，在更高的HOCl浓度下，双氯代醇的量增加。花生四烯酸给出了一个复杂的混合物的单和双氯代醇，相对比例取决于加入的HOCl的量。亚油酸似乎比油酸与HOCl的反应性略高。油酸和亚油酸与髓过氧化物酶、过氧化氢和氯化物的反应得到与HOCl相同的氯代醇产物。脂质氯醇作为中性粒细胞氧化剂反应的产物很少受到关注。它们比母体脂肪酸极性更强，如果在细胞膜中形成，可能会破坏膜结构。由于HOCl的细胞靶点似乎是膜成分，因此不饱和脂质的氯乙醇形成在嗜铬细胞毒介导的细胞毒性中可能是显著的。
Stimulated neutrophils produce hypochlorous acid (HOCl) via the myeloperoxidase-catalyzed reaction of hydrogen peroxide with chloride. The reactions of HOCl with oleic, linoleic, and arachidonic acids both as free fatty acids or bound in phosphatidylcholine have been studied. The products were identified by gas chromatography-mass spectrometry of the methylated and trimethylsilylated derivatives. Oleic acid was converted to the two 9,10-chlorohydrin isomers in near stoichiometric yield. Linoleic acid, at low HOCl:fatty acid ratios, yielded predominantly a mixture of the four possible monochlorohydrin isomers. Bischlorohydrins were also formed, in increasing amounts at higher HOCl concentrations. Arachidonic acid gave a complex mixture of mono- and bischlorohydrins, the relative proportions depending on the amount of HOCl added. Linoleic acid appears to be slightly more reactive than oleic acid with HOCl. Reactions of oleic and linoleic acids with myeloperoxidase, hydrogen peroxide, and chloride gave chlorohydrin products identical to those with HOCl. Lipid chlorohydrins have received little attention as products of reactions of neutrophil oxidants. They are more polar than the parent fatty acids, and if formed in cell membranes could cause disruption to membrane structure. Since cellular targets for HOCl appear to be membrane constituents, chlorohydrin formation from unsaturated lipids could be significant in neutrophil-mediated cytotoxicity.