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 Abstract：The interaction between unsaturated phosphatidylcholines and either exogenous or endogenous (produced by the enzyme system involving myeloperoxidase (MPO), H2O2, and Cl–) hypochlorite was studied in multilayer liposomes containing oleic, linoleic, and arachidonic acid residues using MALDI TOF mass spectrometry. At pH 7.4, hypochlorite reacts with the dou ble bond of the oleic acid residue in 1 -stearoyl -2 -oleoyl -sn -glycero -3- phosphocholine producing oleic acid chlorohydrin as the main product. Minor amounts of glycols and epoxides were also detected. The main products of the reaction of hypochlorite with 1 -stearoyl -2- linoleyl -sn -glycero -3 -phosphocholine were mono- and di- chlorohydrins of linoleic acid. The signals of monoglycol, epoxide, and glycol or epoxide containing monochlorohydrin derivatives were also present in the mass spectrum. The main products of the reaction of hypochlorite with 1 -stearoyl -2 -arachidonyl-sn-glycero-3 -phosphocholine were lysophosphatidylcholine (1 –stearoyl- sn -glycero -3 -phosphocholine) and mono , di , and trichlorohydrin. Monoglycol and its derivatives containing one or two chlorohydrin groups were also detected. Along with those, carbonyl compounds (aldehyde and acid) formed as a result of double bond breakage in fifth position of arachidonate weredetected. Monochlorohydrin was also found when liposomes comprising 1-stearoyl -2-oleoyl -sn-glycero-3-phosphocholine were incubated in the presence of enzymatic mixture, MPO + H2O2 + Cl–, at pH 6.0. In the absence of the enzyme or either of its substrates (H2O2 or Cl–) or in the presence of the MPO inhibitor (sodium azide) or hypochlorite scavengers (taurine or methionine), monochlorohydrin formation was not observed. These data confirm the suggestion that just the hypochlorite generated in MPO -catalysis provides for chlorohydrin formation. Thus, the use of MALDI -TOF mass spectrometry has shown, along with chlorohydrins, glycols and epoxides as the products of hypochlorite interaction with unsaturated phosphatidylcholines at physiological pH. It was first determined that hypochlorite breaks double bonds in polyunsaturated phosphatidylcholine and also causes lysophosphatidylcholine formation. 截止日期：2009年5月1日 |
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zyy816
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| 不饱和的卵磷脂之间的互作用和外生或内在(生产由介入myeloperoxidase (MPO)， H2O2和分类)的酵素系统使用MALDI TOF质谱分析，次氯酸盐在多层脂质体包含油，亚麻酸和花生四烯酸残滓被学习了。 在酸碱度7.4，次氯酸盐起反应与十八烯酸残滓的窦ble债券在1硬脂酰2 oleoyl锡glycero 3 phosphocholine的生产十八烯酸氯代醇作为主要产品。 也查出了较小数量甘醇和环氧化物。 次氯酸盐的反应的主要产品与1硬脂酰2 linoleyl锡glycero 3 phosphocholine的是亚油酸单音和二氯代醇。 monoglycol信号、包含一氯醇衍生物的环氧化物和甘醇或者环氧化物也是存在质谱。 次氯酸盐的反应的主要产品与1 -硬脂酰-2 - arachidonyl锡glycero 3 - phosphocholine的是lysophosphatidylcholine (1硬脂酰锡- glycero -3 - phosphocholine)和单音，二和trichlorohydrin。 也查出了包含一两个氯代醇小组的Monoglycol和它的衍生物。 与那些一起，羰基化合物(醋醛和酸)形成了由于在weredetected的花生四烯的第五个位置的双键破损。 也找到一氯醇，当包括1硬脂酰-2-oleoyl的脂质体-锡glycero 3 phosphocholine在酶混合物， MPO + H2O2 +分类面前被孵化了，在酸碱度6.0。 在没有酵素时或它的基体(H2O2或分类)或在MPO抗化剂(钠迭氮)或次氯酸盐净化剂面前(牛磺酸或氨基甲硫基丁酸)，一氯醇形成未被观察。 这些数据证实在MPO引起的次氯酸盐-的建议催化提供氯代醇形成。 因此，使用MALDI - TOF质谱分析与氯代醇、甘醇和环氧化物一起显示了，作为次氯酸盐互作用产品与不饱和的卵磷脂的在生理pH。 首先确定次氯酸盐打破在多未饱和的卵磷脂的双键并且导致lysophosphatidylcholine形成。 |
4楼2009-04-26 17:53:36