AUTOXIDATION OF POLY-UNSATURATED LIPIDS - FACTORS CONTROLLING THE STEREOCHEMISTRY OF PRODUCT HYDROPEROXIDES
AUTOXIDATION OF POLY-UNSATURATED LIPIDS - FACTORS CONTROLLING THE STEREOCHEMISTRY OF PRODUCT HYDROPEROXIDES
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DOI：
10.1021/ja00537a032
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
KHAN, JA
中科院分区：
文献类型：
--
作者：
PORTER, NA;WEBER, BA;KHAN, JA
对亚油酸及其磷脂酯的自氧化机理进行了研究。在还原为相应的羟基脂肪酸后，通过LC [液相色谱]分析自氧化产物13-羟基过氧-9-顺式，11-反式-十八碳二烯酸（4）、13-羟基过氧-9-反式，11-反式-十八碳二烯酸（5）、9-羟基过氧-10-反式，12-顺式-十八碳二烯酸（6）和9-羟基过氧-10-反式，12-反式-十八碳二烯酸（7）。在氧化的初始阶段形成的反式、顺式：反式、反式产物的比率（4 + 6/5 + 7）（对于游离酸< 2%）取决于温度和亚油酸的浓度。该反式、顺式：反式、反式比率变化为4.2（在10 ℃下纯亚油酸氧化）。C）至0.23（0.24M亚油酸在苯中，50 ℃）。C）。在1，2-二亚油酰甘油磷脂酰胆碱和1，2-二棕榈酰甘油磷脂酰氯的混合物的乳液氧化中发现了类似的产物分布，其中反式、顺式：反式、反式产物比例取决于二亚油酰卵磷脂与二棕榈酰卵磷脂的比例。亚油酸和对甲氧基苯酚的混合物得到反式、顺式：反式、反式产物的比例取决于加入的苯酚的浓度。与这些意见一致的动力学计划。脂质过氧化在不同的生物系统中导致具有有趣和独特性质的过氧化物产物。
The mechanism of the autoxidation of linoleic acid and phospholipid esters of this acid was investigated. The products of autoxidation, 13-hydroperoxy-9-cis,11-trans-octadecadienoic (4), 13-hydroxyperoxy-9-trans,11-trans-octadecadienoic (5), 9-hydroperoxy-10-trans,12-cis-octadecadienoic (6) and 9-hydroxyperoxy-10-trans,12-trans-octadecadienoic (7) acids, were analyzed by LC [liquid chromatography] after reduction to the corresponding hydroxy fatty acids. The ratio of trans,cis:trans,trans products, (4 + 6/5 + 7), formed during the initial stages of oxidation (< 2% for the free acids) was dependent on temperature and the concentration of linoleic acid. This trans,cis:trans,trans ratio varied 4.2 (with neat linoleic acid oxidations at 10.degree. C) to 0.23 (0.24 M linoleic acid in benzene at 50.degree. C). A similar product distribution was found in emulsion oxidation of mixtures of 1,2-dilinoleoylglycerophosphatidylcholine and 1,2-dipalmitoylglycerophosphatidylchlorine with the trans,cis:trans,trans product ratio, depending on the ratio of dilinoleoyllecithin to dipalmitoyllecithin. Mixtures of linoleic acid and p-methoxyphenol give trans,cis:trans,trans product ratios dependent on the concentration of added phenol. A kinetic scheme consistent with these observations is presented. Lipid peroxidation in diverse biological systems leads to peroxide products that have interesting and unique properties.