过氧化氢
化学
磷脂酰胆碱
碰撞诱导离解
碱金属
碎片(计算)
多不饱和脂肪酸
质谱法
有机化学
色谱法
脂肪酸
生物化学
磷脂
串联质谱法
膜
激进的
操作系统
计算机科学
作者
Shunji Kato,Naoki Shimizu,Yusuke Ogura,Yurika Otoki,Junya Ito,Masayoshi Sakaino,Takashi Sano,Shigefumi Kuwahara,Susumu Takekoshi,Jun Imagi,Kiyotaka Nakagawa
标识
DOI:10.1021/jasms.1c00039
摘要
Lipid oxidation is involved in various biological phenomena (e.g., oxylipin generation and oxidative stress). Of oxidized lipid structures, the hydroperoxyl group position of lipid hydroperoxides (LOOHs) is a critical factor in determining their biological roles. Despite such interest, current methods to determine hydroperoxyl group positions possess some drawbacks such as selectivity. While we previously reported mass spectrometric methods using Na+ for the highly selective determination of hydroperoxyl group positions, nothing was known except for the fact that sodiated LOOHs (mainly linoleate) provide specific fragment ions. Thus, this study was aimed to investigate the effects of different alkali metals on the fragmentation of LOOHs, assuming its further application to analysis of other complex LOOHs. From the analysis of PC 16:0/18:2;OOH (phosphatidylcholine) and FA 18:2;OOH (fatty acid), we found that fragmentation pathways and ion intensities largely depend on the binding position and type of alkali metals (i.e., Li+, Hock fragmentation; Na+ and K+, α-cleavage (Na+ > K+); Rb+ and Cs+, no fragmentation). Furthermore, we proved that this method can be applied to determine the hydroperoxyl group position of esterified lipids (e.g., phospholipids and cholesterol esters) as well as polyunsaturated fatty acids (PUFAs) including n-3, n-6, and n-9 FA. We anticipate that the insights described in this study provide additional unique insights to conventional lipid oxidation research.
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