Direct mass spectrometric analysis of ozonides: Application to unsaturated glycerophosphocholine lipids
Direct mass spectrometric analysis of ozonides: Application to unsaturated glycerophosphocholine lipids
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DOI：
10.1021/ac960302c
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发表时间：
1996-09-15
影响因子：
7.4
通讯作者：
Murphy, RC
中科院分区：
文献类型：
--
作者：
Harrison, KA;Murphy, RC
臭氧与甘油磷酸胆碱脂质中存在的双键的反应导致形成臭氧化物，臭氧化物可以通过质谱法直接分析为通过电喷雾电离产生的正或负分子离子物质。酯化到磷脂上的多不饱和脂肪酰基产生臭氧化物物质的混合物，其中添加的臭氧分子的最大数目等于双键的总数，臭氧分解导致ω-醛和ω-羧酸产品所揭示的ESI-MS。碰撞激活的单和多不饱和磷脂的臭氧加合物产生的碎片离子指示在这些分子中的双键的位置。正或负臭氧化物离子物种的主要分解途径涉及通过过氧化物桥的均裂引发的臭氧化物的电荷远程碎片化，然后重排形成ω-醛和ω-羧酸酰基物种。臭氧与含有多不饱和脂肪酰基的磷脂的反应是通过电喷雾电离质谱探测双键位置的有用方法。
The reaction of ozone with double bonds present in glycerophosphocholine lipids results in formation of ozonides that can be directly analyzed by mass spectrometry as either positive or negative molecular ion species generated by electrospray ionization, Polyunsaturated fatty acyl groups esterified to the phospholipid yielded a mixture of ozonide species with the maximum number of ozone molecules added equal to the total number of double bonds, Ozonide decomposition resulted in omega-aldehyde and omega-carboxylic acid products as revealed by ESI-MS. Collisional activation of the ozone adducts for mono- and polyunsaturated phospholipids gave rise to fragment ions indicative of the position of the double bonds in these molecules. The major decomposition pathway for either positive or negative ozonide ion species involved charge remote fragmentation of the ozonide initiated by homolytic cleavage of the peroxide bridge followed by rearrangement to form the omega-aldehyde and omega-carboxylate acyl species. The reaction of ozone with phospholipids containing polyunsaturated fatty acyl groups is a useful method to probe the position of double bonds by electrospray ionization mass spectrometry.