Ion-trap tandem mass spectrometric analysis of squalene monohydroperoxide isomers in sunlight-exposed human skin
Ion-trap tandem mass spectrometric analysis of squalene monohydroperoxide isomers in sunlight-exposed human skin
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DOI：
10.1194/jlr.d700016-jlr200
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发表时间：
2007-12-01
影响因子：
6.5
通讯作者：
Miyazawa, Teruo
中科院分区：
文献类型：
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作者：
Nakagawa, Kiyotaka;Ibusuki, Daigo;Miyazawa, Teruo
我们以前发现，角鲨烯单氢过氧化物（SQ-OOH）在人前额皮肤上产生，并建议皮肤角鲨烯（SQ）可能是氧化应激的主要靶脂质（例如，氧化应激）。例如，在一个实施例中，阳光照射）。由于其六个双键，SQ过氧化可以产生各种位置的氢过氧化物异构体。然而，皮肤SQ-OOH异构体的结构表征从未报道。在这里，我们制备了纯SQ-OOH异构体，并开发了SQ-OOH异构体的分析方法，使用四极杆/线性离子阱质谱仪（QTRAP）MS/MS系统。碰撞诱导解离产生特定的碎片离子的每一个SQ-OOH异构体，这使得SQ-OOH异构体之间的歧视多反应监测（MRM）。当从人前额皮肤的脂质提取物进行LC-MS/MS与MRM，个别SQ-OOH异构体可以分离和检测的灵敏度为0.05纳克/注射。前额皮肤中SQ-OOH异构体的总浓度与956 μ g/g皮肤脂质相似，但在阳光照射3小时后增加至2，760 μ g/g皮肤脂质。LC-MS/MS方法可用于研究SQ以及SQ-OOH介导的皮肤疾病的过氧化机制。
We previously discovered that squalene monohydroperoxide (SQ-OOH) was produced on human forehead skin and suggested that skin squalene (SQ) may be the principal target lipid for oxidative stress ( e. g., sunlight exposure). Because of its six double bonds, SQ peroxidation can yield various positional hydroperoxide isomers. However, the structural characterization of skin SQ-OOH isomers has never been reported. Here, we prepared pure SQ-OOH isomers and developed an analytical method for SQ-OOH isomers using a quadrupole/linear ion-trap mass spectrometer (QTRAP) MS/MS system. Collision-induced dissociation produced specific fragment ions for each SQ-OOH isomer, which permitted discrimination between SQ-OOH isomers by multiple reaction monitoring (MRM). When lipid extract from human forehead skin was subjected to LC-MS/MS with MRM, individual SQ-OOH isomers could be separated and detected with a sensitivity of 0.05 ng/injection. The total concentration of SQ-OOH isomers in forehead skin was similar to 956 mu g/g skin lipids, but it increased up to 2,760 mu g/g skin lipids after 3 h of sunlight exposure. The LC-MS/MS method was useful for investigating the peroxidation mechanisms of SQ as well as SQ-OOH-mediated skin disorders.