出版社:American Society for Biochemistry and Molecular Biology
摘要:We previously discovered that squalene monohydroperoxide (SQ-OOH)was produced on human forehead skin and suggested that skinsqualene (SQ) may be the principal target lipid for oxidativestress (e.g., sunlight exposure). Because of its six doublebonds, SQ peroxidation can yield various positional hydroperoxideisomers. However, the structural characterization of skin SQ-OOHisomers has never been reported. Here, we prepared pure SQ-OOHisomers and developed an analytical method for SQ-OOH isomersusing a quadrupole/linear ion-trap mass spectrometer (QTRAP)MS/MS system. Collision-induced dissociation produced specificfragment ions for each SQ-OOH isomer, which permitted discriminationbetween SQ-OOH isomers by multiple reaction monitoring (MRM).When lipid extract from human forehead skin was subjected toLC-MS/MS with MRM, individual SQ-OOH isomers could be separatedand detected with a sensitivity of 0.05 ng/injection. The totalconcentration of SQ-OOH isomers in forehead skin was 956 µg/gskin lipids, but it increased up to 2,760 µg/g skin lipidsafter 3 h of sunlight exposure. The LC-MS/MS method was usefulfor investigating the peroxidation mechanisms of SQ as wellas SQ-OOH-mediated skin disorders.Supplementary key words lipid peroxidation • QTRAP mass spectrometer • skin pathogenicity
Abbreviations: LC-CL, liquid chromatography-chemiluminescence detection; MRM, multiple reaction monitoring; QqLIT, hybrid quadrupole/linear ion trap; SQ, squalene; SQ-OOH, squalene monohydroperoxide; UV, ultraviolet