Mass Spectrometric Discrimination of Squalene Monohydroperoxide Isomers

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  • Shimizu Naoki
    Food and Biodynamic Chemistry Laboratory, Graduate School of Agricultural Science, Tohoku University
  • Bersabe Hannah
    Food and Biodynamic Chemistry Laboratory, Graduate School of Agricultural Science, Tohoku University
  • Ito Junya
    Food and Biodynamic Chemistry Laboratory, Graduate School of Agricultural Science, Tohoku University
  • Kato Shunji
    Food and Biodynamic Chemistry Laboratory, Graduate School of Agricultural Science, Tohoku University
  • Towada Ryo
    Laboratory of Applied Bioorganic Chemistry, Graduate School of Agricultural Science, Tohoku University
  • Eitsuka Takahiro
    Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences
  • Kuwahara Shigefumi
    Laboratory of Applied Bioorganic Chemistry, Graduate School of Agricultural Science, Tohoku University
  • Miyazawa Teruo
    Food and Biotechnology Innovation Project, New Industry Creation Hatchery Center (NICHe), Tohoku University Food and Health Science Research Unit, Graduate School of Agricultural Science, Tohoku University
  • Nakagawa Kiyotaka
    Food and Biodynamic Chemistry Laboratory, Graduate School of Agricultural Science, Tohoku University

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Abstract

<p>Squalene (SQ), a main component of human sebum, is readily photooxidized by exposure to sunlight, producing six squalene monohydroperoxide (SQ-OOH) isomers. Despite its known connection to various skin conditions, few studies have sought to analyze SQ-OOH at the isomeric level. In this study, we aimed to develop a method to discriminate each SQ-OOH isomer with the use of tandem mass spectrometry (MS/MS). The six standard SQ-OOH isomers were prepared by photooxidizing SQ in the presence of rose bengal, a photosensitizer, and isolated by semipreparative high-performance liquid chromatography (HPLC). To purify each isomer, 2-methoxypropene, which reversibly reacts with the hydroperoxide group of SQ-OOH, was utilized. Product ion scanning was then performed on the standard SQ-OOH isomers in the absence and presence of the sodium ion. In the absence of the sodium ion, the fragmentation patterns produced by atmospheric pressure chemical ionization were similar between the isomers, whereas in the presence of the sodium ion by electrospray ionization, unique fragmentation patterns were achieved. Based on these fragment ions, HPLC-MS/MS multiple reaction monitoring analysis was conducted on a mixture of the standard SQ-OOH isomers. We achieved discrimination of SQ-OOH isomers with high selectivity and detected SQ-OOH isomers at nanogram levels. These results may improve our understanding of the effect of SQ-OOH on skin conditions as well as the mechanism behind SQ peroxidation.</p>

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