Linoleic acid and squalene are oxidized by discrete oxidation mechanisms in human sebum
Linoleic acid and squalene are oxidized by discrete oxidation mechanisms in human sebum
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DOI：
10.1111/nyas.14615
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发表时间：
2021-05-31
影响因子：
5.2
通讯作者：
Nakagawa, Kiyotaka
中科院分区：
文献类型：
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作者：
Ishikawa, Ayano;Ito, Junya;Nakagawa, Kiyotaka
先前的研究表明，皮脂中的角鲨烯（SQ）通过光氧化机制（即，单线态氧氧化）以产生SQ氢过氧化物（SQOOH），这是一种引起不良皮肤状况的化合物。然而，皮脂中的其他脂质（如亚油酸（LA））的氧化尚未完全了解。阐明它们的氧化，特别是其机制，可能会导致进一步了解皮脂氧化和皮肤状况之间的关系。本研究采用HPLC-MS/MS技术，直接从皮脂中检测LA过氧化氢（LAOOH），并通过分析LAOOH异构体来确定LA在皮脂中的氧化机制。我们开发了提取和HPLC-MS/MS分析条件，可以充分定量皮脂中的每种LAOOH异构体。使用该方法，在来自健康个体的样品中检测到LAOOH，证明人皮脂中存在LAOOH。此外，LAOOH和SQOOH的异构体分析表明，LA和SQ在皮脂中通过离散的氧化机制被氧化（LA通过自由基氧化被氧化，而SQ通过单线态氧氧化被氧化）。这样的结果可能进一步导致通过选择适当的抗氧化剂来防止皮脂氧化的机制特异性方法的发展，最终导致促进皮肤健康。
Previous studies suggest that squalene (SQ) in sebum is oxidized by a photooxidation mechanism (i.e., singlet oxygen oxidation) to create SQ hydroperoxide (SQOOH), a compound that causes adverse skin conditions. However, oxidation of other lipids in sebum, such as linoleic acid (LA), has not been fully understood. Elucidating their oxidation, especially its mechanisms, may lead to a further understanding of the relationship between sebum oxidation and skin conditions. In this study, using HPLC-MS/MS, we aimed to detect LA hydroperoxide (LAOOH) directly from sebum and identify the oxidation mechanism of LA in sebum through analysis of LAOOH isomers. We developed extraction and HPLC-MS/MS analysis conditions that can sufficiently quantify each LAOOH isomer in sebum. Using this method, LAOOH was detected in samples from healthy individuals, demonstrating the presence of LAOOH in human sebum. Moreover, isomer analysis of LAOOH and SQOOH indicated that LA and SQ are oxidized in sebum by discrete oxidation mechanisms (LA oxidized by free radical oxidation, whereas SQ oxidized by singlet oxygen oxidation). Such results may further lead to the development of mechanism-specific ways to prevent oxidation of sebum via a selection of appropriate antioxidants, ultimately leading to the promotion of skin health.