Lipidomic analysis for lipid peroxidation-derived aldehydes using gas chromatography-mass spectrometry
Lipidomic analysis for lipid peroxidation-derived aldehydes using gas chromatography-mass spectrometry
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DOI：
10.1021/tx060199e
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发表时间：
2007-01-01
影响因子：
4.1
通讯作者：
Terao, Junji
中科院分区：
文献类型：
--
作者：
Kawai, Yoshichika;Takeda, Sayaka;Terao, Junji
本文描述了一种脂质组学方法，该方法使用气相色谱/电子电离/质谱法与选定的离子监测（GC/EI/MS-SIM）测量脂质过氧化衍生的醛。用PFB-羟胺将样品中的醛转化为五氟苯(PFB)-肟，其他官能团（如羟基）进一步衍生为三甲基硅醚。pfb -肟类衍生物的特征片段离子m/z 181的SIM可以全面检测到pfb -肟类衍生物。同时，通过结构特异性片段离子的SIM将每种醛分为5个基团（烷醛、2-烯醛、2,4-alkadienals、2-羟基烷醛和4-羟基-2-烯醛）。4-羟基-2-烯醛的测定也证实了它们与巯基有较高的反应活性。在质谱表征的基础上，我们在体外鉴定了至少33种醛，这些醛是由fe - ii介导的花生四烯酸-、亚油酸-和二十二碳六烯酸-氢过氧化物分解形成的。然后，我们将该系统应用于体内样品，并成功观察到腹腔注射溴苯（脂质过氧化实验动物模型）的小鼠肝脏中醛的增加。通过这种综合分析，可以观察到每种醛形成的独特差异。该方法可用于同时监测体内氧化应激下形成的脂质过氧化衍生醛。
A lipidomic method is described for the measurement of lipid peroxidation-derived aldehydes using gas chromatography/electron ionization/mass spectrometry with selected ion monitoring (GC/EI/MS-SIM). Aldehydes in the samples were converted into their pentafluorobenzyl (PFB)-oximes using PFB-hydroxylamine, and other functional groups such as the hydroxyl groups were further derivatized into the trimethylsilyl ethers. The PFB-oxime derivatives could be comprehensively detected by the SIM of m/z 181, which is a characteristic fragment ion of the PFB-oxime derivatives. At the same time, each aldehyde was classified into five groups (alkanals, 2-alkenals, 2,4-alkadienals, 2-hydroxyalkanals, and 4-hydroxy-2-alkenals) by SIM of the structure-specific fragment ions. Determination of the 4-hydroxy-2-alkenals was also performed by confirmation of their higher reactivity with the sulfhydryl group. On the basis of the mass spectrometric characterization, we have identified at least 33 aldehydes formed upon the Fe-II-mediated decomposition of the arachidonic acid-, linoleic acid-, and docosahexaenoic acid-hydroperoxides in vitro. We then applied this system to the in vivo samples and successfully observed the increase in aldehydes in the liver of mice intraperitoneally injected with bromobenzene, an experimental animal model for lipid peroxidation. Using this comprehensive analysis, unique differences in the formation between each aldehyde could be observed. This method is useful for simultaneously monitoring the lipid peroxidation-derived aldehydes formed under oxidative stress in vivo.