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Using ambient ozone for assignment of double bond position in unsaturated lipids

机译:使用环境臭氧分配不饱和脂质中的双键位置

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摘要

Unsaturated lipids deposited onto a range of materials are observed to react with the low concentrations of ozone present in normal laboratory air. Parent lipids and ozonolysis cleavage products are both detected directly from surfaces by desorption electrospray ionisation mass spectrometry (DESI-MS) with the resulting mass spectra providing clear evidence of the double bond position within these molecules. This serendipitous process has been coupled with thin-layer chromatography (TLC) to provide a simple but powerful approach for the detailed structural elucidation of lipids present in complex biological extracts. Lipid extracts from human lens were deposited onto normal phase TLC plates and then developed to separate components according to lipid class. Exposure of the developed plates to laboratory air for ca. 1 h prior to DESI-MS analysis gave rise to ozonolysis products allowing for the unambiguous identification of double bond positions in even low abundant, unsaturated lipids. In particular, the co-localization of intact unsaturated lactosylceramides (LacCer) with products from their oxidative cleavage provide the first evidence for the presence of three isomeric LacCer (d18:0/24:1) species in the ocular lens lipidome, i.e., variants with double bonds at the n-9, n-7 and n-5 positions. This journal is
机译:观察到沉积在多种材料上的不饱和脂质会与正常实验室空气中存在的低浓度臭氧发生反应。脱脂电喷雾电离质谱(DESI-MS)可以直接从表面检测母体脂质和臭氧分解产物,所得质谱图清楚地表明了这些分子中的双键位置。这个偶然的过程已经与薄层色谱法(TLC)相结合,为复杂生物提取物中存在的脂质的详细结构解析提供了一种简单而有效的方法。将人晶状体的脂质提取物沉积在正相TLC板上,然后根据脂质类别进行分离。将显影后的板暴露在实验室空气中约。在进行DESI-MS分析之前1小时,产生了臭氧分解产物,从而可以明确鉴定即使在低丰度,不饱和脂质中的双键位置。特别地,完整的不饱和乳糖基神经酰胺(LacCer)与它们的氧化裂解产物的共定位提供了第一个证据,表明在晶状体脂质组中存在三种同分异构的LacCer(d18:0/24:1)物种,即变体在n-9,n-7和n-5位置带有双键。这本日记是

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