Characterization of glycosphingolipid epimers by radical-directed dissociation mass spectrometry
Characterization of glycosphingolipid epimers by radical-directed dissociation mass spectrometry
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DOI：
10.1039/c5an02383a
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发表时间：
2016-01-01
期刊：
影响因子：
4.2
通讯作者：
Julian, Ryan R.
中科院分区：
文献类型：
--
作者：
Pham, Huong T.;Julian, Ryan R.
鞘糖脂（GSL）是重要的代谢调节剂，控制关键的细胞功能，并发现在所有细胞膜。GSL差向异构体仅在单个OH基团的方向上不同，是不同溶酶体贮积病的指示剂。在这项研究中，我们调查的GSL异构体的结构歧视使用自由基定向解离（RDD）。可以通过非共价或共价修饰策略实现不同GSL物质的自由基片段化。结果表明，RDD可以定量区分溶血-GSL差向异构体，而不需要事先通过液相色谱分离。此外，它表明，与硼酸的共价标记，使两种糖脂异构体的化学分离，由于各自的糖moiteties的差异reactivity，提供了另一种途径的分子鉴定和自由基表征。
Glycosphingolipids (GSLs) are important metabolic regulators that control critical cellular functions and are found in all cell membranes. GSL epimers which only differ in the orientation of a single OH group are indicators for different lysosomal storage diseases. In this study, we investigate structural discrimination of GSL isomers using radical-directed dissociation (RDD). Radical fragmentation of different GSL species can be enabled by either noncovalent or covalent modification strategies. The results reveal that RDD can quantitatively distinguish lyso-GSL epimers without the requirement of prior separation by liquid chromatography. In addition, it is demonstrated that covalent labeling with boronic acid enables chemical separation of the two glycolipids isomers due to differential reactiviy of the respective sugar moiteties, offering another avenue for both molecular identification and radical characterization.