Electron detachment dissociation of dermatan sulfate oligosaccharides
Electron detachment dissociation of dermatan sulfate oligosaccharides
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DOI：
10.1016/j.jasms.2007.10.007
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发表时间：
2008-02-01
影响因子：
3.2
通讯作者：
Amster, I. Jonathan
中科院分区：
文献类型：
--
作者：
Wolff, Jeremy J.;Laremore, Tatiana N.;Amster, I. Jonathan
糖胺聚糖(GAG)低聚糖的结构表征一直是质谱学领域的一大挑战。在这项工作中，我们提出了应用电子分离解离(EDD)傅立叶变换质谱仪分析长达10个残基的硫酸皮肤素(DS)寡糖。将DS寡糖的EDD质谱图与红外多光子解离(IRMPD)质谱图进行了比较。由于不稳定的硫酸盐修饰，EDD比IRMPD产生更丰富的碎片，而SO的损失要小得多。EDD裂解所有的糖苷键，既产生传统的糖苷键断裂，也产生由于额外损失1或2个氢原子而产生的卫星峰。EDD也比IRMPD产生更多的交叉环碎片。对于EDD，观察到大量的A-和X-离子形式的跨环断裂，除还原和非还原末端外，所有IoA残基和许多GalNAc4S残基都发生了X-1，5(N)裂解。相反，IRMPD对长低聚糖(dp6-dp10)只产生A型交叉环碎裂。由于IRMPD观察到的所有结构信息片段离子都是EDD质谱峰的子集，EDD在单级串联质谱学实验中对GaG寡糖的表征显示出巨大的潜力。
The structural characterization of glycosaminoglycans (GAG) oligosaccharides has been a long-standing challenge in the field of mass spectrometry. In this work, we present the application of electron detachment dissociation (EDD) Fourier transform mass spectrometry to the analysis of dermatan sulfate (DS) oligosaccharides up to 10 residues long. The EDD mass spectra of DS oligosaccharides were compared with their infrared multiphoton dissociation (IRMPD) mass spectra. EDD produces more abundant fragmentation than IRMPD with far less loss of SO, from labile sulfate modifications. EDD cleaves all glycosidic bonds, yielding both conventional glycosidic bond fragmentation as well as satellite peaks resulting from the additional loss of 1 or 2 hydrogen atoms. EDD also yields more cross-ring fragmentation than IRMPD. For EDD, abundant cross-ring fragmentation in the form of A- and X-ions is observed, with X-1,5(n) cleavages occurring for all IdoA residues and many of the GalNAc4S residues, except at the reducing and nonreducing ends. In contrast, IRMPD produces only A-type cross-ring fragmentation for long oligosaccharides (dp6-dp10). As all the structurally informative fragment ions observed by IRMPD appear as a subset of the peaks found in the EDD mass spectrum, EDD shows great potential for the characterization of GAG oligosaccharides using a single tandem mass spectrometry experiment.