TANDEM MASS-SPECTROMETRIC ANALYSIS OF FIXED-CHARGE DERIVATIZED OLIGOSACCHARIDES
TANDEM MASS-SPECTROMETRIC ANALYSIS OF FIXED-CHARGE DERIVATIZED OLIGOSACCHARIDES
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DOI：
10.1002/oms.1210291204
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发表时间：
1994-12-01
期刊：
影响因子：
--
通讯作者：
RICHTER, WJ
中科院分区：
文献类型：
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作者：
DOMON, B;MUELLER, DR;RICHTER, WJ
制备了一组三种异构（线性和支化）五糖（LNF-1，LNF-2和LNF-3）的各种衍生物，并通过高效串联质谱进行了研究，以比较它们的碰撞诱导解离（CID）行为。全乙酰化衍生物的[M + H]（+）离子的快原子轰击串联质谱主要显示含有非还原末端（B型离子）的片段，并允许直接分配糖序列和分支以及鉴定一些糖苷间键。全甲基化衍生物在较大寡糖的情况下更好地适应串联质谱仪的质量范围，产生类似的结果，即B离子占优势，但必须从不完整的B-i和Y-i离子系列中检索必要的信息。相比之下，CID的全甲基或全乙酰基衍生物携带预先形成的电荷，由于前还原胺化的寡糖与三甲基（对氨基苯基）氯化铵产生排他性的碎片离子，包括还原端。在这种情况下，观察到的四个不同系列的碎片涉及电荷远程碎片化过程。因此，光谱图案不受另外引入的糖O-取代基的性质（即甲基或乙酰基）的显著影响。
Various derivatives of a set of three isomeric (linear and branched) pentasaccharides (LNF-1, LNF-2 and LNF-3) were prepared and investigated by high-performance tandem mass spectrometry in order to compare their collision-induced dissociation (CID) behaviour. The fast atom bombardment tandem mass spectra of [M + H](+) ions of peracetylated derivatives mainly display fragments containing the non-reducing terminus (B-type ions) and allow a straightforward assignment of sugar sequence and branching together with the identification of some interglycosidic linkages. Permethylated derivatives, which better accommodate the mass range of tandem mass spectrometers in the case of larger oligosaccharides, yield similar results, i.e. predominance of B ions, but the necessary information has to be retrieved from incomplete B-i and Y-i ion series. By contrast, CID of permethyl or peracetyl derivatives carrying a preformed charge due to prior reductive amination of the oligosaccharides with trimethyl(p-aminophenyl)ammonium chloride yields exclusively fragment ions comprising the reducing end. In this case, the four distinct series of fragments observed involve charge-remote fragmentation processes. As a consequence, the spectral patterns are not significantly affected by the nature of the sugar O-substituents additionally introduced (i.e. methyl or acetyl).