On-target derivatization of keratan sulfate oligosaccharides with pyrenebutyric acid hydrazide for MALDI-TOF/TOF-MS.
On-target derivatization of keratan sulfate oligosaccharides with pyrenebutyric acid hydrazide for MALDI-TOF/TOF-MS.
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DOI：
10.1002/jms.1373
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发表时间：
2008-06
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通讯作者：
Yuntao Zhang;T. Iwamoto;G. Radke;Y. Kariya;Kiyoshi Suzuki;A. H. Conrad;J. Tomich;G. Conrad
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文献类型：
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作者：
Yuntao Zhang;T. Iwamoto;G. Radke;Y. Kariya;Kiyoshi Suzuki;A. H. Conrad;J. Tomich;G. Conrad
本工作建立了一种用于基质辅助激光解吸电离(MALDI)分析的硫酸角蛋白(KS)低聚糖的快速、新颖的靶板衍生化方法。标记KS低聚糖的MALDI-飞行时间光谱显示，可以显著提高电离度，每个光谱中最丰富的峰对应于单电荷分子离子[M-H]-或[M+(n-1)Na-NH]-，其中n=硫酸盐的数目(n=1，2，3…)。标记的KS寡糖的高能碰撞诱导解离(HeCID)谱显示了与激光诱导解离(LID)分析相似的化合物碎片，这表明HeCID和LID碎片都可以用于分析KS寡糖。用MALDI-TOF/TOF-MS对所有标记的KS寡糖进行了裂解分析。在LID模式下，钠加合物显示了主要与Y/B/C离子的糖苷键的断裂，以及各种交叉环裂解，为硫酸盐基团沿KS寡糖链的位置提供了准确的信息。这种一步目标衍生化方法使MALDI-TOF/TOF-MS鉴定KS快速、简便、高通量，适用于痕量生物样品。
In the present work, a rapid and novel method of on-target plate derivatization of keratan sulfate (KS) oligosaccharides for subsequent analysis by matrix-assisted laser desorption and ionization (MALDI) mass spectrometry is described. MALDI-(time-of-flight)-TOF spectra of labeled KS oligosaccharides revealed that significantly improved ionization can be accomplished through derivatization with pyrenebutyric acid hydrazide (PBH), and the most abundant peak in each spectrum corresponds to the singly charged molecular ion [M - H]- or [M + (n - 1)Na - nH]-, where n = the number of sulfates (n = 1, 2, 3...). The high-energy collision-induced dissociation (heCID) spectra of labeled KS oligosaccharides displayed fragments of compounds similar to those observed with laser-induced dissociation (LID) analysis, suggesting that both heCID and LID fragmentations can be used to analyze KS oligosaccharides. Moreover, fragmentation analysis of all labeled KS oligosaccharides was performed by MALDI-TOF/TOF-MS. With LID mode, sodium adducts showed fragmentation of glycosidic linkages with mainly Y/B/C ions, as well as various cross-ring cleavages providing exact information for the positions of sulfate groups along the KS oligosaccharide chains. This one-step on-target derivatization method makes MALDI-TOF/TOF-MS identification of KS fast, simple and highly throughput for trace amounts of biological samples.