Structural assignment of isomeric 2-aminopyridine derivatized monosialylated biantennary N-linked oligosaccharides using negative-ion MSn spectral matching
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概要
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To investigate the possibility of structural assignment based on negative-ion MSn spectral matching, four isomers of 2-aminopyridine-derivatized (PA) monosialylated oligosaccharides (i.e., complex type N-glycans with an α2-3 or α2-6 linked sialic acid on α1-6 or α1-3 antennae) were analyzed by using high-performance liquid chromatography/electrospray ion trap time-of-flight mass spectrometry(HPLC/ESI-IT-TOF MS). The negative ion [M-2H]2- is observed dominantly in the MS1 spectra without the loss of a sialic acid. The MS2 spectra derived from it are sufficiently reproducible that MS2 spectral matching based on correlation coefficients can be applied to the assignment of these isomers. Theisomers containing a sialic acid on α1-6 or α1-3 antennae can be distinguished by MS2 spectralmatching, but the α2-3 and α2-6 linkage types of sialic acid cannot be distinguished by their MS2spectra. However, MS3 spectra derived from fragment ions containing a sialic acid (i.e., C4- and D-type ions) clearly differentiate the α2-3 and α2-6 linkage types of sialic acid in their MS3 spectral patterns.This difference might be rationalized in terms of a proton transfer from the reducing-end mannose to the negatively-charged sialic acid. These two moieties are very close in the structural conformations of the precursor C4-type fragment ions, as predicted by molecular mechanics calculations. Thus, negative-ion MSn (n=2, 3) spectral matching was proven to be useful for the structural assignment of these four monosialylated PA N-glycan isomers.
- John Wiley & Sonsの論文
著者
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Nishimura S
Graduate School Of Advanced Life Science Frontier Research Center For Post-genomic Science And Techn
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Ito Hiroki
Hitachi High-technologies Company
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Nishimura Shin-ichiro
Graduate School Of Advanced Life Science Frontier Research Center For Post-genomic Science And Techn
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Nishimura Shin-ichiro
Laboratory For Bio-macromolecular Chemistry Frontier Research Center For Post-genomic Science And Te
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Takegawa Yasuhiro
Graduate School Of Advanced Life Science Frontier Research Center For Post-genomic Science And Techn
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Nakagawa Hiroaki
Graduate School Of Advanced Life Science Frontier Research Center For Post-genomic Science And Techn
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Deguchi Kisaburo
Graduate School Of Advanced Life Science Frontier Research Center For Post-genomic Science And Techn
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