Document Detail


Structural assignment of isomeric 2-aminopyridine-derivatized monosialylated biantennary N-linked oligosaccharides using negative-ion multistage tandem mass spectral matching.
MedLine Citation:
PMID:  16381065     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
To investigate the possibility of structural assignment based on negative-ion tandem multistage (MSn) mass spectral matching, four isomers of 2-aminopyridine (PA)-derivatized monosialylated oligosaccharides (i.e., complex-type N-glycans with an alpha2-3- or alpha2-6-linked sialic acid on alpha1-6 or alpha1-3 antennae) were analyzed using high-performance liquid chromatography/electrospray ion trap time-of-flight mass spectrometry (HPLC/ESI-IT-TOFMS). The negative ion [M-2H]2- is observed predominantly 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. The isomers containing a sialic acid on alpha1-6 or alpha1-3 antennae can be distinguished by MS2 spectral matching, but the alpha2-3 and alpha2-6 linkage types of sialic acid cannot be distinguished by their MS2 spectra. However, MS3 spectra derived from fragment ions containing a sialic acid (i.e., C4- and D-type ions) clearly differentiate the alpha2-3 and alpha2-6 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 of alpha2-6 linkage type, as predicted by molecular mechanics calculations. Thus, negative-ion MSn (n = 2, 3) spectral matching was demonstrated to be useful for the structural assignment of these four monosialylated PA N-glycan isomers.
Authors:
Kisaburo Deguchi; Yasuhiro Takegawa; Hiroki Ito; Nobuaki Miura; Shinji Yoshioka; Shinji Nagai; Hiroaki Nakagawa; Shin-Ichiro Nishimura
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  Rapid communications in mass spectrometry : RCM     Volume:  20     ISSN:  0951-4198     ISO Abbreviation:  Rapid Commun. Mass Spectrom.     Publication Date:  2006  
Date Detail:
Created Date:  2006-01-17     Completed Date:  2006-03-23     Revised Date:  2006-11-15    
Medline Journal Info:
Nlm Unique ID:  8802365     Medline TA:  Rapid Commun Mass Spectrom     Country:  England    
Other Details:
Languages:  eng     Pagination:  412-8     Citation Subset:  IM    
Copyright Information:
Copyright (c) 2005 John Wiley & Sons, Ltd.
Affiliation:
Division of Biological Sciences, Graduate School of Science, Hokkaido University, Sapporo 001-0021, Japan. deguchi@glyco.sci.hokudai.ac.jp
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MeSH Terms
Descriptor/Qualifier:
Aminopyridines / chemistry*
Carbohydrate Sequence
Isomerism
Mass Spectrometry / methods*
Molecular Sequence Data
Molecular Structure
Oligosaccharides / chemistry*
Reference Standards
Reproducibility of Results
Chemical
Reg. No./Substance:
0/Aminopyridines; 0/Oligosaccharides; 504-29-0/alpha-aminopyridine
Comments/Corrections
Erratum In:
Rapid Commun Mass Spectrom. 2006;20(9):1480-1

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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