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Stabilization of Sialic Acids in N-linked Oligosaccharides and Gangliosides for Analysis by Positive Ion Matrix-assisted Laser Desorption/Ionization Mass Spectrometry

✍ Scribed by Andrew K. Powell; David J. Harvey

Publisher: John Wiley and Sons
Year: 1996
Tongue: English
Weight: 482 KB
Volume: 10
Category: Article
ISSN: 0951-4198
DOI: 10.1002/(sici)1097-0231(19960715)10:9<1027::aid-rcm634>3.0.co;2-y

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✦ Synopsis

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry of oligosaccharides and gangliosides normally causes loss of sialic acid, particularly when a-cyano-4-hydroxycinnamic acid is used as the matrix. In addition, the potential signal is split because both positive and, to a greater extent, negative ions are formed while signals are frequently complicated as the result of partial alkali-salt formation. In order to stabilize the sialic acid moieties under MALDI conditions and to divert all of the signal into the positive-ion mode, a method involving their conversion into methyl esters has been developed. The method is relatively rapid and produces strong positive-ion signals from N-linked oligosaccharides containing sialic acid and from gangliosides. The latter compounds are stable, even in the presence of a-cyano-4-hydroxycinnamic acid. They give abundant molecular (MNa') ions, but with sufficient residual in-source fragmentation to allow the sequence of the sugar chain to be determined. The sialic acid residue is stable after methylation, irrespective of its linkage to the parent molecule.

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