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. 2009 Jul 1;5(3):225-237.
doi: 10.2174/157341109788680291.

Sequence Analysis of Native Oligosaccharides Using Negative ESI Tandem MS

Affiliations

Sequence Analysis of Native Oligosaccharides Using Negative ESI Tandem MS

Zhenqing Zhang et al. Curr Anal Chem. .

Abstract

Carbohydrates exhibit many physiologically and pharmacologically important activities, yet their complicated structure and sequence pose major analytical challenges. Although their structural complexity makes analysis of carbohydrate difficult, mass spectrometry (MS) with high sensitivity, resolution and accuracy has become a vital tool in many applications related to analysis of carbohydrates or oligosaccharides. This application is essentially based on soft ionization technique which facilitates the ionization and vaporization of large, polar and thermally labile biomolecules. Electrospray-ionization (ESI), one of the soft ionization technique, tandem MS has been used in the sequencing of peptides, proteins, lipids, nucleic acids and more recently carbohydrates. The development of the ESI and tandem MS has begun to make carbohydrate analysis more routine. This review will focus on the application of the ESI tandem MS for the sequence analysis of native oligosaccharides, including neutral saccharides with multiple linkages, and the uronic acid polymers, alginate and glycosaminoglycans structures containing epimers.

Keywords: ESI tandem MS; Glycosaminoglycan oligosaccharides; Neutral oligosaccharide; Sequence; Uronic acid oligosaccharides.

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Figures

Fig. (1)
Fig. (1)
Negative-ion ES-CID-MS/MS product-ion spectra of G3 and M3. (a) G3, (b) M3. Structures are shown to indicate the proposed fragmentation (-h: dehydrated ion). Figure taken with permission from ref. [42].
Fig. (2)
Fig. (2)
Expansion of the m/z 450-800 region of EDD tandem MS spectra of the [M-2H]2− precursor-ions of HS epimers: (a) ΔUA-GlcNS-GlcA-GlcNAc, (b) ΔUA-GlcNS-IdoA-GlcNAc. Figure taken with permission from ref. [41].
Fig. (3)
Fig. (3)
Tandem mass spectra of the [M-2H]2− precursor ion of tetrasaccharide (ΔUA-GlcNS-IdoA-GlcNAc6S), obtained by using (a) EDD, (b) IRMPD, and (c) CAD. Figure taken with permission from ref. [84].
Scheme 1
Scheme 1
Fragmentation patterns of two linear neutral oligosaccharides under ESI-CID-MS/MS.
Scheme 2
Scheme 2
Fragmentation patterns of fucose substituted neutral oligosaccharides under ESI-CID-MS/MS.
Scheme 3
Scheme 3
Fragmentation patterns of branched neutral oligosaccharide under ESI-CID-MS/MS.

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