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. 2007 Feb;18(2):234-44.
doi: 10.1016/j.jasms.2006.09.020. Epub 2006 Oct 30.

Electron detachment dissociation of glycosaminoglycan tetrasaccharides

Jeremy J Wolff  1 , I Jonathan Amster, Lianli Chi, Robert J Linhardt
Affiliations

Electron detachment dissociation of glycosaminoglycan tetrasaccharides

Jeremy J Wolff et al. J Am Soc Mass Spectrom. 2007 Feb.

Abstract

The first application of electron detachment dissociation (EDD) to carbohydrates is presented. The structural characterization of glycosaminoglycan (GAG) oligosaccharides by mass spectrometry is a longstanding problem because of the lability of these acidic, polysulfated carbohydrates. Doubly-charged negative ions of four GAG tetrasaccharides are examined by EDD, collisionally activated dissociation (CAD), and infrared multiphoton dissociation (IRMPD). EDD is found to produce information-rich mass spectra with both cross ring and glycosidic cleavage product ions. In contrast, most of the product ions produced by CAD and IRMPD result from glycosidic cleavage. EDD shows great potential as a tool for locating the sites of sulfation and other modifications in glycosaminoglycan oligosaccharides.

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Figures

Figure 1
Figure 1
Fragment ion naming convention used in this paper, adapted from Domon and Costello [37]. Superscripts in cross ring cleavage products refer to the bonds that are broken, which are numbered as shown for the second saccharide from the nonreducing end.
Figure 2
Figure 2
Tandem mass spectra of the [M-2H]2− precursor ion of tetrasaccharide 1, obtained by using (A) EDD, (B) IRMPD, and (C) CAD.
Figure 3
Figure 3
EDD mass spectrum of the [M-2H]2− precursor ion of tetrasaccharide 2. The 2,4A3 product in 1 is not observed since it overlaps with the Z2 product. The 1,4X2 product in 1 is not observed since it overlaps with the 1,5A3 product. C2 and Z2 are not observed since the products overlap with the precursor ion.
Figure 4
Figure 4
EDD mass spectrum of the [M-2H]2− precursor ion of tetrasaccharide 3. The B2 and Y2 product ions are not observed as they overlap with the precursor ion.
Figure 5
Figure 5
Tandem mass spectra of the [M-2H]2− precursor ion of tetrasaccharide 4, obtained by using (A) EDD, (B) IRMPD, and (C) CAD.
Scheme 1
Scheme 1
Fragmentation observed when sulfated GAGs are irradiated with 19 eV electrons.
Scheme 2
Scheme 2
Proposed fragmentation mechanism of 1 to form the C2-H product ion.
Scheme 3a
Scheme 3a
Proposed mechanism for H• transfer followed by fragmentation to form the 3,5A3 and 0,2A3 product ions.
Scheme 3b
Scheme 3b
Alternative mechanism for H• transfer followed by fragmentation to form the 3,5A3 and 0,2A3 product ions.
STRUCTURES
STRUCTURES
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