Characterization of O-Sulfopeptides by Negative Ion Mode Tandem Mass Spectrometry: Superior Performance of Negative Ion Electron Capture Dissociation

2012 ◽  
Vol 84 (15) ◽  
pp. 6370-6377 ◽  
Author(s):  
Katherine E. Hersberger ◽  
Kristina Håkansson
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Electron Capture ◽  
Electron Capture Dissociation ◽  
Negative Ion ◽  
Superior Performance ◽  
Tandem Mass ◽  
Negative Ion Mode

Structural analysis of small to medium-sized molecules by mass spectrometry after electron-ion fragmentation (ExD) reactions

The Analyst ◽  
2016 ◽  
Vol 141 (3) ◽  
pp. 794-806 ◽  
Author(s):  
Yulin Qi ◽  
Dietrich A. Volmer
Keyword(s):  
Mass Spectrometry ◽  
Structural Analysis ◽  
Tandem Mass Spectrometry ◽  
Electron Capture ◽  
Electron Capture Dissociation ◽  
Tandem Mass ◽  
Ion Fragmentation

Electron capture dissociation (ECD) is a tandem mass spectrometry (MS/MS) method that utilizes the interaction of ions and electrons.

Characterization of Oligosaccharides of the Lactosamine Series Derived from Keratan Sulfates by Tandem Mass Spectrometry

2000 ◽  
Vol 6 (2) ◽  
pp. 193-203 ◽  
Author(s):  
Masayuki Kubota ◽  
Keiichi Yoshida ◽  
Akira Tawada ◽  
Mamoru Ohashi
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Bond Cleavage ◽  
The Other ◽  
Negative Ion ◽  
Ring Cleavage ◽  
Tandem Mass ◽  
Fragment Ions ◽  
Glycosidic Bond Cleavage

Positive- and negative-ion fast-atom bombardment tandem mass spectrometry with collision-induced dissociation (FAB-CID-MS/MS) has been used in the characterization of di-and tetra-saccharides of the lactosamine series from keratan sulfates. FAB-CID-MS/MS of Galβ1-4GlcNAc (L1) exhibited strong fragment ions originating from ring cleavage at the reducing-terminal sugar moiety together with glycosidic bond-cleavage ions, whereas GlcNAcβ1-3Gal (K1) showed strong glycosidic bond-cleavage ions but no ring-cleavage ions. A series of ring-cleavage fragment ions was observed with members of the L-series which have free hydroxyl groups at the C1 and C3 positions. CID-MS/MS spectra of the [M + Na – SO3]+ ion ( m/z 406) from L2 and the [M + Na − 2SO3]+ ion ( m/z 406) from L4 were almost identical with the CID-MS/MS spectrum of the [M + Na]+ ion ( m/z 406) from L1, which indicated that the sugar skeletons of L2 and L4 are the same as that of L1. On the other hand, the CID-MS/MS spectrum of the [M + Na – SO3]+ ion ( m/z 508) from L4 did not resemble that of the [M + Na]+ ion ( m/z 508) from L2. The former showed peaks that were additional to the peaks in the latter. Since these extra peaks were accounted for on the basis of the structure of L3 [Galβ1(6S)-4GlcNAc, S = sulfate], the in-source loss of sulfate groups by ester exchange upon FAB ionization takes place in a dual manner; one reaction at the non-reducing terminal sugar to give L2 and the other at the reducing-terminal sugar to give L3. The CID-MS/MS spectra were characteristic for the tetrasaccharides L1-L1, L2-L2 and L4-L4 while in-source fragmentation confirms the component disaccharides of each tetrasaccharide. The structure of a tetrasaccharide trisulfate was confirmed as L2–L4 and not L4–L2 by CID-MS/MS. Negative-ion FAB-CID-MS/MS spectra of the sulfated di-and tetra-saccharides showed a pattern similar to that of the positive-ion spectra. Subtraction of the CID-MS/MS spectrum of the [M – H]− ion of L2 [Galβ1-4GlcNAc(6S)] from that of the [M – H – SO3]− ion of L4 [Gal(6S)β1-4GlcNAc(6S)] gave several specific ions whose origins were nicely explained on the basis of the structure of L3. The structure of a pentasaccharide consisting of N-acetylneuraminic acid and a tetrasaccharide trisulfate was confirmed, on the basis of FAB-CID-MS/MS, as NeuNAcα2-6L2-L4.

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