Dj. Harvey, Electrospray mass spectrometry and fragmentation of N-linked carbohydratesderivatized at the reducing terminus, J AM SOC M, 11(10), 2000, pp. 900-915
Citations number
49
Categorie Soggetti
Spectroscopy /Instrumentation/Analytical Sciences
Journal title
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
Derivatives were prepared from N-linked glycans by reductive amination from
2-aminobenzamide, 2-aminopyridine, 3-aminoquinoline, 2-aminoacridone, 4-am
ino-N-(2-diethylaminoethyl)benzamide, and the methyl, ethyl, and butyl este
rs of 4-aminobenzoic acid. Their electrospray and collision-induced dissoci
ation (CID) fragmentation spectra were examined with a Q-TOF mass spectrome
ter. The strongest signals were obtained from the [M + Na](+) ions for all
derivatives except sugars derivatized with 4-amino-N-(2-diethylaminoethyl)b
enzamide which gave very strong doubly charged [M + H + Na](2+) ions. The s
trongest [M + Na](+) ion signals were obtained from the butyl ester of 4-am
inobenzoic acid and the weakest from 2-aminopyridine. The most informative
spectra were recorded from the [M + Li](+) or [M + Na](+) ions. These spect
ra were dominated by ions produced by sequence-revealing glycosidic cleavag
es and "internal" fragments. Linkage-revealing cross-ring cleavage ions wer
e reasonably abundant, particularly from high-mannose glycans. Although the
nature of the derivative was found to have little effect upon the fragment
ation pattern, 3-aminoquinoline derivatives gave marginally more abundant c
ross-ring fragments than the other derivatives. [M + H](+) ions formed only
glycosidic fragments with few, if any, cross-ring cleavage ions. Doubly ch
arged molecular ions gave less informative spectra; singly charged fragment
s were weak, and molecular ions containing hydrogen ([M + 2H](2+) and [M H + Na](2+)) fragmented as the [M + H](+) singly charged ions with no signi
ficant cross-ring cleavages. (J Am Soc Mass Spectrom 2000, 11, 900-915) (C)
2000 American Society for Mass Spectrometry.