Negative electron transfer dissociation of glycosaminoglycans

Jeremy J. Wolff, Franklin E. Leach, Tatiana Nikolaevna Laremore, Desmond A. Kaplan, Michael L. Easterling, Robert J. Linhardt, I. Jonathan Amster

Research output: Contribution to journalArticle

83 Citations (Scopus)

Abstract

Structural characterization of glycosaminoglycans (GAGs) has been a challenge in the field of mass spectrometry, and the application of electron detachment dissociation (EDD) Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) has shown great promise to GAG oligosaccharide characterization in a single tandem mass spectrometry experiment. In this work, we apply the technique of negative electron transfer dissociation (NETD) to GAGs on a commercial ion trap mass spectrometer. NETD of GAGs, using fluoranthene or xenon as the reagent gas, produces fragmentation very similar to previously observed EDD fragmentation. Using fluoranthene or xenon, both glycosidic and cross-ring cleavages are observed, as well as even- and odd-electron products. The loss of SO3 can be minimized and an increase in cross-ring cleavages is observed if a negatively charged carboxylate is present during NETD, which can be controlled by the charge state or the addition of sodium. NETD effectively dissociates GAGs up to eight saccharides in length, but the low resolution of the ion trap makes assigning product ions difficult. Similar to EDD, NETD is also able to distinguish the epimers iduronic acid from glucuronic acid in heparan sulfate tetrasaccharides and suggests that a radical intermediate plays an important role in distinguishing these epimers. These results demonstrate that NETD is effective at characterizing GAG oligosaccharides in a single tandem mass spectrometry experiment on a widely available mass spectrometry platform.

Original languageEnglish (US)
Pages (from-to)3460-3466
Number of pages7
JournalAnalytical Chemistry
Volume82
Issue number9
DOIs
StatePublished - May 1 2010

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Glycosaminoglycans
Electrons
Mass spectrometry
Ions
Xenon
Oligosaccharides
Iduronic Acid
Cyclotron resonance
Glucuronic Acid
Heparitin Sulfate
Mass spectrometers
Fourier transforms
Gases
Sodium
Experiments

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry

Cite this

Wolff, J. J., Leach, F. E., Laremore, T. N., Kaplan, D. A., Easterling, M. L., Linhardt, R. J., & Amster, I. J. (2010). Negative electron transfer dissociation of glycosaminoglycans. Analytical Chemistry, 82(9), 3460-3466. https://doi.org/10.1021/ac100554a
Wolff, Jeremy J. ; Leach, Franklin E. ; Laremore, Tatiana Nikolaevna ; Kaplan, Desmond A. ; Easterling, Michael L. ; Linhardt, Robert J. ; Amster, I. Jonathan. / Negative electron transfer dissociation of glycosaminoglycans. In: Analytical Chemistry. 2010 ; Vol. 82, No. 9. pp. 3460-3466.
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Wolff, JJ, Leach, FE, Laremore, TN, Kaplan, DA, Easterling, ML, Linhardt, RJ & Amster, IJ 2010, 'Negative electron transfer dissociation of glycosaminoglycans', Analytical Chemistry, vol. 82, no. 9, pp. 3460-3466. https://doi.org/10.1021/ac100554a

Negative electron transfer dissociation of glycosaminoglycans. / Wolff, Jeremy J.; Leach, Franklin E.; Laremore, Tatiana Nikolaevna; Kaplan, Desmond A.; Easterling, Michael L.; Linhardt, Robert J.; Amster, I. Jonathan.

In: Analytical Chemistry, Vol. 82, No. 9, 01.05.2010, p. 3460-3466.

Research output: Contribution to journalArticle

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AU - Wolff, Jeremy J.

AU - Leach, Franklin E.

AU - Laremore, Tatiana Nikolaevna

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Wolff JJ, Leach FE, Laremore TN, Kaplan DA, Easterling ML, Linhardt RJ et al. Negative electron transfer dissociation of glycosaminoglycans. Analytical Chemistry. 2010 May 1;82(9):3460-3466. https://doi.org/10.1021/ac100554a