Journal of The American Society for Mass Spectrometry

, Volume 24, Issue 11, pp 1798–1806

Electron Capture Dissociation of Divalent Metal-adducted Sulfated N-Glycans Released from Bovine Thyroid Stimulating Hormone

Research Article

DOI: 10.1007/s13361-013-0700-3

Cite this article as:
Zhou, W. & Håkansson, K. J. Am. Soc. Mass Spectrom. (2013) 24: 1798. doi:10.1007/s13361-013-0700-3


Sulfated N-glycans released from bovine thyroid stimulating hormone (bTSH) were ionized with the divalent metal cations Ca2+, Mg2+, and Co by electrospray ionization (ESI). These metal-adducted species were subjected to infrared multiphoton dissociation (IRMPD) and electron capture dissociation (ECD) and the corresponding fragmentation patterns were compared. IRMPD generated extensive glycosidic and cross-ring cleavages, but most product ions suffered from sulfonate loss. Internal fragments were also observed, which complicated the spectra. ECD provided complementary structural information compared with IRMPD, and all observed product ions retained the sulfonate group, allowing sulfonate localization. To our knowledge, this work represents the first application of ECD towards metal-adducted sulfated N-glycans released from a glycoprotein. Due to the ability of IRMPD and ECD to provide complementary structural information, the combination of the two strategies is a promising and valuable tool for glycan structural characterization. The influence of different metal ions was also examined. Calcium adducts appeared to be the most promising species because of high sensitivity and ability to provide extensive structural information.

Key words

bTSH Bovine thyroid stimulating hormone Oligosaccharides Glycan N-glycan Sulfonation Sulfation Metal cations Metal complexes ECD Electron capture Dissociation Fourier transform ion cyclotron resonance FT-ICR FTMS Tandem mass spectrometry Structural characterization IRMPD Infrared multiphoton dissociation 

Supplementary material

13361_2013_700_MOESM1_ESM.docx (205 kb)
ESM 1(DOCX 205 kb)

Copyright information

© American Society for Mass Spectrometry 2013

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of MichiganAnn ArborUSA
  2. 2.Baxter HealthcareThousand OaksUSA

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