Research Article

Journal of The American Society for Mass Spectrometry

, Volume 24, Issue 11, pp 1798-1806

First online:

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

  • Wen ZhouAffiliated withDepartment of Chemistry, University of MichiganBaxter Healthcare
  • , Kristina HåkanssonAffiliated withDepartment of Chemistry, University of Michigan Email author 

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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