Assessment of Dimeric Metal-Glycan Adducts via Isotopic Labeling and Ion Mobility-Mass Spectrometry

  • Kelsey A. Morrison
  • Brad K. Bendiak
  • Brian H. ClowersEmail author
Research Article


Adduction of multivalent metal ions to glycans has been shown in recent years to produce altered tandem mass spectra with collision-induced dissociation, electron transfer techniques, and photon-based fragmentation approaches. However, these approaches assume the presence of a well-characterized precursor ion population and do not fully account for the possibility of multimeric species for select glycan-metal complexes. With the use of ion mobility separations prior to mass analysis, doubly charged dimers are not necessarily problematic for tandem MS experiments given that monomer and dimer drift times are sufficiently different. However, multistage mass spectrometric experiments performed on glycans adducted to multivalent metals without mobility separation can yield chimeric fragmentation spectra that are essentially a superposition of the fragments from both the monomeric and dimeric adducts. For homodimeric adducts, where the dimer contains two of the same glycan species, this is less of a concern but if heterodimers can form, there exists the potential for erroneous and misleading fragment ions to appear if a heterodimer containing two different isomers is fragmented along with a targeted monomer. We present an assessment of heterodimer formation between a series of six tetrasaccharides, of which three are isomers, adducted with cobalt(II) and a monodeuterated tetrasaccharide. Using ion mobility separations prior to single-stage and tandem mass analysis, the data shown demonstrate that heterodimeric species can indeed form, and that ion mobility separations are highly necessary prior to using tandem techniques on metal-glycan adducts.

Graphical Abstract


Carbohydrates Glycans Ion mobility Mass spectrometry IM-MS Metal adduction Metal-glycan adducts Glycomics and IMS Transition metal-glycan dimers 



Support for K.A.M. was provided in part by the Defense Threat Reduction Agency under Grant Award Number HDTRA-14-1-0023. The authors received support from the New Faculty Seed Grant from Washington State University.

Supplementary material

13361_2018_1982_MOESM1_ESM.docx (633 kb)
ESM 1 (DOCX 633 kb)


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Copyright information

© American Society for Mass Spectrometry 2018

Authors and Affiliations

  • Kelsey A. Morrison
    • 1
  • Brad K. Bendiak
    • 2
  • Brian H. Clowers
    • 1
    Email author
  1. 1.Washington State UniversityPullmanUSA
  2. 2.University of Colorado Health Sciences CenterAuroraUSA

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