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

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

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.

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Acknowledgments

This work was supported by Award Number R21CA138331 from the National Cancer Institute. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Cancer Institute or the National Institutes of Health. W.Z. was partially supported by a George Ashworth Analytical Chemistry Fellowship from the University of Michigan.

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  1. Wen Zhou

    Present address: Department of Chemistry, University of Michigan, Ann Arbor, MI, 48109-1055, USA

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  1. Department of Chemistry, University of Michigan, Ann Arbor, MI, 48109-1055, USA

    Kristina Håkansson

  2. Baxter Healthcare, 1700 Rancho Conejo Blvd, Thousand Oaks, CA, 91320, USA

    Wen Zhou

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  1. Wen Zhou
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Correspondence to Kristina Håkansson.

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Zhou, W., Håkansson, K. Electron Capture Dissociation of Divalent Metal-adducted Sulfated N-Glycans Released from Bovine Thyroid Stimulating Hormone. J. Am. Soc. Mass Spectrom. 24, 1798–1806 (2013). https://doi.org/10.1007/s13361-013-0700-3

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