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Linkage Determination of Linear Oligosaccharides by MSn (n > 2) Collision-Induced Dissociation of Z1 Ions in the Negative Ion Mode

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

Obtaining unambiguous linkage information between sugars in oligosaccharides is an important step in their detailed structural analysis. An approach is described that provides greater confidence in linkage determination for linear oligosaccharides based on multiple-stage tandem mass spectrometry (MSn, n >2) and collision-induced dissociation (CID) of Z1 ions in the negative ion mode. Under low energy CID conditions, disaccharides 18O-labeled on the reducing carbonyl group gave rise to Z1 product ions (m/z 163) derived from the reducing sugar, which could be mass-discriminated from other possible structural isomers having m/z 161. MS3 CID of these m/z 163 ions showed distinct fragmentation fingerprints corresponding to the linkage types and largely unaffected by sugar unit identities or their anomeric configurations. This unique property allowed standard CID spectra of Z1 ions to be generated from a small set of disaccharide samples that were representative of many other possible isomeric structures. With the use of MSn CID (n = 3 – 5), model linear oligosaccharides were dissociated into overlapping disaccharide structures, which were subsequently fragmented to form their corresponding Z1 ions. CID data of these Z1 ions were collected and compared with the standard database of Z1 ion CID using spectra similarity scores for linkage determination. As the proof-of-principle tests demonstrated, we achieved correct determination of individual linkage types along with their locations within two trisaccharides and a pentasaccharide.

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Acknowledgments

C.K. and Y.X. acknowledge the financial support from Purdue Research Foundation. B.B. acknowledges NSF grant in part, CHE-0137986.

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Authors and Affiliations

  1. Department of Chemistry, Purdue University, West Lafayette, IN, 47907-2084, USA

    Chiharu Konda & Yu Xia

  2. Department of Cell and Developmental Biology, and Program in Structural Biology and Biophysics, University of Colorado Denver, Anschutz Medical Campus, Aurora, CO, 80045, USA

    Brad Bendiak

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  1. Chiharu Konda
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Correspondence to Yu Xia.

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Konda, C., Bendiak, B. & Xia, Y. Linkage Determination of Linear Oligosaccharides by MSn (n > 2) Collision-Induced Dissociation of Z1 Ions in the Negative Ion Mode. J. Am. Soc. Mass Spectrom. 25, 248–257 (2014). https://doi.org/10.1007/s13361-013-0769-8

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