Simple Approach for De Novo Structural Identification of Mannose Trisaccharides
- 265 Downloads
Oligosaccharides have diverse functions in biological systems. However, the structural determination of oligosaccharides remains difficult and has created a bottleneck in carbohydrate research. In this study, a new approach for the de novo structural determination of underivatized oligosaccharides is demonstrated. A low-energy collision-induced dissociation (CID) of sodium ion adducts was used to facilitate the cleavage of desired chemical bonds during the dissociation. The selection of fragments for the subsequent CID was guided using a procedure that we built from the understanding of the saccharide dissociation mechanism. The linkages, anomeric configurations, and branch locations of oligosaccharides were determined by comparing the CID spectra of oligosaccharide with the fragmentation patterns based on the dissociation mechanism and our specially prepared disaccharide CID spectrum database. The usefulness of this method was demonstrated to determine the structures of several mannose trisaccharides. This method can also be applied in the structural determination of oligosaccharides larger than trisaccharides and containing hexose other than mannose if authentic standards are available.
KeywordsOligosaccharide Structure CID
This work was financially supported in part by the Ministry of Science and Technology, Taiwan (103-2113-M-001-011-NY3).
- 1.Varki, A., Cummings, R.D., Esko, J.D., Freeze, H.H., Stanley, P., Bertozzi, C.R., Hart, G.W., Etzler, M.E. (eds.): Essentials of Glycobiology, 2nd edn. Cold Spring Harbor Laboratory Press, Cold Spring Harbor (2009)Google Scholar
- 3.National Research Council: Transforming Glycoscience: A Roadmap for the Future. The National Academies Press, Washington, DC (2012)Google Scholar
- 4.Laine, R.A.: A Calculation of All Possible Oligosaccharide Isomers Both Branched and Linear Yields 1.05x10(12) Structures for a Reducing Hexasaccharide - the Isomer-Barrier to Development of Single-Method Saccharide Sequencing or Synthesis Systems. Glycobiology. 4(6), 759–767 (1994)CrossRefGoogle Scholar
- 8.Chen, J.L., Lee, C., Lu, I.C., Chien, C.L., Lee, Y.T., Hu, W.P., Ni, C.K.: Theoretical investigation of low detection sensitivity for underivatized carbohydrates in ESI and MALDI. J. Mass Spectrom. 51(12), 1180–1186 (2016)Google Scholar
- 12.Vijayakrishnan, B., Issaree, A., Corilo, Y.E., Ferreira, C.R., Eberlin, M.N., Peter, M.G.: MSn of the six isomers of (GlcN) 2(GlcNAc) 2aminoglucan tetrasaccharides (diacetylchitotetraoses): Rules of fragmentation for the sodiated molecules and application to sequence analysis of hetero-chitooligosaccharides. Carbohydr. Polym. 84(2), 713–726 (2011)Google Scholar
- 21.Xue, J., Song, L., Khaja, S.D., Locke, R.D., West, C.M., Laine, R.A., Matta, K. L.: Determination of linkage position and anomeric configuration in Hex-Fuc disaccharides using electrospray ionization tandem mass spectrometry. Rapid Commun. Mass Spectrom. 18(17), 1947–1955 (2004)Google Scholar
- 22.Mendonca, S., Cole, R.B., Zhu, J., Cai, Y., French, A.D., Johnson, G.P., Laine R.A.: Incremented alkyl derivatives enhance collision induced glycosidic bond cleavage in mass spectrometry of disaccharides. J. Am. Soc. Mass. Spectrom. 14(1), 63–78 (2003)Google Scholar
- 26.Fang, T.T., Zirrolli, J., Bendiak, B.: Differentiation of the anomeric configuration and ring form of glucosyl-glycolaldehyde anions in the gas phase by mass spectrometry: isomeric discrimination between m/z 221 anions derived from disaccharides and chemical synthesis of m/z 221 standards. Carbohydr. Res. 342(2), 217–235 (2007)Google Scholar
- 27.Fang, T.T., Bendiak, B.: The stereochemical dependence of unimolecular dissociation of monosaccharide-glycolaldehyde anions in the gas phase: a basis for assignment of the stereochemistry and anomeric configuration of monosaccharides in oligosaccharides by mass spectrometry via a key discriminatory product ion of disaccharide fragmentation, m/z 221. J. Am. Chem. Soc. 129(31), 9721–9736 (2007)Google Scholar
- 29.Ni, C.K.: Simple methods for de novo structural determination of glucose-containing underivatized oligosaccharides. In the division of carbohydrate chemistry, 254th American Chemical Society National Meeting & Exposition August 20-24, 2017, Washington, DC USAGoogle Scholar
- 35.Chen, J.L., Nguan, H.S., Hsu, P.J., Tsai, S.T., Liew, C.Y., Kuo, J.L., Hu, W.P., Ni, C.K.: Collision-induced dissociation of sodiated glucose and identification of anomeric configuration. Phys. Chem. Chem. Phys. 19, 15454–15462 (2017)Google Scholar