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Separation of isomeric glycans by ion mobility spectrometry–the impact of fluorescent labelling

MPS-Authors
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Manz,  Christian
Institute of Chemistry and Biochemistry, Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Grabarics,  Márkó
Institute of Chemistry and Biochemistry, Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Hoberg,  Friederike
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Pugini,  Michele
Institute of Chemistry and Biochemistry, Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Pagel,  Kevin
Institute of Chemistry and Biochemistry, Freie Universität Berlin;
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Citation

Manz, C., Grabarics, M., Hoberg, F., Pugini, M., Stuckmann, A., Struwe, W. B., et al. (2019). Separation of isomeric glycans by ion mobility spectrometry–the impact of fluorescent labelling. Analyst, 144(17), 5292-5298. doi:10.1039/C9AN00937J.


Cite as: http://hdl.handle.net/21.11116/0000-0004-57E8-5
Abstract
The analysis of complex oligosaccharides is traditionally based on multidimensional workflows where liquid chromatography is coupled to tandem mass spectrometry (LC-MS/MS). Due to the presence of multiple isomers, which cannot be distinguished easily using tandem MS, a detailed structural elucidation is still challenging in many cases. Recently, ion mobility spectrometry (IMS) showed great potential as an additional structural parameter in glycan analysis. While the time-scale of the IMS separation is fully compatible to that of LC-MS-based workflows, there are very few reports in which both techniques have been directly coupled for glycan analysis. As a result, there is little knowledge on how the derivatization with fluorescent labels as common in glycan LC-MS affects the mobility and, as a result, the selectivity of IMS separations. Here, we address this problem by systematically analyzing six isomeric glycans derivatized with the most common fluorescent tags using ion mobility spectrometry. We report >150 collision cross-sections (CCS) acquired in positive and negative ion mode and compare the quality of the separation for each derivatization strategy. Our results show that isomer separation strongly depends on the chosen label, as well as on the type of adduct ion. In some cases, fluorescent labels significantly enhance peak-to-peak resolution which can help to distinguish isomeric species