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IR action spectroscopy of glycosaminoglycan oligosaccharides

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

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

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Mucha,  Eike
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Thomas,  Daniel
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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

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Meijer,  Gerard
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Helden,  Gert von
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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

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Citation

Lettow, M., Grabarics, M., Mucha, E., Thomas, D., Polewski, L., Freyse, J., et al. (2020). IR action spectroscopy of glycosaminoglycan oligosaccharides. Analytical and Bioanalytical Chemistry, 412(3), 533-537. doi:10.1007/s00216-019-02327-7.


Cite as: http://hdl.handle.net/21.11116/0000-0005-699B-7
Abstract
Glycosaminoglycans (GAGs) are a physio- and pharmacologically highly relevant class of complex saccharides, possessing a linear sequence and strongly acidic character. Their repetitive linear core makes them seem structurally simple at first glance, yet differences in sulfation and epimerization lead to an enormous structural diversity with only a few GAGs having been successfully characterized to date. Recent infrared action spectroscopic experiments on sulfated mono- and disaccharide ions show great promise. Here, we assess the potential of two types of gas-phase action spectroscopy approaches in the range from 1000 to 1800 cm-1 for the structural analysis of complex GAG oligosaccharides. Synthetic tetra- and pentasaccharides were chosen as model compounds for this benchmark study. Utilizing infrared multiple photon dissociation action spectroscopy at room temperature, diagnostic bands are largely unresolved. In contrast, cryogenic infrared action spectroscopy of ions trapped in helium nanodroplets yields resolved infrared spectra with diagnostic features for monosaccharide composition and sulfation pattern. The analysis of GAGs could therefore significantly benefit from expanding the conventional MS-based toolkit with gas-phase cryogenic IR spectroscopy.