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The Impact of Leaving Group Anomericity on the Structure of Glycosyl Cations of Protected Galactosides |
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| Authors: | Kim Greis Dr. Eike Mucha Maike Lettow Dr. Daniel A. Thomas Carla Kirschbaum Sooyeon Moon Alonso Pardo-Vargas Prof. Dr. Gert von Helden Prof. Dr. Gerard Meijer Dr. Kerry Gilmore Prof. Dr. Peter H. Seeberger Prof. Dr. Kevin Pagel |
| Affiliation: | 1. Institute of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany;2. Department of Molecular Physics, Fritz Haber Institute of the Max Planck Society, Faradayweg 4–6, 14195 Berlin, Germany;3. Institute of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany Department of Molecular Physics, Fritz Haber Institute of the Max Planck Society, Faradayweg 4–6, 14195 Berlin, Germany;4. Institute of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, 14195 Berlin, Germany Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, 14476 Potsdam, Germany;5. Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, 14476 Potsdam, Germany |
| Abstract: | It has been reported that fragments produced by glycosidic bond breakage in mass spectrometry-based experiments can retain a memory of their anomeric configuration, which has major implications for glycan sequencing. Herein, we use cryogenic vibrational spectroscopy and ion mobility-mass spectrometry to study the structure of B-type fragments of protected galactosides. Cationic fragments were generated from glycosyl donors carrying trichloroacetimidate or thioethyl leaving groups of different anomeric configuration. The obtained infrared signatures indicate that the investigated fragments exhibit an identical structure, which suggests that there is no anomeric memory in B-type ions of fully protected monosaccharides. |
| Keywords: | anomeric memory IR spectroscopy mass spectrometry glycosylation glycosyl cation |