Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2018 May 16;140(19):6034-6038.
doi: 10.1021/jacs.8b01236. Epub 2018 May 7.

Direct Experimental Characterization of Glycosyl Cations by Infrared Ion Spectroscopy

Hidde Elferink  1 , Marion E Severijnen  2 , Jonathan Martens  2 , Rens A Mensink  1 , Giel Berden  2 , Jos Oomens  2 , Floris P J T Rutjes  1 , Anouk M Rijs  2 , Thomas J Boltje  1
Affiliations

Direct Experimental Characterization of Glycosyl Cations by Infrared Ion Spectroscopy

Hidde Elferink et al. J Am Chem Soc. .

Abstract

Glycosyl cations are crucial intermediates formed during enzymatic and chemical glycosylation. The intrinsic high reactivity and short lifetime of these reaction intermediates make them very challenging to characterize using spectroscopic techniques. Herein, we report the use of collision induced dissociation tandem mass spectrometry to generate glycosyl cations in the gas phase followed by infrared ion spectroscopy using the FELIX infrared free electron laser. The experimentally observed IR spectra were compared to DFT calculated spectra enabling the detailed structural elucidation of elusive glycosyl oxocarbenium and dioxolenium ions.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Reactive Intermediates in Glycosylation Reactions and Their Respective Reaction Pathways
LG = Leaving group, E = Electrophile, A = Anion, P = Protecting group.
Scheme 2
Scheme 2. Structures of the Mannosyl Donors Used in This Study
Figure 1
Figure 1
Comparison of the calculated spectra (filled) of 2-O-acetyl- (1a) or 3-O-acetyl- (1b) participation with the measured IR ion spectrum of mannosyl cation derived from 1 (black line in both panels).
Figure 2
Figure 2
Comparison of the calculated spectra (filled) of the 3E (2a) or 4H3 (2b) oxocarbenium ion conformer with the measured IR ion spectrum of the m/z = 219 CID fragment of 2 (black line in both panels). Energies are relative to the 0.0 kJ/mol structure as reported in Figure S6.
Figure 3
Figure 3
Comparison of calculated spectra (filled) with the measured IR ion spectra (black line) of mannuronic acids 3a, 4a, 4b (A–C) and a mixture of isomers 4a and 4b (D).
See this image and copyright information in PMC

References

    1. Boltje T. J.; Buskas T.; Boons G.-J. Nat. Chem. 2009, 1, 611.10.1038/nchem.399. - DOI - PMC - PubMed
    1. Horenstein N. A. In Advances in Physical Organic Chemistry; Richard J. P., Ed.; Elsevier: New York, 2006; Vol. 41, p 275.
    1. Crich D. Acc. Chem. Res. 2010, 43, 1144.10.1021/ar100035r. - DOI - PubMed
    1. Fang T.; Gu Y.; Huang W.; Boons G.-J. J. Am. Chem. Soc. 2016, 138, 3002.10.1021/jacs.5b08436. - DOI - PMC - PubMed
    1. Mensink R. A.; Boltje T. J. Chem. - Eur. J. 2017, 23, 17637.10.1002/chem.201700908. - DOI - PubMed

Publication types

LinkOut - more resources