Cryogenic Infrared Spectroscopy Reveals Structural
Modularity in the Vibrational Fingerprints of Heparan Sulfate Diastereomers
Posted on 2020-07-21 - 16:13
Heparan
sulfate and heparin are highly acidic polysaccharides with
a linear sequence, consisting of alternating glucosamine and hexuronic
acid building blocks. The identity of hexuronic acid units shows a
variability along their sequence, as d-glucuronic acid and
its C5 epimer, l-iduronic acid, can both
occur. The resulting backbone diversity represents a major challenge
for an unambiguous structural assignment by mass spectrometry-based
techniques. Here, we employ cryogenic infrared spectroscopy on mass-selected
ions to overcome this challenge and distinguish isomeric heparan sulfate
tetrasaccharides that differ only in the configuration of their hexuronic
acid building blocks. High-resolution infrared spectra of a systematic
set of synthetic heparan sulfate stereoisomers were recorded in the
fingerprint region from 1000 to 1800 cm–1. The experiments
reveal a characteristic combination of spectral features for each
of the four diastereomers studied and imply structural modularity
in the vibrational fingerprints. Strong spectrum-structure correlations
were found and rationalized by state-of-the-art quantum chemical calculations.
The findings demonstrate the potential of cryogenic infrared spectroscopy
to extend the mass spectrometry-based toolkit for the sequencing of
heparan sulfate and structurally related biomolecules.
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Lettow, Maike; Grabarics, Márkó; Greis, Kim; Mucha, Eike; Thomas, Daniel A.; Chopra, Pradeep; et al. (2020). Cryogenic Infrared Spectroscopy Reveals Structural
Modularity in the Vibrational Fingerprints of Heparan Sulfate Diastereomers. ACS Publications. Collection. https://doi.org/10.1021/acs.analchem.0c02048
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AUTHORS (13)
ML
Maike Lettow
MG
Márkó Grabarics
KG
Kim Greis
EM
Eike Mucha
DT
Daniel A. Thomas
PC
Pradeep Chopra
GB
Geert-Jan Boons
RK
Richard Karlsson
JT
Jeremy E. Turnbull
GM
Gerard Meijer
RM
Rebecca L. Miller
Gv
Gert von Helden
KP
Kevin Pagel
KEYWORDS
heparan sulfatevibrational fingerprintshexuronic acid building blocksquantum chemical calculationsisomeric heparan sulfate tetrasacch...heparan sulfate stereoisomerssequenceStrong spectrum-structure correlationshexuronic acid unitsVibrational Fingerprintsmass spectrometry-based techniquesmass-selected ionsd-glucuronic acidl-iduronic acidfingerprint regionchallengespectroscopyacidic polysaccharidesHeparan Sulfate Diastereomers Hepar...C 5 epimerbackbone diversitymass spectrometry-based toolkitStructural Modularitycryogenic