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Resolving Sphingolipid Isomers Using Cryogenic Infrared Spectroscopy
Author(s) -
Kirschbaum Carla,
Saied Essa M.,
Greis Kim,
Mucha Eike,
Gewinner Sandy,
Schöllkopf Wieland,
Meijer Gerard,
Helden Gert,
Poad Berwyck L. J.,
Blanksby Stephen J.,
Arenz Christoph,
Pagel Kevin
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202002459
Subject(s) - chemistry , structural isomer , infrared spectroscopy , mass spectrometry , lipidome , spectroscopy , double bond , hydrogen bond , infrared , stereochemistry , molecule , lipidomics , organic chemistry , chromatography , biochemistry , physics , quantum mechanics , optics
1‐Deoxysphingolipids are a recently described class of sphingolipids that have been shown to be associated with several disease states including diabetic and hereditary neuropathy. The identification and characterization of 1‐deoxysphingolipids and their metabolites is therefore highly important. However, exact structure determination requires a combination of sophisticated analytical techniques due to the presence of various isomers, such as ketone/alkenol isomers, carbon–carbon double‐bond (C=C) isomers and hydroxylation regioisomers. Here we demonstrate that cryogenic gas‐phase infrared (IR) spectroscopy of ionized 1‐deoxysphingolipids enables the identification and differentiation of isomers by their unique spectroscopic fingerprints. In particular, C=C bond positions and stereochemical configurations can be distinguished by specific interactions between the charged amine and the double bond. The results demonstrate the power of gas‐phase IR spectroscopy to overcome the challenge of isomer resolution in conventional mass spectrometry and pave the way for deeper analysis of the lipidome.