Abstract
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.
Highlights
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 de novo biosynthesis of any sphingoid base is initiated by the condensation of palmitoyl-CoA and l-serine, which is catalyzed by serine palmitoyl transferase (SPT).[4]
As a consequence of the missing OH group, 1-deoxysphingolipids cannot be transformed into phospho- or glycosphingolipids and are not degradable via the canonical pathway, which requires phosphorylation of the 1-hydroxyl group.[6]. Since their first discovery in marine clams[7] and detection in mammals only one decade ago,[5,8] 1deoxysphingolipids have moved into the focus of interest as their accumulation is related to several diseases
Summary
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. Those involve ketone/alkenol isomers, carbon–carbon double bond (C=C) positional- and stereoisomers and hydroxylation (OH) regioisomers, most of which cannot be resolved using established techniques. The difficulty in distinguishing C=C bond isomers is expected to apply to IR spectroscopy as C=C stretching vibrations are generally weak.
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