Tandem mass spectrometric analysis of interfacial lipid alkyl chains selectively modified via reactive ion deposition
- 1Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstr. 2, Leipzig, Germany, 04103
- 2Leibniz Institut für Oberflächenmodifizierung (IOM), Permoserstraße 15, Leipzig, 04318
Abstract
The molecular structures of lipids, including branching, double bonds and substitution within the hydrophobic chains, are key aspects in research fields such as biomarkers and signaling, and determine cell membrane properties. Although mass spectrometry has become the dominant method for lipidomics, determining fatty acid chain structures using widely available methods (MSn via CID) remains challenging. In this study, we present reactive ion deposition as a method for chemically modifying interfacial lipids in thin layers. Highly reactive [B12I11]− anions are mass-selected and deposited onto layers containing various fatty acids, phosphatidylserines, phosphatidylcholines and triacylglycerides. Using isotope-labelled compounds, we observed that [B12I11]− selectively binds to the terminal methyl groups of fatty acid hydrophobic n-alkyl chains (≥95%). The molecular structure of the lipid remains intact during covalent binding of the reactive ion on the surface, effectively charge-tagging the lipid at the alkyl chain. Therefore, ESI-MS analysis of the interfacially active layer components is enabled. Collision-induced dissociation of the anionic reaction products reveals structural information about the lipid via MSn spectra regarding both head group and fatty acid chain structure (i.e., branching, double bonds and substituent positions). This method enables not only analysis of lipids molecular structures, but also reveals information about the interfacial composition and molecular orientation of complex samples due to the binding of molecular groups located at the interface of the probed layer.
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BibTeX
@misc{hoschele2026tandem,
title = {{Tandem mass spectrometric analysis of interfacial lipid alkyl chains selectively modified via reactive ion deposition}},
author = {David Höschele and Markus Rohdenburg and Nataša Negru and Hanna Ziegler and Kay-Antonio Behrend and Harald Knorke and Jonas Warneke},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008476/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008476/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Tandem mass spectrometric analysis of interfacial lipid alkyl chains selectively modified via reactive ion deposition
AU - David Höschele
AU - Markus Rohdenburg
AU - Nataša Negru
AU - Hanna Ziegler
AU - Kay-Antonio Behrend
AU - Harald Knorke
AU - Jonas Warneke
PY - 2026
DA - 2026/09/08
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008476/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008476/v1
AB - The molecular structures of lipids, including branching, double bonds and substitution within the hydrophobic chains, are key aspects in research fields such as biomarkers and signaling, and determine cell membrane properties. Although mass spectrometry has become the dominant method for lipidomics, determining fatty acid chain structures using widely available methods (MSn via CID) remains challenging. In this study, we present reactive ion deposition as a method for chemically modifying interfacial lipids in thin layers. Highly reactive [B12I11]− anions are mass-selected and deposited onto layers containing various fatty acids, phosphatidylserines, phosphatidylcholines and triacylglycerides. Using isotope-labelled compounds, we observed that [B12I11]− selectively binds to the terminal methyl groups of fatty acid hydrophobic n-alkyl chains (≥95%). The molecular structure of the lipid remains intact during covalent binding of the reactive ion on the surface, effectively charge-tagging the lipid at the alkyl chain. Therefore, ESI-MS analysis of the interfacially active layer components is enabled. Collision-induced dissociation of the anionic reaction products reveals structural information about the lipid via MSn spectra regarding both head group and fatty acid chain structure (i.e., branching, double bonds and substituent positions). This method enables not only analysis of lipids molecular structures, but also reveals information about the interfacial composition and molecular orientation of complex samples due to the binding of molecular groups located at the interface of the probed layer.
ER -