Related Experiment Video
Updated: Feb 18, 2026

Chemical Triphosphorylation of Oligonucleotides
Published on: June 2, 2022
Selective phosphatidylcholine double bond fragmentation and localisation using Paternò-Büchi reactions and
Fabian Wäldchen1, Simon Becher, Patrick Esch
1Institute of Inorganic and Analytical Chemistry, Justus Liebig University Giessen, 35392 Giessen, Germany. sven.heiles@anorg.chemie.uni-giessen.de.
Abstract:
The effect of double bond functionalisation for selective double bond localisation by ultraviolet photodissociation of phosphatidylcholines is investigated. Paternò-Büchi reactions in nanoESI emitter tips enable attachment of acetophenone to double bonds of unsaturated phosphatidylcholines after 100 s of 254 nm light irradiation with about 50-80% reaction yield. Functionalized phosphatidylcholines dissociate upon 266 nm irradiation yielding double bond selective fragment ions in contrast to results for ultraviolet photodissociation of unmodified lipids. Ultraviolet photodissociation of Paternò-Büchi modified lipids results in a selectivity increase of up to 2.2 towards double bond localisation compared collision-induced dissociation experiments. Double bond localisation is also possible with ultraviolet photodissociation when alkali metal ion attachment to Paternò-Büchi modified phosphatidylcholines occurs in contrast to classic collision-induced dissociation experiments. The developed methodology is used to differentiate lipid double bond isomers and applied to phosphatidylcholines from egg yolk to identify 15 phosphatidylcholines. Results from this study demonstrate that locally depositing energy in close vicinity to cleavable bonds via ultraviolet photodissociation can result in increased dissociation selectivity. This method can help to disentangle contributions from different structural elements in complex tandem mass spectra of lipids and aid to the structural characterization of phospholipids in a "top-down" approach.
Related Concept Videos
Mass Spectrometry: Molecular Fragmentation Overview
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can occur at...
Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation
For example, the...
¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)
Mass Spectrometry: Branched Alkane Fragmentation
Tandem Mass Spectrometry
Mass Spectrometry: Alkene Fragmentation

