Ion tree-based structure elucidation of acetophenone dimers (AtA) from Acronychia pedunculata and their identification in extracts by liquid chromatography electrospray ionization LTQ-Orbitrap mass spectrometry.

Acronychia-type acetophenones (AtA) is a chemical group of compounds of important structural and biological interest, abundant in Acronychia species. However, there are no data available for their characterization using mass spectrometry. In the current work, AtA have been investigated by multistage high resolution mass spectrometry and both electrospray ionization and atmospheric pressure chemical ionization, in positive and negative mode, were utilized for their structure elucidation and identification. The analysis of AtA using a linear ion trap-Orbitrap analyzer enabled the structural determination of key fragment ions and cleavages, which can be used for the structural characterization thereof. A systematic nomenclature based on protonated and deprotonated fragment ions under collision-induced dissociation conditions and decision trees for the structural determination of AtA are proposed. Furthermore, taking advantage of the characteristic fragmentation patterns, a selective Ultra High Performance Liquid Chromatography Electrospray Ionization multistage Mass Spectrometry (UHPLC-ESI(-)-MS(n)) method was developed and successfully applied for the dereplication of known AtA and the identification of potentially new ones in Acronychia extracts. Despite the structure similarity and the presence of isomers, accurate characterization of known and unknown AtA derivatives was possible.