Dereplication of Acetogenins from Annona muricata by Combining Tandem Mass Spectrometry after Lithium and Copper Postcolumn Cationization and Molecular Networks

Salomé Poyer (1) , Laurent Laboureur (2) , Téo Hebra (2) , Nicolas Elie (2) , Guillaume van Der Rest (3) , Jean-Yves Salpin (1) , Pierre Champy (4) , David Touboul (2)

1 LAMBE - UMR 8587 - Laboratoire Analyse, Modélisation et Matériaux pour la Biologie et l'Environnement
2 ICSN - Institut de Chimie des Substances Naturelles
3 ICP - Institut de Chimie Physique
4 BioCIS - Biomolécules : Conception, Isolement, Synthèse

Annonaceous acetogenins are natural products held responsible for atypical parkinsonism due to chronic consumption in traditional medicine or as food. Due to their long-term neurotoxic effects in humans, the complete chemical characterization of acetogenins in complex mixtures has become crucial. Characterization by tandem mass spectrometry (MS/MS) of acetogenins using collisioninduced dissociation (CID) from lithium adducts provides additional structural information compared to protonated or sodiated species such as ketone location on the acetogenins backbone. However, diagnostic ions are present at a very low intensity limiting this approach to abundant species in the extracts. Copper adducts led to diagnostic fragment ions that allow to identify the position of oxygen rings and hydroxyl substituents. Fragmentation rules were established based on acetogenin standards allowing the identification of 45 over the 77 analogues observed in an extract of Annona muricata by LC-MS/MS using post-column infusion of copper sulfate (CuSO4) solution. Molecular networks that were generated thanks to specific fragmentations obtained with copper, led to the distinction of THF ring position or to the identification of hydroxylated lactone for instance, while networks generated from lithium adducts mainly distinguish analogues with a hydroxyl group at C4 from the other structures.

Domaines: Chimie analytique

Salomé Poyer, Laurent Laboureur, Téo Hebra, Nicolas Elie, Guillaume van Der Rest, et al.. Dereplication of Acetogenins from Annona muricata by Combining Tandem Mass Spectrometry after Lithium and Copper Postcolumn Cationization and Molecular Networks. Journal of The American Society for Mass Spectrometry, 2022, 33 (4), pp.627-634. ⟨10.1021/jasms.1c00303⟩. ⟨hal-03780186⟩