Holistic approach based on high resolution and multiple stage mass spectrometry to investigate ergot alkaloids in cereals

•Fragmentation pathways of ergopeptines, ergoamides and ergopeptams were established.•A simple strategy based on high resolution and ion trap mass spectrometry was proposed for identification of less studied or novel ergot alkaloid derivatives.•Using the proposed strategy, eleven ergot alkaloids (for which reference standards were not available) could be identified in grain samples.

A holistic approach based on high resolution and multiple stage mass spectrometry was developed for identification of less studied or novel ergot alkaloid derivatives. Initially, the fragmentation of nine known ergot alkaloids was studied to establish a strategy for the identification of novel ergot alkaloids. Ions with m/z 223 and m/z 251 were found to be common for all ergopeptines, ergoamides and ergopeptams. Subsequently, parent scan experiments using these ions were performed to screen grain samples for the presence of possible ergot alkaloid derivatives. Besides the six most common ergot alkaloids and their corresponding epimers (for which reference standards were available), eleven other ergot alkaloid derivatives were identified following the proposed strategy.