Electrospray and APCI analysis of polyhydroxyalkaloids using positive and negative collision induced dissociation experiments in a quadrupole ion trap

Atmospheric pressure chemical ionisation (APCI) and electrospray (ES) are compared as ion sources in the analysis of polyhydroxyalkaloids (PHAs) by liquid chromatography mass spectrometry (LC-MS) and collision induced dissociation (CID) product ion spectra, from tandem mass spectrometry (MS-MS) experiments in a quadrupole ion trap, are reported for 12 naturally occurring PHAs. APCI was found to be a more useful source than ES, as APCI could be used to generate deprotonated molecule ions in negative mode and for some isomeric PHAs the negative CID product ion spectra were more diagnostic than the positive product ion spectra. On-column detection limits were also approximately 32 times lower by positive APCI than ES. The work provides data that will facilitate screening and characterisation of this group of important natural products in plant and fungal extracts.