General Fragmentations of Alkaloids in Electrospray Ionization Tandem Mass Spectrometry

Various types of alkaloids observed in several herbal medicines were analyzed by electrospray ionization tandem mass spectrometry in positive ion mode. In the present study, MS/MS spectralpatterns were investigated for eight-types of alka- loids (aporpine, protoberberine, tetrahydroprotoberberine, benzylisoquinoline, protopine, phthalide, morpine, and bisbenzyliso- quinoline). For aporpine- and protoberberine-type alkaloids, main fragmentations occurred at substituted groups on rigid ring structures, not showing ring fusion. Interesting fragmentations due to iminolization and retro-Diels-Alder (RDA) reaction were observed in MS/MS spectra of protopine- and tetrahydroprotobereberine-type alkaloids. Also, several types of fragmentations such as inductive cleavage and α-cleavage, or bond cleavage between two ring structures were observed depending on their structural characteristics. These fragmentation patterns are expected to allow instant classification of the specific alkaloid type in various MS/MS spectra of alkaloids.