Analysis of Amaryllidaceae alkaloids from Crinum by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

A high-performance liquid chromatography/electrospray ionization multi-stage tandem mass spectrometry (HPLC/ESI-MS(n)) method was developed to analyze two structurally related groups of Amaryllidaceae alkaloids (AmAs), crinane- and tazettine-type alkaloids, in the species Crinum latifolium and C. asiaticum, as well as different organs of C. latifolium. In ESI-MS(n) spectra of the two types of alkaloids, characteristic fragmentation reactions were observed that allowed us to determine and differentiate them. Based on the fragmentation rules of reference standards, crinane-type alkaloids displayed concurrent neutral loss of C(2)H(5)N (43 u) and C(2)H(6)N (44 u) as well as characteristic ions of m/z 213 and 211, whereas tazettine-type alkaloids exhibited neutral loss of C(3)H(7)N (57 u) [or C(2)H(5)N (43 u), C(3)H(7)NO (73 u)] from the [M+H](+) and [M+H-H(2)O](+) ions. These were supported by quadrupole time-of-flight (Q-Tof)-MS/MS analysis. The chemical complexity of the mixture was resolved by profiling. The compositions of the main crinane- and tazettine-type alkaloids in the above-mentioned species and organs were also compared. Overall, 28 AmAs comprising 14 crinane-type and 14 tazettine-type alkaloids were identified and studied by MS. Among them, 14 AmAs were tentatively characterized from the two species for the first time. This method allowed a rapid analysis of alkaloid distribution and composition of Crinum species, and may also be used for quality control and screening of extracts designated for pharmaceutical application.