Abstract
High performance liquid chromatography-tandem mass spectrometry (LS/MSn) utilizing an ion trap mass spectrometer has been used for the analyses of representative cardiac steroids. In the case of bufotoxin having a polar residue (suberoylarginine), the positive-electrospray ionization (ESI) was 50 times more sensitive than the atmospheric pressure chemical ionization (APCI) and provided information concerning the molecular weight as well as the structures of both aglycone and suberoylarginine. The corresponding bufogenin showed 2 times better sensitivity in the positive-APCI than ESI. The mass spectrum of digoxin with the positive-APCI showed fragment ions not only derived from aglycone but also formed by losses of sugars. The cleavage of the dioxane ring has been observed on the cardiac glycoside having an unusual sugar linkage. Fast atom bombardment mass spectra of these compounds were examined and compared with the data obtained from LC/MSn.
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