MECHANISTIC CONSIDERATIONS OF THE PROTONATION AND FRAGMENTATION OF HIGHLY FUNCTIONALIZED MOLECULES IN FAST-ATOM-BOMBARDMENT - HIGH-RESOLUTION MASS-SPECTROMETRY AND TANDEM MASS-SPECTROMETRY ANALYSIS OF THE IONS FORMED BY FAST-ATOM-BOMBARDMENT OF DIGOXIN AND RELATED CARDIAC-GLYCOSIDES

High resolution mass spectrometry and tandem mass spectrometry analyses of the major ions of digoxin formed by fast atom bombardment are presented and discussed to investigate the mechanisms through which fragment ions are formed. Similar cardiac glycosides are also analyzed to provide support for the proposed fragment assignments. Remote site fragmentation with the charge localized on the aglycone portion of the molecule may provide an explanation for the fragment ions observed in these studies because the majority of these ions contain the aglycone portion of the molecule. The results obtained parallel previously reported results from an ammonia chemical ionization mass spectral study of cardiac glycosides. (J Am Soc Mass Spectrom 1990, 1, 455-472) © 1990 American Society for Mass Spectrometry.