Characteristic Fragmentation Behavior of Steroidal Phosphor‐ amidate Conjugates in Electrospray Ionization Tandem Mass Spectrometry

Abstract

AbstractNovel steroidal phosphoramidate conjugates of 3′‐azido‐2′,3′‐dideoxythymidine (AZT) and amino acid esters were synthesized and determined by positive and negative ion electrospray ionization mass spectrometry. The MS fragmentation behaviors of the steroidal phosphoramidate conjugates have been investigated in conjunction with tandem mass spectrometry of ESI‐MS/MS. There were three characteristic fragment ions in the positive ion ESI mass spectra, which were the Na adduct ions with loss of steroidal moiety, amino acid ester moiety from pseudo molecular ion (M+Na)+, and the phosphoamino acid methyl ester Na adduct ion by α‐cleavage of the phosphoramidate respectively. The main fragment ions in negative ion ESI mass spectra were the ion (M−HN3)−, the ion (M−AZT−H)−, and the ion (M−steroidal moiety−H)− besides the pseudo molecular ion (M−H)−. The fragmentation patterns did not depend on the attached amino acid ester moiety.