Gas-phase fragmentation of protonated C60-pyrimidine derivatives

Abstract

Electrospray ionization mass spectrometry/mass spectrometry (ESI/MS/MS) and multiple stage mass spectrometry (MSn, n > 2) were used in the positive ion mode, with two different types of mass spectrometers, a quadrupole time-of-flight and an ion trap, to characterize two sets of different types of C60-aminopyrimidine exohedral derivatives. In one set, the pyrimidine moiety bears an amino acid methyl ester residue, and in the other the pyrimidine ring is part of a nucleoside-type moiety, the latter existing as two separated diastereoisomers.We have found that retro-cycloaddition processes occur for the closed shell protonated species formed by electrospraying C60 derivatives synthesized by Diels-Alder reactions, whereas for the C60 derivatives synthesized via 1,3-dipolar cycloadditions, these processes did not occur. Formation of diagnostic ions allowed the differentiation between the two groups of fullerene derivatives, and between the diastereoisomers of C60 derivatives with a nucleoside-type moiety. In general, the fragmentation processes are strongly dependent on the protonation sites and on the structure of the exohedral moieties.