Gas-phase
decompositions of magnesium complexes with adenosine-5′-triphosphate
(ATP) and adenosine-5′-diphosphate (ADP) were studied by using
electrospray ionization-collision-induced dissociation-tandem mass
spectrometry, in the negative ion mode. The loss of internal ribose
residue was observed and was found to occur directly from the [ADP-3H+Mg]− ion. The occurrence of this process indicates the
presence of a strong phosphate-Mg-adenine interaction. The performed
quantum mechanics calculations confirmed the occurrence of this interaction
in the [ADP-3H+Mg]− ion, namely the presence of
Mg–N7 bond and hydrogen bond between the phosphate oxygen atom
and amino group. Although the finding concerns the gas phase, it indicates
that phosphate-Mg-adenine interaction may be also of importance for
biological processes. The loss of an internal ribose residue was also
observed for calcium and zinc complexes with ATP/ADP as well as for
magnesium complexes with guanosine-5′-triphosphate (GTP) or
guanosine-5′-diphosphate (GDP). Therefore, it is reasonable
to conclude that the presence of the phosphate-metal-nucleobase interaction
is a feature of gas phase [NDP-3H+metal]− ion (NDP,
nucleoside-5′-diphosphate) and may also be important for biological
processes.