Interactions of nucleobases with alkali earth metal cations-electrospray ionization mass spectrometric study

摘要

Interactions of nucleobases with alkali earth metal cations have been studied by electrospray ionization mass spectrometry (ESI-MS). Nucleobases containing at least one oxygen atom form stable complexes with alkali earth metal cations. This phenomenon can be explained on the grounds of the well known theory of hard and soft acids and bases. Uracil and thymine make complexes only when in their deprotonoted forms. The cations of great radii (Sr2+, Ba2+) are more prone to form complexes of stoichiometry 1:1 with uracil and thymine than the cations of small radii (Mg2+, Ca2+). On the other hand, Mg" forms complexes of stoichiometry 2: 1 and 3:2 with uracil and thymine. Gas-phase stabilities of the 1: 1 complexes are higher for the cations of small radii, in contrast to the solution stabilities. For cytosine and 9-methylhypoxantine the 1: 1 complexes of their deprotonated forms are observed at higher cone voltage as a result of HCI molecule loss from the complexes containing the counter ion (CI-). In solution, more stable complexes are formed with metal cations of low radii. Gas-phase stability of the complexes formed by deprotonated 9-methylhypoxantine increases with increasing metal cation radius.