Electrospray ionization mass spectrometric study of purine base-cisplatin complexes

By mixing cisplatin (cis‐diamminedichloroplatinum(II)) with purine base the following ions have been obtained under electrospray ionization conditions: [A+Pt(NH3)2Cl]+, [A+PtNH3Cl]+, [G+Pt(NH3)2Cl]+ and [G+PtNH3Cl]+. Their collision‐induced dissociation led to the loss of NH3 and HCl and formation of the protonated base. The last process is strongly favoured for adenine over guanine. It confirms that, analogously as for DNA, formation of the guanine‐cisplatin complex is favoured over that of the adenine complex and, as a consequence, it suggests that the mass spectrometric study of nucleic base complexes with platinum may provide some information on the interactions of DNA with other platinum drugs. The loss of NH3 accompanied by that of CO from the guanine ring has experimentally confirmed the presence of a strong hydrogen bond between the NH3 molecule and the OC6 moiety of guanine found by theoretical calculations. Copyright © 2005 John Wiley & Sons, Ltd.