In this work an ion trap mass spectrometer with electrospray ionisation was employed to detect and elucidate the structure of the partially low concentrated cisplatin-DNA-adducts. After a preceding chromatographic separation step which was coupled to the ESI-sprayer, the platinum binding positions to the enzymatically generated smallest possible cisplatin-complexes (adducts to dinucleotides) as well as the sequence of nucleotides directly adjoining the lesions were determined by fragmentation. The existence of several formerly unknown crosslinks (1,2-intrastrand-GT-, 1,2-intrastrand-AA-, 1,3-intrastrand-AG- and 1,2-interstrand-AG-adducts) as well as a distinct but not exclusive sequence specifity for thymidine could be shown.
Additionally experiments to investigate the gas phase behaviour of platinum-complexes in the ion trap were performed using cisplatin-adducts to selected dinucleosidemonophosphates. It could be shown that the complexes are highly reactive, undergoing numerous intramolecular reactions after the unblocking of a coordination site at the platinum center.