Bisintercalation of ditercalinium into a d(CpGpApTpCpG)2 minihelix: A1H- and31P-NMR study

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Abstract
The structure of the complex formed in aqueous solution between ditercalinium, a bisintercalating drug, and the self‐complementary hexanucleotide d(CpGpApTpCpG)2 is investigated by 400‐MHz 1H‐nmr and 162‐MHz 31P‐nmr. Whatever the drug to thlix ratio, ditercaliniun occurred in the bound form, whereas free and complexed hexanucleotide and are in slow exchange. This allows unambiguous resonance assignm, ent through two‐dimensional chemical exvhange experiments. The strong upfield shifts measured on most aromatic protons on both drug and bases as well as on DNA imino protons are consistent with bisintercalation of the dimer. Nuclear Overhauser effects observed between drug and nucleeotide protons give a defined geometry for complexation, and suggest a DNA conformational change upon drug binding.