Direct observation of radical intermediates during electron transfer between DNA and a ternary copper complex

The photoinduced electron transfer (PET) reaction within a ternary copper complex [Cu(phen)(Htrp)]+ (Htrp: l-tryptophanato; phen: 1,10-phenanthroline) (1) and in presence of DNA has been studied in homogeneous buffer medium and in reverse micelles. An intramolecular electron transfer occurs within the photoexcited complex (1) from tryptophan to phen. The copper complex can displace ethidium bromide from DNA backbone and on photoexcitation can oxidize DNA in a deoxygenated environment due to intermolecular electron transfer, although the intramolecular electron transfer is thermodynamically favorable. A prominent magnetic field effect (MFE) has been found even in homogeneous aqueous medium for the triplet born radicals both in case of intra and intermolecular electron transfer reactions. In case of intramolecular electron transfer the observation of MFE is similar to that of linked donor-acceptor system. However the observation of MFE for the intermolecular electron transfer between non-covalently bound complex-DNA systems is rather rare. Some non-covalent weak interaction, e.g. hydrophobic interaction between the phen ligand and DNA base pairs and electrostatic force of attraction between [Cu(phen)(Htrp)]+ complex and DNA may lead to partial intercalation of the copper complex within DNA that is responsible for such a rare observation.