Salt-dependent binding of iron(II) mixed-ligand complexes containing 1,10-phenanthroline and dipyrido[3,2-a:2′,3′-c]phenazine to calf thymus DNA

The salt-dependent binding of racemic iron(II) mixed-ligand complex containing 1,10-phenanthroline (phen) and dipyrido[3,2-a:2′,3′-c]phenazine (dppz), [Fe(phen)2(dppz)]2+ to calf thymus DNA (ct-DNA) has been characterized by UV-VIS spectrophotometric titration. The equilibrium binding constant (Kb) of the iron(II) complex to ct-DNA decreases with the salt concentration in the solution. The slope, SK = (δlog Kb / δlog [Na2+]) has been found to be 0.49, suggesting that, in addition to intercalation, considerable electrostatic interaction is also involved in the ct-DNA binding of [Fe(phen)2(dppz)]2+. The calculation of non-electrostatic binding constant (Kto) based on polyelectrolyte theory has revealed that the non-electrostatic contribution to the total binding constant (Kb) increases significantly with the increase in [Na+] and reaches 36% at 0.1 M NaCl. On the other hand, the contribution of the non-electrostatic binding free energy (ΔGto) to the total binding free energy change (ΔGo) is considerably large, i.e. 87% at [Na+] = 0.1 M, suggesting that the stabilization of the DNA binding is mostly due to the contribution of non-electrostatic process. Moreover, the effect of specific ligand substitutions on ΔGo has been rigorously evaluated using the quantity ΔΔGto, i.e. the difference in ΔGto relative to that of the parent iron(II) complex, [Fe(phen)3]2+, indicating that each substitution of phen by dip and dppz contributes 7.5 and 17.5 kJ mol− 1, respectively to more favorable ct-DNA binding.