The cyclic voltammetric study of iron-tallysomycin in the absence and presence of DNA.

Cyclic voltammetric studies on iron-tallysomycin complexes have been conducted with and without the presence of calf thymus DNA. Fe(II)-TLM samples exhibit a cyclic voltammogram with only a reduction peak at -230 +/- 5 mV vs Ag/AgCl. The addition of DNA substrate causes the shift of this reduction peak to -140 +/- 10 mV vs Ag/AgCl. This large shift in the positive direction implies that the regeneration of Fe(II)-TLM through the reduction of Fe(III)-TLM is facilitated with the aid of DNA. It also implies that the metal-binding/oxygen-activation domain may be directly involved in the formation of iron-tallysomycin-DNA ternary complex. Air oxidation of Fe(II)-TLM produces an activated intermediate with the following CV characteristics, Ipc/Ipa = 0.90; delta E = 65 mV; Ereduction peak = -100 mV vs Ag/AgCl. Addition of DNA abolishes the redox peaks of this voltammogram, signifying inactivation of the activated species through reaction with substrate. Air oxidation of preformed Fe(II)-TLM-DNA complex did not give a discernable cyclic voltammogram, nor did preformed Fe(III)-TLM and Fe(III)-TLM-DNA samples.