The reduction of doxorubicin at a mercury electrode and monitoring its interaction with DNA using constant current chronopotentiometry

Abstract

In this report, voltammetry with linear scan and chronopotentiometric stripping (CPS) with constant current were used for the analysis of doxorubicin (DOX) at a hanging mercury drop electrode (HMDE). CPS was used for the study of DOX in situ electrochemical reduction in adsorbed state and for ex situ (adsorptive transfer) analysis of the drug. For the first time, CPS was used to study the reversible reduction of the DOX quinine moiety at –0.45 V (vs Ag|AgCl|3 M KCl) as well as electrode processes giving rise to an irreversible signal around –1.45 V at the HMDE in 0.2 M acetate or Britton–Robinson buffers at different pH values. The dependence of the latter signal on pH revealed involvement of protonation equilibria; however, neither CV nor CPS data confirmed the catalytic character of the electrode reaction previously suggested by other authors. The CPS method was also applied to monitor the DOX interaction with double- (ds) and single-stranded (ss) DNA. In the presence of dsDNA, more pronounced changes in DOX signal intensity were observed, in agreement with a strong intercalation of the DOX redox centre into the DNA double helix.