Interaction of nucleic acids with electrically charged surfaces. VI. A comparative study on the electrochemical behaviour of native and denatured DNAs at graphite electrodes

Abstract

Adsorption and electrochemical oxidation of deoxyribonucleic acid (DNA) at a pyrolytic graphite electrode (PGE) and a paraffin wax-impregnated spectroscopic graphite electrode (WISGE) were studied using differential pulse voltammetry. DNA is adsorbed at the surface of the graphite electrodes in a broad range of potentials including the potentials of electrochemical oxidation of DNA. Both native and denatured DNAs yield two single, well-defined and separated peaks, G and A, on the differential pulse voltammograms at the PGE and WISGE. The more negative peak, G, corresponds to electrochemical oxidation of guanine residues, whereas the more positive peak, A, corresponds to electrochemical oxidation of adenine residues. Peaks G and A of native DNA occur at the same potentials as peaks G and A of denatured DNA. However, electrochemical oxidation of adenine and guanine residues at graphite electrodes is markedly suppressed in native DNA. The heights of the peaks G and A represent a sensitive indicator of the helix-coil transition of DNA. An analysis of the product of interaction of a sample of native DNA with a large pyrolytic graphite electrode in the presence of formaldehyde at approximately neutral pH did not prove changes in the secondary structure of native DNA due to its interaction with the graphite electrode. It is suggested that the decreased differential pulse-voltammetric activity of native DNA is connected with its decreased flexibility.