Electrochemical Detection of Guanine‐methylation Using Glassy Carbon Electrode

Abstract This work presents a study of the electrochemical oxidation of 7‐methylguanine (7‐mGua) in aqueous solution at glassy carbon electrode by cyclic voltammetry, differential pulse voltammetry, square wave voltammetry and electrochemical impedance spectrometry. The anodic behaviour of 7‐mGua was compared with the electro‐oxidation of guanine and 7‐methylguanosine. The results demonstrated that the methyl and ribose groups are not electroactive but strongly influence the oxidation mechanism of these species. The oxidation of 7‐mGua occurred in a single pH‐dependent step, with the withdrawal of two electrons and two protons of C8, to form 8‐oxo‐7‐methylguanine, while the electro‐oxidation of 7‐methylguanosine also occurred in a single pH‐dependent step, however, with the withdrawal of one electron and one proton of C8 to form a hydroxylated product, since its oxidation to 8‐oxo‐7‐methylguanosine is hindered by the presence of the pendant groups. In addition, the oxidation of 7‐mGua was investigated in the presence of DNA and DNA‐bases, leading to the conclusion that the formation of 7‐mGua, from an interaction of DNA with an alkylating agent, would cause an increase on the deoxyguanosine peak current of the DNA‐biosensor, with no interference of any free DNA bases, which demonstrated that DNA‐electrochemical biosensors find application on detecting DNA methylation, opening a new avenue for applications of DNA biosensors.