Boron-doped diamond electrodes explored for the electroanalytical detection of 7-methylguanine and applied for its sensing within urine samples

Epigenetic modifications have been associated by many studies with several types of diseases and metabolic dysfunctions. Specifically, N7-methyl modification of guanine (7-mG) is well established to be used as a biomarker for the detection and determination of DNA methylation. The use of an electrochemical sensor has the potential to provide a simpler and more economic sensing methodology for the determination of 7-mG compared to traditionally utilised laboratory based approaches. In this paper we demonstrate the feasibility of an electrochemical sensor which could potentially be easily applied towards the determination of 7-mG within biological samples, such as human urine. A practical electrochemical configuration was employed consisting of a boron-doped diamond electrode (BDD) as the working electrode and a screen-printed graphite electrode (SPE) providing the counter electrode and the reference electrode. With this new protocol, the electrochemical behaviour of 7-mG has been investigated via cyclic voltammetry (CV) and square wave voltammetry (SWV) using a BDD electrode with a simplified electrochemical set-up. The electrochemical behaviour of 7-mG within acetate buffer solutions at a BDD electrode has been compared and contrasted to a glassy carbon electrode with the following parameters studied: voltammetric scan rate, solution pH, 7-mG concentration and electrode surface pretreatment. The oxidative mechanism elucidation has been performed at controlled potential and such results have provided the dimer formation as the major product. The simultaneous electroanalytical identification of 7-mG together with the presence of guanine, adenine and 8-oxoguanine has been investigated under the optimum experimental conditions. Furthermore, the feasibility of using a BDD electrode for the detection of 7-mG is explored in a human urine sample.Authors would like to acknowledge funding throughout the University of Alicante. J. Iniesta thanks the programme Salvador de Madariaga from the Ministerio de Economía y Competitividad, grant number PRX14/00363