Electrochemical Reduction and Oxidation of Six Natural 2′‐Deoxynucleosides at a Pyrolytic Graphite Electrode in the Presence or Absence of Ambient Oxygen

Recently we have demonstrated that pyrolytic graphite electrodes (PGE) offer a broad analytically useful potential window, ranging from about ?2.0 V to +1.6 V vs. Ag|AgCl|3 M KCl, which enables to use the PGE not only for anodic measurements, but also for direct reduction of nucleobases in DNA oligonucleotides. In this follow‐up study, we have focused on the electrochemical behavior of four 2′‐deoxynucleosides derived from adenine, guanine, cytosine, thymine, uracil, and 5‐methyl cytosine on the PGE. On one hand we have obtained analogous primary redox responses as previously with the oligonucleotides. On the other hand, significant differences were observed, particularly when considering secondary responses involving products of the primary conversions, suggesting involvement of different mechanisms. Further we have found that presence of the ambient oxygen in the electrolyte does not dramatically affect the redox signals of the nucleosides. This finding is in contrast with DNA responses measured at the mercury‐based electrodes, where deaeration prior to the measurements was necessary. We demonstrate that all studied nucleosides can be analyzed using a simple ex situ (medium exchange) procedure.