New voltammetric method useful for water insoluble or weakly soluble compounds: application to pKa determination of hydroxyl coumarin derivatives

Here, we reveal a different way of doing the voltammetric experiments that considers the electroactive species packaged in the electrodic phase instead of dissolved in solution. In this way, it is possible to obtain voltammograms of insoluble species. In this work, the method is exemplified by obtaining voltammograms for weakly soluble coumarins but it could be extrapolated to other weakly soluble compounds. We have studied a comprehensive series of 3-acetyl-hydroxycoumarins derivatives which are insoluble in aqueous medium but capable of being trapped in a three-dimensional multi-walled carbon nanotubes (MWCNT) network. Consequently, an electrodic phase composed of an MWCNT modified glassy carbon electrode (GCE) containing the coumarin derivative is prepared. The voltammetric experiment is performed with the above electrodic phase and an aqueous medium as the solution phase. All the coumarin derivatives show one anodic peak due to the oxidation of the hydroxyl group in the phenyl ring. The oxidation peaks follow a one-electron, one-proton irreversible, pH-dependent process for all monohydroxylated compounds. The Ep values are closely dependent of the substituent effect being the 7,8-cum derivative more easily oxidized due to both the electron donor effect of neighboring hydroxyls groups and hydrogen bonding interaction between them. On the other hand, the hydroxyl of the 7-cum derivative is the most difficult to oxidize due to the electron-attracting effect of the lactone carbonyl group at position 2 and acetyl carbonyl at position 3 which is conjugated with OH at 7 positions. From the breaks in the graphs Ep versus pH, we estimate the voltammetric pKa values for all the studied coumarin derivatives.