Spectroelectrochemical Evidence of Interconnected Charge and Ion Transfer in Ultrathin Membranes Modulated by a Redox Conducting Polymer

[Image: see text] Previous publications have demonstrated the tuning of ion-transfer (IT) processes across ion-selective membranes (ISMs) with thicknesses in the nanometer order by modulating the oxidation state of a film of a conducting polymer, such as poly(3-octylthiophene) [POT], that is in back-side contact. Attempts on the theoretical description of this charge transfer (CT)–IT system have considered the Nernst equation for the CT, while there is no empirical evidence confirming this behavior. We present herein the first experimental characterization of the CT in POT films involved in different CT–IT systems. We take advantage of the absorbance change in the POT film while being oxidized, to monitor the CT linked to nonassisted and assisted ITs at the sample–ISM interface, from one to three ionophores, therefore promoting a change in the nature and number of the ITs. The CT is visualized as an independent sigmoid in different potential ranges according to the assigned IT. Herein, we have proposed a simple calculation of the empirical CT utilizing the mathematical Sigmoidal–Boltzmann model. The identification of the physical meaning of the mathematical definition of CT opens up new possibilities for the design of sensors with superior analytical features (mainly in terms of selectivity) and the calculation of apparent binding constants in the ISM.