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Negatively charged, pH-sensitive, very thin gel layers with accumulated hexaammineruthenium (II)/(III) were deposited on conducting surfaces. The gel was synthesized by applying an electrochemically induced free-radical polymerization method. This method allowed covering the electrode surface with an uniform and compact layer. The modified electrodes exhibited excellent current switch on/off behavior in response to changes in pH. However, the main goal of this study was to achieve the control of the layer thickness by changing the oxidation state of hexaammineruthenium. The layers could be reversibly swollen/shrinked by applying appropriate potentials.

A series of thermoresponsive hydrogels containing positively charged groups in the polymeric network were synthesized and modified with the electroactive compound 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS). ABTS, which forms a dianion in aqueous solutions, acts as an additional physical cross-linker and strongly affects the swelling ratio of the gels. The influence of the amount of positively charged groups and ABTS oxidation state on the volume phase transition temperature was investigated. A hydrogel that possesses a relatively wide and well-defined temperature window (the temperature range where changes in the ABTS oxidation state affects the swelling ratio significantly) was found. The influence of the presence and oxidation state of ABTS on mechanical properties was investigated using a tensile machine and a rheometer. Then, a very thin layer of the gel was deposited on an Au electrochemical quartz crystal microbalance with dissipation (EQCM-D) electrode using the electrochemically induced free radical polymerization method. Next, chronoamperometry combined with quartz crystal microbalance measurements, obtained with an Au EQCM-D electrode modified by the gel, showed that the size of the thin layer could be controlled by an electrochemical trigger. Furthermore, it was found that the electrosensitivity could be modulated by the temperature. Such properties are desired from the point of view construction of electrochemical actuators.

In this study, we present a thermoresponsive thin hydrogel layer based on poly(N-isopropylacrylamide), functionalized with β-cyclodextrin groups (p(NIPA-βCD)), as a novel electrochemically controlled release system. This thin hydrogel layer was synthesized and simultaneously attached to the surface of a Au quartz crystal microbalance (QCM) electrode using electrochemically induced free radical polymerization. The process was induced and monitored using cyclic voltammetry and a quartz crystal microbalance with dissipation monitoring (QCM-D), respectively. The properties of the thin layer were investigated by using QCM-D and scanning electron microscopy (SEM). The incorporation of β-cyclodextrin moieties within the polymer network allowed rhodamine B dye modified with ferrocene (RdFc), serving as a model metallodrug, to accumulate in the p(NIPA-βCD) layer through host–guest inclusion complex formation. The redox properties of the electroactive p(NIPA-βCD/RdFc) layer and the dissociation of the host–guest complex triggered by changes in the oxidation state of the ferrocene groups were investigated. It was found that oxidation of the ferrocene moieties led to the release of RdFc. It was crucial to achieve precise control over the release of RdFc by applying the appropriate electrochemical signal, specifically, by applying the appropriate potential to the electrode. Importantly, the electrochemically controlled RdFc release process was performed at a temperature similar to that of the human body and monitored using a spectrofluorimetric technique. The presented system appears to be particularly suitable for transdermal delivery and delivery from intrabody implants.