In this paper, we demonstrate the use of a monolayer film electrografted via diazonium chemistry for controlling the potential response of a field-effect transistor (FET)-based sensor. 4-Nitrobenzenediazonium salt is electrografted on an extended-Au-gate FET (EG-Au-FET) with or without using a radical scavenger by cyclic voltammetry (CV), resulting in the formation of a monolayer or multilayer. In particular, the surface coverage of the aryl-derivative monolayer on the Au gate electrode gradually increases with increasing number of potential cycles in CV. Here, Au exhibits a strong catalytic action, resulting in the oxidation of organic compounds. Uric acid is used as a low-molecular-weight biomolecule for interference. The denser the surface coverage of the grafted monolayer, the smaller the potential response of the EG-Au-FET because the redox reaction of uric acid with the Au gate surface is suppressed. On the other hand, the effect of the aryl-derivative multilayer on the suppression of the potential response was smaller than that of the monolayer because the electrogenerated aryl radicals did not react with the Au surface but with the grafted species, resulting in an exposed part of the Au surface among the grafted aryl molecules. Thus, a platform based on such a monolayer film electrografted via diazonium chemistry is suitable for controlling the potential response based on the interference of low-molecular-weight biomolecules in biosamples.

Aryl diazonium chemistry generates a covalently attached thin film on various materials. This chemistry has diverse applications owing to the stability, ease of functionalization, and versatility of the film. However, the uncontrolled growth into a polyaryl film has limited the controllability of the film’s beneficial properties. In this study, we developed a multistep grafting protocol to densify the film while maintaining a thickness on the order of nanometers. This simple protocol enabled the full passivation of a nitrophenyl polyaryl film, completely eliminating the electrochemical reactions at the surface. We then applied this protocol to the grafting of phenylphosphorylcholine films, with which the densification significantly enhanced the antifouling property of the film. Together with its potential to precisely control the density of functionalized surfaces, we believe this grafting procedure will have applications in the development of bioelectrical interfaces.

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A free-standing conductive hydrogel electrode with no coating on a substrate is proposed for potentiometric glucose sensing.

The Belousov–Zhabotinsky (BZ) self-oscillation reaction is an important chemical model to elucidate nonequilibrium chemistry in an open system. However, there are only a few studies on the electrical behavior of pH oscillation induced by the BZ reaction, although numerous studies have been carried out to investigate the mechanisms by which the BZ reaction interacts with redox reactions, which results in potential changes. Needless to say, the electrical characteristic of a self-oscillating polymer gel driven by the BZ reaction has not been clarified. On the other hand, a solution-gated ion-sensitive field-effect transistor (ISFET) has a superior ability to detect ionic charges and includes capacitive membranes on the gate electrode. In this study, we carried out the electrical monitoring of self-oscillation behaviors at the chemoelectrical interface based on the BZ reaction using ISFET sensors, focusing on the pH oscillation and the electrical dynamics of the self-oscillating polymer brush. The pH oscillation induced by the BZ reaction is not only electrically observed using the ISFET sensor, the electrical signals of which results from the interfacial potential between the solution and the gate insulator, but also visualized using a large-scale and high-density ISFET sensor. Moreover, the N-isopropylacrylamide (NIPAAm)-based self-oscillating polymer brush with Ru(bpy)3 as a catalyst clearly shows a periodic electrical response based on the swelling–deswelling behavior caused by the BZ reaction on the gate insulator of the ISFET sensor. Thus, the elucidation of the electrical self-oscillation behaviors induced by the BZ reaction using the ISFET sensor provides a solution to the problems of nonequilibrium chemistry.