Direct Electrochemical Signaling in Organic Electrochemical Transistors Comprising High-Conductivity Double-Network Hydrogels

In composite hydrogels, the high electrical performance of poly(3,4-ethylenedioxythiophene) complexed with poly(styrenesulfonate) (PEDOT:PSS) is integrated with complementary structural and electrochemical functions via a rationally designed poly(acrylamide) second network incorporating phenylboronic acid (PBA). Free-standing double-network hydrogels prepared by a simple one-pot radical polymerization exhibit state-of-the-art electrical conductivity (∼20 S cm–1 in phosphate buffered saline) while retaining a degree of hydration similar to that of biological soft tissues. Low resistance contacts to Au electrodes are formed via facile thermo-mechanical annealing and demonstrate stability over a month of continuous immersion, thus enabling hydrogels to serve as channels of organic electrochemical transistors (OECTs). Despite thicknesses of ∼100 μm, gating of hydrogel OECTs is efficient with transconductances gm ∼ 40 mS and on/off ratios of 103 in saturation mode operation, whereas sufficiently high conductivity enables linear mode operation (gm ∼ 1 mS at −10 mV drain bias). This drives a shift of sensing strategy toward detection of electrochemical signals originating within the bulky channel. A kinetic basis for glucose detection via diol esterification on PBA is identified as the coupling of PBA equilibrium to electrocatalyzed O2 reduction occurring on PEDOT in cathodic potentials. Hydrogel OECTs inherently amplify this direct electrochemical signal, demonstrating the viability of a new class of soft, structural biosensors.