In nature, electrical signalling occurs with ions and protons, rather than electrons. Artificial devices that can control and monitor ionic and protonic currents are thus an ideal means for interfacing with biological systems. Here we report the first demonstration of a biopolymer protonic field-effect transistor with proton-transparent PdH x contacts. In maleic-chitosan nanofibres, the flow of protonic current is turned on or off by an electrostatic potential applied to a gate electrode. The protons move along the hydrated maleic-chitosan hydrogen-bond network with a mobility of ~4. . This study introduces a new class of biocompatible solid-state devices, which can control and monitor the flow of protonic current. This represents a step towards bionanoprotonics.

The electrical properties of eumelanin, a ubiquitous natural pigment, have fascinated scientists since the late 1960s. For several decades, the hydrationdependent electrical properties of eumelanin have mainly been interpreted within the amorphous semiconductor model. Recent works undermined this paradigm. Here we study protonic and electronic charge carrier transport in hydrated eumelanin in thin film form. Thin films are ideal candidates for these studies since they are readily accessible to chemical and morphological characterization and potentially amenable to device applications. Current−voltage (I-V) measurements, transient current measurements with proton-transparent electrodes, and electrochemical impedance spectroscopy (EIS) measurements are reported and correlated with the results of the chemical characterization of the films, performed by X-ray photoelectron spectroscopy. We show that the electrical response of hydrated eumelanin films is dominated by ionic conduction (10 −4 −10 −3 S cm −1 ), largely attributable to protons, and electrochemical processes. To propose an explanation for the electrical response of hydrated eumelanin films as observed by EIS and I-V, we considered the interplay of proton migration, redox processes, and electronic transport. These new insights improve the current understanding of the charge carrier transport properties of eumelanin opening the possibility to assess the potential of eumelanin for organic bioelectronic applications, e.g. protonic devices and implantable electrodes, and to advance the knowledge on the functions of eumelanin in biological systems.

Proton conduction is essential in biological systems. Oxidative phosphorylation in mitochondria, proton pumping in bacteriorhodopsin, and uncoupling membrane potentials by the antibiotic Gramicidin are examples. In these systems, H+ hop along chains of hydrogen bonds between water molecules and hydrophilic residues – proton wires. These wires also support the transport of OH− as proton holes. Discriminating between H+ and OH− transport has been elusive. Here, H+ and OH− transport is achieved in polysaccharide- based proton wires and devices. A H+- OH− junction with rectifying behaviour and H+-type and OH−-type complementary field effect transistors are demonstrated. We describe these devices with a model that relates H+ and OH− to electron and hole transport in semiconductors. In turn, the model developed for these devices may provide additional insights into proton conduction in biological systems.