Fabrication of Electronically Conductive Protein-Heme Nanowires for Power Harvesting.

Electronically conductive protein-based materials can enable the creation of bioelectronic components and devices from sustainable and nontoxic materials, while also being well-suited to interface with biological systems, such as living cells, for biosensor applications. However, as proteins are generally electrical insulators, the ability to render protein assemblies electroactive in a tailorable manner can usher in a plethora of useful materials. Here, an approach to fabricate electronically conductive protein nanowires is presented by aligning heme molecules in proximity along protein filaments, with these nanowires also possessing charge transfer abilities that enable energy harvesting from ambient humidity. The heme-incorporated protein nanowires demonstrate electron transfer over micrometer distances, with conductive atomic force microscopy showing individual nanowires having comparable conductance to other previously characterized heme-based bacterial nanowires. Exposure of multilayer nanowire films to humidity produces an electrical current, presumably through water molecules ionizing carboxyl groups in the filament and creating an unbalanced total charge distribution that is enhanced by the heme. Incorporation of heme and potentially other metal-center porphyrin molecules into protein nanostructures could pave the way for structurally- and electrically-defined protein-based bioelectronic devices.

Organic Mixed Ionic-Electronic Conductors Based on Tunable and Functional Poly(3,4-ethylenedioxythiophene) Copolymers.

Organic mixed ionic-electronic conductors (OMIECs) are being explored in applications such as bioelectronics, biosensors, energy conversion and storage, and optoelectronics. OMIECs are largely composed of conjugated polymers that couple ionic and electronic transport in their structure as well as synthetic flexibility. Despite extensive research, previous studies have mainly focused on either enhancing ion conduction or enabling synthetic modification. This limited the number of OMIECs that excel in both domains. Here, a series of OMIECs based on functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) copolymers that combine efficient ion/electron transport with the versatility of post-functionalization were developed. EDOT monomers bearing sulfonic (EDOTS) and carboxylic acid (EDOTCOOH) groups were electrochemically copolymerized in different ratios on oxygen plasma-treated conductive substrates. The plasma treatment enabled the synthesis of copolymers containing high ratios of EDOTS (up to 68%), otherwise not possible with untreated substrates. This flexibility in synthesis resulted in the fabrication of copolymers with tunable properties in terms of conductivity (2-0.0019 S/cm) and ion/electron transport, for example, as revealed by their volumetric capacitances (122-11 F/cm3). The importance of the organic nature of the OMIECs that are amenable to synthetic modification was also demonstrated. EDOTCOOH was successfully post-functionalized without influencing the ionic and electronic transport of the copolymers. This opens a new way to tailor the properties of the OMIECs to specific applications, especially in the field of bioelectronics.

A PEDOT based graft copolymer with enhanced electronic stability.

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) remains the most investigated conjugated polymer in bioelectronics, due to its biocompatibility, high conductivity, and commercial availability. Despite these advantages, it suffers from structural and electronic instability, associated with the PSS component. Here, a graft copolymer based on ionised sulfonic modified PEDOT, poly(EDOTS-g-EDOT), was electrochemically synthesised with demonstrated structural and electronic stability and enhanced electrochemical performance. The graft copolymer was insoluble in water without crosslinking, and exhibited enhanced ion diffusion upon electrochemical switching, as revealed by its volumetric capacitance (159 ± 8 F cm-3), which was significantly higher than that of spin-coated PEDOT:PSS films (41 ± 5 F cm-3). Similarly, its performance as an active channel material in organic electrochemical transistors (OECTs) was superior to the spin-coated PEDOT:PSS, as shown for instance by its high normalised transconductance (273 ± 79 S cm-1) and a significantly high ION/IOFF ratio (19 345 ± 1205). Its short- and long-term electronic stability were also confirmed with no drop in its output drain current, despite its high swelling degree. In contrast, the spin-coated PEDOT:PSS experienced a significant deterioration in its performance over the same operational time. The facile synthesis and improved performance of poly(EDOTS-g-EDOT) highlight the importance of innovative material design in overcoming existing operational shortcomings in electronic devices.

Self-Doping and Self-Acid-Doping of Conjugated Polymer Bioelectronics: The Case for Accuracy in Nomenclature.

Conjugated polymers are enabling the development of flexible bioelectronics, largely driven by their organic nature which facilitates modification and tuning to suit a variety of applications. As organic semiconductors, conjugated polymers require a dopant to exhibit electrical conductivity, which in physiological conditions can result in dopant loss and thereby deterioration in electronic properties. To overcome this challenge, "self-doped" and self-acid-doped conjugated polymers having ionized pendant groups covalently bound to their backbone are being developed. The ionized group in a "self-doped" polymer behaves as the counterion that maintains electroneutrality, while an external dopant is required to induce charge transfer. The ionized group in a self-acid-doped polymer induces charge transfer and behaves as the counterion balancing the charges. Despite their doping processes being different, the two terms, self-doped and self-acid-doped, are often used interchangeably in the literature. Here, the differences are highlighted in the doping mechanisms of self-doped and self-acid-doped polymers, and it is proposed that the term "self-doped" should be replaced by "self-compensated," while reserving the term self-acid-doped for polymers that are intrinsically doped without the need of an external dopant. This is followed by a summary of examples of self-acid-doping in bioelectronics, highlighting their stability in the conductive state under physiological conditions.

A flexible polyaniline-based bioelectronic patch.

Bioelectronic materials based on conjugated polymers are being developed in the hope to interface with electroresponsive tissues. We have recently demonstrated that a polyaniline chitosan patch can efficiently electro-couple with cardiac tissue modulating its electrophysiology. As a promising bioelectronic material that can be tailored to different types of devices, we investigate here the impact of varying the synthesis conditions and time of the in situ polymerization of aniline (An) on the sheet resistance of the bioelectronic patch. The sheet resistance increases significantly for samples that have either the lowest molar ratio of oxidant to monomer or the highest molar ratio of dopant to monomer, while the polymerization time does not have a significant effect on the electrical properties. Conductive atomic force microscopy reveals that the patch with the lowest sheet resistance has a connected network of the conductive phase. In contrast, patches with higher sheet resistances exhibit conductive areas of lower current signals or isolated conductive islands of high current signals. Having identified the formulation that results in patches with optimal electrical properties, we used it to fabricate patches that were implanted in rats for two weeks. It is shown that the patch retains an electroactive nature, and only mild inflammation is observed with fibrous tissue encapsulating the patch.

Direct imaging of defect formation in strained organic flexible electronics by Scanning Kelvin Probe Microscopy.

The development of new materials and devices for flexible electronics depends crucially on the understanding of how strain affects electronic material properties at the nano-scale. Scanning Kelvin-Probe Microscopy (SKPM) is a unique technique for nanoelectronic investigations as it combines non-invasive measurement of surface topography and surface electrical potential. Here we show that SKPM in non-contact mode is feasible on deformed flexible samples and allows to identify strain induced electronic defects. As an example we apply the technique to investigate the strain response of organic thin film transistors containing TIPS-pentacene patterned on polymer foils. Controlled surface strain is induced in the semiconducting layer by bending the transistor substrate. The amount of local strain is quantified by a mathematical model describing the bending mechanics. We find that the step-wise reduction of device performance at critical bending radii is caused by the formation of nano-cracks in the microcrystal morphology of the TIPS-pentacene film. The cracks are easily identified due to the abrupt variation in SKPM surface potential caused by a local increase in resistance. Importantly, the strong surface adhesion of microcrystals to the elastic dielectric allows to maintain a conductive path also after fracture thus providing the opportunity to attenuate strain effects.