Various attractive materials are being used in bioelectronics recently. In this paper, hydroxymethyl-3,4-ethylenedioxythiophene (EDOT-OH) has been in situ integrated and polymerized on the surface of the regenerated silk fibroin (RSF) film to construct a biocompatible electrode. In order to improve the efficiency of in situ polymerization, sodium dodecyl sulfate (SDS) was adopted as surfactant to construct a well-organized and stable poly­(hydroxymethyl-3,4-ethylenedioxythiophene) (PEDOT-OH) coating, whereas ammonium persulfate was used as oxidant. The effects of dosages of surfactant and oxidant, initial pH value, and monomer concentration on the polymerization were studied. Under the optimal conditions, the RSF/PEDOT-OH film exhibited a square resistance of 3.28 × 105 Ω corresponding to a conductance of 6.1 × 10–3 S/cm. Scanning electron microscope images indicated that PEDOT-OH was deposited uniformly on the surface of the RSF film with SDS. Furthermore, Fourier transform infrared spectroscopy confirmed that interactions existed between the peptide linkages of silk fibroin (SF) macromolecules and PEDOT-OH. The RSF/PEDOT-OH film displayed favorable electrochemical stability, biocompatibility, and fastness. This study provides a feasible method to endow conductivity to RSF materials in various forms. In addition, the conductive layer and biocompatible silk substrate make the RSF/PEDOT-OH biomaterial highly suitable for potential applications in bioelectric devices, sensors, and tissue engineering.

Biomimetic scaffolds with a gradient gap distance and robust mechanical properties were prepared using silk fibroin and bacterial cellulose.

Bioelectronics based on biomaterial substrates are advancing toward biomedical applications. As excellent conductors, poly­(3,4-ethylenedioxythiophene) (PEDOT) and its derivatives have been widely developed in this field. However, it is still a big challenge to obtain a functional layer with a good electroconductive property, transparency, and strong adhesion on the biosubstrate. In this work, poly­(hydroxymethyl-3,4-ethylenedioxythiophene) (PEDOT–OH) was chemically polymerized and deposited on the surface of a regenerated silk fibroin (RSF) film in an aqueous system. Sodium dodecyl sulfate (SDS) was used as the surfactant to form micelles which are beneficial to the polymer structure. To overcome the trade-off between transparency and the electroconductive property of the PEDOT–OH coating, a composite oxidant recipe of FeCl3 and ammonium persulfate (APS) was developed. Through electrostatic interaction of oppositely charged doping ions, a well-organized conductive nanoscale coating formed and a transparent conductive RSF/PEDOT–OH film was produced, which can hardly be achieved in a traditional single oxidant system. The produced film had a sheet resistance (R s) of 5.12 × 104 Ω/square corresponding to a conductivity of 8.9 × 10–2 S/cm and a maximum transmittance above 73% in the visible range. In addition, strong adhesion between PEDOT–OH and RSF and favorable electrochemical stability of the film were demonstrated. Desirable transparency of the film allowed real-time observation of live cells. Furthermore, the PEDOT–OH layer provided an improved environment for adhesion and differentiation of PC12 cells compared to the RSF surface alone. Finally, the feasibility of using the RSF/PEDOT–OH film to electrically stimulate PC12 cells was demonstrated.

Silk fibroin (SF)-based electroactive biomaterials with favorable electroconductive property and transparency have great potential applications for cell culture and tissue engineering. Poly­(3,4-ethylenedioxythiophene)-poly­(styrenesulfonate) (PEDOT:PSS) is an excellent candidate as a conductive component, which has been widely used in the field of bioelectronics; however, it is hard to be directly coated onto the surface of regenerated SF (RSF) materials with good stability under a cell culture environment. In this study, a one-step facile PEDOT:PSS modification approach for RSF films based on a suitable post-treatment process of RSF was developed. PEDOT:PSS was successfully embedded and fixed into the shallow surface of an RSF film, forming a tightly conjunct conductive layer on the film surface based on the conformation transition of RSF during the post-treatment process. The conductive layer demonstrated a PSS-rich surface and a PEDOT-rich bulk structure and showed excellent stability under a cell culture environment. More specifically, the robust RSF/PEDOT:PSS film achieved in the post-treatment formula with 70% ethanol proportion possessed best comprehensive properties such as a sheet resistance of 3.833 × 103 Ω/square, a conductivity of 1.003 S/cm, and transmittance over 80% at maximum in the visible range. This kind of electroactive biomaterial also showed good electrochemical stability and degradable properties. Moreover, pheochromocytoma-derived cell line (PC12) cells were cultured on the RSF/PEDOT:PSS film, and an effective electrical stimulation cell response was demonstrated. The facile preparation strategy and the good electroconductive property and transparency make this RSF/PEDOT:PSS film an ideal candidate for neuronal tissue engineering and further for biomedical applications.