The rapidly emerging field of organic bioelectronics exploits the functional versatility of conducting polymers to transduce biological recognition events into electronic signals. For the majority of biosensors or biomedical devices, immobilization of a biorecognition element is a critical step to improve the biotic/abiotic interface. In this work, a simple strategy is described to construct large‐area all‐plastic poly(3,4‐ethylenedioxythiophene) (PEDOT) electrodes displaying carbohydrate biorecognizable motifs. First, the method involves the preparation of PEDOT‐poly(allylamine) composites through supramolecular interactions. It is demonstrated by Raman and X‐ray spectroscopy and cyclic voltammetry that the PEDOT:poly(allylamine) ratio and the film electoactivity can be easily controlled. Then, carbohydrate motifs are covalently anchored to the primary amine groups by a straightforward route using divinylsulfone chemistry. The recognition‐driven assembly of the lectin concanavalin A (Con A) and the glycoenzyme glucose oxidase (GOx) onto mannosylated surfaces is demonstrated by surface plasmon resonance spectroscopy. Furthermore, the bioelectrocatalytic glucose detection mediated by the assembled enzyme is studied for all‐plastic and gold electrodes. Interestingly, the synergistic combination of conducting polymers and recognition‐directed assembly leads to a 2.7‐fold enhancement of the bioelectrocatalitic signal. Finally, it is proved that Con A/GOx nanoarchitectures can be constructed onto PEDOT platforms using the layer‐by‐layer technique.

conducting polymer with the biggest prospects in the emerging field of bioelectronics due to their combination of characteristics (mixed conductivity, stability, transparency, and biocompatibility). [1] In this emerging field, PEDOT is currently being investigated in a number of new applications such as conducting hydrogels, biosensors, organic electrochemical transistors, selective detachment of cells, scaffolds for tissue engineering, electrodes for electrophysiology, implantable electrodes, stimulation of neuronal cells, electronic skin, or pan-bio electronics. [2] The most used PEDOT version is the commercially available aqueous dispersion poly(3,4-ethylen edioxythiophene):poly(styrene sulfonate) (PEDOT: PSS) which is usually processed by casting or spin-coating. However, in order to well connect the two fields of biology and electronics, [3] PEDOT:PSS presents some limitations associated with the low (bio)functionality of the PEDOT polymer and acidity/toxicity of the PSS stabilizer. [4-7] For this reason, in the last few years a number of functional EDOT monomer derivatives has been synthesized including hydroxymethyl, [8] chloromethyl, [9] azidomethyl, [10] carboxylic Poly(3,4-ethylenedioxythiophene) (PEDOT) is the most popular conducting polymer in the emerging field of bioelectronics. Besides its excellent properties and commercial availability, its success is due to the aqueous processability of its anionically stabilized solutions or dispersions. In this work, a water soluble version of PEDOT is shown, which is cationically stabilized. This work reports the chemical oxidative (co)polymerization of EDOT-ammonium derivative leading to PEDOT-N (co)polymers. PEDOT-N shows the typical features of PEDOT such as UV absorbance, bipolaron band, electrical conductivity, electrochemical behavior, and film formation ability. Furthermore, the PEDOT-N films show good biocompatibility in the presence of the human embryonic kidney-293 cell line. The water solubility of PEDOT-N and its cationic nature allows its processability in the form of thin films obtained by the layer-by-layer technique or as conducting hydrogels.

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