Evaluation of the electrochemical response of aromatic peptides for biodetection of dopamine.

Biologically inspired aromatic peptide-based materials are gaining increasing interest as novel charge transport materials for bioelectronics due to their remarkable electrical response and inherent biocompatibility. In this work, the electrochemical response of ten aromatic amino acids and eleven aromatic peptides has been evaluated to assess the potential of incorporating peptides into electrochemical sensors not as biorecognition elements but as biocompatible electronic materials. While the electrochemical response of amino acids is null in all cases, the hexapeptide of phenylalanine (Phe) capped with eight polyethylene glycol units at the N-terminus and, especially, the cyclic dipeptide formed by two dehydro-phenylalanine residues (cyclo(ΔPhe)), which organize in fibrillary self-assembled structures of nano- and submicrometric size, respectively, are the most electroactive peptides. Electrodes to electrochemically detect the oxidation of dopamine have been prepared using a plasma-activated polyethylene terephthalate glycol substrate covered with a poly(3,4-ethylenedioxythiophene) layer and a peptide coating deposited at the surface. The highest analytical sensitivity and the lowest limits of detection and quantifications have been obtained for the electrode coated with cyclo(ΔPhe), which shows much better results than that without peptide. These results, on the one hand, confirm the significant role of electron transport through π-stacking interactions in the electrochemical response of peptides and, on the other hand, demonstrate that peptides can be directly used as electronic materials rather than as simple recognition elements in electrochemical biosensors.