Tailoring Diffusional Fields in Zwitterion/Dopamine Copolymer Electropolymerized at Carbon Nanowalls for Sensitive...

The importance of neurotransmitter sensing in the diagnosis and treatment of many psychological illnesses and neurodegenerative diseases is non-negotiable. For electrochemical sensors to become widespread and accurate, a long journey must be undertaken for each device, from understanding the materials at the molecular level to real applications in biological fluids. We report a modification of diamondized boron-doped carbon nanowalls (BCNWs) with an electropolymerized polydopamine/polyzwitterion (PDA|PZ) coating revealing tunable mechanical and electrochemical properties. Zwitterions are codeposited with PDA and noncovalently incorporated into a structure. This approach causes a specific separation of the diffusion fields generated by each nanowall during electrochemical reactions, thus increasing the contribution of the steady-state currents in the amperometric response. This phenomenon has a profound effect on the sensing properties, leading to a 4-fold enhancement of the sensitivity (3.1 to 14.3 μA cm^-2 μM^-1) and a 5-fold decrease of the limit of detection (505 to 89 nM) in comparison to the pristine BCNWs. Moreover, as a result of the antifouling capabilities of the incorporated zwitterions, this enhancement is preserved in bovine serum albumin (BSA) with a high protein concentration. The presence of zwitterion facilitates the transport of dopamine in the direction of the electrode by intermolecular interactions such as cation-π and hydrogen bonds. On the other hand, polydopamine units attached to the surface form molecular pockets driven by hydrogen bonds and π-π interactions. As a result, the intermediate state of dopamine-analyte oxidation is stabilized, leading to the enhancement of the sensing properties.