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.