A simple
and highly sensitive photoelectrochemical (PEC) immunoassay
sensor was fabricated by using the two forms of polydopamine (PDA),
the thin film and nanosphere, to serve as the photoelectrode-modified
material and signal reporting label, respectively. The two forms of
PDA show similar light absorption behavior but totally different PEC
activities. The PDA film can extend the light absorption from the
ultraviolet to near infrared light range, transfer a photoelectron
to TiO2 nanoparticles and the underlying photoelectrode,
and largely amplify the photocurrent response. However, the PDA nanospheres
have insignificant photoelectron transport ability. When they are
brought close to the PDA film and TiO2 nanocomposite-modified
electrode via the sandwich immunoreaction, they function
like a black hole to compete with the PDA film for light absorption,
resist the access of the electron donor to regenerate the photoactive
material, and capture the photoelectron generated from the PDA film.
Besides, the heat generated from the PDA nanospheres also contributes
to the photocurrent decrease. The PDA nanospheres with multiple quenching
effects on the PDA film greatly decrease the photocurrent signal and
lead to a highly sensitive PEC immunosensing strategy. Under optimal
conditions, a wide linear range from 0.1 to 106 pg·mL–1 is obtained toward carcinoembryonic antigen, with
a low limit of detection of 40 fg·mL–1. Besides,
the PDA with excellent biosafety can be readily assembled with proteins,
which thus simplifies the preparation procedures and decreases the
costs. All these features indicate that the whole PDA-based PEC sensing
strategy may have great application prospects for the point-of-care
assay of various kinds of tumor markers.