To achieve high sensitivity for biomolecule
detection in photoelectrochemical
(PEC) bioanalysis, the ideal photoelectrode and ingenious signaling
mechanism play crucial roles. Herein, the feasibility of the photogenerated
hole-induced chemical–chemical redox cycling amplification
strategy on a Z-scheme heterostructure photoelectrode
was validated, and the strategy toward enhanced multiple signal amplification
for advanced PEC immunoassay application was developed. Specifically,
a direct Z-scheme Bi2S3/Bi2MoO6 heterostructure was synthesized via a classic hydrothermal
method and served as a photoelectrode for the signal response. Under
the illumination, the PEC chemical–chemical redox cycling (PECCC)
among 4-aminophenol generated by the enzymatic catalysis from a sandwich
immunoassay, ferrocene as a mediator, and tris (2-carboxyethyl) phosphine
as a reducing agent was run on the Z-scheme Bi2S3/Bi2MoO6 heterostructure photoelectrode. Exemplified
by interleukin-6 (IL-6) as the target, the applicability of the strategy
was studied in a PEC immunoassay. Thanks to the multiple signal amplification
originating from the high efficiency of the PECCC redox cycling system,
the enzymatic amplification, and the fine performance of the Z-scheme
Bi2S3/Bi2MoO6 heterostructure
photoelectrode, the assay for IL-6 exhibits a very low detection limit
of 2.0 × 10–14 g/mL with a linear range from
5.0 × 10–14 to 1.0 × 10–8 g/mL. This work first validates the feasibility of the PECCC redox
cycling on the Z-scheme heterostructure photoelectrode and the good
performance of the strategy in PEC bioanalysis. We envision that it
would provide a new prospective for highly sensitive PEC bioanalysis
on the basis of a Z-scheme heterostructure.