A carbon quantum layer modified BiVO4 photoelectrochemical aptamer biosensor for ultra-sensitive cTnI biomarker detection based on the interface nephelauxetic effect and heterojunction assistance

Abstract

The sensitivity and specificity of a semiconductor photoelectrochemical (PEC) aptamer biosensor are determined by the separation and transport of the photoinduced carriers as well as aptamer probe immobilization. In this study, an in situ thermal transformation organic polymer strategy was employed to produce an ∼2.5 nm carbon quantum layer on the surface of the BiVO₄(BVO) photoanode. Experimental tests and theoretical calculations have revealed that this carbon quantum layer-coated BVO(C@BVO) heterostructure could generate surface charge depletion regions through an interface nephelauxetic effect. These charge depletion regions facilitated the efficient immobilization of DNA aptamer probes of the acute myocardial infarction biomarker cardiac troponin I (cTnI), while showing almost no immobilization capability on a pure-phase C quantum layer or BVO crystals. Simultaneously, the formation of the C@BVO heterostructure also enhanced the directional transport of photo-generated holes from BVO to the C quantum layer. Due to the above reasons, the C@BVO PEC aptamer biosensor achieved a linear detection range for cTnI from 10⁻¹⁴ g L⁻¹ to 10⁻¹⁰ g L⁻¹, with a record detection limit (LOD) of ∼0.33 × 10⁻¹⁴ g L⁻¹ (N > 3). Meanwhile, the biosensor also demonstrated well the detection reproducibility and specificity for cTnI detection. Therefore, the strategy of using a carbon quantum layer-coated PEC electrode shows good potential to develop PEC biosensors with high sensitivity, specificity, and robustness.