Snowflake-like CdS@ZnIn2S4 heterojunction-based photocatalyst-electrolyte effect: An innovative mode for photoelectrochemical immunoassay

Exploiting innovative strategies with signal amplification in photoelectrochemical (PEC) biosensing systems to realize sensitive screening of low-abundance proteins has become one of the mainstream research orientations. Herein we reported a new strategy to amplify photocurrent signal employing a photocatalyst-electrolyte effect in alkaline media for the sensitive monitoring of prostate-specific antigen (PSA) using snowflake-liked CdS@ZnIn2S4 heterojunction as photosensitizer. In this strategy, both the band-edge position and surface redox reaction process were subtly altered by modulating the alkalinity of electrolyte. The hydroxyl anions (OH-) from NaOH could be oxidized to hydroxyl radicals (·OH) by the holes in CdS@ZnIn2S4, thus accelerating the scavenging of holes and promoting the photocurrent. Based on the above-mentioned mechanism, a sensitive split-type glucose oxidase-mediated PEC immunosensor for PSA detection was fabricated. Upon target PSA introduction, the glucose acid was generated through the sandwich-type immunoreaction to affect the alkalinity of PEC detection environment, thereby suppressing the photocurrent intensity. The CdS@ZnIn2S4-based PEC immunosensor exhibited satisfactory photocurrent responses with a good linear range of 0.04-40 ng mL-1 at a limit of detection of 14 pg mL-1. Significantly, this research not only introduces an effective strategy to detect PSA with good sensitivity and specificity, but also provides a new insight to amplify the signal by regulating the electrolyte.