A dual-signal self-checking photoelectrochemical immunosensor based on the sole composite of MIL-101(Cr) and CdSe quantum dots for the detection of α-fetoprotein.

Designing a photoelectrochemical (PEC) immunosensor that can produce dual photocurrent signals which can refer to each other is a great importance but a big challenge. In this manuscript, a novel dual photocurrent signals immunosensor was constructed for the detection of α-fetoprotein (AFP). Unlike the usual method of using two composite materials to provide cathode and anode photocurrent respectively, this work applies only one compound of MIL-101 (Cr) and CdSe quantum dots (QDs). Thereinto, we found that the photocurrent polarity of MIL-101(Cr) would switch by adjusting applied voltage. And then CdSe QDs was introduced by simple ultrasound mixing to boost the dual photocurrent signals. Furthermore, in the composite of M&C, the electron transfer path between MIL-101(Cr) and CdSe QDs may switch between "Z-type" and "Ⅱ-type" by adjusting voltage. Benefiting by the dual signals, the proposed sensor can not only perform sensitively quantitative detection of α-fetoprotein (AFP), but also can intuitively estimate the accuracy and reliability of the test result by determining whether the corresponding relationship of "cathode photocurrent-analyte concentration-anode photocurrent" is established. The linear ranges of the sensing electrodes as cathode and anode are the same, both from 0.1 to 300 ng mL-1. The limit of detection (LOD) is 0.082 ng mL-1 (S/N = 3) when it used as an anode, and the LOD is 0.054 ng mL-1 (S/N = 3) when it served as cathode. Furthermore, this sensor showed acceptable stability, reproducibility, specificity, and feasibility of detecting AFP in human serum, which has broad development prospects in the early clinical diagnosis.