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This work proposes the first photoelectrochemical proximity assay (PECPA) method via the sensitization of CdTe quantum dots (QDs) on photoelectrochemical response of ITO/TiO2/CdS electrode for highly selective and sensitive detection of proteins. This detection was performed on a sensing interface formed via the hybridization of capture DNA immobilized on ITO/TiO2/CdS electrode with labeled antibody-DNA (DNA-Ab1). Upon the recognition of Ab1 to target protein, the immunocomplex of DNA-Ab1, target, and the detection antibody-DNA (DNA-Ab2) was formed, which led to the proximity hybridization of the DNA in DNA-Ab2, capture DNA, and signal DNA-CdTe QDs, and brought CdTe QDs to the ITO/TiO2/CdS electrode to produce a sensitized photocurrent. The photocurrent intensity increased with the increasing concentration of the specific target protein. Using insulin as a target, this sensitized method showed a detectable range of 10 fM to 10 nM and a detection limit of 3.0 fM without the need of a washing step. It possessed high selectivity and good accuracy for detection of proteins in biological matrixes. This method is extremely flexible and can be extended to varieties of protein targets.

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