Photoelectrochemical (PEC) sensing techniques have attracted considerable concerns because of the intrinsic merit of complete separation between the excitation light and responsive current but still remain a great challenge for further potential application. It is assigned to the scarcity of photoactive materials with narrow band gap, good biosafety, and high photon-to-electron conversion efficiency and unfavorable processing methods for photoactive materials on indium tin oxide. Herein, we employed a perylene-based polymer (PTC-NH2) with exceptional photoelectrical properties to develop a red-light-driven PEC sensor for ultrasensitive biosensing based on its superior electrostatic intercalation efficiency in double-stranded DNA to that in single-stranded DNA, with DNA adenine methyltransferase (Dam MTase) as the model target. The prepared PTC-NH2 was characterized by Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and PEC techniques, and the results demonstrated that PTC-NH2 rather than metal oxides/metal sulfides/C3N4/metal complexes enjoyed the prominent capacity of converting light to current. Benefiting from the unique PEC properties of PTC-NH2 and target-initiated hybridization chain reaction (HCR) signal amplification, ultrasensitive detection of Dam MTase was accessibly realized with the detection limit of 0.015 U/mL, which is lower than that of PEC, electrochemical, or fluorescent biosensors previously reported. Furthermore, the proposed PEC sensor has been also applied in screening Dam MTase activity inhibitors. Therefore, the perylene-based PEC sensor exhibits great potential in early accurate diagnosis of DNA methylation-related diseases.
Keywords: DNA adenine methyltransferase; electrostatic intercalation efficiency; hybridization chain reaction; perylene-based polymer; photoelectrochemical sensing.