Efficient photoelectrochemical aptasensing of di-2-ethylhexyl phthalate in environmental samples based on N, S co-doped graphene quantum dots/TiO2 nanorods

An efficient photoelectrochemical (PEC) sensing platform was developed for detection of di-2-ethylhexyl phthalate (DEHP) based on nitrogen and sulfur co-doped graphene quantum dots/TiO2 nanorods (N, S-GQDs/TiO2 NRs) coupling with exonuclease I (Exo I)-assisted target recycling for remarkable signal amplification. N, S-GQDs uniformly grown on TiO2 NRs by simple hydrothermal method showed high electron-hole separation efficiency and superior photoelectric performance, which was explored as the photoactive substrate for anchoring anti-DEHP aptamer and its complementary DNA (cDNA). With the addition of DEHP, aptamer molecules fell from the electrode surface owing to the specific recognition of aptamer to DEHP, resulting in the increment of photocurrent signal. At this moment, Exo I could stimulate aptamer hydrolysis in the aptamer-DEHP complexes, so that DEHP was released from the complexes to take part in the next reaction cycling, which remarkably increasing the photocurrent response and achieving signal amplification. The designed PEC sensing platform exhibited excellent analytical performance for DEHP with a low detection limit of 0.1 pg L-1. Also, its applications in real samples were further investigated in detail. Thus, the established method would provide a simple and efficient tool for DEHP or other pollutants monitoring in the environment.