In-situ synthesis of covalent organic polymer thin film integrates with palladium nanoparticles for the construction of a cathodic photoelectrochemical cytosensor.

Sensitive detection of cancer cells is essential to early clinic diagnosis, and the photoelectrochemical (PEC) sensors with high sensitivity and good selectivity may provide new approaches for cytosensing. Herein, we demonstrate the development of a new cathodic PEC cytosensor based on the integration of covalent organic polymer (COP) with palladium nanoparticles (PdNPs). The COP films are in-situ grown at room temperature on the transparent indium tin oxide-coated glass substrates, and they subsequently assemble with PdNPs to immobilize aptamers via palladium-sulfur chemistry. PdNPs can catalyze the oxidation of dopamine to produce aminochrome and its derivative, which may function as the electron acceptors of COP for the generation of an enhanced photocurrent. In the absence of cancer cells, the electrons on the conduction band of COP on the electrode transfer to the aminochrome and O, while the electrons on the electrode transfer to the hole of valence band, resulting in a high cathodic photocurrent. In the presence of cancer cells, the trapped cancer cells efficiently cover the electrode to reduce the surface of COP/PdNPs, resulting in the decrease of catalytic precipitation on the electrode and consequently the generation of a low PEC signal. This PEC cytosensor exhibits high sensitivity with a detection limit of 8 cells mL and a large dynamic range from 10 to 10 cells mL. Moreover, this PEC cytosensor has distinct advantages of high selectivity, good reproducibility and excellent stability, and it can be extended to directly detect various cancer cells through the integration with corresponding specific aptamers.