ZnO-reduced graphene oxide composite based photoelectrochemical aptasensor for sensitive Cd(II) detection with methylene blue as sensitizer.

In this paper a photoelectrochemical (PEC) aptasensor based on specific recognition with conformational changed after the target Cd(II) identification was fabricated. A ZnO and reduced graphene oxide (ZnO-rGO) nanocomposite with enhanced PEC activity was designed as photoactive material. After the further incorporation of gold nanoparticles (AuNPs) with ZnO-rGO nanocomposite, the enhanced photocurrent signal could be detected owing to the localized surface plasmon resonance and good conductivity of AuNPs. In addition, AuNPs were used as anchors for immobilization of -SH modified aptamer S1. After that aptamer S2 was paired with S1 sequence to form complementary double stranded DNA (dsDNA) on the electrode surface. Methylene blue (MB) was acted as sensitizer and assembled in dsDNA structure to amplify photocurrent response. When Cd(II) was bound to the aptamer presented on the sensing interface, S2 specifically recognized and captured Cd(II), which resulted in the unwinding of dsDNA structure and the separation of MB molecules from the electrode surface with photocurrent response decreased. The photocurrent was detected by a double-working-electrode system, which used the modified electrode as the first working electrode and glassy carbon electrode (GCE) as the second working electrode. Dopamine (DA) was added to the electrolyte and acted as the electron donor, which could be oxidized on the modified electrode and reduced on the GCE to form a cyclic reaction, leading to the enhanced photocurrent response with improved photocurrent stability. This MB sensitized PEC aptasensor exhibited a high sensitivity with a detection limit of 1.8 × 10-12 mol/L (3σ). Thus, a highly sensitive aptasensor with double-working-electrode detection method for Cd(II) determination were established and further applied to the water samples analysis.

Photoelectrochemical aptasensor for lead(II) by exploiting the CdS nanoparticle-assisted photoactivity of TiO2 nanoparticles and by using the quercetin-copper(II) complex as the DNA intercalator.

A photoelectrochemical (PEC) aptasensor for Pb(II) detection is described. A nanocomposite consisting of CdS (2.5 µm) and TiO2 nanoparticles (10 nm) was used as a photoactive material, and gold nanochains (Au NCs) as the support for immobilization of the Pb(II)-binding aptamer. The quercetin-copper(II) complex was further employed as the intercalator for the improvement of the photoactivity by embedding it into dsDNA. In the presence of Pb(II), a Pb(II)-stabilized G-quadruplex was formed between Pb(II) and DNA S1. This is accompanied by unwinding of the dsDNA and the release of the quercetin-copper(II) complex from the surface of the sensor. This results in a decrease of the photocurrent that drops linearly from 5.0 × 10-12 to 1.0 × 10-8 mol·L-1 Pb(II) concentration range with a detection limit of 1.6 × 10-12 mol·L-1. The method was applied to the determination of Pb(II) in various samples and gave satisfactory results. Graphical abstractA photoelectrochemical aptasensor was fabricated for the detection of Pb(II) based on CdS-TiO2 nanocomposite modified indium tin oxide (ITO) electrode. Gold nanochains (AuNCs) were used as anchor to immobilize the aptamers S1 and S2 that form a double helix structure by DNA hybridization. After embedding of quercetin-copper(II) complex as intercalator and electron donor, the concentrations of Pb(II) were determined by the changes of photocurrents.