A Photoelectrochemical Sensor Based on DNA Bio-Dots-Induced Aggregation of AuNPs for Methionine Detection

Based on DNA bio-dots-induced aggregation of gold nanoparticles (AuNPs), a methionine (Met) photoelectrochemical (PEC) sensor with CS–GSH–CuNCs/TiO2 NPs as the photoelectric conversion element and AuNPs as the specific recognition element was constructed. First, a TiO2 NPs/ITO electrode and CS–GSH–CuNCs were prepared, and then the CS–GSH–CuNCs/TiO2 NPs/ITO photosensitive electrode was obtained by self-assembly. Next, DNA bio-dots were modified to the upper surface of the electrode using a coupling reaction to assemble the DNA bio-dots/CS–GSH–CuNCs/TiO2 NPs electrode. Amino-rich DNA bio-dots were used to induce the aggregation of AuNPs on the electrode surface via Au–N interactions and prepare the AuNPs/DNA bio-dots/CS–GSH–CuNCs/TiO2 NPs electrode. Due to the fluorescence resonance energy transfer (FRET) between CS–GSH–CuNCs and AuNPs, the complexation chance of electron-hole (e−-h+) pair in CS–GSH–CuNCs increased, which, in turn, led to a decrease in photocurrent intensity. When Met was present, AuNPs aggregated on the electrode surface were shed and bound to Met since the Au–S interaction is stronger than the Au–N interaction, resulting in the recovery of the photocurrent signal. Under optimal conditions, the photocurrent intensity of the PEC sensor showed good linearity with the logarithm of Met concentration in the range of 25.0 nmol/L–10.0 μmol/L with the limit of detection (LOD) of 5.1 nmol/L (S/N = 3, n = 10).