Ratiometric electrogenerated chemiluminescence sensing microRNA based on electrochemically controlled release of lucigenin from silica/chitosan/lucigenin nanoparticles

The dye-doped silica nanoparticles-based electrogenerated chemiluminescence (ECL) has been widely explored for analytical purposes due to its high sensitivity, simplicity and wide dynamic concentration range. However, only a few of dye molecules located at the near surface of nanoparticles can participate in the ECL reaction due to the poor conductivity of silica nano-matrix. In addition, the ECL signal is easy to be affected by environmental interference, which results in poor accuracy. Herein, a ratiometric ECL sensing method is established based on the electrochemically controlled release of lucigenin molecules from silica/chitosan/lucigenin composite nanoparticles (Lu/CS NPs) with the aid of sulfide ions. Firstly, H+ produced from the electrochemical oxidation of HS- ions can combine with SiO- and displace lucigenin from Lu/CS NPs. The released lucigenin molecules react with the reactive oxygen species (ROS) generated from the electroreduction of dissolved oxygen to produce the cathodic ECL signal. In addition, the excited elemental sulfur from the electrooxidation of HS- ions transfers its energy to lucigenin molecules and makes them be excited to produce energy-transfer anodic ECL signal. Based on these findings, a ratiometric ECL sensor is developed taking the anodic ECL intensity of lucigenin as a reference signal for the cathodic ECL of lucigenin. The proposed ratiometric ECL sensor has been successfully applied to the detection of let-7a with a wide linear range of 0.1-9.0 pM, a low detection limit of 28 fM, high selectivity and good reproducibility. Moreover, the developed approach was used to detect let-7a in human serum composite samples with good recoveries