Ferrocyanide-Ferricyanide Redox Couple Induced Electrochemiluminescence Amplification of Carbon Dots for Ultrasensitive Sensing of Glutathione.

Here we report a novel solid-state ECL sensor for ultrasensitive sensing of glutathione (GSH) based on ferrocyanide-ferricyanide redox couple (Fe(CN)6(3-/4-)) induced electrochemiluminescence (ECL) amplification of carbon dots (C-dots). The electropolymerization of C-dots and (11-pyrrolyl-1-yl-undecyl) triethylammonium tetrafluoroborate (A2) enabled immobilization of the hydrophilic C-dots on the surface of glassy carbon electrode (GCE) perfectly, while the excellent conductivity of polypyrrole was exploited to accelerate electron transfer between them. The Fe(CN)6(3-/4-) can expeditiously convert the C-dots and S2O8(2-) to C-dot(•-) and SO4(•-), respectively. High yields of the excited state C-dots (C-dots*) were obtained, and a ∼10-fold ECL amplification was realized. The C-dots* obtained through the recombination of electron-injected and hole-injected processes may be impeded due to the interference of GSH to K2S2O8. Therefore, the constructed sensor for GSH showed a detection limit down to 54.3 nM (S/N = 3) and a wide linear range from 0.1-1.0 μM with a correlation coefficient of 0.997.