Enhanced electrochemiluminescence of Ru(bpy)₃ ²⁺ -doped silica nanoparticles by chitosan/Nafion shell@carbon nanotube core-modified electrode

Although Ru(bpy)₃ ²⁺ -doped silica nanoparticles have been widely explored as the labelling tags for electrochemiluminescence (ECL) sensing different targets, the poor electrical conductive properties of the silica nano-matrix greatly limit their ECL sensitivity. Therefore, a novel scheme to overcome this drawback on Ru(bpy)₃ ²⁺ -doped silica nanoparticles ECL is desirable. Here, a new scheme for this purpose was developed based on electrochemically depositing a nanoscale chitosan hydrogel layer on the carbon nanotube (CNT) surface to form chitosan hydrogel shell@CNT core nanocomposites. In this case, the nanoscale chitosan hydrogel layer only formed on the CNT surface due to the superior electrocatalytic effect of CNT on H⁺ reduction compared with the basic glass carbon electrode. Due to both the superhydrophilic properties and polyelectrolyte features of nanoscale chitosan hydrogel on the CNT surface, chemical affinity as well as the electric conductivity between Ru(bpy)₃ ²⁺ -doped silica nanoparticles and CNT were obviously enhanced, and then the ECL effectivity of Ru(bpy)₃ ²⁺ inside silica nanoparticles was improved. Furthermore, based on the discriminative interaction of these Ru(bpy)₃ ²⁺ -doped silica nanoparticles towards both the ssDNA probes and the ssDNA probe/miRNA complex, as well as the specific adsorption effect of these nanoparticles on the nanoscale chitosan shell@Nafion/CNT core-modified glass carbon electrode, a highly sensitive ECL method for miRNA determination was developed and successfully used to detect miRNA in human serum samples.