Electrogenerated Chemiluminescence Sensor Based on Tris(2,2'-bipyridyl) ruthenium(II) Immobilized in the Composite Film of Multi-walled Carbon Nanotube/Sol-gel Zinc oxide/Nafion

A composite film of multi-walled carbon nanotube (MWCNT)/sol-gel-derived zinc oxide(ZnO)/Nafion has been utilized as an efficient immobilization matrix for the construction of a highly sensitive and stable tris(2,2'-bipyridyl) ruthenium(II) (Ru(${bpy)_3}^{2+})$ electrogenerated chemiluminescence (ECL) sensor. The electrochemical and ECL behaviors of Ru(${bpy)_3}^{2+})$ ion-exchanged into the composite film were strongly dependent upon the sol-gel preparation condition, the amount of MWCNT incorporated into the ZnO/Nafion composite film, and the buffer solution pH. The synergistic effect of MWCNTs and ZnO in the composite films increased not only the sensitivity but also the long-term stability of the ECL sensor. The present ECL sensor based on the MWCNT/ZnO/Nafion gave a linear response ($R^2$ = 0.999) for tripropylamine concentration from 500 nM to 1.0 mM with a remarkable detection limit (S/N = 3) of 15 nM. The present ECL sensor showed outstanding long-term stability (94% initial signal retained for 5 weeks). Since the present ECL sensor exhibits large response towards NADH, it could be applied as a transduction platform for the ECL biosensor in which the NADH is produced from the dehydrogenase-based enzymatic reaction in the presence of NA$D^+$ cofactor.