Modification of indium tin oxide with dendrimer-encapsulated nanoparticles to provide enhanced stable electrochemiluminescence of Ru(bpy)3(2+)/tripropylamine while preserving optical transparency of indium tin oxide for sensitive electrochemiluminescence-based analyses

Anal Chem. 2014 Feb 4;86(3):1654-60. doi: 10.1021/ac403415m. Epub 2014 Jan 17.

Abstract

Here, we report highly enhanced stable electrogenerated chemiluminescence (ECL) of Ru(bpy)3(2+) (bpy = 2,2'-bipyridyl) with tripropylamine (TPrA) coreactant on indium tin oxide (ITO) electrodes modified with amine-terminated dendrimers encapsulating catalytic nanoparticles while maintaining optical transparency of ITO and feasibility of the modified ITOs to sensitive ECL-based assays. As model systems, we prepared Pt and Au dendrimer-encapsulated nanoparticles (DENs) using amine-terminated sixth-generation poly(amido amine) dendrimers and subsequently immobilized the DENs onto ITO surfaces via electrooxidative grafting of the terminal amines of dendrimers to the surfaces. The resulting DEN-modified ITOs preserved good optical transparency of ITO and exhibited highly catalyzed electrochemical oxidation of Ru(bpy)3(2+)/TPrA, leading to significantly increased ECL emission. Especially, the Pt DEN-modified ITO electrode provides negligible transmittance drop, i.e., only ∼1.99% over the entire visible region, and exhibited not only much enhanced (i.e., ∼213-fold increase compared to ECL obtained from bare ITO) but also stable ECL emission under consecutive potential scans from 0.00 to 1.10 V for 10 cycles, which allowed ∼329 times more sensitive ECL-based analysis of nicotine using the Pt DEN-modified ITO compared with the use of bare ITO.