Bimodal Electrogenerated Chemiluminescence of the Luminol/Dicyclohexylamine (DCHA) System: A Novel and Highly Sensitive Detection of DCHA via ECL-Flow Injection Analysis

Though luminol is one of the most prominent and extensively studied luminophores in ECL studies, only H2O2 has been widely used as a co-reactant. This limits the variety of applications because of the short-time radical stability and low quantum efficiency. In the present work, we identified dicyclohexylamine (DCHA) as a new and highly efficient anodic co-reactant in ECL for the luminol molecule. The electrochemical and ECL behavior of the luminol/DCHA system was studied on a simple bare GCE surface, which results in two anodic ECL peaks at the potential region of +0.38 and +0.94 V vs Ag/AgCl. The evidence of (DCHA•+) and O2•– generated in the system was detected via flat-cell electron spin resonance (ESR) spectroscopy experiments at ∼20 °C. Using the bimodal ECL system, the highly sensitive detection of luminol was achieved with the detection limit down to 1.5 pM. Further, a homebuilt electrochemiluminescent detector coupled with a flow injection analysis (ECL-FIA) system was adopted to detect the DCHA contaminant in harvested honey, which achieved higher detection and sensitivity under the optimized experimental conditions. DCHA was detected in the range of 10 nM to 100 μM with the detection limit of 2 nM (S/N = 3). The present findings of new luminol/DCHA ECL signals produced a strong ECL emission, which leads to a greater potential to meet the fast-developing analytical application of a luminol-based ECL system.