An intermolecular hydrogen-bond-induced quench-type Ru(dcbpy)₃²⁺/TPA electrochemiluminescence system by...

Here, we show that nitrogen-doped carbon quantum dots (NCQDs) strongly inhibits the anodic electrochemiluminescence (ECL) signal of a tris(4,4'-dicarboxylic acid-2,2'-bipyridyl) ruthenium(II) (Ru(dcbpy)₃²⁺)/tripropylamine (TPA) aqueous system. To determine the ECL-quenching mechanism, we used photoluminescence spectroscopy, UV-Visible absorption spectroscopy and dynamic simulation technology. Quenching of the ECL signal of Ru(dcbpy)₃²⁺/TPA by NCQDs was predominantly attributed to the interaction between Ru(dcbpy)₃²⁺ and NCQDs rather than that between TPA and NCQDs. Specifically, when Ru(dcbpy)₃²⁺ and NCQDs were in aqueous solution together, the carboxyl (-COOH) groups of Ru(dcbpy)₃²⁺ were in contact with oxygen- and nitrogen-containing groups on the surface of NCQDs and formed intermolecular hydrogen bonds. This process involved energy transfer from the excited-state Ru(dcbpy)₃²⁺ to the intermolecular hydrogen bonds, thus resulting in a decrease in the Ru(dcbpy)₃²⁺ ECL signal. On this basis, a quenching-type ECL sensor for the quantification of NCQDs was fabricated. The sensor had a wide linear range and an estimated detection limit of 0.0012 mg mL^-1, as well as excellent stability and selectivity. Satisfactory recoveries of 97.0-99.5% were obtained using the ECL sensor to quantify NCQDs in tap water. NCQDs could potentially be used as a quenching probe of Ru(dcbpy)₃²⁺ to construct various biosensors with widespread applications in the sensing field.