N-Carbamoylmaleimide-treated carbon dots: stabilizing the electrochemical intermediate and extending it for the ultrasensitive detection of organophosphate pesticides

Abstract

To date, numerous methods have been reported for the detection of organophosphorus pesticides (OP) due to their severe potential hazard to the environment, public health and national security. However, very few works have ever found that the signal loss of thiocholine (TCh) during electrochemical processing is a key factor leading to the low sensitivity of acetylcholinesterase (AChE)-based OP electrochemical sensing platforms. Herein, we propose an ultrasensitive detection method for multiple OPs including parathion-methyl, paraoxon, dimethoate and O,O-dimethyl-O-2,2-dichlorovinyl-phosphate using N-carbamoylmaleimide-functionalized carbon dots (N-MAL-CDs) as a nano-stabilizer. For the first time, Michael addition is introduced into an AChE-based OP electrochemical sensing platform to enrich the electrochemical intermediate TCh. The Michael addition between TCh and N-MAL-CDs is demonstrated via XRD, FTIR, SEM and EDS elemental mapping experiments. Due to the stabilization and enhancement of TCh with N-MAL-CDs, the as prepared OP sensing platform achieves ultrahigh sensitivity by detecting the initial electrochemical signals of TCh without signal loss, showing a wide linear range of 3.8 × 10⁻¹⁵–3.8 × 10⁻¹⁰ M for parathion-methyl and 1.8 × 10⁻¹⁴–3.6 × 10⁻¹⁰ M for paraoxon, with a limit of detection of 1.4 × 10⁻¹⁵ M for parathion-methyl and 4.8 × 10⁻¹⁵ M for paraoxon.