Strategy of In Situ Electrochemical Regulation for Highly Enhanced Nonenzymatic Sensing of Carbaryl.

Specific and sensitive sensing of most pesticide residues relies on enzymes such as acetylcholinesterase and advanced materials, which need to be loaded on the surface of working electrodes, leading to instability, uneven surface, tedious process, and high cost. Meanwhile, employing certain potential or current in electrolyte solution could also modify the surface in situ and overcome these drawbacks. However, this method is only regarded as electrochemical activation widely applied in the pretreatment of electrodes. In this paper, by means of regulating the electrochemical technique and its parameters, we prepared a proper sensing interface and derivatized the carbaryl (a carbamate pesticide) hydrolyzed form (1-naphthol) to enhance sensing by 100 times within several minutes. After regulation I by chronopotentiometry with 0.2 mA for 20 s or chronoamperometry with 2 V for 10 s, abundant oxygen-containing groups form and the ordered carbon structure is destroyed. Sweeping from -0.5 to 0.9 V through cyclic voltammetry for only one segment, following regulation II, the composition of oxygen-containing groups changes and the disordered structure is alleviated. Finally, on the constructed sensing interface, test by regulation III through differential pulse voltammetry from 0.8 to -0.4 V, resulting in derivatization of 1-naphthol during 0.8-0 V, followed by electroreduction of the derivative at around -0.17 V. Compared with the electro-oxidation peak at 0.5 V in previous reports, it is essential to improve specificity, even toward several other carbamate pesticides with similar structures. Hence, the in situ electrochemical regulation strategy has demonstrated great potential for effective sensing of electroactive molecules.

Subtle adjustment of the cyclic potential on electro-activated glassy carbon electrodes for sensitive sensing of methyl parathion.

Facile electro-activated glassy carbon electrodes (e-GCEs), which are prepared in electrolyte solution with a certain potential for a few seconds, have been verified to improve analytical performance toward not a few electro-active molecules recently. Nevertheless, how and why the potential plays an important role is not clear, and has even not received enough consideration. In this paper, we found that the mode and the range of applied potential significantly impacted the sensitivity of methyl parathion (MP), which is a typical pesticide with the electro-active group of -NO2. Compared with constant potential, the e-GCE with cyclic potential provided a much more stable baseline during MP detection. Additionally, the electro-oxidation peak current of MP at around -0.1 V on it was higher than another changeable potential (constant current). What's more interesting, with cyclic potential for 50 segments from -2 to 1.5 V, the peak current value increased by 30 times in comparison with a bare GCE, but only 2 times from -2 to 1 V. Then after systematic investigation including structures of the electrode surface and functional groups, we speculated that the produced group of O-CO in the process of activation and remaining groups of C-O and CO on the bare GCE surface are beneficial for adsorbing MP molecules leading to enhanced peak current. Employing the proposed e-GCE, the limit of detection of MP reached 0.015 µM and the reproducibility was perfect. This work elucidates the potent impact of electro-activation potential parameters on electroanalysis behaviors.