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.

A "two-step" assay based on electro-activation for rapid determination of methylglyoxal in honey and beer.

Methylglyoxal (MGO), a dicarbonyl compound in living organism, food and environment, has been associated with disease diagnosis and human health. The current electrochemical detection methods rely on the use of advanced materials. In this work, a non-advanced materials "two-step" assay including electrode electro-activation and MGO detection was developed. In the section of electro-activation, an activation method of GCE for MGO detection was established; and the composition changes on GCE surface caused by electro-activation, including functional groups and surface defects, have been carefully studied. The effect of carbonyl and surface defects induced by electro-activation on MGO detection was discussed. In section of MGO detection, the raise of background current caused by electro-activation was minimized by background subtraction; and the effect of interferences can be weakened by adjusting pH. The MGO signal on proposed activated GCE improved 20-fold than bare GCE. The recoveries were 72.38-109.16% in honey and beer, and RSDs were 0.24-9.63% without significant difference with HPLC method and comparable with advanced material modified sensors.

A facile, inexpensive and green electrochemical sensor for sensitive detection of imidacloprid residue in rice using activated electrodes.

The development of sensitive, facile, cost-effective and eco-friendly sensors is essential for monitoring imidacloprid (IDP) residue on a large scale. Compared with popular modification of electrodes with advanced materials, electrochemical activation is promising at this point. In this paper, we found that strongly basic electrolytes (e.g. KOH and K3PO4) and applying cyclic potential during the activating process are beneficial to greatly amplify the electro-reduction response of IDP by nearly 16 times. Combining the characterization of activated electrodes with electrochemical behavior analysis of IDP, it is speculated that specific oxygen-contained functional groups were formed to bond with IDP molecules, leading to fast electron transfer kinetics. Then a sensitive IDP sensor has been developed with a low limit of detection (LOD) of 0.03 µM in the range of 0.1-100 µM. The methodological evaluation including reproducibility, stability and recovery has been also carefully studied, verifying the potential of proposed activated electrodes for application in rice samples.

Regulation of nitrogen dynamics at the sediment-water interface during HAB degradation and subsequent reoccurrence.

The effects of harmful algal blooms (HABs) on nutrient dynamics have been extensively studied; however, the response of nitrogen to continuous HAB degradation and subsequent reoccurrence is not well understood. Here, a small-scale experiment was conducted to assess how nitrogen in the sediment-water interface (SWI) responds to HAB degradation and subsequent reoccurrence at different initial algal densities. The results showed that during the algae decomposition stage, the NH4 +-N flux of the SWI remained positive but decreased with the increase in algal density from 3.5 × 107 to 2.3 × 108 cells per L, indicating that the sediment was the source of NH4 +-N. In contrast, the deposit was a sink of NO3 --N. However, during the reoccurrence of HAB, the distribution of NH4 +-N and NO3 --N fluxes was completely converted. Nitrogen flux analysis throughout algae decomposition and reoccurrence indicated that although the sediment acted as a sink of nitrogen, the flux was dependent on the initial algal density. Our results confirmed that algae decomposition and reoccurrence would greatly affect the nitrogen cycle of the SWI, during which dissolved oxygen (DO) and initial algal density dominated. This study is the first to show that the regulation of nitrogen flux and migration changes during continuous HAB decomposition and subsequent reoccurrence.

Correction: Regulation of nitrogen dynamics at the sediment-water interface during HAB degradation and subsequent reoccurrence.

[This corrects the article DOI: 10.1039/C9RA10673A.].