Bionanocomposite materials for electroanalytical applications: current status and future challenges.

Bionanocomposites are materials composed of particles with at least one dimension in the range of 1-100 nm and a constituent of biological origin or biopolymers. They are the subject of current research interest as they provide exciting platforms and act as an interface between materials science, biology, and nanotechnology and find applications in disciplines such as electrochemistry, biomedicine, biosorption, aerospace, tissue engineering and packaging. They have different properties such as high conductivity, thermal stability, electrocatalytic ability, biocompatibility, adsorption ability and biodegradability, which can be tuned by their preparation methods, functionalities and applications. However, depending on the objective or the goal of a research project, specific preparation and characterization of bionanocomposites can be undertaken to understand the behavior and confirm the applicability of a bionanocomposite in a given field. Like in electroanalysis applications, electrode materials should be porous (meso- and macro-porosities), having large specific area (at least having a Brunauer-Emmett-Teller surface of 200 m2 g-1), higher stability over time with acceptable power recovery between 95% and 105%, good electrocatalytic ability, and be a good absorbent and a good conductor of electricity (that is to say, it facilitates the transfer of electrons from the solution to the surface of the electrode and vice versa). The present review focuses on the most used method of preparation of bionanocomposites with the critical aspect and their physicochemical and electrochemical characterization techniques, and finally, the practical situations of application of bionanocomposite materials as modified electrodes for electroanalysis of several groups of analytes and a comparison with non-bionanocomposite electrodes are discussed. The future scope of bionanocomposites in the field of electroanalysis is also addressed in this review. But before that, a general overview of bionanocomposite materials in relation to other types of materials is presented to avoid any misunderstanding.

Electrochemistry coupled with mass spectrometry for the prediction of the environmental fate and elucidation of the degradation mechanisms of pesticides: current status and future prospects.

One of the crucial steps in the development of a new pesticide (active molecule) is predicting its environmental and in vivo fate, so as to determine potential consequences to a living organism's health and ecology as a whole. In this regard, pesticides undergo transformation processes in response to biotic and abiotic stress. Therefore, there is a need to investigate pesticide transformation products (TPs) and the formation processes they could undergo during the manufacturing process and when discharged into the ecosystem. Although methods based on biological in vitro and in vivo experimental models are tools of choice for the elucidation of metabolic pathways of pesticides (xenobiotics in general), electrochemistry-based techniques offer numerous advantages such as rapid and low-cost analysis, easy implementation, low sample volume requirement, no matrix effects, and miniaturization to improve the performance of the developed methods. However, for greater efficiency, electrochemistry (EC) should be coupled with analytical techniques such as mass spectrometry (MS) and sometimes liquid chromatography (LC), leading to the so-called EC-MS and EC-LC-MS hybrid techniques. In this review, past studies, current applications and utilization of EC-MS and EC-LC-MS techniques for the simulation of environmental fate/degradation of pesticides were reviewed by selected studies with chemical transformation, structures of metabolites, and some experimental conditions. The current challenges and future trends for the mimicry and prediction of the environmental fate/degradation of pesticides based on electrochemical methods combined with mass spectrometry were highlighted.

Electrochemistry-coupled to liquid chromatography-mass spectrometry-density functional theory as a new tool to mimic the environmental degradation of selected phenylurea herbicides.

In vitro and in vivo experimental models, mainly based on cell cultures, animals, healthy humans and clinical trials, are useful approaches for identifying the main metabolic pathways. However, time, cost, and matrix complexity often hinder the success of these methods. In this study, we propose an alternative non-enzymatic method, using electrochemistry (EC) coupled to liquid chromatography (LC) - high resolution mass spectrometry (HRMS) - DFT theoretical calculations (EC/LC-MS/DFT) for the mimicry/simulation of the environmental degradation of phenylurea herbicides, and for the mechanism elucidation of this class of herbicides. Fenuron, monuron, isoproturon, linuron, monolinuron, metoxuron and chlortoluron were selected as relevant model compounds. The intended compounds are oxidized by EC, separated by LC and detected using electrospray ionization HRMS. The main oxidation products were hydroxylated compounds obtained by substitution and addition reactions. Unstable quinone imines/methines, rarely observed by conventional methods, have been identified during the oxidative degradation of phenylurea herbicides for the first time in this study. Some were directly observed and the others were trapped by glutathione GSH. Reactions such as hydrolytic substitutions (-Cl/+OH and -C3H7/+OH and -CH3/+OH and -OCH3/+OH), aromatic hydroxylation, alkyl carbon hydroxylation, dehydrochlorination/dehydromethylation/dehydromethoxylation and conjugation have been successfully mimicked. The obtained results, supported by theoretical calculations, are useful for simulating/understanding and predicting the oxidative degradation pathways of pesticides in the environment.