One-step construction of multiplexed enzymatic biosensors using light-addressable electrochemistry on a single silicon photoelectrode.

The multiplexed detection of metabolites in parallel within a single biosensor plate is sufficiently valuable but also challenging. Herein, we combine the inherent light addressability of silicon with the high selectivity of enzymes, for the construction of multiplexed photoelectrochemical enzymatic biosensors. To conduct a stable electrochemistry and reagentless biosensing on silicon, a new strategy involving the immobilization of both redox mediators and enzymes using an amide bond-based hydrogel membrane was proposed. The membrane characterization results demonstrated a covalent coupling of ferrocene mediator to hydrogel, in which the mediator acted as not only a signal generator but also a renewable sacrifice agent. By adding corresponding enzymes on different spots of hydrogel membrane modified silicon and recording local photocurrents with a moveable light pointer, this biosensor setup was used successfully to detect multiple metabolites, such as lactate, glucose, and sarcosine, with good analytical performances. The limits of detection of glucose, sarcosine and lactate were found to be 179 µM, 16 µM, and 780 µM with the linear ranges of 0.5-2.5 mM, 0.3-1.5 mM, and 1.0-3.0 mM, respectively. We believe this proof-of-concept study provides a simple and rapid one-step immobilization approach for the fabrication of reagentless enzymatic assays with silicon-based light-addressable electrochemistry.

Combining a Commercial Mixer with a Wall-Tube Electrode Allows the Arbitrary Control of Concentrations in Protein Film Electrochemistry.

Protein film electrochemistry is a technique in which an enzyme is immobilized on an electrode in a configuration that allows following the changes in turnover frequency as a response to changes in the experimental conditions. Insights into the reactivity of the enzyme can be obtained by quantitatively modeling such responses. As a consequence, the more the technique allows flexibility in changing conditions, the more useful it becomes. The most commonly used setup, based on the rotating disc electrode, allows easy stepwise increases in the concentration of nongaseous substrates, or exposure to constant concentration of dissolved gas, but does not permit to easily decrease the concentration of nongaseous substrates, or to change the concentration of dissolved gas in a stepwise fashion. To overcome the limitation by mass transport of the substrate toward the electrode when working with fast enzymes, we have designed another kind of electrochemical cell based on the wall-tube electrode (WTE). We demonstrate here that by using a system combining two syringe pumps, a commercial mixer, and the WTE, it is possible to change the concentration of species in a stepwise fashion in all directions, opening new possibilities to study redox enzymes. As a proof of concept, this device was applied to the study of the electrochemical response of the cytochrome c nitrite reductase of Desulfovibrio desulfuricans.

Pb2+-Selective Nanoemulsion-Integrated Single-Entity Electrochemistry for Ultrasensitive Sensing of Blood Lead.

Unequivocally, Pb2+ as a harmful substance damaging children's brain and nerve systems, thereby causing behavior and learning disabilities, should be detected much lower than the elevated blood lead for children, 240 nM, endorsed by US CDC considering the unknown neurotoxic effects, yet the ultralow detection limit up to sub-ppb level remains a challenge due to the intrinsically insufficient sensitivity in the current analytical techniques. Here, we present nanoemulsion (NE)-integrated single-entity electrochemistry (NI-SEE) toward ultrasensitive sensing of blood lead using Pb-ion-selective ionophores inside a NE, i.e., Pb2+-selective NE. Through the high thermodynamic selectivity between Pb2+ and Pb-ionophore IV, and the extremely large partition coefficient for the Pb2+-Pb-ionophore complex inside NEs, we modulate the selectivity and sensitivity of NI-SEE for Pb2+ sensing up to an unprecedentedly low detection limit, 20 ppt in aqueous solutions, and lower limit of quantitation, 40 ppb in blood serums. This observation is supported by molecular dynamics simulations, which clearly corroborate intermolecular interactions, e.g., H-bonding and π*-n, between the aromatic rings of Pb-ionophore and lone pair electrons of oxygen in dioctyl sebacate (DOS), plasticizers of NEs, subsequently enhancing the current intensity in NI-SEE. Moreover, the highly sensitive sensing of Pb2+ is enabled by the appropriate suppression of hydroxyl radical formation during NI-SEE under a cathodic potential applied to a Pt electrode. Overall, the experimentally demonstrated NI-SEE approach and the results position our new sensing technology as potential sensors for practical environmental and biomedical applications as well as a platform to interrogate the stoichiometry of target ion-ionophore recognition inside a NE as nanoreactors.

Homogeneous and Label-Free Detection and Monitoring of Protein Kinase Activity Using the Impact Electrochemistry of Silver Nanoparticles.

Protein kinase activity correlates closely with that of many human diseases. However, the existing methods for quantifying protein kinase activity often suffer from limitations such as low sensitivity, harmful radioactive labels, high cost, and sophisticated detection procedures, underscoring the urgent need for sensitive and rapid detection methods. Herein, we present a simple and sensitive approach for the homogeneous detection of protein kinase activity based on nanoimpact electrochemistry to probe the degree of aggregation of silver nanoparticles (AgNPs) before and after phosphorylation. Phosphorylation, catalyzed by protein kinases, introduces two negative charges into the substrate peptide, leading to alterations in electrostatic interactions between the phosphorylated peptide and the negatively charged AgNPs, which, in turn, affects the aggregation status of AgNPs. Via direct electro-oxidation of AgNPs in nanoimpact electrochemistry experiments, protein kinase activity can be quantified by assessing the impact frequency. The present sensor demonstrates a broad detection range and a low detection limit for protein kinase A (PKA), along with remarkable selectivity. Additionally, it enables monitoring of PKA-catalyzed phosphorylation processes. In contrast to conventional electrochemical sensing methods, this approach avoids the requirement of complex labeling and washing procedures.

Complex molecule synthesis by electrocatalytic decarboxylative cross-coupling.

Modern retrosynthetic analysis in organic chemistry is based on the principle of polar relationships between functional groups to guide the design of synthetic routes1. This method, termed polar retrosynthetic analysis, assigns partial positive (electrophilic) or negative (nucleophilic) charges to constituent functional groups in complex molecules followed by disconnecting bonds between opposing charges2-4. Although this approach forms the basis of undergraduate curriculum in organic chemistry5 and strategic applications of most synthetic methods6, the implementation often requires a long list of ancillary considerations to mitigate chemoselectivity and oxidation state issues involving protecting groups and precise reaction choreography3,4,7. Here we report a radical-based Ni/Ag-electrocatalytic cross-coupling of substituted carboxylic acids, thereby enabling an intuitive and modular approach to accessing complex molecular architectures. This new method relies on a key silver additive that forms an active Ag nanoparticle-coated electrode surface8,9 in situ along with carefully chosen ligands that modulate the reactivity of Ni. Through judicious choice of conditions and ligands, the cross-couplings can be rendered highly diastereoselective. To demonstrate the simplifying power of these reactions, concise syntheses of 14 natural products and two medicinally relevant molecules were completed.

Versatile MXene composite probe-mediated homogeneous electrochemiluminescence biosensor with integrated signal transduction and near-infrared modulation strategy for concanavalin A detection.

Based on the highly specific interaction between concanavalin A (Con A) and glucose (Glu), a competitive electrochemiluminescence (ECL) biosensor was constructed for ultrasensitive detection of Con A. Nanocomposites with excellent electrocatalytic and photothermal properties were obtained by covalently bonding zinc oxide quantum dots (ZnO QDs) to vanadium carbide MXene (V2C MXene) surfaces. The modification of ZnO QDs hinders the aggregation of V2C MXene and increases the catalytic activity of oxygen reduction reaction, thus amplifying the luminol cathodic emission. In addition, the excellent photothermal performance of the V2C MXene-ZnO QDs can convert light energy into heat energy under the irradiation of 808 nm near infrared laser, thus increasing the temperature of the reaction system and accelerating the electron transfer process to realize the synergistic amplified homogeneous ECL system. This innovative work not only enriches the fundamental research on multifunctional MXene nanomaterials for biosensing, but also provides an effective strategy for ECL signal amplification.

Dynamic imaging of interfacial electrochemistry on single Ag nanowires by azimuth-modulated plasmonic scattering interferometry.

Direct visualization of surface chemical dynamics in solution is essential for understanding the mechanisms involved in nanocatalysis and electrochemistry; however, it is challenging to achieve high spatial and temporal resolution. Here, we present an azimuth-modulated plasmonic imaging technique capable of imaging dynamic interfacial changes. The method avoids strong interference from reflected light and consequently eliminates the parabolic-like interferometric patterns in the images, allowing for a 67-fold increase in the spatial resolution of plasmonic imaging. We demonstrate that this optical imaging approach enables comprehensive analyses of surface chemical dynamics and identification of previously unknown surface reaction heterogeneity by investigating electrochemical redox reactions over single silver nanowires as an example. This work provides a general strategy for high-resolution plasmonic imaging of surface electrochemical dynamics and other interfacial chemical reactions, complementing existing surface characterization methods.

Electrochemistry/mass spectrometry (EC/MS) for fast generation and identification of novel reactive metabolites of two unsymmetrical bisacridines with anticancer activity.

The development of a new drug requires knowledge about its metabolic fate in a living organism, regarding the comprehensive assessment of both drug therapeutic activity and toxicity profiles. Electrochemistry (EC) coupled with mass spectrometry (MS) is an efficient tool for predicting the phase I metabolism of redox-sensitive drugs. In particular, EC/MS represents a clear advantage for the generation of reactive drug transformation products and their direct identification compared to biological matrices. In this work, we focused on the characterization of novel electrochemical products of two representative unsymmetrical bisacridines (C-2028 and C-2045) with demonstrated high anticancer activity. The electrochemical thin-layer flow-through cell µ-PrepCell 2.0 (Antec Scientific) was used here for the effective metabolite electrosynthesis. The electrochemical simulation of C-2028 reductive and C-2045 oxidative metabolism resulted in the generation of new products that were not observed before. The formation of nitroso [M-O+H]+ and azoxy [2M-3O+H]+ species from C-2028, as well as a series of hydroxylated and/or dehydrogenated products, including possible quinones [M-2H+H]+ and [M+O-2H+H]+ from C-2045, was demonstrated. For the latter, a glutathione S-conjugate (m/z 935.3130) was also obtained in measurements supplemented with the excess of reduced glutathione. For the identification of the products of interest, structural confirmation based on MS/MS fragmentation experiments was performed. Novel products of electrochemical conversions of unsymmetrical bisacridines were discussed in the context of their possible biological effect on the human organism.

Newly Developed Electrochemiluminescence Based on Bipolar Electrochemistry for Multiplex Biosensing Applications: A Consolidated Review.

Recently, there has been an upsurge in the extent to which electrochemiluminescence (ECL) working in synergy with bipolar electrochemistry (BPE) is being applied in simple biosensing devices, especially in a clinical setup. The key objective of this particular write-up is to present a consolidated review of ECL-BPE, providing a three-dimensional perspective incorporating its strengths, weaknesses, limitations, and potential applications as a biosensing technique. The review encapsulates critical insights into the latest and novel developments in the field of ECL-BPE, including innovative electrode designs and newly developed, novel luminophores and co-reactants employed in ECL-BPE systems, along with challenges, such as optimization of the interelectrode distance, electrode miniaturization and electrode surface modification for enhancing sensitivity and selectivity. Moreover, this consolidated review will provide an overview of the latest, novel applications and advances made in this field with a bias toward multiplex biosensing based on the past five years of research. The studies reviewed herein, indicate that the technology is rapidly advancing at an outstanding purse and has an immense potential to revolutionize the general field of biosensing. This perspective aims to stimulate innovative ideas and inspire researchers alike to incorporate some elements of ECL-BPE into their studies, thereby steering this field into previously unexplored domains that may lead to unexpected, interesting discoveries. For instance, the application of ECL-BPE in other challenging and complex sample matrices such as hair for bioanalytical purposes is currently an unexplored area. Of great significance, a substantial fraction of the content in this review article is based on content from research articles published between the years 2018 and 2023.

MnO2 Nanoflower Integrated Optoelectronic Biointerfaces for Photostimulation of Neurons.

Optoelectronic biointerfaces have gained significant interest for wireless and electrical control of neurons. Three-dimentional (3D) pseudocapacitive nanomaterials with large surface areas and interconnected porous structures have great potential for optoelectronic biointerfaces that can fulfill the requirement of high electrode-electrolyte capacitance to effectively transduce light into stimulating ionic currents. In this study, the integration of 3D manganese dioxide (MnO2 ) nanoflowers into flexible optoelectronic biointerfaces for safe and efficient photostimulation of neurons is demonstrated. MnO2 nanoflowers are grown via chemical bath deposition on the return electrode, which has a MnO2 seed layer deposited via cyclic voltammetry. They facilitate a high interfacial capacitance (larger than 10 mF cm-2 ) and photogenerated charge density (over 20 µC cm-2 ) under low light intensity (1 mW mm-2 ). MnO2 nanoflowers induce safe capacitive currents with reversible Faradaic reactions and do not cause any toxicity on hippocampal neurons in vitro, making them a promising material for biointerfacing with electrogenic cells. Patch-clamp electrophysiology is recorded in the whole-cell configuration of hippocampal neurons, and the optoelectronic biointerfaces trigger repetitive and rapid firing of action potentials in response to light pulse trains. This study points out the potential of electrochemically-deposited 3D pseudocapacitive nanomaterials as a robust building block for optoelectronic control of neurons.

Advanced electrochemical potential monitoring for improved understanding of electrical neurostimulation protocols.

Objective.Current-controlled neurostimulation is increasingly used in the clinical treatment of neurological disorders and widely applied in neural prostheses such as cochlear implants. Despite its importance, time-dependent potential traces of electrodes during microsecond-scale current pulses, especially with respect to a reference electrode (RE), are not precisely understood. However, this knowledge is critical to predict contributions of chemical reactions at the electrodes, and ultimately electrode stability, biocompatibility, and stimulation safety and efficacy.Approach.We assessed the electrochemistry of neurostimulation protocolsin vitrowith Pt microelectrodes from millisecond (classical electroanalysis) to microsecond (neurostimulation) timescales. We developed a dual-channel instrumentation amplifier to include a RE in neurostimulation setups. Uniquely, we combined potential measurements with potentiostatic prepolarization to control and investigate the surface status, which is not possible in typical stimulation setups.Main results.We thoroughly validated the instrumentation and highlighted the importance of monitoring individual electrochemical electrode potentials in different configurations of neurostimulation. We investigated electrode processes such as oxide formation and oxygen reduction by chronopotentiometry, bridging the gap between milli- and microsecond timescales. Our results demonstrate how much impact on potential traces the electrode's initial surface state and electrochemical surface processes have, even on a microsecond scale.Significance.Our unique use of preconditioning in combination with stimulation reveals that interpreting potential traces with respect to electrode processes is misleading without rigorous control of the electrode's surface state. Especiallyin vivo, where the microenvironment is unknown, simply measuring the voltage between two electrodes cannot accurately reflect the electrode's state and processes. Potential boundaries determine charge transfer, corrosion, and alterations of the electrode/tissue interface such as pH and oxygenation, particularly in long-termin vivouse. Our findings are relevant for all use-cases of constant-current stimulation, strongly advocating for electrochemicalin situinvestigations in many applications like the development of new electrode materials and stimulation methods.

MIL-101(Fe) based biomass as permeable reactive barrier applied to EK-PRB remediation of antimony contaminated soil.

Numerous studies have demonstrated that electrokinetic-permeable reactive barrier (EK-PRB) can be used for the remediation of heavy metal contaminated soils, and their remediation efficiency is mainly determined by the filler material selected. By growing MIL-101(Fe) in situ on hollow loofah fiber (HLF), a novel material entitled HLF@MIL-101(Fe) was developed. The morphological characteristics and loading conditions were investigated, the adsorption characteristics were analyzed, and finally the synthesized composite material was applied to treat antimony-contaminated soil with EK-PRB as the reaction medium. The results show that MIL-101(Fe) is stably loaded on HLF. The adsorption capacity of Sb(III) can reach up to 82.31 mg g-1, and the adsorption is in accordance with the quasi-secondary kinetic model, which indicates that chemisorption is dominant. The isothermal adsorption model indicates that the adsorption form of HLF@MIL-101(Fe) is mainly monolayer adsorption with more uniform adsorption binding energy. In the EK-PRB experiment, when ethylenediaminetetraacetic acid (EDTA) is used as the cathodic electrolyte, it can effectively enhance the electromigration and electroosmotic effects, and the overall remediation efficiency of the soil is increased by 38.12% compared with the citric acid (CA) group. These demonstrate the feasibility of HLF@MIL-101(Fe) in collaboration with EK-PRB in the treatment of antimony-contaminated soil.

Molten Salts-Driven Discovery of a Polar Mixed-Anion 3D Framework at the Nanoscale: Zn4 Si2 O7 Cl2 , Charge Transport and Photoelectrocatalytic Water Splitting.

Mixed-anion compounds widen the chemical space of attainable materials compared to single anionic compounds, but the exploration of their structural diversity is limited by common synthetic paths. Especially, oxychlorides rely mainly on layered structures, which suffer from low stability during photo(electro)catalytic processes. Herein we report a strategy to design a new polar 3D tetrahedral framework with composition Zn4 Si2 O7 Cl2 . We use a molten salt medium to enable low temperature crystallization of nanowires of this new compound, by relying on tetrahedral building units present in the melt to build the connectivity of the oxychloride. These units are combined with silicon-based connectors from a non-oxidic Zintl phase to enable precise tuning of the oxygen content. This structure brings high chemical and thermal stability, as well as strongly anisotropic hole mobility along the polar axis. These features, associated with the ability to adjust the transport properties by doping, enable to tune water splitting properties for photoelectrocatalytic H2 evolution and water oxidation. This work then paves the way to a new family of mixed-anion solids.

Elucidation of the environmental reductive metabolism of the herbicide tritosulfuron assisted by electrochemistry and mass spectrometry.

The environmental impact of pesticides and other pollutants is, to a great extent, determined by degradation and accumulation processes. Consequently, degradation pathways of pesticides have to be elucidated before approval by the authorities. In this study, the environmental metabolism of the sulfonylurea-herbicide tritosulfuron was investigated using aerobic soil degradation studies, during which a previously unidentified metabolite was observed using high performance liquid chromatography and mass spectrometry. The new metabolite was formed by reductive hydrogenation of tritosulfuron but the isolated amount and purity of the substance were insufficient to fully elucidate its structure. Therefore, electrochemistry coupled to mass spectrometry was successfully applied to mimic the reductive hydrogenation of tritosulfuron. After demonstrating the general feasibility of electrochemical reduction, the electrochemical conversion was scaled up to the semi-preparative scale and 1.0 mg of the hydrogenated product was synthesized. Similar retention times and mass spectrometric fragmentation patterns proved that the same hydrogenated product was formed electrochemically and in soil studies. Using the electrochemically generated standard, the structure of the metabolite was elucidated by means of NMR spectroscopy, which shows the potential of electrochemistry and mass spectrometry in environmental fate studies.

Electrochemical Protein-based Bioanalytical Devices for Drug Analysis.

Proteins are vital components of living cells and the loss of their native functions has been associated with a wide variety of medical conditions. From this point of view, investigation of the protein microenvironment is crucial to support the development of therapeutic approaches capable of ensuring cellular functions. Therefore, analytical assays for the detection, quantification, and characterization of proteins, drugs, and protein-drug complexes play an essential role in fundamental research and clinical applications. Electrochemistry arises as an alternative methodology for fast assessment of proteins and drugs and is attractive due to the adaptability to miniaturization and scalability of electroanalytical devices, which then can be further employed as strategies towards personalized medical care. Thus, this review summarizes electrochemical investigations in the past 10 years on protein-based analytical devices and biosensors. A general overview of electrochemical assays that integrate proteins with nanostructured materials and conductive polymers is presented. Applications of electrochemical assays and biosensors were divided into four categories. First, those designed for drug screening strategies that focus on targeting specific intracellular, extracellular, or membrane protein subdomains to modulate their functions, aggregation/misfolding of proteins, and protein degradation pathways. Then, drug metabolism assays that involve mimicking natural metabolic pathways to identify potential safety and efficacy issues related to a drug or its metabolites. The third was dedicated to electrochemical drug delivery systems with anchored drugs in the form of bioconjugates, while the fourth was dedicated to electroanalytical methodologies for quantitative drug assays, where the electroactivity of the target species is often used to correlate the electrochemical signal to their concentration.

Direct Electrochemistry of Glucose Dehydrogenase-Functionalized Polymers on a Modified Glassy Carbon Electrode and Its Molecular Recognition of Glucose.

A glucose biosensor was layer-by-layer assembled on a modified glassy carbon electrode (GCE) from a nanocomposite of NAD(P)+-dependent glucose dehydrogenase, aminated polyethylene glycol (mPEG), carboxylic acid-functionalized multi-wall carbon nanotubes (fMWCNTs), and ionic liquid (IL) composite functional polymers. The electrochemical electrode was denoted as NF/IL/GDH/mPEG-fMWCNTs/GCE. The composite polymer membranes were characterized by cyclic voltammetry, ultraviolet-visible spectrophotometry, electrochemical impedance spectroscopy, scanning electron microscopy, and transmission electron microscopy. The cyclic voltammogram of the modified electrode had a pair of well-defined quasi-reversible redox peaks with a formal potential of -61 mV (vs. Ag/AgCl) at a scan rate of 0.05 V s-1. The heterogeneous electron transfer constant (ks) of GDH on the composite functional polymer-modified GCE was 6.5 s-1. The biosensor could sensitively recognize and detect glucose linearly from 0.8 to 100 µM with a detection limit down to 0.46 µM (S/N = 3) and a sensitivity of 29.1 nA µM-1. The apparent Michaelis-Menten constant (Kmapp) of the modified electrode was 0.21 mM. The constructed electrochemical sensor was compared with the high-performance liquid chromatography method for the determination of glucose in commercially available glucose injections. The results demonstrated that the sensor was highly accurate and could be used for the rapid and quantitative determination of glucose concentration.

Electrochemical therapy (EChT) of cancer tumor with an external anode, a way to achieve pathological complete response.

There is a critical need for re-evaluation of electrochemical therapy (EChT) approaches of solid tumors to address the challenges of the currently used method: incomplete pathological response. The coexistence of anode and cathode in the tumor region resulted in acid-alkaline mixation (buffered pH) when the electrodes are so near each other (d < 1 cm), and in the non-affected lesions when the electrodes are far from each other (d > 1 cm), both have resulted in intact tumoral lesions in EChT field. Here, we presented a designation model study of EChT with an external anode out of the tumor and filled the tumor with dense distribution of cathode electrodes to completely destroy the tumoral lesions without any remaining vital tumoral residues. Anode was located in a biological ionic gel chamber (located on top of the skin) which mediates the ionic interface between the external anode and intratumoral cathode. Our newly reported method can solve the lack of a comprehensive therapeutic guideline for any solid tumors. A remarkable increase in the efficiency of EChT without any over-treating was achieved by alkaline therapy of the tumor (without any limitation in locating cathodic needles all over the tumor) and an external acidic region on top of the skin in a cylindrical gel chamber. We found that the destructive volumes and treating ability of mice tumors by this newly represented method were more significant than the conventional EChT method in fewer therapy sessions and no damage to the skin (both anode and cathode electrodes inside the tumor) (P < 0.05). Results of this study applied to mouse model tumors shed new light on returning attraction to EChT as a valuable complementary method for treating different types of solid breast tumors.

Dual-Mode Sensing Platform for Cancer Antigen 15-3 Determination Based on a Silica Nanochannel Array Using Electrochemiluminescence and Electrochemistry.

An electrochemiluminescence-electrochemistry (ECL-EC) dual-mode sensing platform based on a vertically-ordered mesoporous silica films (VMSF) modified electrode was designed here for the sensitive and selective determination of cancer antigen 15-3 (CA 15-3), a specific biomarker of breast cancer. VMSF was assembled through a rapid electrochemically assisted self-assembly (EASA) method and plays a crucial role in signal amplification via a strong electrostatic interaction with the positively charged bifunctional probe Ru(bpy)32+. To construct the biorecognition interface, epoxy functional silane was linked to the surface of VMSF for further covalent immobilization of the antibody. As a benefit from the specific combination of antigen and antibody, a non-conductive immunocomplex layer was formed in the presence of CA 15-3, leading to the hinderance of the mass and electron transfer of the probes. Based on this strategy, the dual-mode determination of CA 15-3 ranging from 0.1 mU/mL to 100 mU/mL with a LOD of 9 µU/mL for ECL mode, and 10 mU/mL to 200 U/mL with a LOD of 5.4 mU/mL for EC mode, was achieved. The proposed immunosensor was successfully employed for the detection of CA 15-3 in human serum without tedious pretreatment.

Study and voltammetric determination of fipronil in bovine lactose-free milk by differential pulse voltammetry using a carbon paste electrode.

A novel voltammetric screening method has been developed for the rapid determination of fipronil (FPN) residues in lactose-free milk samples with the use of a carbon-paste electrode (CPE) by differential-pulse voltammetry (DPV). Cyclic voltammetry indicated the occurrence of an irreversible anodic process at approximately +0.700 V (vs. Ag|AgCl, 3.0 mol L-1 KCl) in a 0.100 mol L-1 NaOH supporting electrolyte prepared as a 30% (v/v) ethanol-water solution. Quantification of FPN was carried out by DPV and analytical curves were constructed. In the absence of a matrix, the limits of detection (LOD) and quantification (LOQ) were 0.568 mg L-1 and 1.89 mg L-1, respectively. In the presence of a lactose-free skim milk matrix, the values of LOD and LOQ were 0.331 mg L-1 and 1.10 mg L-1. The recovery percentages for three different concentrations of FPN in lactose-free skim milk samples ranged between 95.3% and 109%. All assays could be conducted with milk samples without any prior extraction steps or pre-concentration of FPN, making this novel method rapid, simple, and relatively cheap.

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.