Reviewing neonicotinoid detection with electroanalytical methods.

Neonicotinoids, as the fastest-growing class of insecticides, currently account for over 25% of the global pesticide market. Their effectiveness in controlling a wide range of pests that pose a threat to croplands, home yards/gardens, and golf course greens cannot be denied. However, the extensive use of neonicotinoids has resulted in significant declines in nontarget organisms such as pollinators, insects, and birds. Furthermore, the potential chronic, sublethal effects of these compounds on human health remain largely unknown. To address these pressing issues, it is crucial to explore and understand the capabilities of electrochemical sensors in detecting neonicotinoid residues. Surprisingly, despite the increasing importance of this topic, no comprehensive review article currently exists in the literature. Therefore, our proposed review aims to bridge this gap by providing a thorough analysis of the use of electrochemical methods for neonicotinoid determination. In this review article, we will delve into various aspects of electrochemical analysis, including the influence of electrode materials, employed techniques, and the different types of electrode mechanisms utilized. By synthesizing and analysing the existing research in this field, our review will offer valuable insights and guidance to researchers, scientists, and policymakers alike.

Recent Advancement and Structural Engineering in Transition Metal Dichalcogenides for Alkali Metal Ions Batteries.

Currently, transition metal dichalcogenides-based alkaline metal ion batteries have been extensively investigated for renewable energy applications to overcome the energy crisis and environmental pollution. The layered morphologys with a large surface area favors high electrochemical properties. Thermal stability, mechanical structural stability, and high conductivity are the primary features of layered transition metal dichalcogenides (L-TMDs). L-TMDs are used as battery materials and as supporters for other active materials. However, these materials still face aggregation, which reduces their applicability in batteries. In this review, a comprehensive study has been undertaken on recent advancements in L-TMDs-based materials, including 0D, 1D, 2D, 3D, and other carbon materials. Types of structural engineering, such as interlayer spacing, surface defects, phase control, heteroatom doping, and alloying, have been summarized. The synthetic strategy of structural engineering and its effects have been deeply discussed. Lithium- and sodium-ion battery applications have been summarized in this study. This is the first review article to summarize different morphology-based TMDs with their intrinsic properties for alkali metal ion batteries (AMIBs), so it is believed that this review article will improve overall knowledge of TMDs for AMIBS applications.

The Influence of Graphene Oxide Composition on Properties of Surface-Modified Metal Electrodes.

The present paper describes the effect of the concentration of two graphene oxides (with different oxygen content) in the modifier layer on the electrochemical and structural properties of noble metal disk electrodes used as working electrodes in voltammetry. The chemistry of graphene oxides was tested using EDS, FTIR, UV-Vis spectroscopy, and combustion analysis. The structural properties of the obtained modifier layers were examined by means of scanning electron and atomic force microscopy. Cyclic voltammetry was employed for comparative electrochemical studies.

Electrode kinetics from a single experiment: multi-amplitude analysis in square-wave chronoamperometry.

The recently introduced technique of square-wave chronoamperometry (SWCA) is studied under conditions of progressively increasing height of potential pulses (square-wave amplitude) within a single experiment. In multi-amplitude square-wave chronoamperometry (MA-SWCA) a potential modulation consisting of square-wave forward and reverse potential pulses is imposed on a constant mid-potential; the amplitude of pulses increases progressively during the experiment. This allows the fast and reliable estimation of kinetic parameters at a constant pulse frequency in a single experiment, based on the resulting feature known as the amplitude-based quasireversible maximum. The proposed methodology is tested by simulating the responses of a simple quasireversible electrode reaction of a dissolved redox couple and a surface confined electrode reaction. Compared with conventional square-wave voltammetry (SWV) and SWCA, MA-SWCA shows advantages in estimation of the standard rate constant in terms of simplicity, speed and efficiency for both studied electrode mechanisms.

Screen-Printed Carbon Electrodes with Macroporous Copper Film for Enhanced Amperometric Sensing of Saccharides.

A porous layer of copper was formed on the surface of screen-printed carbon electrodes via the colloidal crystal templating technique. An aqueous suspension of monodisperse polystyrene spheres of 500 nm particle diameter was drop-casted on the carbon tracks printed on the substrate made of alumina ceramic. After evaporation, the electrode was carefully dipped in copper plating solution for a certain time to achieve a sufficient penetration of solution within the polystyrene spheres. The metal was then electrodeposited galvanostatically over the self-assembled colloidal crystal. Finally, the polystyrene template was dissolved in toluene to expose the porous structure of copper deposit. The morphology of porous structures was investigated using scanning electron microscopy. Electroanalytical properties of porous copper film electrodes were evaluated in amperometric detection of selected saccharides, namely glucose, fructose, sucrose, and galactose. Using hydrodynamic amperometry in stirred alkaline solution, a current response at +0.6 V vs. Ag/AgCl was recorded after addition of the selected saccharide. These saccharides could be quantified in two linear ranges (0.2-1.0 µmol L-1 and 4.0-100 µmol L-1) with detection limits of 0.1 µmol L-1 glucose, 0.03 µmol L-1 fructose, and 0.05 µmol L-1 sucrose or galactose. In addition, analytical performance of porous copper electrodes was ascertained and compared to that of copper film screen-printed carbon electrodes, prepared ex-situ by the galvanostatic deposition of metal in the plating solution. After calculating the current densities with respect to the geometric area of working electrodes, the porous electrodes exhibited much higher sensitivity to changes in concentration of analytes, presumably due to the larger surface of the porous copper deposit. In the future, they could be incorporated in detectors of flow injection systems due to their long-term mechanical stability.

Analytical Performance of Clay Paste Electrode and Graphene Paste Electrode-Comparative Study.

The analytical performance of the clay paste electrode and graphene paste electrode was compared using square wave voltammetry (SWV) and cyclic voltammetry (CV). The comparison was made on the basis of a paracetamol (PA) determination on both working electrodes. The influence of pH and SWV parameters was investigated. The linear concentration ranges were found to be 6.0 × 10-7-3.0 × 10-5 and 2.0 × 10-6-8.0 × 10-5 mol L-1 for clay paste electrode (ClPE) and graphene paste electrode (GrPE), respectively. The detection and quantification limits were calculated as 1.4 × 10-7 and 4.7 ×10-7 mol L-1 for ClPE and 3.7 × 10-7 and 1.2 × 10-6 mol L-1 for GrPE, respectively. Developed methods were successfully applied to pharmaceutical formulations analyses. Scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to characterize ClPE and GrPE surfaces. Clay composition was examined with wavelength dispersive X-ray (WDXRF).

Highly Sensitive Determination of Tenofovir in Pharmaceutical Formulations and Patients Urine-Comparative Electroanalytical Studies Using Different Sensing Methods.

This paper discusses the electrochemical behavior of antiviral drug Tenofovir (TFV) and its possible applicability towards electroanalytical determination with diverse detection strategies using square-wave voltammetry. Namely, oxidation processes were investigated using glassy carbon electrode with graphene oxide surface modification (GO/GCE), while the reduction processes, related to the studied analyte, were analyzed at a renewable silver amalgam electrode (Hg(Ag)FE). Scanning electron microscopy imaging confirmed the successful deposition of GO at the electrode surface. Catalytic properties of graphene oxide were exposed while being compared with those of bare GCE. The resultant modification of GCE with GO enhanced the electroactive surface area by 50% in comparison to the bare one. At both electrodes, i.e., GO/GCE and Hg(Ag)FE, the TFV response was used to examine and optimize the influence of square-wave excitation parameters, i.e., square wave frequency, step potential and amplitude, and supporting electrolyte composition and its pH. Broad selectivity studies were performed with miscellaneous interfering agents influence, including ascorbic acid, selected saccharides and aminoacids, metal ions, non-opioid analgesic metamizole, non-steroidal anti-inflammatory drug omeprazole, and several drugs used along with TFV treatment. The linear concentration range for TFV determination at GO/GCE and Hg(Ag)FE was found to be 0.3-30.0 µmol L-1 and 0.5-7.0 µmol L-1, respectively. The lowest LOD was calculated for GO/GCE and was equal to 48.6 nmol L-1. The developed procedure was used to detect TFV in pharmaceutical formulations and patient urine samples and has referenced utilization in HPLC studies.

Detection of siloxane thin films on glass substrate using IR ratio-reflectance spectrum.

In case of thin films of siloxane obtained from different organo-silane derivatives (alkoxy and chloro) on soda lime silica glass substrates, IR-ATR and IR-SR could not detect the organic functional groups of the coating. This becomes even more problematic for the case of tetraethoxysilane (when fully hydrolyzed), the coating of which possesses the same functional groups as the glass substrate. In this work we propose to employ the so-called ratio-reflectance spectra in the v(Si-O) wavenumber region, where both glass and the siloxane coating give most prominent bands, important for the evaluation of the quality of coating formation and qualitative knowledge on its structure. We show that the reflectance-absorbance spectra obtained from the ratio-reflectance spectra are in direct connection to the structure of the siloxane network which depends not only on the chemical nature of the parent silane, but also on the dipping time and the solvent composition. Some characteristics of the reflectance-absorbance spectra, like the appearance of a two well defined bands at 1110 and 975 cm-1, can be correlated to the film morphology and bridging oxygen number. We support our conclusions using principal component analysis of reflectance spectra, contact angle, AFM and SEM measurements.

Differential Square-Wave Voltammetry.

A new voltammetric technique designed as a hybrid between differential pulse and square-wave voltammetry is proposed for the purpose of unifying the advantages of both techniques, i.e., the ability to provide mechanistic information, studying electrode kinetics of both sluggish and very fast electrode reactions, and the ability to suppress effectively residual background current. Voltammetric modulation of the hybrid technique consists of a staircase potential combined with square-wave potential modulation superimposed at the end of each potential step. By measuring the current at the end of each potential step and pulse, differential forward and backward voltammetric components can be composed, which is a unique ability of the hybrid technique. In addition, by analogy to square-wave voltammetry, a net differential component can be contracted with improved analytical performances compared to square-wave voltammetry. The proposed technique opens a new avenue for an advanced analysis of electrochemical processes and analytical application.

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel-Crafts/Bradsher Cyclization Reaction.

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp. =331-354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60-70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel-Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen.

Graphene oxide activation with a constant magnetic field.

The effect of constant magnetic field strength on activation of sensors modified with graphene oxide monolayers was investigated. The use of constant magnetic field resulted in improved electroanalytical properties of the sensors. It was proven that level of GO activation is clearly related to constant magnetic field strength. Moreover, it was demonstrated that observed phenomenon is stable in time.

Improved electroanalytical characteristics for flumetralin determination in the presence of surface active compound.

ABSTRACT: The use of square wave voltammetry (SWV) and square wave adsorptive stripping voltammetry (SWAdSV) in conjunction with a cyclic renewable silver amalgam film electrode for the determination of flumetralin is presented. Poor separation of two overlapped reduction peaks is significantly improved when hexadecyltrimethylammonium bromide is used as a component of the supporting electrolyte solution (together with BR buffer pH 9.5). The SW technique parameters were investigated and found optimal as follows: frequency 50 Hz, amplitude 40 mV, and step potential 5 mV. Accumulation time and potential were studied to select the optimal conditions in adsorptive voltammetry. The analytical curve was linear for the flumetralin concentration range from 1.0 × 10-6 to 1.0 × 10-5 mol dm-3 and from 5.0 × 10-9 to 1.0 × 10-7 mol dm-3 for SWV and SWAdSV, respectively. Detection limit of 6.5 × 10-10 mol dm-3 was calculated for accumulation time 60 s at -0.2 V. The repeatability of the method was determined at a flumetralin concentration level equal to 5.0 × 10-9 mol dm-3 and expressed as %RSD = 5.0% (n = 6). The proposed method was applied and validated successfully by studying the recovery of herbicide content in spiked environmental samples.

Rapid and Sensitive Voltammetric Determination of Aclonifen in Water Samples.

This paper presents the use of square wave voltammetry (SWV) and square wave adsorptive stripping voltammetry (SWAdSV) in conjunction with a cyclic renewable silver amalgam film electrode (Hg(Ag)FE) for the determination of aclonifen in spiked water samples. A reduction peak at -0.65 V versus Ag/AgCl was obtained in the selected buffer (borax buffer with pH 9.2), exhibiting the characteristics of an irreversible reaction. The effect of square wave (SW) frequency, SW amplitude and step potential, as well as accumulation parameters (time and potential) were studied to select the optimal experimental conditions. The calibration curve was linear in the aclonifen concentration range from 1.0×10(-7) to 1.0×10(-6) mol L(-1) and from 1.0×10(-8) to1.0×10(-7) mol L(-1) for SWV and SWAdSV, respectively. The detection and quantification limits were found to be 3.1×10(-8) mol L(-1); 1.0×10(-7) mol L(-1) and 2.9×10(-9) mol L(-1); 9.6×10(-9) mol L-1 for SWV and SWAdSV, respectively. The proposed method was applied successfully in the determination of aclonifen in spiked water samples. The developed procedure can be adequate at least for screening purposes, where positive results should be confirmed by more selective method.

Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples.

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at -0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10(-8) to 6.0 × 10(-8) mol L(-1) with detection and quantification limit 3.0 × 10(-9) and 1.0 × 10(-8) mol L(-1), respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.

New approach to electrode kinetic measurements in square-wave voltammetry: amplitude-based quasireversible maximum.

The influence of the potential pulse height of square-wave voltammetry (SWV) (i.e., the SW amplitude) is studied for a variety of quasireversible electrode mechanisms, including a simple solution-phase electrode reaction at a planar or spherical electrode, a solution phase electrode reaction coupled with a reversible follow-up chemical reaction, and a diffusionless surface confined electrode reaction. The electrode kinetics of all the electrode mechanisms depends critically on the SW amplitude, and the quasireversible kinetic region is a function of both frequency-related electrode kinetic parameters and the SW amplitude. Thus, a novel methodology for electrode kinetics measurements is proposed by altering the SW amplitude only, at a fixed frequency of the SW potential modulation, that is, at a constant scan rate of the voltammetric experiment. Electrode kinetic measurements at a constant SW frequency are of exceptional importance especially when complex electrode mechanisms are studied, which depend on several frequency-related kinetic parameters. The electrode kinetic measurements are based on a novel feature termed the "amplitude-based quasireversible maximum", manifested as a parabolic dependence of the amplitude-normalized net SW peak current versus the SW amplitude. The position of the amplitude-based quasireversible maximum depends on the standard rate constant of the electrode reaction, enabling estimation of this important kinetic parameter in a simple and fast procedure. The novel quasireversible maximum is attributed to all studied electrode mechanisms, implying that it is a general feature of most electrode mechanisms under conditions of SWV.

Square wave adsorptive stripping voltammetric determination of diazinon in its insecticidal formulations.

The pesticide diazinon was determined in its insecticidal formulations by square wave adsorptive stripping voltammetry. The method of its determination is based on the irreversible reduction reaction at the hanging mercury drop electrode. The optimal signal was detected at -1.05 V vs. Ag/AgCl in Britton-Robinson buffer at pH 4.4. Various parameters such as pH, buffer concentration, frequency, amplitude, step potential, accumulation time, and potential were investigated to enhance the sensitivity of the determination. The highest response was recorded at an accumulation potential -0.4 V, accumulation time 60 s, amplitude 75 mV, frequency 100 Hz, and step potential 5 mV. The pesticide electrochemical behavior was considered under experimental conditions. The electroanalytical procedure enabled diazinon determination in the concentration range 4.0 × 10(-8)-3.9 × 10(-7) mol L(-1) in supporting electrolyte. The detection and quantification limit were found to be 1.1 × 10(-8) and 3.7 × 10(-8) mol L(-1), respectively. The method was applied successfully in the determination of the active ingredients in the insecticidal formulations Diazinon 10GR and Beaphar 275.