Voltammetric Sensor Based on the Combination of Tin and Cerium Dioxide Nanoparticles with Surfactants for Quantification of Sunset Yellow FCF.

Sunset Yellow FCF (SY FCF) is one of the widely used synthetic azo dyes in the food industry whose content has to be controlled for safety reasons. Electrochemical sensors are a promising tool for this type of task. A voltammetric sensor based on a combination of tin and cerium dioxide nanoparticles (SnO2-CeO2 NPs) with surfactants has been developed for SY FCF determination. The synergetic effect of both types of NPs has been confirmed. Surfactants of various natures (sodium lauryl sulfate (SLS), Brij® 35, and hexadecylpyridinium bromide (HDPB)) have been tested as dispersive media. The best effects, i.e., the highest oxidation currents of SY FCF, have been observed in the case of HDPB. The sensor demonstrates a 4.5-fold-higher electroactive surface area and a 38-fold-higher electron transfer rate compared to the bare glassy carbon electrode (GCE). The electrooxidation of SY FCF is an irreversible, two-electron, diffusion-driven process involving proton transfer. In differential pulse mode in Britton-Robinson buffer (BRB) pH 2.0, the sensor gives a linear response to SY FCF from 0.010 to 1.0 µM and from 1.0 to 100 µM with an 8.0 nM detection limit. The absence of an interferent effect from other typical food components and colorants has been shown. The sensor has been tested on soft drinks and validated with the standard chromatographic method.

A new cysteamine-copper chemically modified screen-printed gold electrode for glyphosate determination.

A chemically modified screen-printed gold electrode has been prepared by covering the electrode surface with a cysteamine-copper self-assembled monolayer (SAM). The sensor was effective for the voltammetric sensing of glyphosate. The method exploits the interaction of glyphosate with copper ions complexed by cysteamine, which results in a decrease in the intensity of copper redox current. Cyclic voltammetry was employed as a measuring technique. When dealing with voltammograms with numerous peaks changing in shape and size, it is difficult to define which signal is the most significant for the analyte determination; in these cases, a helpful approach is chemometrics. In this work, PLS (Partial Least Square regression) has been applied to build models to correlate the signal with the glyphosate concentration in standard aqueous solutions and tap water samples (matrix-matched calibration). The method's figures of merits were evaluated, obtaining a limit of quantification of about 5 µM. The reliability of the proposed sensor was verified by analyzing tap water spiked with glyphosate; recoveries higher than 90 % were achieved.

Recent Advances in Electrochemical Sensors for Sulfur-Containing Antioxidants.

Sulfur-containing antioxidants are an important part of the antioxidant defense systems in living organisms under the frame of a thiol-disulfide equilibrium. Among them, l-cysteine, l-homocysteine, l-methionine, glutathione, and α-lipoic acid are the most typical representatives. Their actions in living systems are briefly discussed. Being electroactive, sulfur-containing antioxidants are interesting analytes to be determined using various types of electrochemical sensors. Attention is paid to the chemically modified electrodes with various nanostructured coverages. The analytical capabilities of electrochemical sensors for sulfur-containing antioxidant quantification are summarized and discussed. The data are summarized and presented on the basis of the electrode surface modifier applied, i.e., carbon nanomaterials, metal and metal oxide nanoparticles (NPs) and nanostructures, organic mediators, polymeric coverage, and mixed modifiers. The combination of various types of nanomaterials provides a wider linear dynamic range, lower limits of detection, and higher selectivity in comparison to bare electrodes and sensors based on the one type of surface modifier. The perspective of the combination of chromatography with electrochemical detection providing the possibility for simultaneous determination of sulfur-containing antioxidants in a complex matrix has also been discussed.

Ni(II)-Salophen-Comprehensive Analysis on Electrochemical and Spectral Characterization and Biological Studies.

New aspects of the Ni(II)-salophen complex and salophen ligand precursor were found during deep electrochemical and optical characterization, as well as biological studies for new pharmacological applications. Physicochemical and spectroscopic methods (1H- and 13C-NMR, FT-IR and UV-Vis, electrospray ionization mass spectroscopy, thermogravimetric analysis, and molar conductance measurements) were also used to prove that the salophen ligand acts as a tetradentate and coordinates to the central metal through nitrogen and oxygen atoms. The electrochemical behavior of the free Schiff salophen ligand (H2L) and its Ni(II) complex (Ni(II)L) was deeply studied in tetrabutylammonium perchlorate solutions in acetonitrile via CV, DPV, and RDE. Blue films on the surfaces of the electrodes as a result of the electropolymerization processes were put in evidence and characterized via CV and DPV. (H2L) and Ni(II)L complexes were tested for their antimicrobial, antifungal, and antioxidant activity, showing good antimicrobial and antifungal activity against several bacteria and fungi.

New approaches in antibiotics detection: The use of square wave voltammetry.

Antibiotics belongs to a class of pharmaceutical compounds widely used due to their effectiveness against bacterial infections. However, if consumed or inappropriately disposed of in the environment can results in environmental and public health problems, because they are considered emerging contaminants and their residues represent damage, whether in the long or short term, to different terrestrial ecosystems, in addition to bringing potential risks to agricultural sectors, such as livestock and fish farming. For this, the development of analytical methods for low-concentration detection and identification of antibiotics in natural waters, wastewaters, soil, foods, and biological fluids is necessary. This review shows the applicability of square wave voltammetry for the analytical determination of antibiotics from different chemical classes and covers a variety of samples and working electrodes that are used as voltammetric sensors. The review involved the analysis of scientific publications from the Science Direct® and Scopus® databases, with scientific manuscripts covering the period between January 2012 and May 2023. Various manuscripts were discussed indicating the applicability of square wave voltammetry in antibiotics detection in urine, blood, natural waters, milk, among other complex samples.

Layer-by-Layer Combination of MWCNTs and Poly(ferulic acid) as Electrochemical Platform for Hesperidin Quantification.

The electrochemical polymerization of suitable monomers is a powerful way to create voltammetric sensors with improved responses to a target analyte. Nonconductive polymers based on phenolic acids were successfully combined with carbon nanomaterials to obtain sufficient conductivity and high surface area of the electrode. Glassy carbon electrodes (GCE) modified with multi-walled carbon nanotubes (MWCNTs) and electropolymerized ferulic acid (FA) were developed for the sensitive quantification of hesperidin. The optimized conditions of FA electropolymerization in basic medium (15 cycles from -0.2 to 1.0 V at 100 mV s-1 in 250 µmol L-1 monomer solution in 0.1 mol L-1 NaOH) were found using the voltammetric response of hesperidin. The polymer-modified electrode exhibited a high electroactive surface area (1.14 ± 0.05 cm2 vs. 0.75 ± 0.03 and 0.089 ± 0.003 cm2 for MWCNTs/GCE and bare GCE, respectively) and decreased in the charge transfer resistance (21.4 ± 0.9 kΩ vs. 72 ± 3 kΩ for bare GCE). Under optimized conditions, hesperidin linear dynamic ranges of 0.025-1.0 and 1.0-10 µmol L-1 with a detection limit of 7.0 nmol L-1 were achieved, which were the best ones among those reported to date. The developed electrode was tested on orange juice and compared with chromatography.

Electrochemical Chemically Based Sensors and Emerging Enzymatic Biosensors for Antidepressant Drug Detection: A Review.

Major depressive disorder is a widespread condition with antidepressants as the main pharmacological treatment. However, some patients experience concerning adverse reactions or have an inadequate response to treatment. Analytical chromatographic techniques, among other techniques, are valuable tools for investigating medication complications, including those associated with antidepressants. Nevertheless, there is a growing need to address the limitations associated with these techniques. In recent years, electrochemical (bio)sensors have garnered significant attention due to their lower cost, portability, and precision. Electrochemical (bio)sensors can be used for various applications related to depression, such as monitoring the levels of antidepressants in biological and in environmental samples. They can provide accurate and rapid results, which could facilitate personalized treatment and improve patient outcomes. This state-of-the-art literature review aims to explore the latest advancements in the electrochemical detection of antidepressants. The review focuses on two types of electrochemical sensors: Chemically modified sensors and enzyme-based biosensors. The referred papers are carefully categorized according to their respective sensor type. The review examines the differences between the two sensing methods, highlights their unique features and limitations, and provides an in-depth analysis of each sensor.

Electrode Based on the MWCNTs and Electropolymerized Thymolphthalein for the Voltammetric Determination of Total Isopropylmethylphenols in Spices.

Isopropylmethylphenols, namely thymol and carvacrol, are natural phenolic monoterpenoids with a wide spectrum of bioactivity making them applicable in the cosmetic, pharmaceutical, and food industry. The dose-dependent antioxidant properties of isopropylmethylphenols require their quantification in real samples. Glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNTs) and electropolymerized thymolphthalein has been developed for the sensitive quantification of isopropylmethylphenols. Conditions of thymolphthalein electropolymerization (monomer concentration, number of cycles, and electrolysis parameters) providing the best response to thymol have been found. Scanning electron microscopy and electrochemical methods confirm the effectivity of the electrode developed. The linear dynamic ranges of 0.050-25 and 25-100 µM for thymol and 0.10-10 and 10-100 µM for carvacrol with detection limits of 0.037 and 0.063 µM, respectively, have been achieved in differential pulse mode in Britton-Robinson buffer pH 2.0. The selectivity of the isopropylmethylphenols response in the presence of typical interferences (inorganic ions, saccharides, ascorbic acid) and other phenolics (caffeic, chlorogenic, gallic and rosmarinic acids, and quercetin) is a significant advantage over other electrochemical methods. The electrode has been used in the analysis of oregano and thyme spices. Total isopropylmethylphenols contents have been evaluated after a single sonication-assisted extraction with methanol.

Electrochemical Characterization of the Antioxidant Properties of Medicinal Plants and Products: A Review.

Medicinal plants are an important source of bioactive compounds with a wide spectrum of practically useful properties. Various types of antioxidants synthesized in plants are the reasons for their application in medicine, phytotherapy, and aromatherapy. Therefore, reliable, simple, cost-effective, eco-friendly, and rapid methods for the evaluation of antioxidant properties of medicinal plants and products on their basis are required. Electrochemical methods based on electron transfer reactions are promising tools to solve this problem. Total antioxidant parameters and individual antioxidant quantification can be achieved using suitable electrochemical techniques. The analytical capabilities of constant-current coulometry, potentiometry, various types of voltammetry, and chrono methods in the evaluation of total antioxidant parameters of medicinal plants and plant-derived products are presented. The advantages and limitations of methods in comparison to each other and traditional spectroscopic methods are discussed. The possibility to use electrochemical detection of the antioxidants via reactions with oxidants or radicals (N- and O-centered) in solution, with stable radicals immobilized on the electrode surface, via oxidation of antioxidants on a suitable electrode, allows the study of various mechanisms of antioxidant actions occurring in living systems. Attention is also paid to the individual or simultaneous electrochemical determination of antioxidants in medicinal plants using chemically modified electrodes.

Voltammetric Sensor Based on the Poly(p-aminobenzoic Acid) for the Simultaneous Quantification of Aromatic Aldehydes as Markers of Cognac and Brandy Quality.

Cognac and brandy quality control is an actual topic in food analysis. Aromatic aldehydes, particularly syringaldehyde and vanillin, are one of the markers used for these purposes. Therefore, simple and express methods for their simultaneous determination are required. The voltammetric sensor based on the layer-by-layer combination of multi-walled carbon nanotubes (MWCNTs) and electropolymerized p-aminobenzoic acid (p-ABA) provides full resolution of the syringaldehyde and vanillin oxidation peaks. Optimized conditions of p-ABA electropolymerization (100 µM monomer in Britton-Robinson buffer pH 2.0, twenty cycles in the polarization window of -0.5 to 2.0 V with a potential scan rate of 100 mV·s-1) were found. The poly(p-ABA)-based electrode was characterized by scanning electron microscopy (SEM), cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). Electrooxidation of syringaldehyde and vanillin is an irreversible two-electron diffusion-controlled process. In the differential pulse mode, the sensor allows quantification of aromatic aldehydes in the ranges of 0.075-7.5 and 7.5-100 µM for syringaldehyde and 0.50-7.5 and 7.5-100 µM for vanillin with the detection limits of 0.018 and 0.19 µM, respectively. The sensor was applied to cognac and brandy samples and compared to chromatography.

Selective Voltammetric Sensor for the Simultaneous Quantification of Tartrazine and Brilliant Blue FCF.

Tartrazine and brilliant blue FCF are synthetic dyes used in the food, cosmetic and pharmaceutical industries. The individual and/or simultaneous control of their concentrations is required due to dose-dependent negative health effects. Therefore, the paper presents experimental results related to the development of a sensing platform for the electrochemical detection of tartrazine and brilliant blue FCF based on a glassy carbon electrode (GCE) modified with MnO2 nanorods, using anodic differential pulse voltammetry. Homogeneous and stable suspensions of MnO2 nanorods have been obtained involving cetylpyridinium bromide solution as a cationic surfactant. The MnO2 nanorods-modified electrode showed a 7.9-fold increase in the electroactive surface area and a 72-fold decrease in the electron transfer resistance. The developed sensor allowed the simultaneous quantification of dyes for two linear domains: in the ranges of 0.10-2.5 and 2.5-15 µM for tartrazine and 0.25-2.5 and 2.5-15 µM for brilliant blue FCF with detection limits of 43 and 41 nM, respectively. High selectivity of the sensor response in the presence of typical interference agents (inorganic ions, saccharides, ascorbic and sorbic acids), other food dyes (riboflavin, indigo carmine, and sunset yellow), and vanillin has been achieved. The sensor has been tested by analyzing soft and isotonic sports drinks and the determined concentrations were close to those obtained involving the chromatography technique.

Polycyclic Aromatic Hydrocarbons: Occurrence, Electroanalysis, Challenges, and Future Outlooks.

The past several decades have seen increasing concern regarding the wide distribution of polycyclic aromatic hydrocarbons (PAHs) in environmental matrices. Primary toxicological data show PAHs' persistent characteristics and possible toxicity effects. Because of this pressing global issue, electroanalytical methods have been introduced. These methods are effective for PAH determination in environmental waters, even outclassing sophisticated analytical techniques such as chromatography, conventional spectrophotometry, fluorescence, and capillary electrophoresis. Herein, the literature published on PAHs is reviewed and discussed with special regard to PAH occurrence. Moreover, the recent developments in electrochemical sensors for PAH determination and the challenges and future outlooks in this field, are also presented.

Electrochemical sensor for tricyclic antidepressants with low nanomolar detection limit: Quantitative Determination of Amitriptyline and Nortriptyline in blood.

Amitriptyline and its metabolite, Nortriptyline are commonly used tricyclic antidepressant (TCA) drugs that are electrochemically active. In this work, the performance characteristics of a plasticized PVC membrane-coated glassy carbon (GC) electrode are described for the voltammetric quantification of Amitriptyline and Nortriptyline in whole blood. The highly lipophilic Amitriptyline and Nortriptyline preferentially partition into the plasticized PVC membrane where the free drug is oxidized on the GC electrode. The concentrations of the drugs in the membrane are orders of magnitude larger than in the sample solution, resulting in superb limit of detection (LOD) of the membrane-coated voltammetric sensor: 3 nmol/L for Amitriptyline and 20 nmol/L for Nortriptyline. Conversely, hydrophilic components of the sample solution, e.g., proteins, the protein-bound fraction of the drugs, and electrochemically active small molecules are blocked from entering the membrane, which provides exceptional selectivity for the membrane-coated sensor and feasibility for the measurements of Amitriptyline in whole blood. In this work, the concentrations of Amitriptyline and Nortriptyline were determined in whole blood using the sensor and the results of our analysis were compared to the results of the standard HPLC-MS method. Based on our experience, the one-step voltammetric methods with the membrane-coated sensor may become a real alternative to the significantly more complex HPLC-MS analysis.

Polymeric membrane-modified voltammetric sensors for lipophilic analytes with nanomolar detection limit: Key parameters influencing the response characteristics.

Thin plasticized PVC membrane-coated glassy carbon working electrodes have been used for the voltammetric measurement of highly lipophilic, electroactive drugs. Compared to conventional working electrodes, these membrane-coated electrodes exhibit remarkable detection limit and selectivity and are less prone to electrode fouling. The unique performance characteristics of these sensors are related to the large partition coefficient of the analyte in the membrane coating where it is oxidized in a non-aqueous membrane phase. To analyze the influence of the key parameters of the response of membrane-coated sensors, we derived theoretical expressions on the voltammetric response of the sensors. In our analysis we considered 1) the partition coefficient (Pmw) of the analyte between the aqueous sample and the organic membrane, 2) the membrane volume to sample volume ratio (Vm/Vw), and 3) the binding constant of constituents in the sample that bind the analyte (K). The results of our theoretical analysis have been tested through voltammetric measurement of highly lipophilic analytes with logPow values (logarithm of the partition coefficient between octanol and water) ranging between 0.3 and 7.5. By understanding of the influence of the sensor design parameters on the overall sensor response, these parameters can be tuned for optimized response slope, detection limit, etc., for solving specific analytical tasks.

Voltammetry of local anesthetics: theoretical and practical aspects.

Local anesthetics (LAs) are widely used in anesthesiology, ophthalmology, and otolaryngology as well as for treatment of chronic and oncological pain. However, anesthetics can cause adverse effects up to lethal ones. In this work, we cited reviews on chromatographic and spectroscopic methods of local anesthetics determination published earlier, and the main purpose was to review the possibilities and advantages of voltammetric methods used for the LAs determination. The electrochemical behavior, mechanism of LAs transformation on the various working electrodes and analytical parameters of voltammetric methods used for their determination were reviewed in the work. Vast majority of these methods were developed for the most widely used anesthetics in medicine like benzocaine, lidocaine and procaine. Special attention was paid to possible mechanisms of electrochemical oxidation and in some cases reduction of LAs or their derivatives. Voltammetry is used for the determination of LAs in pharmaceutical formulations and in biological fluids. The analytical characteristics in terms of sensitivity, selectivity, reproducibility also were discussed in the article.

A descrição matemática da detecção eletroanalítica dos íons de zinco em formas farmacêuticas de uso oftálmico, baseada na complexação de zinco com algumas bases de Schiff / The mathematical description for the electroanalytical detection of zinc ions in ophthalmic pharmaceutical forms, based on zinc complexation with some Schiff bases

RESUMO Um processo eletroanalítico da detecção quantitativa dos íons de zinco bivalente sobre as novas bases de Schiff no modo galvanostático tem sido simulado teoricamente. O respectivo modelo matemático tem sido desenvolvido e analisado mediante a teoria de estabilidade linear e da análise de bifurcações. Foi estabelecido que o sistema é eficiente tanto do ponto de vista eletroanalítico, como do ponto de vista eletrossintético, por ser facilmente estabilizado o estado estacionário. Todavia, o comportamento oscilatorio, neste sistema é mais provável que no caso clássico do desempenho de sensores, baseados em polímeros condutores e outros materiais orgânicos, por haver influências na dupla camada elétrica, causadas pela reação química da formação de complexo.

SUMMARY An electroanalytical process of the quantitative determination of bivalent zinc ions over the novel Schiff bases in galvanostatic mode has been theoretically simulated. The correspondent mathematical model has been developed and analyzed by means of linear stability theory and bifurcation analysis. It was shown that the system is efficient from both electroanalytical and electrosynthetical points of view, as the steady-state is easily stabilized. Nevertheless, the oscillatory behavior in this system is more probable than in the classic case of the sensors, based on conducting polymers and other organic materials, as there are double electric layer influences, caused by complex formation.

Plasticized PVC Membrane Modified Electrodes: Voltammetry of Highly Hydrophobic Compounds.

In the last 50 years, plasticized polyvinyl chloride (PVC) membranes have gained unique importance in chemical sensor development. Originally, these membranes separated two solutions in conventional ion-selective electrodes. Later, the same membranes were applied over a variety of supporting electrodes and used in both potentiometric and voltammetric measurements of ions and electrically charged molecules. The focus of this paper is to demonstrate the utility of the plasticized PVC membrane modified working electrode for the voltammetric measurement of highly lipophilic molecules. The plasticized PVC membrane prevents electrode fouling, extends the detection limit of the voltammetric methods to sub-micromolar concentrations, and minimizes interference by electrochemically active hydrophilic analytes.

Voltammetric sensing of silver nanoparticles on electrodes modified with selective ligands by using covalent and electropolymerization procedures. Discrimination between silver(I) and metallic silver.

New electrochemical sensors are described for the rapid quantification of silver nanoparticles (AgNPs). They are based on the immobilization of L-cysteine on a glassy carbon electrode (GCE) and on the formation of electropolymerized oligomers on the GCE. Ligands with amino, sulfur and carboxy functional groups are used that are capable of selectively retaining AgNPs. The experimental conditions for electropolymerizations were optimized for each of four monomers studied: L-lysine, thiophene-3-carboxamide, thionin, and o-phenylene-diamine. The best retention capabilities and conditions for quantification of AgNPs were found for immobilized nanoparticle voltammetry. This method is more sensitive than others based on the sorption of AgNPs from dispersions. These ligands also retain ionic silver species. Hence, Ag(I) and Ag0 can be discriminated, and the total silver content can be quantified by stripping voltammetry. The best analytical properties (for dispersions of AgNPs of 40 nm diameter) were found with GCEs carrying electropolymerized L-lysine. Figures of merit include (a) sensitivity of 4.329 ± 0.031 µA µg-1 mL cm-2, (b) a detection limit of 0.010 µg mL-1, and (c) a relative standars deviation of about 7.2% (for n = 4). The poly-L-lysine sensors can also evaluate the size of the AgNPs in the range 20 to 80 nm diameter, owing to displacements of the maximum potential of the voltammetry peaks. Graphical abstractSchematic representation of the quantification of silver nanoparticles (AgNPs) with a glassy-carbon electrode (GCE) modified with electropolymerized poly(L-lysine). AgNPs (and Ag+ ions) are selectively preconcentrated in the polymer and determined by differential-pulse stripping voltammetry.

Voltammetry at Hexamethyl-P-Terphenyl Poly(Benzimidazolium) (HMT-PMBI)-Coated Glassy Carbon Electrodes: Charge Transport Properties and Detection of Uric and Ascorbic Acid.

We describe the voltammetric behavior of an anion-exchange membrane, hexamethyl-p-terphenyl poly(benzimidazolium) (HMT-PMBI). The anion-exchange properties of HMT-PMBI chemically modified electrodes were investigated using K4Fe(CN)6 and K2IrCl6 as redox probes. The permselectivity properties of HMT-PMBI chemically modified electrodes were ascertained using tris(2-2')bipyridyl-ruthenium(II) chloride Ru(bpy)32+. Cyclic voltammetry and chronoamperometry were utilized to extract parameters such as the concentration of the redox mediators inside the films and the apparent diffusion coefficients. We found the concentration of K4Fe(CN)6 and K2IrCl6 redox species within HMT-PMBI-coated films to be on the order of 0.04-0.1 mol·dm-3, and values of Dapp ca. 10-10-10-9 cm2·s-1. To evaluate the possibility of using such a polymer coating in electroanalysis, HMT-PMBI-modified electrodes were utilized for the voltammetric detection of uric acid in artificial urine, Surine® and ascorbic acid in Vitamin C samples. The results showed that HMT-PMBI-coated electrodes can detect uric acid in Surine® with a limit of detection (LoD) of 7.7 µM, sensitivity of 0.14 µA·µM-1·cm-2, and linear range between 5 µM and 200 µM, whereas for Vitamin C tablets, the LoD is 41.4 µM, the sensitivity is 0.08 µA·µM-1·cm-2, and the linear range is between 25 µM and 450 µM.