Graphene derivatives-based electrodes for the electrochemical determination of carbamate pesticides in food products: A review.

Graphene (GR) composites have great potential for the determination of carbamates pesticides (CPs) by electrochemical methods. Since the beginning of the 20th century, GR has shown remarkable promise as electrode material for various sensors. The contamination of food products with harmful CPs is a major problem as they do not always damage human health immediately, but can be harmful after prolonged exposure. A range of advantages can be gained from their electrochemical determination, such as high sensitivity, reasonably selectivity, rapid detection, low limit of detection, and easy electrode fabrication. Furthermore, these electrochemical techniques are robust, reproducible, user-friendly, and conform to both "green" and "white" analytical chemistry. This review is focused on results published in the last ten years in the field of electrochemical determination of CPs in food products using GR and its derivatives.

Electrochemical Sensors for the Detection of Reactive Oxygen Species in Biological Systems: A Critical Review.

Reactive oxygen species (ROS) involving superoxide anion, hydrogen peroxide and hydroxyl radical play important role in human health. ROS are known to be the markers of oxidative stress associated with different pathologies including neurodegenerative and cardiovascular diseases, as well as cancer. Accordingly, ROS level detection in biological systems is an essential problem for biomedical and analytical research. Electrochemical methods seem to have promising prospects in ROS determination due to their high sensitivity, rapidity, and simple equipment. This review demonstrates application of modern electrochemical sensors for ROS detection in biological objects (e.g., cell lines and body fluids) over a decade between 2011 and 2021. Particular attention is paid to sensors materials and various types of modifiers for ROS selective detection. Moreover, the sensors comparative characteristics, their main advantages, disadvantages and their possibilities and limitations are discussed.

Antioxidant Properties of New Phenothiazine Derivatives.

Phenothiazine and its derivatives have a number of properties that contribute to their wider practical use in the production of biologically active substances, drugs, dyes, etc. Therefore, the synthesis and study of new compounds is of great relevance. The aim of this work was to investigate the antioxidant activity of a number of new phenothiazine derivatives. The patterns of electroreduction of oxygen and its radicals in the presence of phenothiazine derivatives in aqueous ethanol media were studied by voltammetry. The influence of various factors on antioxidant activity was considered by the methods of experiment planning. The optimal conditions for the manifestation of the antioxidant activity of phenothiazine derivatives have been found, which seems to be relevant since it opens up new possibilities for their further use as complex preparations with antioxidant activity, including in psychiatric practice.

Biological Mechanisms of S-Nitrosothiol Formation and Degradation: How Is Specificity of S-Nitrosylation Achieved?

The modification of protein cysteine residues underlies some of the diverse biological functions of nitric oxide (NO) in physiology and disease. The formation of stable nitrosothiols occurs under biologically relevant conditions and time scales. However, the factors that determine the selective nature of this modification remain poorly understood, making it difficult to predict thiol targets and thus construct informatics networks. In this review, the biological chemistry of NO will be considered within the context of nitrosothiol formation and degradation whilst considering how specificity is achieved in this important post-translational modification. Since nitrosothiol formation requires a formal one-electron oxidation, a classification of reaction mechanisms is proposed regarding which species undergoes electron abstraction: NO, thiol or S-NO radical intermediate. Relevant kinetic, thermodynamic and mechanistic considerations will be examined and the impact of sources of NO and the chemical nature of potential reaction targets is also discussed.

A Laser Reduced Graphene Oxide Grid Electrode for the Voltammetric Determination of Carbaryl.

Laser-reduced graphene oxide (LRGO) on a polyethylene terephthalate (PET) substrate was prepared in one step to obtain the LRGO grid electrode for sensitive carbaryl determination. The grid form results in a grid distribution of different electrochemically active zones affecting the electroactive substance diffusion towards the electrode surface and increasing the electrochemical sensitivity for carbaryl determination. Carbaryl is electrochemically irreversibly oxidized at the secondary amine moiety of the molecule with the loss of one proton and one electron in the pH range from 5 to 7 by linear scan voltammetry (LSV) on the LRGO grid electrode with a scan rate of 300 mV/s. Some interference of the juice matrix molecules does not significantly affect the LSV oxidation current of carbaryl on the LRGO grid electrode after adsorptive accumulation without applied potential. The LRGO grid electrode can be used for LSV determination of carbaryl in fruit juices in the concentration range from 0.25 to 128 mg/L with LOD of 0.1 mg/L. The fabrication of the LRGO grid electrode opens up possibilities for further inexpensive monitoring of carbaryl in other fruit juices and fruits.

Application of ural glauconite for groundwater deironing and demanganation.

Heavy metals are among the most common pollutants affecting biological systems when ingested with drinking water and food. Heavy metal ions are capable of bioaccumulation in a human body and could cause various metabolic disorders. Here we present the results of using a unique glauconite from the Barguzinsky deposit as an adsorbent for heavy metals. The physicochemical properties of glauconite samples, including the specific surface area, specific pore volume, zeta potential, thermal and elemental analyses and scanning electron microscopy of the surface were studied for different fraction sizes. The sorption properties of the glauconite samples were studied under static conditions for extraction of iron and manganese ions from model solutions. Analysis of the content of the detected ions in solutions and filtrates was performed by the methods of stripping voltammetry. We revealed high sorption properties of glauconite for iron elimination, but comparatively lower ones in removing manganese.

A copper nanoparticle-based electrochemical immunosensor for carbaryl detection.

A hapten-protein conjugate with copper nanoparticles (Hap-Car-BSA@CuNPs) was first synthesized in the present work for the determination of carbaryl. The copper nanoparticles (CuNPs) of the conjugate were used as electrochemical labels in the direct solid-phase competitive determination of carbaryl residues in flour from different crops. The signal was read by linear sweep anodic stripping voltammetry (LSASV) of copper (through the electrochemical stripping of accumulated elemental copper) on a gold-graphite electrode (GGE). To form a recognition receptor layer of monoclonal antibodies against the carbaryl on the surface of the GGE, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) and 1-hydroxy-2,5-pyrrolidinedione (NHS) were used as the best covalent cross-linkers. The concentrations of the antibodies and the Hap-Car-BSA@CuNPs conjugate were optimized for carbaryl detection by the electrochemical immunosensor. The electrochemical immunosensor can be used for highly sensitive determination of carbaryl residues in flour samples in the concentration range 0.8-32.3 µg·kg-1, with a limit of detection 0.08 µg·kg-1. The present work paves the path for a novel method for monitoring carbaryl in other food products, drinks, and soil samples.

Non-enzymatic electrochemical approaches to cholesterol determination.

Cholesterol plays a vital role in a human body. It is known as one of the most important sterols, because it forms cell walls and participates in signal transduction. Moreover, cholesterol was recognized as biomarker of cardiovascular diseases and of some metabolic disorders. As a result, cholesterol blood levels should be controlled in a variety of diseases such as ischemic heart disease, cerebrovascular ischemia, stroke, hypertension, type II diabetes, and many others. Hence, the accurate cholesterol quantification plays an important role in diagnosis and treatment of these diseases. Modern voltammetric and amperometric methods are increasingly used for cholesterol monitoring. Consequently, the problem of electrode fabrication for cholesterol detection has high importance for clinical tests. Novel electrode materials initiated the fast growth of electrochemical biosensors. Biomaterials are still the most frequently used modifiers for cholesterol sensors due to their high selectivity. However, biomaterials have low stability complicating their practical applications. This fact is crucial for analytical parameters such as limit of detection (LOD) and sensitivity. Therefore, nanomaterials are used to eliminate disadvantages of biomaterials and to improve sensors performance by increasing the electrode surface, conductivity and sensitivity. This review is focused on the use of non-enzymatic electrodes for cholesterol quantification and on different approaches to their fabrication. Firstly, the necessity and role of modifier is discussed. Afterwards, the advantages and disadvantages of currently used modifiers are critically compared together with all aspects and approaches to sensors fabrication. Finally, the prospects of non-enzymatic electrodes application for cholesterol sensors engineering are summarised.

Label-Free Electrochemical Biosensors for the Determination of Flaviviruses: Dengue, Zika, and Japanese Encephalitis.

A highly effective way to improve prognosis of viral infectious diseases and to determine the outcome of infection is early, fast, simple, and efficient diagnosis of viral pathogens in biological fluids. Among a wide range of viral pathogens, Flaviviruses attract a special attention. Flavivirus genus includes more than 70 viruses, the most familiar being dengue virus (DENV), Zika virus (ZIKV), and Japanese encephalitis virus (JEV). Haemorrhagic and encephalitis diseases are the most common severe consequences of flaviviral infection. Currently, increasing attention is being paid to the development of electrochemical immunological methods for the determination of Flaviviruses. This review critically compares and evaluates recent research progress in electrochemical biosensing of DENV, ZIKV, and JEV without labelling. Specific attention is paid to comparison of detection strategies, electrode materials, and analytical characteristics. The potential of so far developed biosensors is discussed together with an outlook for further development in this field.

Simultaneous voltammetric determination of Brilliant Blue FCF and Tartrazine for food quality control.

Voltammetric determination of Tartrazine (Tz) and Brilliant Blue FCF (BB) in their mixture using novel type of carbon black-polyethylene composite electrode (CBPCE) with renewable surface modified by carbon ink (CI) was developed. Electrochemical properties of the tested dyes were investigated in 0.1 mol L-1 Britton-Robinson (BR) buffer by cyclic voltammetry (CV) and linear scan voltammetry (LSV). Simultaneous determination of the dyes is based on the application of supporting electrolytes with different pH: 2.0 for Tz and 10.0 for BB. Under the optimum experimental conditions, linear concentration dependences in the concentration ranges from 0.037 to 1.38 µmol L-1 for Tz and from 0.025 to 2.52 µmol L-1 for BB were obtained by LSV in the first-order derivative mode. Limits of detection (LODs) for Tz and BB were 0.019 and 0.011 µmol L-1, respectively. The modified electrode showed good stability and reproducibility and was successfully applied for the determination of the mixture Tz and BB in a candy and soft drink products.

Electrochemical immunoassay for the detection of antibodies to tick-borne encephalitis virus by using various types of bioconjugates based on silver nanoparticles.

This work reports for the first time a significantly improved and simplified electrochemical immunoassay to detect antibodies to tick-borne encephalitis virus (TBEV) using a 96-well microtiter plate as a platform for immobilization and silver nanoparticles (AgNPs) as electrochemical labels. The electrochemical assay is performed by detecting the elemental silver oxidation signal where the electroactive signalling silver species are released from the bioconjugates (Ab@AgNP, AbS@AgNP, and ProteinA@AgNP). For this purpose, AgNPs were synthesized and further tagged with biomolecules (antibodies to TBEV, cleaved antibodies to TBEV, and protein A). Signal is read by linear sweep anodic stripping voltammetry (LSASV) of silver ions (through the electrochemical stripping of accumulated elemental silver) on a graphite electrode (GE). AbS@AgNP was chosen as the best option for the new electrochemical immunoassay. The results of electrochemical measurements demonstrated that voltammetric signal increased with the increasing concentration of target antibodies to TBEV within the range from 100 to 1600 IU mL-1, with a detection limit of 90 IU mL-1. To verify the practical application of the novel electrochemical immunosensor, the quantity of immunoglobulins against TBEV in human serum was checked. The results may contribute to the development of alternative methods for monitoring TBEV in biological fluids.

Evaluation of human macrophage functional state by voltammetric monitoring of nitrite ions.

The method for assessing the level of nitric oxide (II) (NO) by voltammetric monitoring of nitrite ions was carried out on models M1 and M2 of polarized macrophages induced from monocytes of human peripheral blood with the addition of lipopolysaccharide (LPS) and interleukin-4 (IL-4), respectively. The model of induction of M1 and M2 macrophages was used in the work to achieve the corresponding shifts in the functional status of studied cells. Ethyl nitrite (EtONO) was used as a standard compound of nitrite ions for electrochemical measurements. Electrochemical determination of nitrite ions was performed by anodic linear sweep voltammetry in the first-order derivative mode (ALSV FOD) in Britton-Robinson (BR) buffer with pH 4.02 on carbon ink modified graphite electrode. EtONO calibrations were linear over a concentration range from 2 to 9 µmol L-1 with corresponding regression equation y = 0.768c - 0.048. Limit of detection (LOD) (S/N = 3) was 0.38 µmol L-1. The results of the study showed the fundamental possibility of using voltammetry to assess indirectly the production of nitric oxide by cells in supernatants of the monocytic macrophage lineage. The level of nitric oxide metabolites (nitrite ions) in supernatants was associated with the functional state of macrophages.

Preparation and Investigation of Silver Nanoparticle⁻Antibody Bioconjugates for Electrochemical Immunoassay of Tick-Borne Encephalitis.

A new simple electrochemical immunosensor approach for the determination of antibodies to tick-borne encephalitis virus (TBEV) in immunological products was developed and tested. The assay is performed by detecting the silver reduction signal in the bioconjugates with antibodies (Ab@AgNP). Here, signal is read by cathodic linear sweep voltammetry (CLSV) through the detection of silver chloride reduction on a gold-carbon composite electrode (GCCE). Covalent immobilization of the antigen on the electrode surface was performed after thiolation and glutarization of the GCCE. Specific attention has been paid to the selection of conditions for stabilizing both the silver nanoparticles and their Ab@AgNP. A simple flocculation test with NaCl was used to select the concentration of antibodies, and the additional stabilizer bovine serum albumin (BSA) was used for Ab@AgNP preparation. The antibodies to TBEV were quantified in the range from 50 IU·mL-1 to 1600 IU·mL-1, with a detection limit of 50 IU·mL-1. The coefficient of determination (r2) is 0.989. The electrochemical immunosensor was successfully applied to check the quality of immunological products containing IgG antibodies to TBEV. The present work paves the path for a novel method for monitoring TBEV in biological fluids.

Lithium Salts of Krebs Cycle Substrates as Potential Normothymic Antioxidant Agents.

OBJECTIVE: Aim of the present work was to study the antioxidant properties of lithium salts of Krebs cycle substrates and their influence on immune cells. Lithium is a well-known and widely used mood stabilizer. These lithium-based substances have a lot of potential properties because of the anionic component of the Krebs cycle substrates, which take part in basic intracellular biochemical process. MATERIALS AND METHODS: Lithium salts of fumarate, pyruvate, malate, succinate, and citrate (as reference drug) were investigated in this study as antioxidants and immunomodulators. The antioxidant properties were studied by the voltammetry method, which evaluates oxygen radical scavenging capacity of lithium substances. Influence of the lithium compounds on the immune cells of human blood was indicated by the reaction of blast transformation of lymphocytes. RESULTS: All tested substances and their mixes possessed antioxidant properties, more expressed in maximal therapeutic concentration. Lithium compounds showed no toxic influence on human blood immune cells and caused no significant changes in both spontaneous and stimulated proliferation. CONCLUSION: The results allow considering lithium salts of Krebs cycle substrates as potential normothymic agents (mood stabilizer) with antioxidant properties and low toxicity.

Electrochemical Oxidability of Antioxidants: Synergism and Antagonism in Mixes.

AIMS: To investigate electrochemical oxidability of antioxidants to reveal synergistic and antagonistic effects in mixes. MATERIALS AND METHODS: Electrochemical oxidability of some widely used antioxidants, including uric acid, glutathione, trolox, ascorbic acid, gallic acid, Mexidol, and potassium fenozan, was investigated by the amperometric approach. RESULTS: All obtained electrochemical oxidability values correlate well with antioxidant activity parameters of the same compounds measured by other methods. The measurements of the electrochemical oxidability for binary mixes of substances were tested to reveal any synergistic actions. The experimental results and calculated values overlap for various combinations of tested mixes. It testifies to the absence of interaction between them (both synergism and antagonism) in the oxidation process. CONCLUSIONS: The constants of oxidation were defined for different antioxidants and mixes by amperometric approach. Most mixes of probed compounds revealed absence of interaction between them in oxidation process. In some cases (mainly with glutathione and ascorbic acid), antagonism takes place, deteriorating effects of their joint application. Apparently, a partial reduction of glutathione by ascorbic acid leads to excess of the measured value over calculated value.

Electrochemical nonenzymatic sensor for cholesterol determination in food.

The treatment of some inborn metabolism errors requires cholesterol substitution therapy. Cholesterol plays a vital role in the human body. Therefore, the majority of cholesterol determination techniques are targeted to blood and blood serum. Nevertheless, cholesterol determination in food is important as well. In this paper, cholesterol determination using differential pulse voltammetry (DPV) in dairy products (e.g., milk, clotted cream, yogurt, butter, etc.) is reported with a novel nonenzymatic sensor based on diphosphonic acid of 1,4-diacetylglycoluril (DPADGU) as an electrode surface modifier. Stable anodic response was obtained from cholesterol on the modified carbon-based electrode. The sensor has high stability, sensitivity (20 µA mol L-1 cm-2), and a wide linear range from 1 up to 200 µM. The LOD and LOQ values are 1.5 and 5.1 µM, respectively. The developed methods were successfully applied to the above mentioned dairy products. Graphical abstract ᅟ.

Comparative investigation of antioxidant activity of human serum blood by amperometric, voltammetric and chemiluminescent methods.

INTRODUCTION: A blood test can provide important information about the functional state of the antioxidant system. Malfunction of this system increases the concentration of free radicals and can cause oxidative stress. A difficulty in assessing oxidative stress is the lack of a universal method for determining the antioxidant activity (AOA) of blood components, because of their different nature. MATERIAL AND METHODS: The objects of investigation were sera of 30 male patients with a diagnosis of alcohol dependence syndrome and healthy donors. Comparative investigation of total antioxidant activity (TAA) of human serum blood was carried out by voltammetric (VA), amperometric (AM) and chemiluminescent (HL) methods. RESULTS: All applied methods revealed that serum TAA of the patients with alcoholism is lower than TAA of healthy donors (control group); according to amperometric method the average value of serum TAA was 850 ±210 nA × s, and 660 ±150 nA × s for healthy donors and alcoholics respectively (p < 0.05). Similar trend was revealed by chemiluminescence and voltammetry methods. The results confirm that thiol compounds make a significant contribution to the antioxidant activity of serum. The average thiol concentrations were 0.94 ±0.34 mmol/l and 1.21 ±0.36 mmol/l (p < 0.05) for alcoholics and healthy donors respectively. Decreasing thiol concentration in blood of alcoholics leads to depletion of antioxidant systems of blood. However, the differences between the results of AM, VA and HL methods were significant, because they reflected different aspects of antioxidant activity. CONCLUSIONS: For objective assessment of antioxidant activity of biological objects, we suggest using methods based on different model systems.

Study of total antioxidant activity of human serum blood in the pathology of alcoholism.

The total antioxidant activity (TAA) of human serum blood of patients suffering from alcoholism was tested by cathode voltammetry with a model process of oxygen electroreduction. A known spectrophotometrical method was used for comparison. As results the total antioxidant activity of serum blood of patients with alcoholism was estimated by voltammetry during therapy in hospital. It was shown the TAA of serum blood of patients in pathology before and after treatment is lower than that one of healthy people. However, during the process of 10 days of alcoholism treatment the TAA coefficient increases. The relationship between the coefficient of total antioxidant activity of human serum blood and the stage of treatment was detected.

Production of metabolites with antioxidant and emulsifying properties by antarctic strain Sporobolomyces salmonicolor AL1.

The Sporobolomyces salmonicolor AL(1) Antarctic strain was cultivated and two bioproducts were obtained: exopolysaccharide and biomass. The biologically active substances ergosterol, torularhodin, torulene, ß-carotene and CoQ(10) were extracted from the biomass and were quantified as follows: ergosterol 5.2 ± 0.2 mg/g, torularhodin 458.3 ± 24.5 µg/g, torulene 273.7 ± 14.5 µg/g, ß-carotene 129.2 ± 7.3 µg/g and coenzyme Q(10) (CoQ(10)) 236.1 ± 12.1 µg/g. Their antioxidant activity was estimated according to the cathode voltammetry method. The most pronounced antioxidant activity (according to trolox) was exhibited by ß-carotene 3.78, followed by CoQ(10) 3.60, both of them being the main contributors to the total extract activity of 3.19. The biologically active metabolites in combination with exoglucomannan as emulsifier were used for the creation of model emulsion systems characterised by great stability. The absorption of UVA rays by the model emulsions was studied.

Study of OH radicals in human serum blood of healthy individuals and those with pathological schizophrenia.

The human body is constantly under attack from free radicals that occur as part of normal cell metabolism, and by exposure to environmental factors such as UV light, cigarette smoke, environmental pollutants and gamma radiation. The resulting "Reactive Oxygen Species" (ROS) circulate freely in the body with access to all organs and tissues, which can have serious repercussions throughout the body. The body possesses a number of mechanisms both to control the production of ROS and to cope with free radicals in order to limit or repair damage to tissues. Overproduction of ROS or insufficient defense mechanisms leads to a dangerous disbalance in the organism. Thereby several pathomechanisms implicated in over 100 human diseases, e.g., cardiovascular disease, cancer, diabetes mellitus, physiological disease, aging, etc., can be induced. Thus, a detailed investigation on the quantity of oxygen radicals, such as hydroxyl radicals (OH(•)) in human serum blood, and its possible correlation with antioxidant therapy effects, is highly topical. The subject of this study was the influence of schizophrenia on the amount of OH(•) in human serum blood. The radicals were detected by fluorimetry, using terephthalic acid as a chemical trap. For all experiments the serum blood of healthy people was used as a control group.