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.

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.

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.

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.

Electropolymerized 4-Aminobenzoic Acid Based Voltammetric Sensor for the Simultaneous Determination of Food Azo Dyes.

Electrochemical sensors with polymeric films as a sensitive layer are of high interest in current electroanalysis. A voltammetric sensor based on multi-walled carbon nanotubes (MWCNTs) and electropolymerized 4-aminobenzoic acid (4-ABA) has been developed for the simultaneous determination of synthetic food azo dyes (sunset yellow FCF and tartrazine). Based on the voltammetric response of the dyes' mixture, the optimal conditions of electropolymerization have been found to be 30-fold potential scanning between -0.3 and 1.5 V, at 100 mV s-1 in the 100 µmol L-1 monomer solution in phosphate buffer pH 7.0. The poly (4-ABA)-based electrode shows a 10.5-fold increase in its effective surface area and a 17.2-fold lower electron transfer resistance compared to the glassy carbon electrode (GCE). The sensor gives a sensitive and selective response to sunset yellow FCF and tartrazine, with the peak potential separation of 232 mV in phosphate buffer pH 4.8. The electrooxidation parameters of dyes have been calculated. Simultaneous quantification is possible in the dynamic ranges of 0.010-0.75 and 0.75-5.0 µmol L-1 for both dyes, with detection limits of 2.3 and 3.0 nmol L-1 for sunset yellow FCF and tartrazine, respectively. The sensor has been tested on orange-flavored drinks and validated with chromatography.

Constant-Current Coulometry with Electrogenerated Titrants as a Novel Tool for the Essential Oils Screening Using Total Antioxidant Parameters.

Essential oils are widely used in aromatherapy, medicine, and food industries due to a wide spectrum of bioactivity. Their antioxidant properties can be considered as markers of therapeutic effect and quality. Constant-current coulometry with electrogenerated titrants has been successfully applied for these purposes for the first time. Fifteen types of essential oils from various plant materials have been studied. Their composition has been identified by gas chromatography with mass-spectrometric detection (GC-MS). The reactivity of individual antioxidants of essential oils towards electrogenerated titrants (bromine and ferricyanide ions) has been estimated. Total antioxidant parameters, in particular total antioxidant capacity (TAC) and ferric reducing power (FRP) based on the reactions of essential oil antioxidants with electrogenerated bromine and ferricyanide ions, respectively, have been evaluated. Positive correlations (r = 0.7051-0.9558) with common antioxidant tests (antioxidant activity by reaction with 2,2-diphenyl-1-picrylhydrazyl (DPPH•) and total phenolic content by the Folin-Ciocalteu method) have been obtained. Coulometric approaches overcome the limitations of spectrophotometry and are applicable to a wider range of essential oils.

Voltammetric Sensor Based on SeO2 Nanoparticles and Surfactants for Indigo Carmine Determination.

Indigo carmine is a widely used colorant in the food and pharmaceutical industry a high concentration of which can lead to a wide range of negative effects on human health. Therefore, colorant contents have to be strictly controlled. SeO2-nanoparticle-modified glassy carbon electrodes (GCE) have been developed as a voltammetric sensor for indigo carmine. Various types and concentrations of surfactants have been used as reagents for the stabilization of SeO2 nanoparticle dispersions and as electrode surface co-modifiers. An amount of 1.0 mM cationic cetylpyridinium bromide (CPB) provides the best response of the indigo carmine on the modified electrode. The electrodes were characterized by cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy (EIS). SeO2 nanoparticle-CPB-modified electrodes show 4.2-fold higher electroactive area vs. GCE as well as a dramatic 5043-fold decrease in the electron transfer resistance indicating effectivity of the modifier developed. The surface-controlled electrooxidation of indigo carmine proceeds irreversibly (αa = 0.46) with the participation of two electrons and two protons. A linear dynamic range of 0.025-1.0 and 1.0-10 µM of indigo carmine were obtained with the detection and quantification limits of 4.3 and 14.3 nM, respectively. The practical applicability of the sensor was successfully shown on the pharmaceutical dosage forms.

Sensitive voltammetric quantification of carminic acid in candies using selenium dioxide nanoparticles based electrode.

Carminic acid is a food colorant which concentration has to be controlled due to the possible negative health effects. Sensitive voltammetric method is developed for carminic acid determination using electrode modified with SeO2 nanoparticles (SeO2 NPs) and hexadecyltriphenylphosphonium bromide (HDTPPB) acting as dispersive agent for nanoparticles and electrode surface co-modifier. SeO2 NPs of 37-45 nm are uniformly distributed at the electrode increasing its electroactive area (41 ± 2 vs. 8.9 ± 0.2 mm2 for bare glassy carbon electrode (GCE)). Electrochemical impedance spectroscopy data confirm an 18.3-fold decrease of charge transfer resistance compared to GCE (12.7 ± 0.3 vs. 232 ± 7 kΩ, respectively). In differential pulse mode, the linear dynamic ranges of carminic acid are 0.010-2.5 and 2.5-10 µmol L-1 with a detection limit of 3.4 nmol L-1. The method is successfully employed in candies and lozenges for sore throat treatment. The approach is simple, reliable, and can be used as an alternative to chromatography in routine analysis.

Electrochemical Sensors Based on the Electropolymerized Natural Phenolic Antioxidants and Their Analytical Application.

The design and fabrication of novel electrochemical sensors with high analytical and operational characteristics are one of the sustainable trends in modern analytical chemistry. Polymeric film formation by the electropolymerization of suitable monomers is one of the methods of sensors fabrication. Among a wide range of the substances able to polymerize, the phenolic ones are of theoretical and practical interest. The attention is focused on the sensors based on the electropolymerized natural phenolic antioxidants and their analytical application. The typical electropolymerization reaction schemes are discussed. Phenol electropolymerization leads to insulating coverage formation. Therefore, a combination of electropolymerized natural phenolic antioxidants and carbon nanomaterials as modifiers is of special interest. Carbon nanomaterials provide conductivity and a high working surface area of the electrode, while the polymeric film properties affect the selectivity and sensitivity of the sensor response for the target analyte or the group of structurally related compounds. The possibility of guided changes in the electrochemical response for the improvement of target compounds' analytical characteristics has appeared. The analytical capabilities of sensors based on electropolymerized natural phenolic antioxidants and their future development in this field are discussed.

Cerium(IV) and Iron(III) Oxides Nanoparticles Based Voltammetric Sensor for the Sensitive and Selective Determination of Lipoic Acid.

A novel voltammetric sensor based on CeO2·Fe2O3 nanoparticles (NPs) has been developed for the determination of lipoic acid, playing an essential role in aerobic metabolism in the living organism. Sensor surface modification provides a 5.6-fold increase of the lipoic acid oxidation currents and a 20 mV anodic shift of the oxidation potential. The best voltammetric parameters have been obtained for the 0.5 mg mL-1 dispersion of CeO2·Fe2O3 NPs. Scanning electron microscopy (SEM) confirms the presence of spherical NPs of 25-60 nm, and their aggregates evenly distributed on the electrode surface and formed porous coverage. This leads to the 4.4-fold increase of the effective surface area vs. bare glassy carbon electrode (GCE). The sensor shows a significantly higher electron transfer rate. Electrooxidation of lipoic acid on CeO2·Fe2O3 NPs modified GCE is an irreversible diffusion-controlled pH-independent process occurring with the participation of two electrons. The sensor gives a linear response to lipoic acid in the ranges of 0.075-7.5 and 7.5-100 µM with the detection limit of 0.053 µM. The sensor is selective towards lipoic acid in the presence of inorganic ions, ascorbic acid, saccharides, and other S-containing compounds. The sensor developed has been tested on the pharmaceutical dosage forms of lipoic acid.

Simultaneous Determination of Ferulic Acid and Vanillin in Vanilla Extracts Using Voltammetric Sensor Based on Electropolymerized Bromocresol Purple.

Natural phenolic antioxidants are one of the widely studied compounds in life sciences due to their important role in oxidative stress prevention and repair. The structural similarity of these antioxidants and their simultaneous presence in the plant samples stipulate the development of methods for their quantification. The current work deals with the simultaneous determination of vanillin and its bioprecursor ferulic acid using a voltammetric sensor for the first time. A sensor based on the layer-by-layer deposition of the polyaminobenzene sulfonic acid functionalized single-walled carbon nanotubes (f-SWCNTs) and electropolymerized bromocresol purple has been developed for this purpose. The best response of co-existing target analytes was registered for the polymer obtained from the 25 µM dye by 10-fold potential cycling from 0.0 to 1.2 V with the scan rate of 100 mV s-1 in 0.1 M phosphate buffer (PB), pH 7.0. Scanning electron microscopy (SEM), cyclic voltammetry and electrochemical impedance spectroscopy (EIS) confirmed the effectivity of the sensor developed. The linear dynamic ranges of 0.10-5.0 µM and 5.0-25 µM for both analytes with the detection limits of 72 nM and 64 nM for ferulic acid and vanillin, respectively, were achieved in differential pulse mode. The sensor was applied for the analysis of vanilla extracts.

Hydrogen Sulfide Alleviates Anxiety, Motor, and Cognitive Dysfunctions in Rats with Maternal Hyperhomocysteinemia via Mitigation of Oxidative Stress.

Hydrogen sulfide (H2S) is endogenously produced from sulfur containing amino acids, including homocysteine and exerts neuroprotective effects. An increase of homocysteine during pregnancy impairs fetal growth and development of the offspring due to severe oxidative stress. We analyzed the effects of the H2S donor-sodium hydrosulfide (NaHS) administered to female rats with hyperhomocysteinemia (hHcy) on behavioral impairments and levels of oxidative stress of their offspring. Rats born from females fed with control or high methionine diet, with or without H2S donor injections were investigated. Rats with maternal hHcy exhibit increased levels of total locomotor activity and anxiety, decreased muscle endurance and motor coordination, abnormalities of fine motor control, as well as reduced spatial memory and learning. Oxidative stress in brain tissues measured by activity of glutathione peroxidases and the level of malondialdehyde was higher in rats with maternal hHcy. Concentrations of H2S and the activity and expression of the H2S generating enzyme-cystathionine-beta synthase-were lower compared to the control group. Administration of the H2S donor to females with hHcy during pregnancy prevented behavioral alterations and oxidative stress of their offspring. The acquisition of behavioral together with biochemical studies will add to our knowledge about homocysteine neurotoxicity and proposes H2S as a potential agent for therapy of hHcy associated disorders.

Ammonium-Charged Sterically Hindered Phenols with Antioxidant and Selective Anti-Gram-Positive Bacterial Activity.

The increase in the resistance of pathogens, in particular Staphylococcus aureus, to the action of antibiotics necessitates the search for new readily available and non-toxic drugs. In solving this problem, phenolic acylhydrazones have high potential. In this communication, the synthesis of quaternary ammonium compounds containing a differently substituted phenolic moiety has been performed. An initial study of antimicrobial activity showed that these compounds are highly selective against S. aureus and B. cereus. The highest activity (MIC 2.0 µm) was shown by hydrazones containing a catechol fragment. These compounds are more than 3-fold more active against S. aureus and 3-10-fold more active against B. cereus than norfloxacin. Low hemolytic and high antioxidant activities of all new compounds were also established.

Prenatal hyperhomocysteinemia induces oxidative stress and accelerates 'aging' of mammalian neuromuscular synapses.

Enhanced levels of homocysteine during pregnancy induce oxidative stress and contribute to many age-related diseases. In this study, we analyzed age-dependent synaptic modifications in developing neuromuscular synapses of rats with prenatal hyperhomocysteinemia (hHCY). One of the main findings indicate that the intensity and the timing of transmitter release in synapses of neonatal (P6 and P10) hHCY rats acquired features of matured synaptic transmission of adult rats. The amplitude and frequency of miniature end-plate currents (MEPCs) and evoked transmitter release were higher in neonatal hHCY animals compared to the control group. Analysis of the kinetics of neurotransmitter release demonstrated more synchronized release in neonatal rats with hHCY. At the same time lower release probability was observed in adults with hHCY. Spontaneous transmitter release in neonates with hHCY was inhibited by hydrogen peroxide (H2O2) whereas in controls this oxidant was effective only in adult animals indicating a higher susceptibility of motor nerve terminals to oxidative stress. The morphology and the intensity of endocytosis of synaptic vesicles in motor nerve endings was assessed using the fluorescence dye FM 1-43. Adult-like synapses were found in neonates with hHCY which were characterized by a larger area of presynaptic terminals compared to controls. No difference in the intensity of FM 1-43 fluorescence was observed between two groups of animals. Prenatal hHCY resulted in reduced muscle strength assessed by the Paw Grip Endurance test. Using biochemical assays we found an increased level of H2O2 and lipid peroxidation products in the diaphragm muscles of hHCY rats. This was associated with a lowered activity of superoxide dismutase and glutathione peroxidase. Our data indicate that prenatal hHCY induces oxidative stress and apparent faster functional and morphological "maturation" of motor synapses. Our results uncover synaptic mechanisms of disrupted muscle function observed in hHCY conditions which may contribute to the pathogenesis of motor neuronal diseases associated with enhanced level of homocysteine.

Chronocoulometry of wine on multi-walled carbon nanotube modified electrode: Antioxidant capacity assay.

Phenolic antioxidants of wine were electrochemically oxidized on multi-walled carbon nanotubes modified glassy carbon electrode (MWNT/GCE) in phosphate buffer solution. Three oxidation peaks were observed at 0.39, 0.61 and 0.83V for red dry wine and 0.39, 0.80 and 1.18 V for white dry wine, respectively, using differential pulse voltammetry at pH 4.0. The oxidation potentials for individual phenolic antioxidants confirmed the integral nature of the analytical signals for the wines examined. A one-step chronocoulometric method at 0.83 and 1.18 V for red and white wines, respectively, has been developed for the evaluation of wine antioxidant capacity (AOC). The AOC is expressed in gallic acid equivalents per 1L of wine. The AOC of white wine was significantly less than red wine (386 ± 112 vs. 1224 ± 184, p<0.0001), as might be expected. Positive correlations were observed between gallic acid equivalent AOC of wine and total antioxidant capacity, based on coulometric titration with electrogenerated bromine (r=0.8957 at n=5 and r=0.8986 at n=4 for red and white wines, respectively).

Chronoamperometric estimation of cognac and brandy antioxidant capacity using MWNT modified glassy carbon electrode.

Cognac and brandy components are electrochemically oxidized on multi-walled carbon nanotube modified glassy carbon electrode at 0.44 and 0.59 V in 0.1 М phosphate buffer solution pH 3.0. Voltammetric behavior of the main antioxidant constituents of cognac (ellagic and gallic acids, syringaldehyde, coniferaldehyde, vanillin, 5-hydroxymethylfurfural and furfural) has been investigated. The peak at the less positive potential of cognacs is caused by oxidation of gallic acid as well as syringaldehyde- and coniferaldehyde. The second peak corresponds to ellagic acid oxidation. One-step chronoamperometry at 0.59 V for 75 s has been applied for the cognac and brandy antioxidant capacity (AOC) evaluation. Ellagic acid, being the main antioxidant of cognac, has been used as a reference substance. The chronoamperometric response of ellagic acid is linear in the range of 0.66-52.8 µM with the limit of detection and quantification at 0.19 and 0.63 µM, respectively. AOC in ellagic acid equivalents per 100mL of cognac and brandy for different denominations (11 cognacs and 11 ordinary and vintage brandies) has been estimated. AOC of cognacs and brandies increases with the age of the beverages. Positive correlations (r=0.9134-0.9703) with common parameters characterizing antioxidant properties of beverages, in particular antiradical activity, total phenolics content, total antioxidant capacity and ferric reducing power have been observed.

Coulometric titration with electrogenerated oxidants as a tool for evaluation of cognac and brandy antioxidant properties.

Stoichiometric coefficients for reactions of cognac antioxidants with coulometric titrants (electrogenerated bromine and hexacyanoferrate(III) ions) have been found. Ellagic and gallic acids react with both titrants while aldehydes (vanillin, syringic and coniferaldehyde) - with electrogenerated bromine only. Furfurals do not show significant reactivity toward both oxidants. Cognac and brandy total antioxidant capacity (TAC) and ferric reducing power (FRP) based on reactions with electrogenerated bromine and hexacyanoferrate(III) ions, respectively, have been evaluated. Both parameters for cognacs are statistically significant higher than for brandies and grow with the age increase. Beverages under investigation has shown relatively high antiradical activity toward 2,2-diphenyl-1-picrylhydrazyl (7-92% and 5-93% for cognacs and brandies, respectively). Total phenolics content has been evaluated by Folin-Ciocalteu method. Older beverages represent the higher phenolics content caused by more time of extraction from oak barrels. Positive correlations (r=0.8077-0.9617) have been observed for TAC and FRP with antiradical activity and total phenolics content.