Determination of molybdenum by adsorptive anodic stripping voltammetry of molybdenum–alizarin violet complex at an acetylene black paste electrode

A reliable and sensitive procedure for the determination of trace levels of molybdenum by adsorptive anodic stripping voltammetry is proposed. The method is based on adsorptive accumulation of the molybdenum (Mo)–alizarin violet (AV) complex onto an acetylene black paste electrode (ABPE), followed by oxidation of the adsorbed species by voltammetric scan using a second-order derivative modulation. For voltammetric determination of molybdenum, the parameters influencing the peak current have been optimized. Under the selected conditions, the electrode demonstrated linear response over a wide range of Mo(VI) concentration (6.0 × 10⁻⁹–1.0 × 10⁻⁵ mol/L), the detection limit was 2.0 × 10⁻⁹ mol/L (S/N = 3) for 120 s accumulation. The effects of potential interfering ions were studied, and it was found that the proposed procedure was free from most interferences. The method has been applied to the determination of molybdenum in plant foodstuffs, and satisfied results were obtained.     

Sensitive determination of kojic acid in foodstuffs using PVP (polyvinylpyrrolidone) modified acetylene black paste electrode

The voltammetric behaviors of kojic acid (KA) were investigated at polyvinylpyrrolidone (cross-linked) modified acetylene black paste electrode (denoted as PVP/ABPE) in 0.1 mol/L, pH 5.0 HAc–NaAc buffer. A well-defined and sensitive oxidation peak appears at 0.84 V. Compared with an unmodified acetylene black paste electrode (ABPE), the PVP/ABPE remarkably enhances the oxidation peak current of kojic acid, indicative of good potential in sensitive determination of kojic acid. After optimization of experimental conditions, a fast and sensitive electrochemical method was developed for the determination of kojic acid. This method exhibits good linearity over the range from 1.0 × 10⁻⁶ mol/L to 1.0 × 10⁻⁴ mol/L, and the detection limit is as low as 5.0 × 10⁻⁷ mol/L. In order to validate the feasibility of this proposed method, it was used for quantitative analysis of kojic acid in some food samples and the results were satisfying.     

Voltammetric behaviour and square-wave voltammetric determination of the potent antioxidant and anticarcinogenic agent ellagic acid in foodstuffs

The voltammetric behaviour of ellagic acid (EA) is investigated by cyclic, differential pulse and square-wave voltammetry (CV, DPV and SWV, respectively). Based on the anodic oxidation peak at approximately 0.42 V in acetic/acetate buffer (pH 5.5) a robust and a highly reliable square-wave voltammetric method is presented for the determination of EA. The oxidation peak current was linearly dependent on the concentration of EA in the range of 1.0 × 10⁻⁷–1.5 × 10⁻⁶ mol/L (r = 0.9997), with a detection limit of 1.0 × 10⁻⁸ mol/L (S/N = 3) and a quantification limit of 3.4 × 10⁻⁸ mol/L (S/N = 10), good reproducibility and a satisfactory level of selectivity towards others polyphenols. The proposed method was applied to the determination of free and total EA in fruits, nuts and juices with good analytical results being obtained.     

Voltammetric determination of the herbicides nitralin and oryzalin in agricultural formulations,vegetables and grape juice samples

A sensitive method for the determination of the herbicides nitralin and oryzalin by adsorptive stripping voltammetry (AdSV) at a hanging mercury drop electrode (HMDE) (pH 6.0) was described. The cyclic voltammograms demonstrate the adsorption of these compounds at the mercury electrode. A symmetric study of the various operational parameters that affect the stripping response was carried out by differential pulse voltammetry. With an accumulation potential of −0.5 V and a 80 s accumulation time, the limit of detection was 2.47 × 10⁻⁸ mol/L and 1.5 × 10⁻⁸ mol/L, the relative standard deviation (n = 10), correlation coefficient values 1.14%, 0.998, 1.48%, 0.999 at concentration levels of 8.3 × 10⁻⁸ mol/L to 1.5 × 10⁻⁶ mol/L and 2 × 10⁻⁸ mol/L to 1.0 × 10⁻⁵ mol/L for both compounds. The degree of interference of some other pesticides on the differential pulse adsorptive stripping signal for nitralin and oryzalin was evaluated. Finally the proposed method was applied for determination of nitralin and oryzalin in agricultural formulations, vegetables and grape juice samples.     

Electrochemical determination of Sudan I using montmorillonite calcium modified carbon paste electrode

In the current work, a sensitive, rapid and convenient electrochemical method was developed for the determination of Sudan I utilizing the excellent properties of montmorillonite calcium (MMT-Ca). Compared with the unmodified carbon paste electrode (CPE), MMT-Ca modified CPE not only significantly enhances the oxidation peak current of Sudan I but also lowers the oxidation overpotential, suggesting that the MMT-Ca modified CPE can remarkably improve the determining sensitivity of Sudan I. The experimental conditions such as determining medium, the content of MMT-Ca and accumulation time were optimized for the determination of Sudan I. The oxidation peak current is proportional to the concentration of Sudan I over the range from 0.05 mg L⁻¹ (2.01 × 10⁻⁷ mol L⁻¹) to 1.0 mg L⁻¹ (4.03 × 10⁻⁶ mol L⁻¹), and the limit of detection is 0.02 mg L⁻¹ (8.06 × 10⁻⁸ mol L⁻¹) for 2-min accumulation. Finally this newly-proposed sensing method was successfully employed to detect Sudan I in practical samples and good recovery was achieved.     

New voltammetric procedure for determination of thiamine in commercially available juices and pharmaceutical formulation using a lead film electrode

A simple, reliable and reproducible method, based on adsorptive stripping voltammetry (AdSV), for determination of vitamin B₁ (thiamine) in pharmaceutical preparation and food is described in this paper. The in situ plated lead film electrode was used as a working electrode. The lead film was formed and thiamine was accumulated at −1.25 V (vs. Ag/AgCl) on a glassy carbon electrode. Then, the preconcentrated thiamine was reduced by scanning the potential of the electrode from −1.25 to −1.55 V using a square-wave technique. The linear range was from 0.0133 to 0.265 mg L⁻¹ for vitamin B₁, with the regression coefficient of 0.999. The detection limit for vitamin B₁ was 0.0053 mg L⁻¹ for the accumulation time 120 s. The method developed was applied to the determination of thiamine in certified reference material (BCR-485), pharmaceutical formulation and commercially available juices, and the assay results were satisfactory.     

Determination of caffeine content in tea based on poly(safranine T) electroactive film modified electrode

Safranine T was electropolymerised on a glassy carbon electrode and then characterised by scanning electron microscope (SEM), X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS). This uniform electropolymerised film was crystallisable and showed a high electrocatalytic ability towards the oxidation of caffeine. To avoid the interferences of the anions, Nafion was covered on the surface of poly(safranine T) film modified glassy carbon electrode. As a new voltammetric sensor, this modified electrode is sensitive, selective and stable to determine caffeine content in tea. The peak current increased linearly with the concentration of caffeine in the range of 3 × 10⁻⁷–1 × 10⁻⁴ M, with a detection limit of 1 × 10⁻⁷ M. All of these make it a useful tool for determining caffeine content in tea. What’s more, it produces much less organic waste compared with other analytical techniques.     

Selective determination of chloramphenicol at trace level in milk samples by the electrode modified with molecularly imprinted polymer

A novel voltammetric sensor for determination of chloramphenicol (CAP) in milk samples was introduced. The CAP selective molecularly imprinted polymer (MIP) and non imprinted polymer (NIP) were synthesized and then added to the carbon paste (CP) electrode composition in order to prepare MIP-CP electrode. The MIP, embedded in the carbon paste electrode, acted as the selective recognition element and pre-concentrator agent for CAP. CAP was extracted in the electrode for a definite time and then it was analyzed by differential pulse voltametry, found to be an effective determination method. The MIP-CP showed very high CAP recognition ability, compared to NIP-CP. The electrode washing, after CAP extraction, led to an enhanced selectivity. Various factors, known to affect the response behavior of the electrode, were investigated and optimized. This sensor showed a linear response range of 8.0 × 10⁻⁹−1.0 × 10⁻⁶ M and lower detection limit of 2.0 × 10⁻⁹ M (S/N = 3). The sensor was successfully applied to the determination of CAP in milk samples.     

Simultaneous voltammetric determination of phenolic antioxidants in food using a boron-doped diamond electrode

A method for the simultaneous determination of butylated hydroxyanisole (BHA) and butylated hydroxytoluene (BHT) in food was developed using square-wave voltammetry (SWV). The determination of these phenolic antioxidants was carried out using a cathodically pre-treated boron-doped diamond electrode (BDD) and an aqueous-ethanolic (30% ethanol, v/v) 10 mmol L⁻¹ KNO₃ solution (pH_cond. 1.5) as supporting electrolyte. In the SWV measurements using the BDD electrode, the oxidation peak potentials of BHA and BHT present in binary mixtures were separated by about 0.3 V. The attained detection limits for the simultaneous determination of BHA and BHT (0.14 and 0.25 μmol L⁻¹, respectively) are lower than the ones by voltammetric techniques reported in the literature. The proposed method was successfully applied in the simultaneous determination of BHA and BHT in food products, with results similar to those obtained using a high-performance liquid chromatography method, at a 95% confidence level.     

Determination of Sudan I in hot chili powder by using an activated glassy carbon electrode

A novel electroanalytical method is proposed for the determination of Sudan I in hot chili powder. Sudan I was firstly pre-concentrated by adsorption and then electroreduced at the electrochemically activated glassy carbon electrode (AGCE). A linear relationship between the reduction current and concentration of Sudan I was obtained over the range from 2.4 × 10⁻⁶ mol/L to 1.8 × 10⁻⁵ mol/L with a correlation coefficient of 0.9981. The detection limit was estimated to be about 7.1 × 10⁻⁷ mol/L.     

Sensitive electrochemical determination of luteolin in peanut hulls using multi-walled carbon nanotubes modified electrode

A simple and highly sensitive electrochemical method was developed for the determination of trace-level luteolin, based on the multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode (GCE). The electrochemical behaviours of luteolin indicate that MWNTs modified glassy carbon electrode (MWNTs/GCE) can greatly enhance the electrocatalytic activity towards the redox of luteolin. It leads to a considerable improvement of the redox peak current for luteolin and allows the development of a highly sensitive voltammetric sensor for the determination of luteolin. A series of experimental parameters including the pH of supporting electrolyte, accumulation potential and time were optimised. The results showed that the oxidative peak currents increased linearly with the concentration of luteolin in the range of 2.0 × 10⁻¹⁰ to 3.0 × 10⁻⁹ M, with a detection limit of 6.0 × 10⁻¹¹ M (S/N = 3). The analytical performance of this sensor has been evaluated for detection of luteolin in peanut hulls as a real sample.     

Determination of oxalic acid in spinach with carbon nanotubes-modified electrode

This work investigated the electrocatalytic oxidation of oxalic acid on multiwall carbon nanotubes (MWNTs) modified glassy carbon (GC) electrode. The result indicated that the oxidation of oxalic acid was greatly improved at the MWNTs-modified GC (MWNTs/GC) electrode as compared with the bare GC electrode. The effects of the MWNTs suspension amount, pH and scan rate on the electrooxidation response of oxalic acid were studied by voltammetry. The surface concentration and diffusion coefficient (D_R) of oxalic acid at the MWNTs/GC electrode were determined by chronocoulometry. This MWNTs/GC electrode presented a wide linear response ranging from 5.0 × 10⁻⁵ to 1.5 × 10⁻² M for oxalic acid. The detection limit (S/N = 3) was estimated to be 1.20 × 10⁻⁵ M. Based on this MWNTs/GC electrode, the content of oxalic acid in spinach was successfully determined.     

Amperometric determination of bisphenol A in milk using PAMAM–Fe3O4 modified glassy carbon electrode

A simply and sensitively electroanalytical method for determination of bisphenol A (BPA) using poly(amidoamine) (PAMAM) and Fe₃O₄ magnetic nanoparticles modified glassy carbon electrode (GCE) was presented. Compared with bare electrode, PAMAM–Fe₃O₄ modified electrode not only significantly enhanced the oxidation peak current of BPA, but also lowered the oxidation overpotential, suggesting that the modified electrode can remarkably improve the determining sensitivity of BPA. Factors influencing the detection processes were optimised and kinetic parameters were calculated. Under the optimal conditions, the oxidation current increased linearly with increasing the concentration of BPA in the range of 1 × 10⁻⁸–3.07 × 10⁻⁶ M with the correlation coefficient of 0.9996 and the detection limit of 5 × 10⁻⁹ M. The current reached 95% of the steady-state current within about 6 s. The proposed method was successfully applied to determine BPA in milk samples and satisfactory results were obtained.     

Determination of nitrite in food samples by anodic voltammetry using a modified electrode

A glassy carbon (GC) electrode modified with alternated layers of iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeT4MPyP) and copper tetrasulfonated phthalocyanine (CuTSPc) was employed for nitrite determination by differential pulse voltammetry (DPV). This modified electrode showed excellent catalytic activity for the nitrite oxidation. After optimizing the operational conditions, a linear response range from 0.5 to 7.5 μmol l⁻¹ with a low detection limit of 0.1 μmol l⁻¹ was obtained. The proposed sensor was stable with a sensitivity of 20.0 μA, 1 μmol⁻¹ and good repeatability, evaluated in terms of relative standard deviation (R.S.D. = 1.3%) for n = 10. Possible interferences from several common ions were evaluated. This sensor was applied for the voltammetric determination of nitrite in some food samples. The results were consistent with those obtained with the standard spectrophotometric procedure.     

Determination of Ge(IV) in rice in a mercury-coated glassy carbon electrode in the presence of catechol

Electrochemical adsorptive cathodic stripping voltammetry determination of Ge(IV) using the catechol complex on a mercury-coated (MC) electrode was prepared using a glassy carbon electrode (GCE), the peak potential of which was −0.5 V vs. Ag/AgCl on MCGCE. The various parameters of the catechol concentration, its pH, and others were optimized. The linear working ranges were obtained in the concentration of 2–700 μg L⁻¹ Ge(IV). The relative standard deviation at the Ge(IV) concentration of 50 μg L⁻¹ was 1.37% (n = 15) using the optimum condition, and the detection limit was found to be 0.6 μg L⁻¹ (8.26 × 10⁻⁹ M) (S/N = 3), with an adsorption time of 180 s. The Ge(IV) response was highly linear. This developed method was applied to Ge(IV) to determine the presence of rice grains.     

Sensor-containing microspheres of chitosan crosslinked with 8-hydroxyquinoline-5-sulphonic acid for determination of Cu(II) in instant coffee

A novel carbon paste electrode containing chitosan microspheres for the determination of Cu(II) in instant coffee by anodic stripping voltammetry was developed. Chitosan was crosslinked with the chelating agent 8-hydroxyquinoline-5-sulphonic acid and glutaraldehyde. The microspheres of the crosslinked chitosan biopolymer were obtained by the spray drying technique and employed in the construction of the sensor. In acetate buffer solution (0.1 mol L⁻¹, pH 6.0), the calibration curve obtained was linear for concentrations of 5.0 × 10⁻⁷ to 1.4 × 10⁻⁵ mol L⁻¹ (r = 0.9990); the detection limit was 5.5 × 10⁻⁸ mol L⁻¹. The relative standard deviation (n = 8) was lower than 3.0% for solutions containing 6.0 × 10⁻⁶, 5.0 × 10⁻⁵ and 1.5 × 10⁻⁴ mol L⁻¹ of Cu(II). The method was successfully employed for determination of Cu(II) in instant coffee and the results obtained showed good agreement when compared with those using electrothermal atomic absorption spectrometry.     

Comparison of the antioxidative properties of caffeic and chlorogenic acids

The antioxidative properties of caffeic and chlorogenic acids during autoxidation of triacylglycerols of sunflower oil at 100 °C were compared. The effects of the two acids within the concentration range 2.8–56.5 × 10⁻⁴ M (50–2000 ppm) were investigated. The stabilization factor (F) as a measure of the effectiveness of the antioxidants and the oxidation rate ratio (ORR) as a measure of their strength were determined. It was found that at concentration 2.8 × 10⁻⁴ M, the effectiveness and the strength of the two acids were practically the same, while at higher concentrations caffeic acid appeared as a much more effective and stronger inhibitor. The analysis of the kinetic data obtained showed that chlorogenic acid and its radicals participated more readily in side reactions with the hydroperoxides and the lipid substrate than caffeic acid and its radicals did.     

Pico molar assay of riboflavin in human urine using voltammetry

Using a new type of DNA and carbon nano tube (CNT) mixed paste electrode using cyclic and square wave anodic stripping voltammetric (SWASV) methods, this study presents an assay of riboflavin (RF) under optimum conditions. Results of the experiment yielded a low working concentration range of nanograms with 1–10 and 10–170 ng L⁻¹ and 5–105 μg L⁻¹, at an accumulation time of 80 s in a 0.1 M H₃PO₄ electrolyte solution. A relative standard deviation of 30 μg L⁻¹ was observed at an accuracy level of 0.1164% (n = 15) under optimum conditions. The detection limit (S/N) was pegged at 0.2 ng L⁻¹ (5.31 × 10⁻¹³ mol L⁻¹ RF). The proposed method was successfully applied to an actual human urine and drug sample, and can be applied to assays of other biological samples.     

Simultaneous determination of Sunset yellow and Tartrazine in soft drinks using gold nanoparticles carbon paste electrode

The monitoring of synthetic dyes in foods is very important due to their potential harmfulness to human beings. Herein, a carbon-paste electrode (CPE) that is chemically modified with gold nanoparticles (nAu) was fabricated and used for the determination of Sunset yellow (SY) and Tartrazine (Tz). Cyclic and differential pulse voltammetry (CV and DPV) results revealed two well-resolved anodic peaks for SY and Tz with remarkably increase in oxidation signals of these colourants. Based on this, a novel electrochemical method was developed for the simultaneous determination of SY and Tz. High sensitivity and selectivity, sub-micromolar detection limit, high reproducibility and regeneration of the electrode surface by simple polishing make the nAu-CPE electrode very suitable for the determination of SY and Tz in commercially available soft drinks. The detection limits was 3.0 × 10⁻⁸ and 2.0 × 10⁻⁹ mol l⁻¹ for SY and Tz, respectively, which are remarkably lower than those reported previously for SY and Tz using other modified electrodes.