Yavuz Yardım

Determination of vanillin in commercial food product by adsorptive stripping voltammetry using a boron-doped diamond electrode

A method for the determination of food additive vanillin was developed by adsorptive stripping voltammetry. Its determination was carried out at the anodically pre-treated boron-doped diamond electrode in aqueous solutions. Using square-wave stripping mode, the compound yielded a well-defined voltammetric response in phosphate buffer, pH 2.5 at +1.14 V (vs. Ag/AgCl) (a pre-concentration step being carried out at open-circuit condition for 60s). A linear calibration graph was obtained in the concentration range of 0.5-15.0 μg mL(-1) (3.3×10(-6)-9.8×10(-5) mol L(-1)) with a detection limit of 0.024 μg mL(-1) (1.6×10(-7) mol L(-1)). As an example, the practical applicability of the proposed method was tested for the determination of this flavouring agent in commercial pudding powder of Keshkule (Turkish milk pudding with almond flour).

Voltammetric determination of mixtures of caffeine and chlorogenic acid in beverage samples using a boron-doped diamond electrode

Herein, a boron-doped diamond (BDD) electrode that is anodically pretreated was used for the simultaneous determination of caffeine (CAF) and chlorogenic acid (CGA) by cyclic and adsorptive stripping voltammetry. The dependence of peak current and potential on pH, scan rate, accumulation parameters and other experimental variables were studied. By using square-wave stripping mode after 60 s accumulation under open-circuit voltage, the BDD electrode was able to separate the oxidation peak potentials of CAF and CGA present in binary mixtures by about 0.4V in Britton-Robinson buffer at pH 1.0. The limits of detection were 0.107 µg mL(-1) (5.51×10(-7) M) for CAF, and 0.448 µg mL(-1) (1.26×10(-6) M) for CGA. The practical applicability of this methodology was tested in commercially available beverage samples.

Voltammetric studies on the potent carcinogen, 7,12-dimethylbenz[a]anthracene: adsorptive stripping voltammetric determination in bulk aqueous forms and human urine samples and detection of DNA interaction on pencil graphite electrode.

7,12-Dimethylbenz[a]anthracene (DMBA), is a widely studied polycyclic aromatic hydrocarbon that has long been recognized as a very potent carcinogen. Initially, the electrochemical oxidation of DMBA at the glassy carbon and pencil graphite electrodes in non-aqueous media (dimethylsulphoxide with lithium perchlorate) was studied by cyclic voltammetry. DMBA was irreversibly oxidized in two steps at high positive potentials, resulting in the ill-resolved formation of a couple with a reduction and re-oxidation wave at much lower potentials. Special attention was given to the use of adsorptive stripping voltammetry together with a medium exchange procedure on disposable pencil graphite electrode in aqueous solutions over the pH range of 3.0-9.0. The response was characterized with respect to pH of the supporting electrolyte, pre-concentration time and accumulation potential. Using square-wave stripping mode, the compound yielded a well-defined voltammetric response in acetate buffer, pH 4.8 at +1.15V (vs. Ag/AgCl) (a pre-concentration step being carried out at a fixed potential of +0.60V for 360s). The process could be used to determine DMBA concentrations in the range 2-10nM, with an extremely low detection limit of 0.194nM (49.7ngL(-1)). The applicability to assay of spiked human urine samples was also illustrated. Finally, the interaction of DMBA with fish sperm double-stranded DNA based on decreasing of the oxidation signal of adenine base was studied electrochemically by using differential pulse voltammetry with a pencil graphite electrode at the surface and also in solution. The favorable signal-to-noise characteristics of biosensor resulted in low detection limit (ca. 46nM) following a 300-s interaction. These results displayed that the electrochemical DNA-based biosensor could be used for the sensitive, rapid, simple and cost effective detection of DMBA-DNA interaction.

Electrochemical evaluation and adsorptive stripping voltammetric determination of capsaicin or dihydrocapsaicin on a disposable pencil graphite electrode

Capsaicin and dihydrocapsaicin are the two most abundant capsaicinoids in peppers, which are responsible for about 90% of the spiciness. A detailed study of the electrochemical properties of these compounds at pencil graphite (PG) electrode was carried out in the pH range 1.0-12.0 in aqueous solutions. The compounds underwent irreversible oxidation at PG electrode, which was an adsorption-controlled process with two protons and two electrons. The voltammetric data indicated that their oxidation proceeded via an ECE mechanism. Using the square-wave adsorptive stripping voltammetry with accumulation at a fixed potential of -0.1V for 120s, both of them yielded a well-defined voltammetric response at +0.31V (vs. Ag/AgCl) in Britton-Robinson buffer, pH 9.0. Capsaicin and dihydrocapsaicin could be determined with detection limits of 1.12 ng mL(-1) (3.7×10(-9)M) and 0.28 ng mL(-1) (9.1×10(-10)M), respectively. The practical applicability of this methodology was tested in commercial Turkish pepper products. The concentration of total capsaicinoids was determined using capsaicin as standard.

Voltammetric behavior of benzo[a]pyrene at boron-doped diamond electrode: A study of its determination by adsorptive transfer stripping voltammetry based on the enhancement effect of anionic surfactant, sodium dodecylsulfate

Benzo[a]pyrene (BaP), a member of the polycyclic aromatic hydrocarbon (PAH) class, is one of the most potent PAH carcinogens. The electrochemical oxidation of BaP was first studied by cyclic voltammetry at the boron-doped diamond electrode in non-aqueous solvent (dimethylsulphoxide with lithium perchlorate). The compound was irreversibly oxidized in a single step at high positive potential, resulting in the well-resolved formation of a couple with a reduction and re-oxidation wave at much lower potentials. Special attention was given to the use of adsorptive stripping voltammetry together with a medium exchange procedure in aqueous and aqueous/surfactant solutions over the pH range of 2.0-8.0. The technique in aqueous solutions had little value in practice because of too small oxidation peak current. This problem was solved when surfactants were added into the sample solution, by which the oxidation peak currents of BaP were found enhanced dramatically. The employed surfactants were sodium dodecylsulfate (anionic, SDS), cetyltrimethylammonium bromide (cationic, CTAB) and Tween 80 (non-ionic). Using square-wave stripping mode, the compound yielded a well-defined voltammetric response in Britton-Robinson buffer, pH 2.0 containing 2.5×10(-4)M SDS at +1.07 V (vs. Ag/AgCl) (after 120s accumulation at +0.10 V). The process could be used to determine BaP in the concentration range of 16-200 nM (4.04-50.46 ng mL(-1)), with a detection limit of 2.86 nM (0.72 ng mL(-1)). This method was also applied to determine BaP in model water sample prepared by adding its different concentrations into tap water.

Electrochemical Behavior of Chlorogenic Acid at a Boron‐Doped Diamond Electrode and Estimation of the Antioxidant Capacity in the Coffee Samples Based on Its Oxidation Peak

In this study, an electroanalytical methodology for the determination of chlorogenic acid (CGA) was achieved at a boron-doped diamond electrode under adsorptive transfer stripping voltammetric conditions. The values obtained for CGA were used to estimate the antioxidant properties of the coffee sample based on CGA oxidation. By using square-wave stripping mode, the compound yielded a well-defined voltammetric response at +0.49 V with respect to Ag/AgCl in Britton-Robinson buffer at pH 3.0 (after 120 s accumulations at a fixed potential of 0.40 V). At the optimum experimental conditions, linear calibration curve is obtained within the concentration range of 0.25 to 4.0 μg mL⁻¹ with the limit of detection 0.049 μg mL⁻¹ . The developed protocol was successfully applied for the analysis of antioxidant capacity in the coffee products such as Turkish coffee and instant coffee.

Palladium(II) and platinum(II) complexes of a symmetric Schiff base derived from 2,6,diformyl-4-methylphenol with N-aminopyrimidine: synthesis, characterization and detection of DNA interaction by voltammetry.

The two new mononuclear complexes were prepared by reacting symmetric Schiff base, containing pyrimidine rings and the metal chlorides of Pd(II) and Pt(II) in methanol. The mononuclear structure of the complexes was confirmed on the basis of elemental analyses, magnetic susceptibility, IR, UV-Vis, NMR, DTA/TGA and API-ES mass spectral data. The interaction of these metal complexes with fish sperm double-stranded DNA (dsDNA) was studied electrochemically based on the oxidation signals of guanine and adenine. Differential pulse (DP) voltammetry by using renewable pencil graphite electrode was employed to monitor the DNA interaction at the surface or in solution. The results indicate that Pd(II) and (Pt) complexes with Schiff base ligand having pyrimidine rings strongly interacted with DNA.

Graphene/Nafion composite film modified glassy carbon electrode for simultaneous determination of paracetamol, aspirin and caffeine in pharmaceutical formulations

A graphene-Nafion composite film was fabricated on the glassy carbon electrode (GR-NF/GCE), and used for simultaneous determination of paracetamol (PAR), aspirin (ASA) and caffeine (CAF). The electrochemical behaviors of PAR, ASA and CAF were investigated by cyclic voltammetry and square-wave adsorptive anodic stripping voltammetry. By using stripping one for simultaneous determination of PAR, ASA and CAF, their electrochemical oxidation peaks appeared at +0.64, 1.04 and 1.44V, and good linear current responses were obtained with the detection limits of 18ngmL(-1) (1.2×10(-9)M), 11.7ngmL(-1) (6.5×10(-8)M) and 7.3ngmL(-1) (3.8×10(-8)M), respectively. Finally, the proposed electrochemical sensor was successfully applied for quantifying PAR, ASA and CAF in commercial tablet formulations.

Simultaneous voltammetric determination of vanillin and caffeine in food products using an anodically pretreated boron-doped diamond electrode: Its comparison with HPLC-DAD

This paper describes an electroanalytical method for the simultaneous determination of vanillin (VAN) and caffeine (CAF) using an anodically pretreated boron-doped diamond electrode. Selective determination of one compound in the presence of other one was also realized. Both compounds yielded a single irreversible oxidation peak using cyclic voltammetry. The nature of the electrode reaction was found to be diffusion controlled with contribution of adsorption. By using square-wave adsorptive stripping voltammetry after 60s accumulation under open-circuit voltage, method allowed simultaneous determination of VAN and CAF in phosphate buffer, pH 2.5, with detection limits of 0.234µgmL-1 (1.54×10-6M) and 0.071µgmL-1 (3.66×10-7M), respectively. The proposed method was successfully applied in the selective and simultaneous determination of VAN and CAF in commercial food and beverage samples. In addition, for the comparison, high-performance liquid chromatographic method with diode-array detection was developed for the first time for their simultaneous determination.

Voltammetric behavior of rutin at a boron-doped diamond electrode. Its electroanalytical determination in a pharmaceutical formulation

AbstractThis paper examined for the first time, the possibilities of the usage of a boron-doped diamond electrode for the redox behavior of rutin using cyclic and adsorptive stripping voltammetry. The cyclic voltammograms showed a pair of redox peaks at lower potentials followed by an irreversible oxidation peak at higher positive potential. Using square-wave adsorptive stripping voltammetry, the compound yielded a well-defined voltammetric response in Britton-Robinson buffer, pH 4.0 at +0.48 V (vs. Ag/AgCl) (after 60 s accumulations at a fixed potential of 0.2 V). The calibration curve was linear in the concentration range from 0.01 µg mL−1 to 0.1 µg mL−1 (1.64×10−8 M − 1.64×10−7 M). A detection limit of 0.0017 µg mL−1 (2.78×10−9 M) was observed without any chemical modifications and electrochemical surface pretreatments. As an example, the practical applicability of boron-doped diamond electrode was tested with the measurement of rutin in dietary supplement products.