Potentiometric detection of ascorbate using a graphite carbon electrode

A graphite carbon electrode was used for the potentiometric detection of ascorbate. The electrode exhibits a linear response with a slope of -42+/-1.0 mV decade(-1) in concentrations ranging from 5x10(-4) to 5.0x10(-2) M in 0.1 M NaOH solution with a detection limit of 5.0x10(-6) M. The response mechanism of this electrode was investigated by potentiometry, voltammetry, and scanning electron micoscropy (SEM), and it suggests that the electrode potential change resulted from the ion-exchange adsorption and subsequent oxidation of ascorbate on the electrode surface at pH 12-13. The electrode exhibits high sensitivity, selectivity and reproducibility.     

On the behaviour of the dry cell graphite electrode

It is reported that for staircase voltammetric work, a dry cell graphite electrode after wax impregnation and polishing, behaves as well as a glassy carbon electrode.     

Potentiometric Cd-selective electrode with a detection limit in the low ppt range

A recently introduced model describing the response curves of polymer membrane ion-selective electrodes (ISEs) is used here to optimize a Cd²⁺-ISE with a view to achieve very low detection limits. In a first step, the selectivity behavior is determined for two membranes based on the ionophore, N,N,N′,N′-tetradodecyl-3,6-dioxaoctanedithioamide (ETH 5435), but having different concentrations of the ionophore and ion-exchanger. Based on these data, the optimal response curves are calculated with a model that takes into account the ion fluxes induced by interfering ions. The experimental results with different ionic backgrounds correspond very well with the predicted effects. The best lower detection limit of 10⁻¹⁰ M or 11 ppt Cd²⁺ is achieved at pH 7 with an ionic background of 10⁻⁴ M NaNO₃.     

Potentiometric detection in ion chromatography using a metallic copper indicator electrode

Summary A metallic copper electrode housed in a suitable flowcell is shown to be a sensitive and versatile potentiometric detector for ion chromatography. This electrode may be used for direct or indirect detection of many inorganic anions and cations and also for organic acids. In the direct detection mode, electrode response is based on either complexation of copper ions at the electrode surface by eluted species, or on oxidation and reduction reactions for eluted species which are strong oxidants or reductants. Direct detection is therefore applicable to such species as amino acids, organic acids, chloride, bromide, iodide, chlorate, bromate and iodate. Indirect detection is possible for anions which do not complex copper ions, provided a copper complexing ligand (such as phthalate) is used in the eluent; cations which complex this ligand are also detectable. Indirect detection may be used for species such as nitrite, nitrate, acetate, formate, succinate, benzoate, alkaline earth ions and transition metal ions. Electrode calibration relationships are discussed and sample separations are presented, together with some typical detection limits attainable in the direct and indirect detection modes.Presented in part at a National Symposium on Ion Chromatography, held at the University of New South Wales, Kensington, Australia, Nov. 21, 1984.     

New triiodomercurate-modified carbon paste electrode for the potentiometric determination of mercury

A new tetrazolium-triiodomercurate-modified carbon paste electrode has been described for the sensitive and selective determination of mercury. The electrode shows a stable, near-Nernstian response for 1×10⁻³ to 6×10⁻⁶ M [HgI₃]⁻ at 25 °C over the pH range of 4.0-9.0, with an anionic slope of 55.5±0.4 mV. The lower detection limit is 4×10⁻⁶ M with a fast response time of 30-50 s. Selectivity coefficients of a number of interfering anions and iodo complexes of some metal ions have been estimated. The interference from many of the investigated ions is negligible. The determination of 1-200 μg/ml of mercury in aqueous solutions shows an average recovery of 98.5% and a mean relative standard deviation of 1.6% at 50.0 μg/ml. The direct determination of mercury in spiked wastewater, metal amalgams and dental alloy gave results that compare favorably with those obtained by the cold vapor atomic absorption spectrometric method. Potentiometric titration of mercury and phenylmercury acetate with standard potassium iodide has been monitored using the developed triiodomercurate-carbon paste electrode (CPE) as an end point indicator electrode.     

Determination of flunitrazepam and nitrazepam in beverage samples by liquid chromatography with dual electrode detection using a carbon fibre veil electrode

Both nitrazepam and flunitrazepam have been determined by high-performance liquid chromatography dual electrode detection (LC-DED) in the reductive–reductive mode, using a carbon fibre veil electrode (CFVE) in conjugation with a glassy carbon electrode. Initial studies were made to optimise the chromatographic conditions. These were found to be 45% acetonitrile-55% acetate buffer (50 mM, pH 4.1) at a flow rate of 1.0 ml/min, employing a Hypersil C18, 5 μm, 250 mm × 4.6 mm column. Cyclic voltammetric studies performed to ascertain the redox behaviour of nitrazepam and flunitrazepam at a CFVE in the optimised mobile phase. Studies showed that similar voltammetric behaviour was obtained to that report at Hg or glassy carbon based electrodes. Further studies were then carried out to identify the optimum conditions required for the LC-DED determination of nitrazepam and flunitrazepam in beverage samples. Hydrodynamic voltammetry was used to optimise the applied potential at the generator and detector cells; these were identified to be −2.40 and −0.25 V, respectively. A linear range of 2.0 to 100 μg ml⁻¹, with a detection limit of 20 ng ml⁻¹ was obtained. A convenient and rapid method for the determination of both nitrazepam and flunitrazepam in beverage sample was developed. Following a simple sample extraction procedure, extracts were examined using the optimised LC-DED procedure. An average percentage recovery of 95.5% (%CV = 4.5%) for nitrazepam and 78.0% (%CV = 8.8%) was achieved for a sample of “Pepsi Max” spiked at 1.0 μg ml⁻¹ nitrazepam, 1.47 μg ml⁻¹ flunitrazepam. Presented at the 4th Annual Meeting of the Great Western Electrochemistry Group, 8th June 2005, University of the West of England, Bristol, UK.     

Determination of diclofenac in pharmaceutical preparations using a potentiometric sensor immobilized in a graphite matrix

The characteristics, performance, and application of an electrode, namely Pt|Hg|Hg₂(DCF)₂|graphite, where DCF stands for diclofenac ion, are described. This electrode responds to diclofenac with sensitivity of (58.1 ± 0.8) mV/decade over the range 5.0 × 10⁻⁵ to 1.0 × 10⁻² mol l⁻¹ at pH 6.5-9.0 and a detection limit of 3.2 × 10⁻⁵ mol l⁻¹. The electrode is easily constructed at a relatively low cost with fast response time (within 10-30 s) and can be used for a period of 5 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for diclofenac in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used to determine diclofenac in pharmaceutical preparations by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedures.     

Electrochemical behavior and detection of guanine using a sodium montmorillonite-modified carbon paste electrode

Herein, a sodium montmorillonite-modified carbon paste electrode is described for the electrochemical determination of guanine. Guanine yields a well-defined and very sensitive oxidation peak at the sodium montmorillonite-modified carbon paste electrode. Compared with the unmodified carbon paste electrode, the modified electrode facilitates the electron transfer of guanine, since it notably increases the oxidation peak current and lowers the oxidation overpotential of guanine. Based on this, a simple sensitive reliable electrochemical method is proposed for the detection of guanine after all the experimental parameters, such as solution pH value, sodium montmorillonite content in the carbon paste electrode, accumulation potential, and time, are optimized. Under the optimized conditions, the oxidation peak current of guanine varies linearly with its concentration in the range 5.0×10⁻⁸ to 2.0×10⁻⁵ M and the detection limit (signal-to-noise=3) is 2.0×10⁻⁸ M after 4-min accumulation. This method is successfully demonstrated with urine samples. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 2, pp. 178–182. The text was submitted by the authors in English.     

Electrochemical determination of maltol in beverages with glassy carbon electrode and its silica sol-gel modified electrode

The electrochemical behavior of maltol on a glassy carbon (GC) electrode was investigated. The results were applied to differential pulse voltammetric determination of maltol in beverages pretreated by ultrafiltration. Under the optimum experimental conditions, the linear range is 1×10⁻⁵ to 6×10⁻⁴ mol l⁻¹ maltol and the relative standard deviation for 0.4 mmol l⁻¹ maltol is 0.6% (n=9). The detection limit was 5 μmol l⁻¹. Furthermore, silica sol-gel film on GC electrode could be used as suitable selective membrane, which integrated selective membrane on the electrode and substituted for the pretreatment of ultrafiltration. Under the above conditions, maltol was determined by semi-differential linear sweep voltammetry at a silica sol-gel modified GC electrode in the concentration range of 5×10⁻⁶ to 5×10⁻⁴ mol l⁻¹. The detection limit was 2 μmol l⁻¹ and the relative standard deviation for 0.1 mmol l⁻¹ maltol was 0.7% (n=7). The proposed method is of sensitivity, simplicity, rapidness and no contamination. It had been applied to the direct determination of maltol in beverages such as grape wines, drinks and beers without any pretreatment. The results obtained with the present method were satisfactory with those obtained by spectrophotometry. It could be used as a simple and practical method for the determination of the flavor enhancer maltol in beverages.     

A biosensor based on graphite epoxy composite electrode for aspartame and ethanol detection

A gelatin membrane with carboxyl esterase and alcohol oxidase was subsequently integrated onto the surface of a graphite epoxy composite electrode (GECE). The developed biosensors showed linearity in the range of 2.5–400 μM for aspartame and 2.5–25 μM for ethanol with response times of 170 and 70 s for each analyte, respectively. The resulting bienzyme biosensor was used for aspartame detection in diet coke samples and ethanol detection in beer and wine samples. From the obtained results, it can be concluded that the developed biosensor is a selective, practical and economic tool for aspartame and ethanol detection in real samples.     

Potentiometric determination of hydrogen peroxide at MnO2-doped carbon paste electrode

A novel hydrogen peroxide (H₂O₂) potentiometric sensor, made with a MnO₂-doped carbon paste electrode (CPE), is reported. Under optimum conditions, the electrode gives a Nernstian response for H₂O₂ in the concentration range 3.00×10⁻⁷–3.63×10⁻⁴ mol/l, with a slope of 21–19.4 mV/pH₂O₂ and a detection limit of 1.2×10⁻⁷mol/l H₂O₂. In addition, this sensor offers some analytical characteristics such as sensitivity, good reproducibility and a simple preparation procedure. The effects of both the components of the electrode and other conditions on the potential response of the sensor, as well as the possible response mechanism, are discussed.     

活化玻碳电极伏安法测定锰的研究

采用活化玻碳电极(GC)以伏安法对测定锰进行了研究。结果表明:沉积于电极表面的二氧化锰对锰(Ⅱ)的电化学氧化具有自催化作用,活化GC电极可极大地提高测定锰的灵敏度。在0.04mol LNH3 NH4Cl(pH9.0)底液中,锰浓度在6.0×10-8～1.0×10-5mol L范围内成线性关系,检出限为4.0×10-8mol L。用3×10-7mol L锰溶液重复测定9次,RSD为1.6%。     

嵌入式碳纳米管石墨电极测定灯盏花素的研究

制备嵌入式多壁碳纳米管修饰石墨电极,利用循环伏安法(CV)研究灯盏花素在嵌入式多壁碳纳米管修饰石墨电极(ESCFE)上的电化学氧化行为,结果表明,灯盏花素在修饰电极上出现一对明显的准可逆氧化还原峰,峰电位分别为Epa=0.17 V和Epc=0.05 V(△E=0.12 V),峰电流分别为ipa=42.79μA,ipc=...     

Electrochemical detection of selenium using glassy carbon electrode modified with reduced graphene oxide

In this work, a simple experimental procedure was reported for the electroanalytical determination of selenium (IV) using reduced graphene oxide (rGO) to modify glassy carbon electrode (GCE). The rGO was obtained by reduction of graphene oxide obtained via Hummer’s method. The synthesised rGO was characterised using X-ray diffraction, Raman spectroscopy, scanning electron microscope (SEM), energy-dispersive spectroscopy and transmission Electron microscopy (TEM). GCE was modified with rGO and the electrochemical properties of the bare and modified electrode were investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The results obtained showed that the modified electrode exhibited more excellent electrochemical properties than the bare GCE. The optimum conditions for detection of selenium in water using square wave anodic stripping voltammetry were as follows: deposition potential ?500 mV, pH 1, pre-concentration time of 240 s and 0.1 M nitric acid was used as supporting electrolyte. The linear regression equation obtained was I (µA) = 0.8432C + 9.2359 and the detection limit was calculated to be 0.85 μg L^?1. However, Cu(II) and Cd(II) are the two cations that interfered in the analysis of selenium in water.

The sensor was also applied for real sample water analysis and the result obtained was affirmed with inductively coupled plasma optical emission spectroscopic method. It is believed that our proposed sensor hold promise for practical application.     

Development and characterization of a new conducting carbon composite electrode

A new conducting composite flexible material prepared from cellulose acetate (CA) polymer and graphite has been developed and used for the fabrication of electrodes, which were then characterized by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy (SEM) was used to provide information concerning the morphology of the composite electrode surface. The potential window, background currents and capacitance were evaluated by cyclic voltammetry in the pH range from 4.6 to 8.2. The voltammetry of model electroactive species demonstrates a close to reversible electrochemical behaviour, under linear diffusion control. The electroactive area of the composite electrodes increases after appropriate electrode polishing and electrochemical pre-treatment. The electrodes were used as substrate for the electropolymerisation of the phenazine dye neutral red, for future use as redox mediator in electrochemical biosensors. The composite electrodes were also successfully used for the amperometric detection of ascorbate at 0.0 V vs. SCE, and applied to the measurement of ascorbate in Vitamin C tablets; the sensor exhibits high sensitivity and a low detection limit of 7.7 μM. Perspectives for use as a versatile, mechanically flexible and robust composite electrode of easily adaptable dimensions are indicated.     

Ion chromatographic determination of organic acids in food samples using a permanent coating graphite carbon column

From the viewpoint of a graphite carbon column with excellent durability, it was applied to the ion chromatography (IC) of several organic acids. The carbon column was permanently coated with the cetyltrimethylammonium (CTMA) ion, and the elution behaviors of several organic acids (acetic acid, lactic acid, succinic acid, malic acid, tartaric acid, citric acid) and inorganic anions (Cl⁻, NO₂⁻, NO₃⁻, SO₄²⁻) were examined according to a non-suppressed IC coupled with conductivity detector, when an ion-exchange ability was given to the graphite carbon column. When salicylic acid and sodium salicylate were used as a mobile phase, each organic acid are analyzed approximately 10 min. But the separation of malic acid, chloride and nitrite was difficult. When benzoic acid and 2-amino-2-hydroxymethyl-1,3-puropanediol (tris aminomethane) were used as a mobile phase, tartaric acid and citric acid, etc. with large valency showed tendency to which the width of each peaks extended and retention time increased. However, it was possible to separate excellently for the analytes detected within 10 min. The developed method was then applied to the determination of organic acids in several food samples.     

Potentiometric detection of organic acids in ion-exclusion chromatography using different types of liquid-membrane electrodes

Four different liquid-membrane electrodes were tested in a potentiometric flow-cell, in combination with an LC ion chromatography system (Aminex HPX-87H column). This setup was used for the determination of weak organic acids. The flow-through detector was of the wall-jet type. Conditions were established to achieve the best separation and detection characteristics. The sensitivity, selectivity and response time of the different electrodes were compared. Calibration curves and detection limits were measured for several organic acids, and compared with conductometric, and with low-wavelength UV detection. The detection limits were improved by inserting a post-column ion-suppressor system between the column and the detector. Several biological samples were analyzed to demonstrate the possibilities of the potentiometric detector.     

Sensitive detection of cyclophosphamide using DNA-modified carbon paste, pencil graphite and hanging mercury drop electrodes

The interaction of cyclophosphamide (CP) with calf thymus double-stranded DNA (dsDNA) and thermally denatured single-stranded DNA (ssDNA) immobilized at the carbon paste (CPE) and pencil graphite electrodes (PGE), was studied electrochemically based on oxidation signals of guanine and adenine using differential pulse voltammetry (DPV).As a result of the interaction of CP with DNA, the voltammetric signals of guanine and adenine increased in the case of dsDNA while a slight increase was observed in ssDNA. The effect of experimental parameters such as the interaction time between CP and DNA forms and the concentration of CP, were studied using DPV with CPE and PGE. Additionally, reproducibility and detection limits were determined using both electrodes. A comparison of the analytical performance between CPE and PGE was done. Our results showed that these two different DNA biosensors could be used for the sensitive, rapid and cost effective detection of CP itself as well as of CP-DNA interaction.Furthermore, the interaction of CP with dsDNA and ssDNA was studied in solution and at the electrode surface by means of alternating current voltammetry (ACV) in 0.3 M NaCl and 50 mM sodium phosphate buffer (pH 8.5) supporting electrolyte, using a hanging mercury drop electrode (HMDE) as working electrode.The conclusions of this study were mainly based on tensammetric peaks I (at −1.183 V) and II (−1.419 V) of DNA. This study involved the interaction of CP with surface-confined and solution phase DNA where experimental parameters, such as the concentration of CP and the interaction time, were studied. By increasing the concentration of CP, an increase of peak II was observed in both ds and ssDNA, while an increase of peak I was observed only in the case of dsDNA. An overall conclusion of the study using HMDE was that the interaction of CP with surface-confined DNA significantly differed from that with solution phase DNA. The increase of peaks I and II was lower in the case of interaction of CP with surface-confined DNA, probably due to steric positioning of DNA at the electrode surface.     

pH measurements based on a palladium electrode

The feasibility of a metal palladium electrode as the pH sensor in air-saturated aqueous solutions was evaluated. The measurement was based on an “on-site” precleaning step and a potential decay process. The experimental results showed a linear pH response with a sensitivity of around 60 mV/pH and good reproducibiliry. The temperature effect on the measurement was also evaluated.     

Electrochemical determination of 8-hydroxydeoxyguanosine using a carbon nanotube modified electrode

In this work, a multi-wall carbon nanotube (MWNT) film-modified glassy carbon electrode (GCE) was constructed for the determination of 8-hydroxydesoxyguanosine (8-OHdG). The electrochemical behaviors of 8-OHdG were examined using cyclic voltammetry (CV) and linear sweep voltammetry (LSV), suggesting that MWNT film facilitates the electron transfer of 8-OHdG and then significantly enhances the oxidation peak current of 8-OHdG. Finally, a sensitive and simple electrochemical method with a good linear relationship in the range of 8.0 × 10⁻⁸ ∼ 5.0 × 10⁻⁶ mol 1⁻¹, was developed for the determination of 8-OHdG. The detection limit is 9.0 × 10⁻⁹ mol 1⁻¹ for 6-min accumulation. This newly-proposed method was successfully used to detect 8-OHdG in urine samples. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 3, pp. 351–356. The text was submitted by the authors in English.