Electrochemical study of glassy carbon electrodes modified with zirconium phosphate and some azine-type redox dyes

Glassy carbon (GC) electrodes were modified with a layer of zirconium phosphate (ZrP), using either direct chemical synthesis onto the surface or a ZrP gel droplet evaporation procedure. The azine-type dyes nile blue A (NB) and toluidine blue O (TB) were immobilized onto the ZrP-modified GC electrodes either by adsorption onto just the formed layer of ZrP or by inclusion into the ZrP matrix during its chemical synthesis. The electrochemical behavior of the GC·ZrP·dye composite electrodes was studied. For GC·ZrP-modified electrodes prepared by chemical synthesis on the surface, coverage by NB or TB of one or a few monolayers was found, with E _m values for these redox couples slightly shifting by ca. 0.05 V to the negative direction. For the GC·ZrP electrodes prepared by gel droplet evaporation, the E _m values for NB and TB appear initially shifted by ca. 0.2 V to the positive direction; however, both cathodic and anodic peaks return to their usual positions on the potential scale during soaking these electrodes in a buffer solution. Electronic Publication     

Construction of novel simple phosphate screen-printed and carbon paste ion-selective electrodes

The construction and performance characteristics of different phosphate ion-selective electrodes are described. Three types of electrodes are demonstrated, namely screen-printed, carbon paste and the conventional PVC membrane electrodes. The cited electrodes are based on bisthiourea ionophores and show a considerable selectivity towards hydrogenphosphate with Nernstian slopes depending on the type of the electrode and the ionophore used. Matrix compositions of each electrode are optimised on the basis of effects of type and concentration of the ionophore as well as influence of the selected plasticizers. The screen-printed electrodes work satisfactorily in the concentration range 10⁻⁵ to 10⁻² mol L⁻¹ with anionic Nernstian compliance (32.8 mV/decade activity) and detection limit 4.0 × 10⁻⁶ mol L⁻¹. The screen-printed electrodes show fast response time of about 2.2 s and exhibit adequate shelf-life (4 months). The fabricated electrodes can be also successfully used in the potentiometric titration of HPO₄²⁻ with Ba²⁺.     

Bismuth-film-plated carbon paste electrodes

In this preliminary note, carbon paste electrodes (CPEs) plated with a bismuth film are presented. The bismuth film can be generated onto the carbon paste surface either from an external plating solution or in situ; the latter being performed in two ways: (i) as a spike of the Bi³⁺ ions to the solution or (ii) via modifying the carbon paste with solid bismuth oxide (5% m/m). As shown on selected examples, bismuth-film-plated CPEs exhibit a good performance in voltammetric stripping analysis of some heavy metals such as Pb, Cd, and Zn.     

Glassy carbon paste electrodes

A new carbon composite electrode material, based on mixing glassy carbon (GC) microparticles with an organic pasting liquid is described. The resulting glassy carbon paste electrode (GCPE) combines the electrochemical properties of GC with the various advantages of composite electrodes. Glassy carbon pastes (GCPs) offer high electrochemical reactivity, a wide accessible potential window, a low background current, and are inexpensive, easy to prepare, modify, and renew. The new material has a lower double-layer capacitance and a higher heterogeneous rate constant (for ferricyanide) compared to conventional carbon pastes (CPs). Scanning electron microscopy (SEM) images indicate significant differences in the structure of GCPE and carbon paste electrode (CPE). Factors influencing the electrode kinetics of GCPE surfaces are discussed. The electrochemical properties and advantages of GCPE should be of broad utility in electroanalysis.     

Zeolite-modified solid carbon paste electrodes

New zeolite-modified carbon-based electrodes are described. They are based either on the physical anchoring of zeolite particles on the surface of solid carbon paste (the viscosity of which can be tuned by temperature change or controlled dissolution by an organic solvent), or on the dispersion of zeolite particles in the bulk of a carbon paste matrix containing solid paraffin as a binder. Both these systems display superior electrochemical performance in comparison to corresponding "classical" zeolite-modified carbon paste electrodes using mineral oil as binder. These well-described composites usually suffer from poor mechanical stability in stirred media as well as memory effects due to significant ingress of the external solution into the bulk electrode. Advantages of the zeolite-modified solid carbon paste electrodes are reported mostly on the basis of two electroanalytical applications: the voltammetric detection of Cu²⁺ ions after accumulation by ion exchange at open circuit, and the indirect amperometric detection of non-electroactive species (i.e. Na⁺) in flow injection analysis.     

Lead dioxide-coated carbon paste electrodes

Lead dioxide electrodeposited under optimized conditions on carbon paste provides an electroanalytically useful electrode, with an anodic working range extending to 1.9 V. Voltammograms for sulphite are used to study electrode lifetime and reproducibility; calibration graphs are linear up to 10^-3M sulphite in 0.5 M sulphuric acid.     

Voltammetric study of glibenclamide at carbon paste and Sephadex-modified carbon paste electrodes

The oxidative behaviour of the antidiabetic agent glibenclamide on a bare carbon paste electrode (CPE) and a Sephadex-modified carbon paste electrode (SMCPE) was explored by cyclic and differential pulse voltammetry (DPV). The analysis procedure consisted of an open circuit accumulation step in stirred sample solution of Britton-Robinson buffer (0.04 mol L^–1, pH 2.0). This was followed by medium exchange to a clean solution of Britton-Robinson buffer (0.04 mol L^–1, pH 5.0), and subsequently an anodic potential scan was effected to obtain the voltammetric peak. The glibenclamide oxidation peak current obtained by DPV was proportional to the concentration of the glibenclamide in the range of 1.0×10^–9 mol L^–1 to 5.0×10^–8 mol L^–1 for 180 s accumulation time, with a detection limit of 4.0×10^–10 mol L^–1. A method was developed for the determination of glibenclamide in formulation and spiked human serum. Moreover, the proposed procedure was used to estimate the serum concentrations after oral administration of a 5 mg tablet of glibenclamide to three diabetic subjects.     

Voltammetric determination of Celiptium with carbon paste and lipid-modified carbon paste electrodes

The electrooxidation of the antitumour drug 2-methyl-9-hydroxyellipticinium (Celiptium) was investigated by cyclic, differential-pulse and adsorptive voltammetry at carbon paste (CPE) and lipid-modified carbon paste electrodes (LM-CPE). The influence of the paste composition, i.e., the ratio of graphite to binder, was studied in order to elucidate the nature of the accumulation process at the surface of the CPE. The electrode surface coverage at saturation was calculated. A.c. measurements at the CPE and at the LM-CPE during the accumulation of Celiptium demonstrated an increased differential double layer capacity of the LM-CPE. The influence of several parameters that affect the adsorptive step at the CPE was investigated, such as pH, ionic strength and interfering ions. Improved signals were obtained at the CPE and the detection limit in 0.1 M sodium perchlorate (t_acc.=3 min) was found to be 2 × 10^?10 M. Measurements of the drug in dilute standard serum samples were done using the medium-exchange technique.     

Electrocatalytic oxidation of NADH at carbon paste electrodes modified with meldola blue adsorbed on zirconium phosphate: effect of Ca2+ and polyethyleneimine

The basic electrochemistry of carbon paste electrodes modified with Meldola Blue adsorbed on zirconium phosphate (MB-ZP-CPEs) and their ability to oxidize NADH have been investigated. Three types of carbon powder (graphite and glassy carbon-type Sigradur K and G) were used to obtain MB-ZP-CPEs. On comparing cyclic voltammograms recorded at MB-ZP-CPEs, similarly prepared from the three different carbon powders, those made with Sigradur K exhibited the lowest background current, and the best MB electrochemistry, seen as the highest peak intensities and smallest peak separation. Using MB-ZP-CPEs based on Sigradur K a study on NADH oxidation was done focusing on the effect of the Ca²⁺ concentration in the contacting solution and on the addition of polyethyleneimine (PEI) into the paste. It can be stated that MB-ZP-CPEs based on Sigradur K and containing 1.23% (w/w) PEI exhibited the best behavior for NADH oxidation, measured by the highest electrocatalytic rate constant (8.2×10³ M^–1 s^–1).     

Photoelectrochemical investigation of methylene blue immobilised on zirconium phosphate modified carbon paste electrode in flow injection system

The adsorption of methylene blue (MB) onto zirconium phosphate (ZrP) was studied and the adsorption capacity value and isotherms were determined. The adsorption capacity of ZrP was increased after being exposed to gas phase n-butyl amine. The adsorbed MB on ZrP was used as a modifier material in carbon paste electrode (MCPE), which in turn was used in voltammetric investigations and flow injection (FI) amperometric determination of ascorbic acid (AA). A quasi-reversible electrode reaction of adsorbed MB was exhibited. A home made flow-through electrochemical cell with a suitable transparent window for irradiation of the electrode surface was constructed and used for amperometric FI studies. The photoamperometric-FI conditions were optimised as 1.5 mL min⁻¹ flow rate, a 25 cm transmission tubing length, a 100 μL injection volume, and a constant applied potential of +100 mV versus SCE. The calibration curve for AA was linear over the concentration range from 1.0 × 10⁻⁶ to 4.0 × 10⁻⁵ M. The relative standard deviation of four replicate injections of 3.0 × 10⁻⁵ M AA was 1.2%. The results obtained for AA determination in pharmaceutical products are in good agreement with those obtained using the procedure involving the reaction between triiodide and AA.     

Metallic impurity free carbon nanotube paste electrodes

Electrodes modified with carbon nanomaterials find wide ranging applications in electrochemistry such as in energy generation and storage through to applications in electroanalysis. A substantial limitation is the presence of metallic impurities which vary between batches and can produce erroneous results. Consequently we have explored the electrochemical properties of metallic impurity free carbon nanotube paste electrodes using potassium ferrocyanide and hydrogen peroxide as model compounds. In terms of the latter utilising cyclic voltammetry, a linear range from 0.75 to 3 mM with a limit of detection of 0.19 mM is possible using the electrochemical oxidation of hydrogen peroxide while using the electrochemical reduction of the target analyte, a linear range from 0.5 to 249 mM is possible with a detection limit of 0.43 mM.The ultra-small size of the carbon nanotubes and fabrication methodology result in a tightly bound carbon nanotube electrode surface which does not exhibit thin-layer behaviour resulting in highly reproducible electrodes with the %RSD found to be 5.5%. These analytical ranges, detection limits and reproducibility are technologically useful.The carbon nanotubes utilised are completely free from metallic impurities and do not require lengthy processing to remove impurities and consequently have no variation in the purity of the nanomaterial between batches as is commonly the case for other available carbon nanotube material. The impurity free nature of this nanomaterial allows for highly reproducible and intelligent sensors based on carbon nanotubes to be understood and realised for the first time.     

Perspectives of carbon paste electrodes in stripping potentiometry.

The testing of various types of carbon paste electrodes (CPEs) for their use in stripping potentiometry was carried out by means of specially proposed procedures and by using various model analyte systems. CPEs containing three different pasting liquids (paraffin oil, silicone oil, tricresyl phosphate) were tested as supports for mercury- and gold films, and as substrates for electrolytic, adsorptive, ion-pair forming, and extractive accumulation. Test measurements in organic solvent-containing media and studies of some irreversible electrochemical reactions were performed as well. Individual examples to be studied allowed one to formulate and outline some perspectives of CPEs in potentiometric stripping analysis and related constant current stripping analysis.     

Amperometric detection of phenolic compounds by polypyrrole-based composite carbon paste electrodes

This contribution describes new composite carbon paste electrodes (CPEs) for the determination of phenolic compounds. The composite CPEs were prepared by in situ generation of polypyrrole (PPy) within a paste containing the enzyme polyphenol oxidase (PPO). The best paste composition (enzyme/pyrrole monomer/carbon particles/Nujol) was determined for a model enzyme, glucose oxidase (GOx) according to the enzymatic activity of the resulting electrodes and to the enzyme leakage from the paste during storage in phosphate buffer. The in situ electrogenerated PPy improves the enzyme immobilisation within the paste since practically no enzyme was lost in solution after 72 h of immersion. Moreover, the enzyme activity remains particularly stable under storage since the biocomposite structure conserves 80% of its activity after 1 month of storage. Following the optimisation of the paste composition, PPO-based carbon paste biosensors were prepared and presented excellent analytical properties toward catechol detection with a sensitivity of 4.7 A M(-1) cm(-2) and a response time lower than 20 s. The resulting biosensors were applied to the determination of polyphenolic compounds (e.g., epicatechin and ferulic acid).     

Detection of homocysteine at carbon nanotube paste electrodes

The use of a carbon-nanotube paste (CNTP) electrode provides an effective means for the determination of homocysteine. A decrease of ca. 120 mV in the overpotential for the oxidation of homocysteine compared to a traditional carbon paste electrode, is reported along with greatly enhanced signal-to-noise characteristics. The analytical parameters have been assessed with a linear range from 5 to 200 μM and a detection limit of 4.6 μM. Furthermore, the generic nature of this increased reactivity of the CNTP surface towards thiol moieties has been demonstrated with cysteine, glutathione and n-acetylcysteine, providing a greatly enhanced electrochemical response compared to the carbon paste electrode.     

Some observations on carbon paste electrodes in ac voltammetry

Phase-sensitive alternating current (a.c.) voltammetric techniques were used to examine the background current at carbon paste electrodes. Several different mulling agents were used for the pastes. The available potential span depends on the mulling agent; paraffin oil gives the largest span. Peaks in the background current obtained by cyclic a.c. voltammetry are attributed to current arising from surface functional groups. Chemical or electrochemical oxidation of the electrode surface enhanced the peak current. Little evidence of this current could be found in d.c. cyclic voltammograms because it is obscured by charging current. The anodic potential limit is determined by these surface currents. On the cathodic side, dissolved oxygen is reduced in a process which produced two peaks in the a.c. scan. It was shown that the second peak is due to the reduction of hydrogen peroxide to water and a method for the quantitation of H₂O₂ was developed which had a detection limit of a few mg l^?1.     

Layered inorganic materials as redox agents: ferrocenium-intercalated zirconium phosphate

The direct intercalation reaction of ferrocene (bis(eta5-cyclopentadienyl)iron(II), Fc) with a highly hydrated layered zirconium phosphate (ZrP) resulted in the formation of the ferrocenium ion (Fc+) within the ZrP material. The Fc+-intercalated ZrP material has an interlayer distance of 10.7 A. The intercalated material was used as an electron acceptor for the oxidation of both ferro-cytochrome c and the excited state of tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+). Upon contact of the material with a 1.5 x 10(-5) M solution of ferro-cytochrome c, the UV-vis absorption spectrum shows the successful formation of ferri-cytochrome c. Luminescence spectroscopy shows that the Fc+-intercalated ZrP material quenches the luminescence of [Ru(bpy)3]2+. The excited-state quenching mechanism of [Ru(bpy)3]2+* by Fc+-intercalated ZrP follows a dynamic plus sphere of action model. The second-order dynamic quenching rate constant kq is 2.2 x 10(8) M(-1) s(-1).     

PVC-碳糊修饰电极的研制

研制了二茂铁修饰PVC-碳糊电极,采用循环伏安法研究了在pH7．4 KH2PO4-Na2HPO4缓冲溶液中该修饰电极的电化学特性和该修饰电极对抗坏血酸和邻苯二酚的电催化作用,测定结果具有较好的灵敏度和线性关系。研制了α-安息香肟修饰PVC-碳糊电极,研究了该电极对铜(Ⅱ)的特殊选择性。同时初步探讨了电极与铜(Ⅱ)的反应机理。