Electroanalytical applications of carbon fibre electrodes

The analytical uses of carbon fibre electrodes cover such diverse areas as coulometry, potentiometry, anodic stripping voltammetry, potentiometric stripping voltammetry, spectroelectrochemistry and kinetic measurements. The electrodes have been employed in a variety of cell types and locations, including conventional two and three electrode cells, flowing streams and in-vivo. The electroanalytical applications and theory are discussed in this review, along with the structure and surface properties of carbon fibres. Specialist instrumentation is also described.     

Anthraquinone-derivatised carbon powder: reagentless voltammetric pH electrodes

A simple pH probe is developed based upon the covalent chemical derivatisation of carbon particles with anthraquinone. The amperometric response of electrodes constructed from this material is examined and shown to produce a Nernstian linear response to pH from 1 to 9, over a range of temperatures from 20 to 70 °C, consistent with a two-electron, two-proton electrochemical process.     

Cyclic voltammetric responses of horseradish peroxidase multilayers on electrodes

The catalytic responses obtained with step-by-step neutravidin-biotin deposition of successive monolayers of HRP are analyzed by means of cyclic voltammetry. The theoretical tools that have been developed allowed full characterization of the multilayered HRP coatings by means of a combination between closed-form analysis of limiting behaviors and finite difference numerical computations. An analysis of the experiments in which the number of monolayers was extended to 16 allowed an approximate determination of the average thickness of each monolayer, pointing to a compact arrangement of neutravidin and biotinylated HRP. The piling up of so many monolayers on the electrode allowed an improvement of the catalytic current by a factor of ca. 10, leading to very good sensitivities in term of cosubstrate detection.     

Potentiometric stripping analysis and anodic stripping voltammetry with carbon fiber electrodes

High-modulus carbon fibers are used as working electrodes in differential-pulse stripping voltammetry and potentiometric stripping analysis. Different types of electrodes (particularly single-fiber and brush electrodes) are compared with regard to reproducibility, sensitivity, and practical aspects. Zinc, cadmium, and lead are determined in the 100 μg 1^?1 to 1 mg l^?1 range and optimum experimental parameters are described. The cut single-fiber electrode has the best general characteristics.     

Metalloporphyrin chemically modified glassy carbon electrodes as catalytic voltammetric sensors

Metalloporphyrin-coated glassy carbon electrodes are used as electrocatalytic voltammetric sensors for numerous clinically important solutes. For such compounds, heterogeneous charge- transfer rates are often very slow at carbon electrodes, leading to poorly defined voltammetric responses. The metalloporphyrin-modified electrodes are shown to decrease by several hundred millivolts the potential required for the oxidation of ascorbic acid, penicillamine, acetaminophen, dihydronicotinamide adenine dinucleotide, hydralazine, epinephrine, cysteine and oxalic acid. The faster rates of electron transfer result in a well defined voltammetric response and increased sensitivity. The differential pulse peaks for caffeic acid, ascorbic acid, acetaminophen and dopamine are enhanced by 18, 10.5, 9.4 and 8.4, respectively. When used for amperometric monitoring of flowing streams, the coated electrode permitted detection at lower potentials than at the naked surface and greatly facilitated assays of urine samples.     

Potentiometric responses of ion-selective electrodes after galvanostatically controlled incorporation of primary ions

A new method of quantitative incorporation of primary cations into ion-selective membrane by means of galvanostatic cathodic polarization/conditioning, before measurement step, was proposed and tested on the example of potassium-selective electrode with ionophore - valinomycin in poly(vinyl chloride) based membrane and with polypyrrole solid contact. Open circuit potential values recorded after polarization can be quantitatively explained by changes of primary cations and ionophore concentration in the surface part of the membrane. The influence of potassium ions concentration in the membrane (in relation to ion exchange sites amount) on the shape of potentiometric calibration plots was also observed. Improved characteristics, with extended linear range, can be obtained for membrane of minor loading with primary cations (around 25%), the responses are relatively stable in course of following calibrations.     

Simple and rapid voltammetric determination of morphine at electrochemically pretreated glassy carbon electrodes

A simple and rapid method for morphine detection has been described based on electrochemical pretreatment of glassy carbon electrode (GCE) which was treated by anodic oxidation at 1.75 V, following potential cycling in the potential range from 0 V to 1.0 V vs. Ag|AgCl reference electrode. The sensitivity for morphine detection was improved greatly and the detection limit was 0.2 μM. The reproducibility of the voltammetric measurements was usually less than 3% RSD for six replicate measurements. Moreover, this method could readily discriminate morphine from codeine. And an electrochemical detection of morphine in spiked urine sample was succeeded with satisfactory results.     

Amperometric and voltammetric detection of hydrazine using glassy carbon electrodes modified with carbon nanotubes and catechol derivatives

A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with carbon nanotubes (CNTs) and catechol compounds. First, 25 microL of DMSO-CNTs solutions (0.4 mg/mL) was cast on the surface of GC electrode and dried in air to form a CNTs film. Then the GC/CNTs modified electrode immersed into a chlorogenic acid, catechine hydrate and caffeic acid solution (electroless deposition) for a short period of time (2-80s). The cyclic voltammogram of the modified electrode in aqueous solution shows a pair of well-defined, stable and nearly reversible redox couple (quinone/hydroquinone) with surface confined characteristics. The combination of unique electronic and electrocatalytic properties of CNTs and catechol compounds results in a remarkable synergistic augmentation on the response. The electrochemical reversibility and stability of modified electrode prepared with incorporation of catechol compound into CNTs film was evaluated and compared with usual methods for attachment of catechols to electrode surfaces. The transfer coefficient (alpha), heterogeneous electron transfer rate constants (k(s)) and surface concentrations (Gamma) for GC/CNTs/catechol compound modified electrodes were calculated through the cyclic voltammetry technique. The modified electrodes showed excellent catalytic activity, fast response time and high sensitivity toward oxidation of hydrazine in phosphate buffer solutions at pH range 4-8. The modified electrode retains its initial response for at least 2 months if stored in dry ambient condition. The properties of modified electrodes as an amperometric sensor for micromolar or lower concentration detection of hydrazine have been characterized.     

Cyclic voltammetry and chronoamperometry of lead ions at carbon fibre electrodes

Cyclic voltammetry of reversible redox couples. e.g., hexacyanoferrate (III)/(II), at carbon fibre electrodes yields sigmoidal anodic and cathodic scans that are almost superimposed. However, the cyclic voltammogram of lead (II) ions was markedly different. The voltammogram, and results from chronoamperometric measurements, can be interpreted on the basis of lead nucleation.     

Potentiometric differentiation of mono- and macromolecular thiol within human plasma at carbon fiber electrodes

The potentiometric responses of mono- and macromolecular thiol species derivatized with a naphthoquinone indicator have been assessed at electrode designs based on laminated carbon fiber assemblies. The nature of the response for each type of species was found to depend strongly on the electrode geometry and composition and can be used to discriminate between the different thiol moieties. The efficacy of the electrode systems for the measurement of plasma thiols within normal and diabetic blood samples has been assessed, and a possible mechanism for the differing responses has been proposed.     

The use of vitreous carbon and carbon fibre electrodes for the coulometric generation of iodine

Vitreous carbon and carbon fibre can be used as working electrodes for the generation of iodine in coulometric titrations. Results are presented comparing the behaviour of these two materials with platinum in arsenic(III) and/or thiosulphate titrations.     

Computerized flow potentiometric stripping analysis with nafion-modified carbon fibre electrodes

Five to ten carbon fibres (10-μm diameter) are mounted perpendicularly to the flow direction in polyethylene tubes (0.8 mm inner diameter) and modified simultaneously by sucking five 10-μl portions of Nation dissolved in ethanol through the flow electrodes; after each portion, air is sucked through the tubes for some minutes. The modified electrodes can be used for several hundred electrolysis/stripping cycles in solutions containing albumin or Triton X-100. Analysis of a urine reference sample shows that zinc(II), cadmium(II) and lead(II) can be determined after acidification and electrolysis for 5, 35 and 100 s, respectively. For the determination of lead(II), 2 M hydrochloric acid is used as stripping medium but for the two other elements the sample itself is used. The electrochemically available fraction of the trace elements can be assessed by analyzing unacidified samples.     

Glassy carbon and boron doped glassy carbon electrodes for voltammetric determination of linuron herbicide in the selected samples

In this study the application of home-made unmodified (GC) and bulk modified boron doped glassy carbon (GCB) electrodes for the voltammetric determination of the linuron was investigated. The electrodes were synthesized with a moderate temperature treatment (1000°C). Obtained results were compared with the electrochemical determination of the linuron using a commercial glassy carbon electrode (GC-Metrohm). The peak potential (E _p ) of linuron oxidation in 0.1 mol dm⁻³ H₂SO₄ as electrolyte was similar for all applied electrodes: 1.31, 1.34 and 1.28 V for GCB, GC and GC-Metrohm electrodes, respectively. Potential of linuron oxidation and current density depend on the pH of supporting electrolyte. Applying GCB and GC-Metrohm electrodes the most intensive electrochemical response for linuron was obtained in strongly acidic solution (0.1 mol dm⁻³ H₂SO₄). Applying the boron doped glassy carbon electrode the broadest linear range (0.005–0.1 μmol cm⁻³) for the linuron determination was obtained. The results of voltammetric determination of the linuron in spiked water samples showed good correlation between added and found amounts of linuron and also are in good agreement with the results obtained by HPLC-UV method. This appears to be the first application of a boron doped glassy carbon electrode for voltammetric determination of the environmental important compounds.      

Potentiometric and voltammetric detection using a two-channel fountain cell

The design and use of a two-channel fountain cell in potentiometric and voltammetric detection is described. The two flows produced two distinct sectors inside the thin layer region and one of the sectors was used as the internal electrolyte of a reference electrode built into the cell body and the other as the indicator/counter electrode section. The behavior of the flowthrough Ag/AgCl reference electrode was first investigated and found satisfactory and it was then employed as the reference electrode in the subsequent experiments. Continuous and flow-injection measurements were made using the Fe(III)/Fe(II) redox couple in potentiometry and the reduction of Fe(III) in voltammetry.     

Novel approach to bismuth modifying procedure for voltammetric thick film carbon containing electrodes

The novel bismuth modifying technique for disposable thick film carbon containing sensors (TFCC) by means of a surface synthesis of the modifier (bismuth phosphate) have been developed. The optimal composition and the method of cathodic reduction (“activation”) of the modifying BiPO₄ layer has been proposed. These conditions provided the structure of a modifying layer with the bismuth nano particles of size less than 0.1 μm. On the important analytical parameters (sensitivity, accuracy, tolerance to surfactant fouling effect, particularly for Zn), sensor developed (TFCC/BiPO₄) surpasses TFCC with electrolytic bismuth films. The detection limit of 8 nM for zinc, 4 nM for cadmium and 2 nM for lead was achieved after a 2 min accumulation. Therefore, the developed non-toxic and low cost disposable sensor excludes the necessity of mechanical pretreatment of a working surface and can be used in field, laboratory and automatic systems for environmental monitoring (at the trace level inclusive).     

Adsorptive stripping voltammetric determination of ketoconazole in pharmaceutical preparations and urine using carbon paste electrodes

The oxidation of ketoconazole on a bare carbon paste electrode was studied voltammetrically. The results indicated that the process is irreversible and controlled by an adsorption-extraction process which allows the accumulation of the drug at the electrode surface. After the optimization of solution pH, accumulation variables and instrumental parameters, sensitive differential pulse and linear sweep voltammetric peaks were obtained whose peak currents were linearly proportional to the ketoconazole concentration over the ranges 2.4 x 10(-8)-4.8 x 10(-7) and 9.1 x 10(-7)-1.0 x 10(-5) M, respectively. Based on these findings, a simple procedure was developed for the determination of ketoconazole in human urine and formulations.     

Bucky-gel coated glassy carbon electrodes, for voltammetric detection of femtomolar leveled lead ions

Femtomolar (fM) leveled lead ions were electrochemically detected using a bucky-gel coated glassy carbon electrode and differential pulse anodic stripping voltammetry. The bucky-gel was composed of dithizone, ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate), and multi-walled carbon nanotubes (MWCNTs). The fabrication of the bucky-gel coated electrode was optimized. The modified electrode was characterized with voltammetry, electrochemical impedance spectroscopy, and chronoamperometry. After the accumulation of lead ions into the bucky-gel modified electrode at −1.2 V vs. saturated calomel electrode (SCE) for 5 min in a pH 4.4 sodium acetate-acetate acid buffer solution, differential pulse anodic stripping voltammograms of the accumulated lead show an anodic wave at −0.58 V. The anodic peak current is detectable for lead ions in the concentration range from 1.0 μM down to 500 fM. The detection limit is calculated to be 100 fM. The proposed method was successfully applied for the detection of lead ions in lake water.     

Covalent modification of glassy carbon electrodes with glycine for voltammetric separation of dopamine and ascorbic acid

Glycine was covalently grafted on to a glassy carbon electrode (GCE) by amine cation radical formation in electrooxidation of the amino-containing compound. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry proved the immobilization of glycine on the GCE. The modified electrode reduced the overpotentials of dopamine (DA) and ascorbic acid (AA) by approximately 0.15 V and 0.23 V, respectively, and resolved the overlapping voltammetric response of DA and AA into two well-defined voltammetric peaks in cyclic voltammetry (CV) or differential pulse voltammetry (DPV), unlike the unmodified GCE; this can be used for the simultaneous determination of these species in a mixture. The differential pulse peak current was linearly dependent on DA and AA concentration in the range 5 × 10^–6– 8 × 10^–4 mol L^–1 and 6 × 10^–5– 4 × 10^–3 mol L^–1, with correlation coefficients of 0.996 and 0.994, respectively. The detection limits (3δ) for DA and AA were 1.8 × 10^–6 mol L^–1 and 2.1 × 10^–5 mol L^–1, respectively. The modified electrode is very sensitive, selective and stable, and has been applied to the determination of DA and AA simultaneously in samples with satisfactory results. Received: 30 October 2000 / Revised: 9 March 2001 / Accepted: 13 March 2001     

Covalent modification of glassy carbon electrodes with glycine for voltammetric separation of dopamine and ascorbic acid

Glycine was covalently grafted on to a glassy carbon electrode (GCE) by amine cation radical formation in electrooxidation of the amino-containing compound. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry proved the immobilization of glycine on the GCE. The modified electrode reduced the overpotentials of dopamine (DA) and ascorbic acid (AA) by approximately 0.15 V and 0.23 V, respectively, and resolved the overlapping voltammetric response of DA and AA into two well-defined voltammetric peaks in cyclic voltammetry (CV) or differential pulse voltammetry (DPV), unlike the unmodified GCE; this can be used for the simultaneous determination of these species in a mixture. The differential pulse peak current was linearly dependent on DA and AA concentration in the range 5 x 10(-6)-8 x 10(-4) mol L(-1) and 6 x 10(-5)-4 x 10(-3) mol L(-1), with correlation coefficients of 0.996 and 0.994, respectively. The detection limits (3delta) for DA and AA were 1.8 x 10(-6) mol L(-1) and 2.1 x 10(-5) mol L(-1), respectively. The modified electrode is very sensitive, selective and stable, and has been applied to the determination of DA and AA simultaneously in samples with satisfactory results.     

Preconcentration and voltammetric determination of palladium (II) at sodium humate modified carbon paste electrodes

A chemically modified carbon paste electrode was prepared by incorporating appropriate amounts of sodium humate(NaA). Palladium(II) was selectively accumulated in a solution of Britton-Robinson(B-R) buffer (pH 2.8) onto the electrode surface in open circuit mode. The subsequent electrochemical measurement was carried out by cyclic voltammetry (CV) and linear sweep anodic stripping voltammetry (LSASV) in a supporting electrolyte of 1.0 M HCl. The obtained oxidation currents (I_pa1 and L_pa2) were proportional to the Pd(II) concentration in the range of 4.7 × 10^–6 - 9.4 × 10^–8 M. The developed method was applied to the quantitative determination of palladium in real samples.