Electrochemical studies on tetrathiafulvalene-tetracyanoquinodimethane modified acetylcholine/choline sensor

A sensor for acetylcholine/choline is described using a tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) electrode modified with acetylcholine esterase (AChE) and choline oxidase (ChO) enzymes. DC cyclic voltammetry and impedance measurements of the enzyme-modified TTF-TCNQ electrode that indicate the regeneration of choline oxidase at the electrode surface are reported. Effective electrochemical rate constants for the present enzyme electrode are calculated using the expressions derived by Albery et al. (1), which show the enzyme kinetics as the rate-limiting step. The values of the effective electrochemical rate constants are close to those reported by Hale and Wightman (2). The application of the sensor is described for the determination of fluorode ion and nicotine based on the reversible inhibition of AChE activity. The range of detection of fluoride ion and nicotine is found to be 5×10^-6 to 5×10^-4M.     

All-solid-state Fluoride Ion-selective Electrode using LaF3 Single Crystal with Poly(3,4-ethylenedioxythiophene) as Solid Contact Layer

An all-solid-state fluoride ion-selective electrode (ISE) was prepared using LaF₃ single crystal with poly(3,4-ethylenedioxythiophene (PEDOT) as the solid contact layer. In contrast to polymer-based ISEs, crystalline membrane-based ISEs have not been used for all-solid-state device, thereby prohibiting the integration of ISEs on a chip. The all-solid-state fluoride ISE developed in this study exhibited superior sensitivity (−56.0±0.9 mV/dec) and selectivity compared to those of conventional inner filling solution ISE. The effects of PEDOT as a solid contact layer were analyzed using chronopotentiometry and electrochemical impedance spectroscopy, which revealed that PEDOT promoted electrode stability. The all-solid-state device can miniaturize the fluoride ISE and facilitate environmental, industrial, agricultural, and physiological monitoring.     

Voltammetric,potentiometric and amperometric studies with a rotated aluminum wire electrode: The R.Al.E. as indicator electrode in potentiometric and amperometric acid-base titrations

The effect of varying concentrations of fluoride on the potential of the R.AI.E. in acid buffer solutions is reported. In the pH range between 1 and 5.5 the potential becomes 30 mV more negative per unit increase in pH at fluoride concentrations between 10^-3 and 10^-4M. At a given pH the potential becomes 100 mV more negative when the fluoride concentration is increased from 10^-4 to 10^-3it. No depolarization occurs and no reproducible potentials can be measured in phosphate buffers of pH 6 to 8, even in the presence of 10^-3M fluoride. This concentration of fluoride causes depolarization and establishment of reproducible potentials in veronal buffers of reproducible pH 6 to 8. At a pH greater than 9 fluoride has no effect on the electrode potential which now becomes determined by pH. In the presence of fluoride, oxygen shifts the electrode potential to less negative values (mixed potential). Examples of potentiometric and amperometric titrations of strong and weak acids are given with the R.AI.E. as indicator electrode.     

Voltammetric,potentiometric and amperometric studies with a rotated aluminum wire electrode: Voltammetric behavior of the r.al.e.

A rotated aluminum wire electrode (R.Al.E.) is described for the determination of voltammograms and potentials. An aluminum electrode is highly polarizable both cathodically and anodically. Of all ions tested only hydroxyl and fluoride ions depolarize it anodically at highly negative potentials. In the absence of fluoride it is not a pH electrode, but it is a pOH electrode in the presence of an excess of hydroxyl ions. Fluoride in acid medium and hydroxyl ions yield well defined anodic diffusion currents. In the absence of fluoride or of an excess of hydroxyl ions the potential is ill defined. In acid medium a trace of fluoride (2.10^-5M or 0.4 p.p.m.) causes the potential to become approximately 600 mV more negative than in the absence of fluoride. At a pH greater than j l the potential varies 66 mV per unit change of pH.     

Voltammetric,potentiometric and amperometric studies with a rotated aluminum wire electrode : A comparison of the baker and morrison cell with the raie.

In the amperometric determination of fluoride at the RAIE a half cell composed of 5% cadmium amalgam in equilibrum with a solution 1 M in cadmium sulfate and saturated with potassium chloride can be used as a reference electrode in a short-circuited cell instead of applying a potential of -0 75 V versus the saturated calomel electrode The standard addition method can be used in the presence of air, although removal of oxygen is recommended Using the Baker and Morrison electrode versus the above half cell and following their directions (10 ml solution, magnetic stirring) proportionality between current and fluoride concentration in a range between 1 · 10^-5 and 1 · 10^-4M was found in oxygen-free solutions Halides and perchlorates do not interfere. The standard addition technique can be used in the determination of fluoride in an unknown.     

Impedimetric characterization of the changes produced in the electrode–solution interface by bacterial attachment

This paper describes a new method for measuring the attachment of bacteria, specifically Escherichia coli on platinum electrodes using impedance spectroscopy. Impedance spectroscopy measurements showed that the double layer capacitance of the electrode was very sensitive both to the concentration of bacteria in the solution and to the attachment time. Impedance measurements of E. coli were compared with classical measurements of bacterial attachment on identical electrodes such as staining/microscopy and bacterial removal by sonication and plating onto agar. The relationship between the measured impedance of the electrode during attachment and the biophysical processes involved is discussed.     

Parameters of the double electric layer and n-butanol adsorption on lead in methanesulfonate solutions

A differential capacity measurement showed that the zero charge potential of a lead electrode in a sodium methanesulfonate solution was ?0.69 V. Like sulfate anions, methanesulfonate anions had low specific adsorbability on lead. The adsorption of n-butanol from a methanesulfonate electrolyte on a lead electrode was approximated by the Frumkin isotherm equation. The parameters of n-butanol adsorption in a methanesulfonate solution were close to those reported for fluoride and sulfate solutions in the literature.     

A voltammetric method for fluoride

A voltammetric method for the determination of micro amounts of fluoride is described. It is based on the measurement of the amount of free alizarin red S liberated by the fluoride ion from a zirconium-alizarin red S complex. The free dye measurement carried out at 0.7 V vs. S.C.E. depends on the anodic reaction of alizarin red S at the rotating pyrolytic graphite electrode. The method is simple, sensitive and suffers from relatively few interferences.     

Impedance of the SnO<Subscript>2</Subscript>|liquid crystal ZhK-440|SnO<Subscript>2</Subscript> system

The SnO₂|ZhK-440|SnO₂ system, where the ZhK-440 is a liquid crystal mixture consisting of 2/3 parts of p-butyl-p'-methyloxyazoxybenzene and 1/3 part of p-butyl-p'-heptanoyloxyazoxybenzene, was studied by impedance spectroscopy. The impedance spectrum of the system contained the contributions from electric conductivity and bulk and electrode polarizations. The models of bulk and electrode impedance were discussed.     

Determination of diffusion coefficient of lithium in substituted LiMn1.95Cr0.05O4 spinel using impedance technique

Electrodiffusion properties of chromium-substituted lithium-manganese spinel Li _x Mn_1.95Cr_0.05O₄ intended for application as a cathodic material for lithium-ion batteries is studied. The studies are carried out at 25°C using the electrochemical impedance spectroscopy technique in alkyl-carbonate electrolyte. In the analysis of impedance spectra, the apparatus of electric equivalent circuits was employed to determine surface layer resistances, double electric layer capacitance, differential intercalation capacity, chemical diffusion coefficient D of lithium, and other electrode characteristics. The issues of substantiating the choice of electric equivalent circuits and correct interpretation of their elements are discussed; dependences of the calculated model parameters on the electrode potential (lithium concentration in the electrode) are analyzed. The chemical diffusion coefficient of Li⁺ in Li _x Mn_1.95Cr_0.05O₄ found on the basis of the impedance spectra is in the range of 10^?9 to 10^?12 cm²/s under electrode potential variation in the range of 3.5–4.5 V (vs. Li/Li⁺) with a pronounced minimum of D in the middle of this range. Repeated cycling of the electrode is accompanied by a gradual increase in resistance of the solid-electrolyte interphase (SEI).     

Voltammetric,potentiometric and amperometric studies with a rotated aluminum wire electrode : Amperometric titration of fluoride with aluminum

The rotated aluminum electrode is a suitable indicator electrode in the amperometric titration of fluoride, Fluoride in concentrations varying between 1.10^-4 and 2.10^-3M was titrated with a standard aluminum nitrate solution in aqueous buffer solutions (pH between 3.6 and 46) Equilibrium was established within 15 mim. The fluoride-aluminum ratio at the (true) end-point was found to increase from 2 2 in 10^-4M fluoride to 28 in. 2.10^-3M fluoride. The titration calculated from the stability constants of the various aluminum-fluoride complexes were found to be in excellent agreement with the experimental curves.From a practical point of view titration in an acetate buffer in 50% alcohol in the presence of 0 5 M potassium or sodium nitrate is recommended. The fluoride-aluminum ratio at the end-point was found to be 5 9 ± 0 1 and independent of the fluoride concentration.     

Impedance measurements for determination of pore texture of a carbon membrane

The pore texture of a carbon membrane was determined by impedance measurements carried out over a wide frequency range. The impedance obtained could be characterised by a resistance Ω and a double layer capacitance Cn. Ω is the third of electrolyte resistance in pores and Cn is the double layer capacitance corresponding to the developed pore surface. Membrane samples of different length but with the same thickness were studied. As expected, it was shown that the Cn value is proportional to the weight of the membrane whereas the Ω value is inversely proportional. Cn value allowed us to evaluate the specific area of the porous membrane from the value of the double layer capacitance per unit area determined for a plain carbon electrode. Moreover, impedance diagrams obtained were found to be very similar to those of cylindrical pore even though the pore texture is very intricate. Thus, impedance measurements can be applied to porous electrodes of more intricate pore texture and evaluate the radius, depth and pore number of its equivalent cylindrical pore electrode.     

Interfacing cytochrome c to electrodes with a DNA – carbon nanotube composite film

Multi-walled carbon nanotube (MWCNT) is successfully immobilized on the surface of platinum electrode by mixing with DNA. The DNA/MWCNT modified electrodes are characterized by electrochemical impedance spectroscopy and cyclic voltammetry. Further research indicates that cytochrome c can strongly adsorbed on the surface of the modified electrode, and forms an approximate monolayer. The immobilized MWCNT can promote the redox of horse heart cytochrome c which gives reversible redox peaks with a formal potential of 81 mV vs SCE.     

Ionic conductivity and electrode effects on β-PbF2

The a.c. impedance of single crystal specimens of β-PbF₂ has been studied as a function of frequency and temperature in the range 10^?2 to 10⁵ Hz and 25 to 320°C. A variety of ionically blocking electrode configurations were used and equivalent circuits were derived by complex plane analysis. In addition to bulk resistive and capacitive effects, a complex frequency-dependent interface impedance was identified. The algebraic form and temperature dependence of this impedance were found and variations in its magnitude with changes in electrode material and morphology were measured.     

Design of a Fluoride-Selective Electrode with Internal Contact Based on a Cu(II) Ion-Selective Electrode

The design of an electrode body that provides internal contact with a LaF₃ membrane based on a Cu(II) ion-selective electrode is described. The assembled fluoride electrode was examined in terms of potential-concentration curves and potential-time response. The behavior of the fluoride ion-selective electrode with the investigated internal contact was in good agreement with the commercial fluoride electrode.     

Preparative Electrosynthesis of Strong Oxidizers at Boron-Doped Diamond Electrode in Anhydrous HF

The use of the boron-doped diamond electrode as a sufficiently stable electrode for electrochemical measurements/synthesis in liquid anhydrous hydrogen fluoride medium is reported. Electrooxidation of silver(I) has been studied in this solvent by using classical transient electrochemical methods and impedance spectroscopy. It has been found that faradaic currents related to silver(I) oxidation and the fluorine evolution reaction are reasonably separated at the potential scale, which allows efficient electrosynthesis of Ag^IIF₂, a powerful oxidizer. Impedance spectroscopy measurements provide insight into complex mechanism of AgF₂ formation. The procedure for electrosynthesis is provided for the first time in both galvanostatic and potentiostatic condition.     

On the E.S.R. spectra of intermediates generated during the electrochemical oxidation of triphenylacetic acid in acetonitrile

The acidity level and the fluoride ion activity are evaluated in anhydrous HF and in water+HF mixtures of HF content higher than 70% by means of R(H) and R(F) functions. For both functions, the potentials of the ferrocene/ferricinium or perylene⁺/perylene²⁺ systems are used as reference potentials. A hydrogen electrode is used for acidity level evaluation and it is shown that the R(H) function decreases (acidity increases) when HF content increases in the mixture; the value of R(H) is ?15.5 for anhydrous hydrogen fluoride (+KF 0.1 M). A lanthanum trifluoride monocrystal electrode is built and used for F^? activity evaluations and it is shown that the R(F) function increases (activity of fluoride ion decreases) when HF content increases, up to R(F)=13.6 for basic anhydrous HF (KF 0.1 M solution).     

Electrocapillary studies of fluoride solutions on mercury using polyethylene capillary

The electrocapillary curves in concentration range 0.001 M to 1 M in sodium and potassium fluoride solutions and in 12.25 M potassium fluoride were measured using a glass capillary with a polyethylene tip. In very dilute solutions the lowering of the interfacial tension at potentials more positive than p.z.c. described several times in experiments with glass capillary electrometer was not observed, and the electrocapillary curves coincided very well with those obtained from double integration of capacitance data. At large concentration of fluoride an increase of maximum interfacial tension was noticed. The fabrication of polyethylene capillary electrode is described and its advantages discussed.     

Direct electrochemistry and superficial characterization of DNA-cytochrome c-MUA films on chemically modified gold surface

Cytochrome c (Cyt. c) was immobilized on the 11-mercaptohendecanoic acid (MUA)-modified gold electrode. The electrode was stable and sensitive to Cyt. c. Later, DNA was also immobilized on the two-layer modified electrode. Cyclic voltammetry studies show that Cyt. c can interact with dsDNA and ssDNA. The binding site sizes were determined to be 15 base pairs per Cyt. c molecule with dsDNA and 30 nucleotides binding 1 Cyt. c molecule with ssDNA. The modified electrodes were characterized by quartz crystal microbalance (QCM), impedance spectroscopy and atomic force microscope (AFM). The modified electrode can be used for determining DNA.     

Impedance-based total-NOx sensor using stabilized zirconia and ZnCr2O4 sensing electrode operating at high temperature

We report here a new-type zirconia-based sensor that can detect total NO_x content at high temperatures such as 700 °C. A closed-one-end yttria-stabilized zirconia (YSZ) tube was used as a base sensor material. An oxide sensing electrode (SE) and a Pt counter electrode (CE) were formed on the outer and inner surfaces of the YSZ tube, respectively. The complex impedance of the device using a ZnCr₂O₄-sensing electrode was measured with an impedance analyzer in the frequency and the temperature ranges 0.1 Hz–100 kHz and 600–700 °C, respectively. A large semicircular arc was observed in complex impedance plots (Cole–Cole plots) in the lower frequency range examined and it seemed to correspond to the electrolyte/electrode interface. The impedance value at 1 Hz of the present device was found to vary almost linearly with the concentration of NO (or NO₂) from 50 to 400 ppm in the sample gas at 600–700 °C. Furthermore, it is noted that the sensitivity of NO is almost equal to that of NO₂. This means that the present device can detect the total NO_x at higher temperatures.