Chronoamperometric current at finite disk electrodes

The chronoamperometric current at a stationary finite disk electrode is studied using both analytical and digital simulation techniques. The exact long-time expansion of the current is obtained and its short-time behavior is considered. Digital simulation of the current using an explicit hopscotch algorithm is presented. In contrast to the usual explicit difference method, the ‘hopscotch’ algorithm is unconditionally stable, and thus, it is particularly suited for studying electrochemical problems at intermediate and long times. A simple analytic expressions for the current, which is accurate to 0.6% for all times, is presented.     

Direct potentiometric water hardness determination using ion-selective electrodes

Summary The use of ion-selective electrodes for direct potentiometric water hardness determinations is restricted to relatively soft waters if they are to be competitive with other techniques in terms of uncertainty on the water hardness scale. The selectivity factorK _MgCa ^Pot must be within 1.1% of unity if a hardness of 10 degrees on the German scale is to be measured to within 0.1 degrees in the composition rangec _Mg:c _Ca=0.25 to 25. The expressionK _MgNa ^Pot ·a _Na ² / (a _Mg+a _Ca) must be less than 0.001 if freedom from sodium interference is to be achieved. Under these conditions a 1% relative standard deviation can be obtained for an uncertainty of the EMF100V.

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Direkte potentiometrische Bestimmung der Wasserhärte mit ionen-selektiven Elektroden

Zusammenfassung Die direkte potentiometrische Bestimmung der Wasserhärte mit ionenselektiven Elektroden kann nur für relativ weiches Wasser verwendet werden, sofern sie mit anderen Methoden konkurrenzfähig sein soll. Der SelektivitätsfaktorK _MgCa ^Pot sollte nicht mehr als 1,1% von 1 abweichen, um eine Messung von 10 deutschen Härtegraden auf 0,1 Grad genau zu ermöglichen, wenn gleichzeitig das Mischungsverhältnisc _Mg:c _Ca im Bereich 0,25 bis 25 schwankt. Der AusdruckK _MgNa ^Pot ·a _Na ² /(a _Mg +a _Ca) sollte 0,001 nicht überschreiten, wenn eine Störung durch Natrium vermieden werden soll. Unter den obigen Bedingungen läßt sich eine Wasserhärte auf 1% genau bestimmen, wenn die Unsicherheit der gemessenen EMK100V.

     

Direct electrochemical redox of tyrosinase at silver electrodes

The direct electron transfer reactions between tyrosinase and silver electrode were investigated by using cyclic voltammetry and potential-step chronoamperometry as well as current-step chronopotentiometry techniques. The kinetics of these reactions is quasi-reversible with two electron transfer reactions and 0.030 s(-1) apparent electrode reaction rate constant. The results demonstrate that neither electrode surface modification nor the inclusion of mediators is necessary to study the electron transfer reactions of tyrosinase at silver electrodes. Moreover, both the anodic and the cathodic currents are linear relationship with the tyrosinase concentration in the range of 1 x 10(-9) approximately 5 x 10(-8)moll(-1). It is possible to be used as a method of analyzing tyrosinase concentration.     

Direct cytochrome c electrochemistry at boron-doped diamond electrodes

Highly boron-doped diamond electrodes are characterized voltammetrically employing Ru(NH₃)₆^3+/2+, Fe(CN)₆^3−/4−, benzoquinone/hydroquinone, and cytochrome c redox systems. The diamond electrodes, which are polished to nanometer finish, are initially `activated' electrochemically and then pretreated by oxidation, reduction, or polishing. All electrodes give reversible cyclic voltammetric responses for the reduction of Ru(NH₃)₆³⁺ in aqueous solution.Redox systems other than Ru(NH₃)₆^3+/2+ show characteristic electrochemical behavior as a function of diamond surface pretreatment. In particular, the horse heart cytochrome c redox system is shown to give reversible voltammetric responses at Al₂O₃ polished boron-doped diamond electrodes. No voltammetric response for cytochrome c is detected at anodically pretreated diamond electrodes. The observations are attributed to preferential interaction of the polished diamond surface with the reactive region of the cytochrome c molecule and low interference due to a lack of protein electrode fouling.     

两铂电极零电流示波双电位滴定法

本文提出了用阴极射线示波器荧光屏上荧光点的显著位移来指示零电流双电位滴定终点的新方法, 并对其特点进行了研究. 新的终点指示方法能响应两电极间ΔE的瞬时变化, 因而比常用的方法灵敏, 扩大了两铂电极零电流双电位滴定的应用范围.     

Direct electrochemistry of catalase on glassy carbon electrodes.

Catalase was investigated as a possible catalyst of the electrochemical reduction of oxygen on glassy carbon electrodes. The presence of catalase dissolved in solution only provoked a moderate current increase, which was fully explained by the catalase-catalysed disproportionation of hydrogen peroxide (Scheme I). When catalase was adsorbed from dimethylsulfoxide on the surface of electrodes that did not undergo any electrochemical pre-treatment (EP), catalase efficiently catalysed oxygen reduction via direct electron transfer from the electrode (Scheme II). The results are discussed with respect to the electrode surface properties and the enzyme structure.     

Direct oxidation of haemoglobin at bare boron-doped diamond electrodes

The communication reports the direct oxidation of human haemoglobin at a bare boron-doped diamond electrode under moderately alkaline conditions with detection limit of 0.4 microM.     

Direct electrochemical assay of glucose using boron-doped diamond electrodes

We report linear sweep and square wave voltammetric studies on glucose oxidation at boron-doped diamond (BDD) electrodes in an alkaline medium in efforts to evaluate the techniques for electrochemically assaying glucose. The bare BDD electrode showed good linear responses to glucose oxidation for a concentration range from 0.5 to 10 mM glucose, which well encompasses the physiological range of 3-8 mM. The BDD electrodes did not experience interferences from ascorbic acid or uric acid during glucose detection. This method, when applied to real blood samples, gave results similar to those obtained by a commercial glucose monitor.     

Direct electron transfer reactions between human ceruloplasmin and electrodes

In an effort to find conditions favouring bioelectrocatalytic reduction of oxygen by surface-immobilised human ceruloplasmin (Cp), direct electron transfer (DET) reactions between Cp and an extended range of surfaces were considered. Exploiting advances in surface nanotechnology, bare and carbon-nanotube-modified spectrographic graphite electrodes as well as bare, thiol- and gold-nanoparticle-modified gold electrodes were considered, and ellipsometry provided clues as to the amount and form of adsorbed Cp. DET was studied under different conditions by cyclic voltammetry and chronoamperometry. Two Faradaic processes with midpoint potentials of about 400 mV and 700 mV vs. NHE, corresponding to the redox transformation of copper sites of Cp, were clearly observed. In spite of the significant amount of Cp adsorbed on the electrode surfaces, as well as the quite fast DET reactions between the redox enzyme and electrodes, bioelectrocatalytic reduction of oxygen by immobilised Cp was never registered. The bioelectrocatalytic inertness of this complex multi-functional redox enzyme interacting with a variety of surfaces might be associated with a very complex mechanism of intramolecular electron transfer involving a kinetic trapping behaviour.     

Gas electrodes with nickel based current collectors for molten carbonate electrolyte thermo-electrochemical cells

Thermo-electrochemical cells with inexpensive molten carbonate electrolyte and(CO_2|O_2) gas electrodes allow the possible conversion of high temperature waste heat from industrial processes into electricity.The cell containing eutectic(Li,Na)_2CO_3 electrolyte with solid Mg O dispersion delivers a large Seebeck coefficient of-1.7 m V/K. At present, the(CO_2|O_2) gas electrodes use metallic gold as current collectors in order to avoid the formation of interfering oxide layers during operation. For further reduction in energy generation cost, the gold current collectors should be replaced with an inexpensive and stable alternative.In this study, the suitability of the(molten carbonate fuel cell) MCFC's nickel-based cathodes to operate the molten-carbonate thermo-electrochemical cell, was investigated. Ni current collectors were examined in two different states, as Ni O and as lithiated Ni O(LixNi1-xO). The Ni O phase shows higher stability than the LixNi1-xO while the Seebeck coefficient remains above-1.2 m V/K.     

Self-assembling photosynthetic reaction centers on electrodes for current generation

Photosynthetic reaction centers (RCs) made from photosynthetic organisms can be used in solar batteries because their molecules cause light-induced charge separation. We present a simple immobilization system of the intact RCs from Rhodobacter sphaeroides on an electrode that uses nickel ligand binding by the hexameric histidine tag on H subunit (HHisRC). The binding constant of HHisRC to the nickel-nitrilotriacetic acid (Ni−NTA) chip measured with a surface plasmon resonance instrument was 1.6×10⁸M⁻¹. HHisRCs were immobilized on an indium tin oxide electrode overlaid with an Ni−NTA gold substrate. The photoinduced displacement current of this electrode was measured to estimate the orientation of HHisRC on the electrode, and the detachability of HHisRC from the electrode was determined by using an imidazole solution wash. The direction of the flash-light-induced displacement current suggested that the H subunit side of the immobilized HHisRC faced the surface of the electrode. The photoinduced current disappeared after the electrode was washed in the imidazole solution. This simple immobilization and detachment of HHisRC to the electrode might be useful for making a reproducible photocurrent device.     

Direct measurement of electrochemical reaction kinetics in flow-through porous electrodes

This work demonstrates the feasibility of measuring electrochemical reaction rates on common flow-through porous electrodes by traditional Tafel analysis. A customized microfluidic channel electrode was designed and demonstrated by measuring the intrinsic kinetics of the V^2 +/V^3 + and VO^2 +/VO₂⁺ redox reactions in carbon paper electrodes under forced electrolyte flow. The exchange current density of the V^2 +/V^3 + reaction was found to be nearly two orders of magnitude slower than the VO^2 +/VO₂⁺ reaction, indicating that this may be the limiting reaction in vanadium redox flow batteries. The forced convection in this technique is found to generate reproducible exchange current densities which are consistently higher than for conventional electrochemical methods due to improved mass transport.     

Direct electrochemistry of heme multicofactor-containing enzymes on alkanethiol-modified gold electrodes

Direct electrochemistry of heme multicofactor-containing enzymes, e.g., microbial theophylline oxidase (ThOx) and D-fructose dehydrogenase (FDH) from Gluconobacter industrius was studied on alkanethiol-modified gold electrodes and was compared with that of some previously studied complex heme enzymes, specifically, cellobiose dehydrogenase (CDH) and sulphite oxidase (SOx). The formal redox potentials for enzymes in direct electronic communication varied for ThOx from -112 to -101 mV (vs. Ag|AgCl), at pH 7.0, and for FDH from -158 to -89 mV, at pH 5.0 and pH 4.0, respectively, on differently charged alkanethiol layers. Direct and mediated by cytochrome c electrochemistry of FDH correlated with the existence of two active centres in the protein structure, i.e., the heme and the pyrroloquinoline quinone (PQQ) prosthetic groups. The effect of the alkanethiols of different polarity and charge on the surface properties of the gold electrodes necessary for adsorption and orientation of ThOx, FDH, CDH and SOx, favourable for the efficient electrode-enzyme electron transfer reaction, is discussed.     

Direct electron transfer in nanostructured sol-gel electrodes containing bilirubin oxidase

Bilirubin oxidase encapsulated within a silica sol-gel/carbon nanotube composite electrode effectively catalyzed the reduction of molecular oxygen into water through direct electron transfer at the carbon nanotube electrode surface. In this nanocomposite approach, the silica matrix is designed to be sufficiently porous for substrate molecules to have access to the enzyme and yet provides a protective cage for immobilization without affecting biological activity. The incorporation of carbon nanotubes adds electrical connectivity and increases active electrode surface area. The standard surface electron transfer rate constant was calculated to be 59 s(-1) which indicates that the carbon nanotube side walls are primarily responsible for electron transfer. The use of direct electron transfer processes simplifies biofuel cell fabrication by eliminating the need for redox mediator and ion-conducting separators.     

Direct electron transfer in immobilized flavoenzyme chemically modified graphite electrodes

Direct electron transfer between covalently immobilized flavoenzymes and a cyanuric chloride-modified graphite electrode is observed via differential pulse voltammetry. L-Amino acid oxidase and xanthine oxidase display peaks arising from the reduction of flavin adenine dinucleotide. Peak current enhancements are observed for both covalently attached enzymes compared to their free and adsorbed state voltammograms. Studies concerning flavin removal and reconstitution indicate that xanthine oxidase contains multiple flavin chromophores which are nonequivalent.     

High current density 3D electrodes manufactured by technical embroidery

Embroidery techniques allow flexible construction of 3D electrodes, which can form the conductive backbone in ultra-thick electrodes. 3D structures were manufactured by combination of stainless steel yarn, Cu wire, polyester (PES) fabric and Cu/Ni-coated PES web. Alkaline solutions of 9,10-anthraquinone-1,5-disulfonate or 1,2-dihydroxy-9,10-anthraquinone-3-sulfonate (Alizarin Red S) were used as reversible redox systems to characterise the electrodes by voltammetry in a flow cell. The height of the diffusion-limited current for the reversible cathodic reduction of the 9,10-anthraquinoide group was used as measure for the electrode performance. Compared to plane Cu electrodes, an increase in the diffusion-limited cathodic current density by factor 3–5 was obtained.     

Activation of glassy carbon electrodes by alternating current electrochemical treatment

Glassy carbon electrodes subjected to “severe” electrochemical treatment is saturated chloride solutions exhibit enhanced electrochemical reversibility compared to untreated electrodes. Apparently faster rates of electron-transfer result in lowering of the overpotential by 110–300 mV for eight electroactive species tested. Systematic alterations in the response in terms of peak potential, sensitivity, background current, and stability are reported. Scanning electron micrographs show the introduction of pits of random size distribution. From the practical point of view, the most significant improvement is observed in differential pulse measurements, that are highly sensitive to small changes in the rate of electron transfer. In amperometric detection for liquid chromatography, the pretreated electrodes are shown to facilitate the quantitation of different eluting species. It appears that the surface and bulk properties of the glassy carbon have profound effects on the observed behavior.     

Use of blocked electrodes in thermally stimulated depolarization current measurements

The use of blocked electrodes in thermally stimulated depolarization current (TSDC) measurements has been studied on phenol–formaldehyde novolac resin blocked by one or two Teflon foils. The measurements were performed after polarization at different temperatures T_p separately for the Teflon and the resin. Blocking decreases the effectiveness of a nominal polarizing field and suppresses the background current. It is explained here for the first time that the charge released from the charged Teflon interferes with the conductivity relaxation peak of the resin. The influence of the blocking is very dependent upon T_p, and this dependence is specific in regard to the type of current peak. The application of blocking at different T_p is recommended for the determination of the origin of peaks in TSDC measurements.