Electroactive layers reaction

This three-enzyme scheme suffers interference from endogenous creatine in the sample, requiring correction. Low concentrations of creatinine found in blood (<100p,moI/L) must be measured in the presence of oxidizable interfering substances, sometimes present at higher concentrations than the analyte. Special electroactive layers within the biosensor have been proposed to remove redox-active interfering substances. Since the useful life of the creatinine biosensor based on these reactions requires three enzymes to retain activity, reusable commercial biosensors for creatinine based on this measurement principle typically suffer from a short useful life of only a few days. 

A macrohomogeneous electrode can be established in different dimensional structures and the resulting models, which can present analytical or numerical solutions, could relate the global performance of the cathodic or anodic layer to unmeasurable local distributions of reactants, electrode potential, and reaction rates. These unmeasurable local distributions define a penetration depth of the active zone and suggest an optimum range of current density and electroactive layer thickness with minimal performance losses and highest electroactive effectiveness. In addition, the macrohomogeneous theory can be extended to include concepts of percolation theory. 

This section concerns heterogeneous electron transfer reactions coupled with homogeneous chemical reactions in which either the electroactive species A or the product of the electron transfer B participate as reactants. Perturbations of electrochemical responses of different techniques evoked by these reactions enable the elucidation of the mechaism and the evaluation of the kinetic parameters of the chemical steps. Chemical reactions that are indicated in the electrochemical way occur in the thin layer reaction layer) adjacent to the electrode surface only. This is illustrated in Fig. 1 where the concentration dependence of the product B on the distance from the electrode plane (with and without follow-up chemical reaction) is plotted. It must be stressed that the kinetics and the electrode mechanism are affected not only by the nature of the electroactive as well as electroinactive species including the type of the solvent, but also by the electrode material and substances adsorbed on the electrode surface. 

The theory of rate measurements by electrochemistry is mathematically quite difficult, although the experimental measurements are straightforward. The techniques are widely applicable, because conditions can be found for which most compounds are electroactive. However, many questionable kinetic results have been reported, and some of these may be a consequence of unsuitable approximations in applying theory. Another consideration is that these methods are mainly applicable to aqueous solutions at high ionic strengths and that the reactions being observed are not bulk phase reactions but are taking place in a layer of molecular dimensions near the electrode surface. Despite such limitations, useful kinetic results have been obtained. 

The background (residual) current that flows in the absence of the electroactive species of interest is composed of contributions due to double-layer charging process and redox reactions of impurities, as well as of the solvent, electrolyte, or electrode. 

The observed complexity of the Se(IV) electrochemistry due to adsorption layers, formation of surface compounds, coupled chemical reactions, lack of electroactivity of reduction products, and other interrelated factors has been discussed extensively. Zuman and Somer [31] have provided a thorough literature-based review with almost 170 references on the complex polarographic and voltammetric behavior of Se(-i-IV) (selenous acid), including the acid-base properties, salt and complex formation, chemical reduction and reaction with organic and inorganic... 

If the electrolyte components can react chemically, it often occurs that, in the absence of current flow, they are in chemical equilibrium, while their formation or consumption during the electrode process results in a chemical reaction leading to renewal of equilibrium. Electroactive substances mostly enter the charge transfer reaction when they approach the electrode to a distance roughly equal to that of the outer Helmholtz plane (Section 5.3.1). It is, however, sometimes necessary that they first be adsorbed. Similarly, adsorption of the products of the electrode reaction affects the electrode reaction and often retards it. Sometimes, the electroinactive components of the solution are also adsorbed, leading to a change in the structure of the electrical double layer which makes the approach of the electroactive substances to the electrode easier or more difficult. Electroactive substances can also be formed through surface reactions of the adsorbed substances. Crystallization processes can also play a role in processes connected with the formation of the solid phase, e.g. in the cathodic deposition of metals. 

Figure 5.37 depicts the stationary distribution of the electroactive substance (the reaction layer) for kc—> oo. The thickness of the reaction layer is defined in an analogous way as the effective diffusion layer thickness (Fig. 2.12). It equals the distance [i of the intersection of the tangent drawn to the concentration curve in the point x = 0 with the line c = cA/K,...

The existence of a maximum thickness beyond which the performance deteriorates is due to the concerted impact of oxygen and proton transport limitations. Considered separately, each of these limitations would only serve to define a minimum thickness below which performance worsens due to an insufficient electroactive surface. The thickness of the effective layer, in which current density is predominantly generated, is given by the reaction penetration depth ... 

Zhao et al. prepared magnetite (FesO nanoparticles modified with electroactive Prussian Blue [44]. These modified NPs were drop-cast onto glassy-carbon electrodes. They observed the redox processes commonly observed for PB (similar to that seen in Figure 4.8), and also demonstrated that the Prussian White material produced by PB reduction at 0.2 V served as an electrocatalyst for Fi202 reduction. They also prepared LbL films in which PB NPs and glucose oxidase were alternated between PD DA layers [99]. These were demonstrated to act as electrocatalysts for Fi202 reduction. Based on the ability to sense the product of the enzymatic reaction, these structures were shown to act as glucose sensors. 

A detennination of t, the transition time, involves an E-t relation such as that in Fig. 8.7. The value of T is given by Sand s equation (7.190), which contains c0, the reactant concentrations in solution, so that, if X and n are known, c0 can be obtained. This chronopotentiometiy is (or was) an analytical technique, but it is no longer much used for the original purpose of detennining the concentration of an electroactive reactant in solution because there are more accurate methods. Thus, if the time is short, there may be confusion with double-layer charging tune if the time is too long, irrelevant side reactions may interfere. The method can, however, be used to determine... 

Supporting Electrolyte The electrolyte that is added to the electrolytic solution to make it electrically conductive as well as to control the reaction conditions. The supporting electrolyte also works to eliminate the migration current that flows in its absence. It may be a salt, an acid, a base or a pH buffer, which is difficult to oxidize or to reduce. It is used in concentrations between 0.05 and 1 M, which is much higher than that of electroactive species (usually 10-5 to 10 2 M). The supporting electrolyte sometimes has a great influence on the electrode reaction, changing the potential window of the solution, the double layer structure, or react-... 

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