Other Microelectrodes

They do present a long-time better approximation, but it is in Laplace-transformed form. 

Coen and coworkers [167, 177, 180] have presented solutions to the diffusion-limited current at a band electrode in the form of integral equations these must then be evaluated numerically, so this might be regarded as simulation. 

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The analysis of the EC and CE mechanisms under steady-state conditions at other microelectrode geometries is much more complex. In the case of microdiscs,... 

Of course, in order to vary the mass transport of the reactant to the electrode surface, the radius of the electrode must be varied, and this unplies the need for microelectrodes of different sizes. Spherical electrodes are difficult to constnict, and therefore other geometries are ohen employed. Microdiscs are conunonly used in the laboratory, as diey are easily constnicted by sealing very fine wires into glass epoxy resins, cutting... 

The formation of a PbO coating on Pb when it is anodically polarised in Cl is achieved more readily by alloying lead with silver or other metals, or by incorporating inert conducting microelectrodes in the Pb surface. 

Microelectrodes exhibit several other attractive and important properties that have expanded the possibilities of electrochemistry ... 

Other similar cyclic structures may present quite unexpected behaviour. Let us give the example of 46, where X is Cl or Br. Such structures are very easily reduced44 (polished platinum microelectrodes are preferred owing to the reaction of mercury with C—X linkages), and the presence of an anion radical of some stability can be demonstrated in the... 

Recently, there has been a growth of interest in the development of in vitro methods for measuring toxic effects of chemicals on the central nervous system. One approach has been to conduct electrophysiological measurements on slices of the hippocampus and other brain tissues (Noraberg 2004, Kohling et al. 2005). An example of this approach is the extracellular recording of evoked potentials from neocortical slices of rodents and humans (Kohling et al. 2005). This method, which employs a three-dimensional microelectrode array, can demonstrate a loss of evoked potential after treatment of brain tissue with the neurotoxin trimethyltin. Apart from the potential of in vitro methods such as this as biomarkers, there is considerable interest in the use of them as alternative methods in the risk assessment of chemicals, a point that will be returned to in Section 16.8. 

Another important property of the outer membranes of nerve and muscle cells is their susceptibility to excitation under the effect of electric action. Excitation can be brought about, for example, by an external electric current pulse. Pulses can be applied to the membrane with the aid of two microelectrodes, one residing in the extracellular fluid and the other introduced through the membrane into the cytoplasm. 

Conventional colloid chemistry and elaitrochemistry have always been clo ly related with each other, the keywords electrophoresis, double layer theory, and specific adsorption describing typical asp ts of this relationship. In more ro nt times, new aspects have arisen which again bring colloid chemistry into contact with modem developments in electrcolloidal particles as catalysts for electron transfer reactions and as photocatalysts. In fact, the similarity between the reactions that occur on colloidal particles and on compact electrodes has often been emphasized by calling the small particles microelectrodes . 

Figure 4 illustrates that our present knowledge about the dependence of the standard potential of very small silver microelectrodes on the agglomeration number is rather fragmentary. Even less is known about this dependence for other metals. The experiments of Fig. 5 prove that the rate of an electrochemical reaction in which a small microelectrode is involved, may strongly depend on the size of the microelectrode. 

The main classes of plasticizers for polymeric ISEs are defined by now and comprise lipophilic esters and ethers [90], The regular plasticizer content in polymeric membranes is up to 66% and its influence on the membrane properties cannot be neglected. Compatibility with the membrane polymer is an obvious prerequisite, but other plasticizer parameters must be taken into account, with polarity and lipophilicity as the most important ones. The nature of the plasticizer influences sensor selectivity and detection limits, but often the reasons are not straightforward. The specific solvation of ions by the plasticizer may influence the apparent ion-ionophore complex formation constants, as these may vary in different matrices. Ion-pair formation constants also depend on the solvent polarity, but in polymeric membranes such correlations are rather qualitative. Insufficient plasticizer lipophilicity may cause its leaching, which is especially undesired for in-vivo measurements, for microelectrodes and sensors working under flow conditions. Extension of plasticizer alkyl chains in order to enhance lipophilicity is only a partial problem solution, as it may lead to membrane component incompatibility. The concept of plasticizer-free membranes with active compounds, covalently attached to the polymer, has been intensively studied in recent years [91]. 

An inner filling solution and internal reference electrode are used in macro ISEs due to a very good stability of the potential at the inner membrane-solution interface in such a setup (see Fig. 4.4). However, the presence of a solution inside a sensor could be a serious limitation for development of microelectrodes and may be undesired for a variety of other reasons, including ionic fluxes in the membrane and limited temperature range of sensor operation. There are several requirements for such an inner contact. First of all, a reversible change of electricity carriers ions-electrons must take place at the membrane-substrate interface. The potential of the electrochemical reaction, ensuring this transfer, has to be constant, stable, and must not depend on the sample composition. At last, the substrate must not influence the membrane analytical performance. 

Although a few amperometric pH sensors are reported [32], most pH electrodes are potentiometric sensors. Among various potentiometric pH sensors, conventional glass pH electrodes are widely used and the pH value measured using a glass electrode is often considered as a gold standard in the development and calibration of other novel pH sensors in vivo and in vitro [33], Other pH electrodes, such as metal/metal oxide and ISFETs have received more and more attention in recent years due to their robustness, fast response, all-solid format and capability for miniaturization. Potentiometric microelectrodes for pH measurements will be the focus of this chapter. 

Some earlier developments and applications of various implantable pH sensors or measurement systems have been reported [128, 129, 130, 131]. However, reliable pH sensors for long-term implantations are still not available, and widespread clinical usage of implantable pH sensors has not been reached. Similar to other implantable sensors, the development of implantable pH microelectrodes, either fully implanted in the body or needle type sensors applied through the skin (percutaneous), has faced serious obstacles including sensor stability deterioration, corrosion, and adverse body reactions [48, 132, 133], Among them, encapsulation to prevent corrosion represents a major challenge for the implantable sensor devices [51]. Failure of encapsulation can cause corrosion damage on internal components, substrate materials, and electrical contacts [48], The dissolution of very thin pH sensitive layers will also limit the stability and lifetime of implantable micro pH sensors. 

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