Electrochemical sensors voltammetric sensor

Special electrochemical sensors that operate on the principle of the voltammetric cell have been developed. The area of chemically modified solid electrodes (CMSEs) is a rapidly growing field, giving rise to the development of new electroanalytical methods with increased selectivity and sensitivity for the determination of a wide variety of analytes [490]. CMSEs are typically used to preconcentrate the electroactive target analyte(s) from the solution. The use of polymer coatings showing electrocatalytic activity to modify electrode surfaces constitutes an interesting approach to fabricate sensing surfaces useful for analytical purposes [491]. 

With the introduction of modern electronics, inexpensive computers, and new materials there is a resurgence of voltammetric techniques in various branches of science as evident in hundreds of new publications. Now, voltammetry can be performed with a nano-electrode for the detection of single molecular events [1], similar electrodes can be used to monitor the activity of neurotransmitter in a single living cell in subnanoliter volume electrochemical cell [2], measurement of fast electron transfer kinetics, trace metal analysis, etc. Voltammetric sensors are now commonplace in gas sensors (home CO sensor), biomedical sensors (blood glucose meter), and detectors for liquid chromatography. Voltammetric sensors appear to be an ideal candidate for miniaturization and mass production. This is evident in the development of lab-on-chip... 

The intercalation of polycyclic aromatic compounds into duplex DNA structures was used to develop nucleic acid-based electrochemical sensors.66 For example, the bis-ferrocene-tethered naphthalene diimide (16) was used as a redox-active intercalator to probe DNA hybridization.67 The thiolated probe was assembled on a Au electrode, and the formation of the duplex DNA with the complementary analyte nucleic acid was probed by the intercalation of (16) into the double-stranded nucleic acid structure and by following the voltammetric response of the ferrocene units (Fig. 12.17a). The method enabled the analysis of the target DNA with a sensitivity that corresponded to ca. 1 x 10-20mol. 

Contrary to potentiometric methods that operate under null current conditions, other electrochemical methods impose an external energy source on the sample to induce chemical reactions that would not otherwise spontaneously occur. It is thus possible to measure all sorts of ions and organic compounds that can either be reduced or oxidised electrochemically. Polarography, the best known of voltammetric methods, is still a competitive technique for certain determinations, even though it is outclassed in its present form. It is sometimes an alternative to atomic absorption methods. A second group of methods, such as coulometry, is based on constant current. Electrochemical sensors and their use as chromatographic detectors open new areas of application for this arsenal of techniques. 

Special electrochemical sensors that operate on the principle of the voltammetric cell have been developed to measure substrates such as oxygen and glucose. In the Clark oxygen sensor, a 1.5 V potential difference is applied between a silver anode and a platinum cathode which are both in contact with a KCl solution separated from the sample by a membrane permeable to oxygen (Fig. 19.6). 

Chapters 1 to 5 deal with ionophore-based potentiometric sensors or ion-selective electrodes (ISEs). Chapters 6 to 11 cover voltammetric sensors and biosensors and their various applications. The third section (Chapter 12) is dedicated to gas analysis. Chapters 13 to 17 deal with enzyme based sensors. Chapters 18 to 22 are dedicated to immuno-sensors and genosensors. Chapters 23 to 29 cover thick and thin film based sensors and the final section (Chapters 30 to 38) is focused on novel trends in electrochemical sensor technologies based on electronic tongues, micro and nanotechnologies, nanomaterials, etc. 

Our research group recently approached the problem of radical determination starting from the determination of oxygen free radicals, in particular superoxide radical, and assembling several new kinds of electrochemical sensors and biosensors suitable for this purpose [21-24]. Firstly, a voltammetric system based on the detection of reduced cytochrome c this system was also applied to develop a... 

A self-contained system, which integrated the remote carbon-fiber electrochemical sensor with a voltammetric analyzer and a wireless communication system, was described by Fu et al. [21]. The mobile remote underwater systems were applied for field measurements of explosive residues in marine environments. 

Ozoemena K, Nyokong T (2002) Voltammetric characterization of the self-assembled mono-layer (SAM) of octa butyl thiophthalocyaninatoiron(II) a potential electrochemical sensor. Electrochim Acta 47(25) 4035-4043... 

In the third part of the book areas in which there are important applications of electrochemistry are described. Chapters 13 and 14 look at potentiometric and amperometric/voltammetric sensors respectively, focusing particularly on recent developments such as new electrode materials and miniaturization. Electrochemistry in industry, which produces many materials used directly or indirectly in everyday life, as well as batteries, is described in Chapter 15. The electrochemical phenomenon... 

An electrochemical sensor is generally an electrochemical cell containing two electrodes, an anode and a cathode, and an electrolyte. Electrochemical sensors in general are classified, based on the mode of its operation, and they are conductivity sensors potentiometric sensors, and voltammetric sensors. Amperometric sensors can be considered as a special type of voltammetric sensors. The fundamentals of these sensors operational principles are described exceptionally well in several excellent electro-analytical books. In this entry, only the essential features are included. 

A voltammetric sensor is characterized by the current and potential relationship of an electrochemical cell. Voltammetric sensor utilizes the concentration effect on the current-potential relationship. This relationship depends on the rate by which the reactant (commonly the sensing species) is brought to the electrode surface (mass transfer) and the kinetics of the faradaic or charge transfer reaction at the electrode surface. In an electrochemical reaction, the interdependence between the reaction kinetics and the mass transfer processes establishes the concentration of the sensing species at the electrode surface relative to its bulk concentration and, hence, the rate of the faradaic process. This provides a basis for the operation of the voltammetric sensor. 

Potentiometric probes are the oldest forms of electrochemical sensors. They can conveniently be used for studying many interesting chemical systems not accessible to voltammetric techniques. In particular, alkali and alkaline earth metal ion concentrations, of importance in biological systems,... 

Potentiometric ion-selective electrodes are passive probes, which in contrast to voltammetric sensors do not convert the analyte in the sample. The response of an ISE depends linearly on the logarithm of the activity (concentration) of a potential determining ion (primary ion) in the presence of other ions. The schematic layout of a complete potentiometric cell including an ion-selective electrode is shown in Figure 2. The electrochemical notation of the cell assembly is given as ... 

Voltammetric measurements are not simply restricted to analytical laboratories. The applications of these methods are more numerous than is at first obvious. A large number of analytical instruments, whether portable or not, intended to make precise measurements of substrates present in gas mixtures, vapours or solutions are equipped with electrochemical sensors. These devices operate on the principle of the 2- or 3- electrode cell enclosed in the sensor housing. 

Hart J and Wring S 1994 Screen-printed voltammetric and amperometric sensors for decentralized testing Electroanalysis 6 617-24 Wang J 1991 Modified electrodes for electrochemical sensors Electroanalysis 3 255-9... 

Electrochemical sensors can be classified according to their mode of operation, e.g. conductivity/capacitance sensors, potentiometric sensors, and voltammetric sensors. Amperometric sensors can be considered a specific type of voltammetric sensor. The general principles of electrochemical sensors have been extensively described in other chapters of this volume or elsewhere. This chapter will focus on the fabrication of electrochemical sensors of micro or miniature size. 

A reference electrode is used in both two- and three-electrode electrochemical sensors. The three-electrode configuration is used mainly for voltammetric or amperometric modes of sensing. The first design considerations for an electrochemical sensor should include the size, geometric shape, relative location, and material used for the electrode elements. A description of each of these design parameters is given below. 

Micromachined and microfabricated electrochemical sensors have been used either per se, or as part of a sensor system, in many practical applications. This includes various biosensors and chemical sensors reported in research literature. An example of a practical electrochemical sensor is the yttria-stabilized zirconium dioxide potentiometric oxygen sensor used for fuel-air control in the automotive industry. Thick-film metallization is used in the manufacture of this sensor. Even though the sensor is not microsize, this solid electrolyte oxygen sensor has proven to be reliable in a relatively hostile environment. It is reasonable to anticipate that a smaller sensor based on the same potentiometric or the voltammetric principle can be developed using advanced microfabrication and micromachining techniques. 

In this chapter, we discuss voltammetric methods and associated electrochemical sensors, including chemically modified electrodes. Voltammetric techniques use a microelectrode for microelectrolysis. Here, the potential is scanned and a dilute solution of the analyte produces, at a given potential, a limiting current (microampere range or less), which is proportional to the analyte concentration. Am-perometry is the application of voltammetry at a fixed potential to follow, via the current, changes in concentration of a given species, for example, during a titration. Amperometric measurements also form the bases of electrochemical sensors. 

Amperometry is the application of voltammetric measurements at a fixed potential to detect changes in currents as a function of concentration of electroactive species. Electrochemical sensors can be designed based on amperometric measurement. An important example is the oxygen electrode. 

Another electrochemical sensor for heavy metal detection in liquids has been fabricated by Miu et A three-electrode cell on silicon and voltammetric techniques for... 

The discussion is restricted to immunoassays based on voltammetric electroanalysis, involving the application of a potential to an electrochemical cell and measurement of the current resulting from an oxidation or reduction at the electrode surface. Immunoassays based on potentiomet-ric electrochemical techniques are also under active development. Additionally, electrochemical sensors in which immunological reactions provide the selectivity are being developed for a variety of purposes Proceedings, 1983 Czaban, 1985). 

Voltammetric sensors based on chemically modified electrodes (conducting polymers, phthalocyanine complexes) with improved cross-selectivity were developed for the discrimination of bitter solutions [50], The performance and capability were tested by using model solutions of bitterness such as magnesium chloride, quinine, and four phenolic compounds responsible for bitterness in olive oils. The sensors gave electrochemical responses when exposed to the solutions. A multichannel taste sensor was constructed using the sensors with the best stabilities and cross-selectivities and PCA of the signals allowed distinct discrimination of the solutions. 

The current-potential relationship of an electrochemical ceU provides the basis for voltammetric sensors. Amperometric sensors, that are also based on the current-potential relationship of the electrochemical cell, can be considered a subclass of voltammetric sensors. In amperometric sensors, a fixed potential is applied to the electrochemical cell, and a corresponding current, due to a reduction or oxidation reaction, is then obtained. This current can be used to quantify the species involved in the reaction. The key consideration of an amperometric sensor is that it operates at a fixed potential. However, a voltammetric sensor can operate in other modes such as linear cyclic voltammetric modes. Consequently, the respective current potential response for each mode will be different. 

The objective of this review has been to show how supramolecular chemistry has made, and is continuing to make, an important contribution to the area of electrochemical sensing. From an applications point of view, future developments will continue to be directed toward recognition and read out at a surface, so that robust voltammetric sensors that are viable alternatives to other sensors (e.g., biosensors) can be produced. However, fundamental studies are required to further our understanding of how to maximize substrate selectivity, while maintaining an effective electrochemical response to... 

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