Amperometric chemical

Berney, H. (2004) Impedometric and amperometric chemical and biological sensors. In V.M. 

This type of diffusion/reaction mechanism has been treated semi-analyti-cally by Albery et al. [42, 44, 45], under steady-state conditions and its applications to amperometric chemical sensors has been described by Lyons et al. [46]. In both models, only diffusion and reaction within a boundary layer is considered, while the effect of concentration polarisation in the solution is neglected. Thus, to apply the model to an experimental system it is necessary to be able to accurately determine the concentration of substrate at the polymer/solution interface. Assuming that the system is in the steady state, the use of the rotating disc electrode allows simple determination of the substrate concentration at the interface from the bulk concentration and the experimentally determined flux using [47]... 

The catalytic detection of ammonium ions has not been extensively investigated in contrast with the large variety of potentiometric and amperometric chemical sensors and optical sensors described in the literature [236], Similarly, the detection of ammonia in air has merited diflierent approaches in the field of chemical sensors. Screen-printed electrodes modified with Meldola s Blue and covered with a polycarbonate membrane constitute the basis of the catalytic detection of NHj. The measurement is based on the electrocatalytic reduction of NADH upon addition of glutamate dehydrogenase to a stirred solution containing NADH, 2-oxoglutarate and ammonium ions. The rate of current decrease (nA s ), measured at 50 mV, correlates to the concentration of ammonium ions in the sample. Recoveries of ammonium ions in spiked pond and tap waters at the level of 0.1 ppm are close to 100%, which demonstrates the feasibility of this assay for the detection of ammonium ions in waters [237],... 

Faradaic processes of electrode reactions, which are principle mechanism of obtaining analytical signal in amperometric sensors, significantly depend on working electrode material and state of its surface. The common working electrode materials include noble and seminoble metals, solid oxides of various elements and different kinds of carbon materials including carbon nanostructures. They are employed in conventional voltammetric measurements with various modes of electrode polarization, as amperometric chemical sensors, as well as for construction of amperometric biosensors. 

Lyons, M.E.G., Lyons, C.H., Michas, A., and Bartlett, P.N. 1992. Amperometric chemical sensors using microheterogeneous systems. Analyst 117, 1271-1280. 

In Chapter 2 we discuss the use of electroactive polymer films in the important area of electrocatalysis. The material presented is also relevant for the quantitative description of the operation of amperometric chemical and biological sensors. In the latter context, the efficient operation of the amperometric sensor depends largely on how readily the polymer layer enhances the rate of substrate oxidation or reduction. This of course is related to electrocatalytic properties of the polymer film. 

E-tongues have reportedly been used to obtain data for sourness, bitterness, and astringency for foodstuffs such as beers, wines, and teas. This involved detecting sensory attributes of bitter, sweet, sour, fruity, caramel, artificial, burnt, intensity, and body using potentiometric/amperometric chemical sensors along with the same pattern recognition techniques described above for the e-nose technology. 

Instead of detecting them amperometrically, chemical species diffusing from the surface in generation-collection experiments can be detected potentiometrically with an ion-selective electrode (Fig. 18B). Potentiomet-ric SECM has been used successfully to image dissolution across ionic crystal surfaces, such as Na+ dissolution from NaCl surfaces. Potentiometric detection has the advantage that the concentration of diffusing species is not perturbed, i.e., molecules or ions are not electro-chemically oxidized or reduced to some other charge state. 

SECM is a scaiming-probe teclmiqiie introduced by Bard et aJ in 1989 [49, and M ] based on previous studies by the same group on in situ STM [ ] and simultaneous work by Engstrom et aJ [53 and M], who were the first to show that an amperometric microelectrode could be used as a local probe to map the concentration profile of a larger active electrode. SECM may be envisaged as a chemical microscope based on faradic current changes as a microelectrode is moved across a surface of a sample. It has proved iisefiil for... 

One important application of amperometry is in the construction of chemical sensors. One of the first amperometric sensors to be developed was for dissolved O2 in blood, which was developed in 1956 by L. C. Clark. The design of the amperometric sensor is shown in Figure 11.38 and is similar to potentiometric membrane electrodes. A gas-permeable membrane is stretched across the end of the sensor and is separated from the working and counter electrodes by a thin solution of KCl. The working electrode is a Pt disk cathode, and an Ag ring anode is the... 

In the area of consumer products, amperometric glucose sensors hold high potential. Industrially, process monitors for the manufacture of consumer chemicals are under development. However, replacement of defective reference electrodes, which in a laboratory environment may be trivial, may be prohibitively difficult m vivo or in an industrial process environment. 

The main techniques employed in quantitative analysis are based upon (a) the quantitative performance of suitable chemical reactions and either measuring the amount of reagent needed to complete the reaction, or ascertaining the amount of reaction product obtained (b) appropriate electrical measurements (e.g. potentiometry) (c) the measurement of certain optical properties (e.g. absorption spectra). In some cases, a combination of optical or electrical measurements and quantitative chemical reaction (e.g. amperometric titration) may be used. 

In scanning electrochemical microscopy (SECM) a microelectrode probe (tip) is used to examine solid-liquid and liquid-liquid interfaces. SECM can provide information about the chemical nature, reactivity, and topography of phase boundaries. The earlier SECM experiments employed microdisk metal electrodes as amperometric probes [29]. This limited the applicability of the SECM to studies of processes involving electroactive (i.e., either oxidizable or reducible) species. One can apply SECM to studies of processes involving electroinactive species by using potentiometric tips [36]. However, potentio-metric tips are suitable only for collection mode measurements, whereas the amperometric feedback mode has been used for most quantitative SECM applications. 

The use of non-inert and chemically modified electrodes and other strategies for the detection of species that are difficult to analyze with the normal electrode materials have been reviewed.55 Photosensitization prior to amperometric detection is another tactic that has proved useful for the analysis of substances that are normally considered to be electrochemically inert.56 The use of pulsed amperometry has recently been reviewed.57... 

Nonspectroscopic detection schemes are generally based on ionisation (e.g. FID, PID, ECD, MS) or thermal, chemical and (electro)chemical effects (e.g. CL, FPD, ECD, coulometry, colorimetry). Thermal detectors generally exhibit a poor selectivity. Electrochemical detectors are based on the principles of capacitance (dielectric constant detector), resistance (conductivity detector), voltage (potentiometric detector) and current (coulometric, polarographic and amperometric detectors) [35]. 

A.A. Ciucu, C. Negulescu, and R.P. Baldwin, Detection of pesticides using an amperometric biosensor based on ferophthalocyanine chemically modified carbon paste electrode and immobilized bienzymatic system. Biosens. Bioelectron. 18, 303-310 (2003). 

Y.-M. Zhou, Z.-Y. Wu, G.-L. Shen, and R.-Q. Yu, An amperometric immunosensor based on Nafion-modified electrode for the determination of Schistosoma japonicum antibody. Sensors and Actuators, B Chemical 89, 292-298 (2003). 

FIGURE 6.11 Typical current—time responses of Fe-SOD/MPA-modified Au electrode toward 02 in 25 mM phosphate buffer (02-saturated, pH 7.5) containing 0.002 unit of XOD upon the addition of 50 nM xanthine at +300 (a) and —lOOmV (b). The arrows represent the addition of 10 j,M of Cu, Zn-SOD (a) and 580 units of catalase and 10 pM of Cu, Zn-SOD to the solution (b). The solution was stirred with a magnetic stirrer at 200rpm. Inset mechanism for the amperometric response of SODs/MPA-modified Au electrodes to 02, based on enzymatic catalytic oxidation (a) and reduction (b) of 02 (M metal ions of SODs). (Reprinted from [138], with permission from the American Chemical Society.)... 

J. Pei and X. Li, Amperometric glucose enzyme sensor prepared by immobilizing glucose oxidase on CuPtC16 chemically modified electrode. Electroanalysis 11, 1266-1272 (1999). 

R.M. Ianniello and A.M. Yacynych, Immobilized enzyme chemically modified electrode as an amperometric sensor. Anal. Chem. 53, 2090-2095 (1981). 

Agents for chemical bleaching rely on different types of peroxides. Potentiometric or amperometric biosensors that detect the highly specific and sensitive reaction of enzymes like katalases with their corresponding substrates can be used for on-line measurement [84]. The sensors can be manufactured with simple technologies at moderate cost, but their stability is not sufficient for integration in household appliances. 

A derived combined approach uses an amperometric biosensor [57] with a whole-cell (E. coli) sensing part, for industrial application (textile and tannery wastewaters) and detection of phenolic compounds, non-ionic surfactants and benzenesulphonate compounds. As in the previous studies, chemical analysis (SSPE followed by LC-MS) revealed the pollutants responsible for the observed toxicity. 

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