Electrodes potentiometric sensors

Amperometry is a voltammetric method in which a constant potential is applied to the electrode and the resulting current is measured. Amperometry is most often used in the construction of chemical sensors that, as with potentiometric sensors, are used for the quantitative analysis of single analytes. One important example, for instance, is the Clark O2 electrode, which responds to the concentration of dissolved O2 in solutions such as blood and water. 

More recendy, two different types of nonglass pH electrodes have been described which have shown excellent pH-response behavior. In the neutral-carrier, ion-selective electrode type of potentiometric sensor, synthetic organic ionophores, selective for hydrogen ions, are immobilized in polymeric membranes (see Membrane technology) (9). These membranes are then used in more-or-less classical glass pH electrode configurations. 

By using different membranes, it is possible to obtain potentiometric sensors for gases such as sulfur dioxide or nitrogen dioxide. Such sensors employ similar (acid-base) or other equilibrium processes. These devices, along with their equilibrium processes and internal electrodes, are summarized in Table 6-2. Membrane coverage... 

Potentiometric instrnments are nsed most often when analyzing harmful contaminants in the air at production sites or in cities. Electrodes, whose potential is, as a rule, a linear fnnction of the logarithm of concentration of the substance to be determined (by Nemst s law), are the sensing elements in snch instruments. Most potentiometric sensors are highly selective. 

Ion-selective electrodes are membrane systems used as potentiometric sensors for various ions. In contrast to ion-exchanger membranes, they contain a compact (homogeneous or heterogeneous) membrane with either fixed (solid or glassy) or mobile (liquid) ion-exchanger sites. 

A. Ivanov, G. Evtugyn, L.V. Lukachova, E.E. Karyakina, HC. Budnikov, S.G. Kiseleva, A.V. Orlov, G.P. Karpacheva, and A.A. Karyakin, Cholinesterase potentiometric sensor based on graphite screen-printed electrode modified with processed polyaniline. IEEE Sensors J. 3, 333-340 (2003). 

Detection of Li+ in artificial serum with a voltammetric Li-selective electrode in a flowthrough system was demonstrated [64], Lithium salts such as lithium carbonate have been extensively used for treatment of manic depressive and hyperthyroidism disorders. The therapeutic range of Li concentration is generally accepted to be 0.5-1.5mM in blood serum. The authors used normal pulse voltammetry in which a stripping potential was applied between pulses in order to renew the membrane surface and expel all of the extracted ions from the membrane, similar to galvanostatically controlled potentiometric sensors described above. Unfortunately, the insufficient selectivity... 

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. 

Reference electrodes provide a standard for the electrochemical measurements. For potentiometric sensors, an accurate and stable reference electrode that acts as a halfcell in the measurement circuit is critical to providing a stable reference potential and for measuring the change in potential difference across the pH sensitive membrane as the pH concentration changes. This is especially important in clinical applications such as pH measurements in the blood, heart, and brain, where the relevant physiological pH range is restricted to a very small range, usually less than one unit. 

Besides, potentiometric sensors with ion-selective ionophores in modified poly(vinyl chloride) (PVC) have been used to detect analytes from human serum [128], Cellular respiration and acidification due to the activity of the cells has been measured with CMOS ISFETS [129], Some potentiometric methods employ gas-sensing electrodes for NH3 (for deaminase reactions) and C02 (for decarboxylase reactions). Ion-selective electrodes have also been used to quantitate penicillin, since the penicillinase reaction may be mediated with I or GST. 

Composite potentiometric sensors involve systems based on ion-selective electrodes separated from the test solution by another membrane that either selectively separates a certain component of the analyte or modifies this component by a suitable reaction. This group includes gas probes, enzyme electrodes and other biosensors. Gas probes are discussed in this section and chapter 8 is devoted to potentiometric biosensors. 

L. C. Clark first suggested in 1956 that the test solution be separated from an amperometric oxygen sensor by a hydrophobic porous membrane, permeable only for gases (for a review of the Clark electrode see [88]). The first potentiometric sensor of this type was the Severinghaus CO2 electrode [150], with a glass electrode placed in a dilute solution of sodium hydrogenocarbonate as the internal sensor (see fig. 4.10). As an equilibrium pressure of CO2, corresponding to the CO2 concentration in the test solution, is established in the... 

Enzyme electrodes with amperometric indication have certain advantages over potentiometric sensors, chiefly because the product of the enzymic reaction is consumed at the electrode and thus the response time is decreased. For this reason, the potentiometric glucose enzyme electrode, based on reaction (8.1) followed by the reaction of HjO, with iodide ions sensed by an iodide ISE [39], has not found practical use. 

Figure 1.11 — Average number of papers on (bio)chemical sensors published annually, based on data from Janata s biannual review. E electrochemical sensors ISEs ion-selective electrodes P potentiometric sensors A amperometric sensors C conductimetric sensors O optical sensors M mass sensors T thermal sensors. (Adapted from [23] with permission of the American Chemical Society).

One other difference lies in the type of detection technique used, which dictates the flow-cell design. Thus, a distinction can be made in this respect between optical (absorptiometric, luminemetric) sensors, which make measurements of the bulk solution where the flow-cell is immersed, and electroanalytical (amperometric, potentiometric) sensors, where measurements are based on phenomena occurring at the electrode-solution interface. 

The classic potentiometric enzyme electrode is a combination of an ion-selective electrode-based sensor and an immobilized (insolubilized) enzyme. Few of the many enzyme electrodes based on potentiometric ion- and gas-selective membrane electrode transducers have been included in commercially available instruments for routine measurements of biomolecules in complex samples such as blood, urine or bioreactor media. The main practical limitation of potentiometric enzyme electrodes for this purpose is their poor selectivity, which does not arise from the biocatalytic reaction, but from the response of the base ion or gas transducer to endogenous ionic and gaseous species in the sample. 

Several classical ion-selective electrodes (some of which are commercially available) have been incorporated into continuous systems via suitable flow-cells. In fact, Lima et al. [112] used a tubular homogeneous crystal-membrane (AgjS or AgCl) sensor for the determination of sulphide and chloride in natural and waste waters. However, the search for new active materials providing higher selectivity and/or lower detection limits continues. Thus, Smyth et al [113] tested the suitability of a potentiometric sensor based on calix[4]arene compounds for use in flow injection systems. They found two neutral carriers, viz. methyl-j3-rerr-butylcalix[4]aryl acetate and... 

Some ISEs containing no inner reference solution, as well as tubular potentiometric sensors, has been used in conjunction with FI systems for the determination of vitamins B, and Bg in pharmaceutical preparations. The membranes used for this purpose were prepared from the vitamin tetra(2-chlorophenyl)borate dissolved in o-nitrophenyloctyl ether and immobilized in PVC. The intrinsic behaviour of the tubular electrodes was assessed by using a low-dispersion single-channel FI manifold and compared with those of conventionally-shaped electrodes using the same membrane the results provided by both were very similar [119]. 

In the method proposed by van Staden for the determination of three halides, these are separated in a short colunm packed with a strongly basic ion-exchange resin (Dowex i-X8) that is placed in an FI manifold. A laboratory-made tubular silver/silver halide ion-selective electrode is used as a potentiometric sensor. Van Staden compared the response capabilities of the halide-selective electrodes to a wide concentration range (20-5000 pg/mL) of individual and mixed halide solutions in the presence and absence of the ion-exchange column. By careful selection of appropriate concentrations of the potassixun nitrate carrier/eluent stream to satisfy the requirements of both the ion-exchange column and the halide-selective electrode, he succeeded in separating and determining chloride, bromide and iodide in mixed halide solutions with a detection limit of 5 /xg/mL [130]. 

In potentiometric sensors, an electrical potential between the working electrode and a reference electrode is measured at zero current conditions in a solution containing ions that exchange with the surface. The first potentiometric MIP sensor was prepared in 1992 by Vinokurov (1992). The substrate-selective polyaniline electrode was electrosynthesized with polypyrrole, polyaniline, and aniline-p-aminophenol copolymers. The development of an MIP-based potentiometric sensor was reported in 1995 by Hutchins and Bachas (1995). This potentiometric sensor has high selectivity for nitrite with a low detection limit of (2 + l)x 10 M (Fig. 15.10). 

Recent research in the field of polymer membrane ion-selective electrodes [389-391], has revealed that their se-lectivities [392-396] and limits of detections [394-397] could be improved by several orders of magnitude. The review of Bakker and Pretsch [398] summarized recent progress in the development and application of potentiometric sensors with low detection limit in the range 10-8-10-11 M. 

Potentiometric Sensors Inthe field of ion-selective electrodes, considerable progress has been achieved in the last few years. By buffering the primary ions concentration on a low level in the internal solution, ionic fluxes in the membrane are affected [424-426]. Thus, primary ion leakage into sample solution is hindered, resulting in a tremendous shift of detection limits to lower values for Pb +-selective electrodes, the detection limit up to 10 M level has been achieved for internal solution electrodes [424, 427] and below 10 M for all-solid-state electrodes with conducting polymer solid... 

Many simple ions such as K+.Na+.Cl, and Ca are normally kept within a narrow range of concentrations in the body, and they must be monitored during critical care. Potentiometric sensors for ion, also called ion-selective electrodes or ISEs, utilize a membrane that is primarily semipermeable to one ionic species. The ionic species is used to generate a voltage that generally obeys the Nemst equation [cf. Section 3.1.3.2 and Eq. (3.24)]... 

A potentiometric sensor for the determination of hydroxyzine in tablets and biological fluids has been reported by Javanbakht et al. [121]. This is probably the first carbon paste electrode described in the literature based on MIPs and potentiometric detection. The polymer was prepared with a very general composition, MAA as functional monomer, EDMA as the cross linker, and chloroform as porogen. Response range was found to be 0.01-100 mM, with a moderate response time (SOTO min). The method was applied to the analysis of hydroxyzine in tablets, spiked human serum, and human urine. 

Another interface that needs to be mentioned in the context of polarized interfaces is the interface between the insulator and the electrolyte. It has been proposed as a means for realization of adsorption-based potentiometric sensors using Teflon, polyethylene, and other hydrophobic polymers of low dielectric constant Z>2, which can serve as the substrates for immobilized charged biomolecules. This type of interface happens also to be the largest area interface on this planet the interface between air (insulator) and sea water (electrolyte). This interface behaves differently from the one found in a typical metal-electrolyte electrode. When an ion approaches such an interface from an aqueous solution (dielectric constant Di) an image charge is formed in the insulator. In other words, the interface acts as an electrostatic mirror. The two charges repel each other, due to the low dielectric constant (Williams, 1975). This repulsion is called the Born repulsion H, and it is given by (5.10). 

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