Potentiometric ion-selective sensors

The principle of pH electrode sensing mechanisms which are based on glass or polymer membranes is well investigated and understood. Common to all potentiometric ion selective sensors, a pH sensitive membrane is the key component for a sensing mechanism. When the pH sensitive membrane separates the internal standard solution with a constant pH from the test solution, the potential difference E across the membrane is determined by the Nemst equation ... 

Ciosek et al. (2005) used potentiometric ion-selective sensors for discriminating different brands of mineral waters and apple juices. PC A and ANN classification were used as pattern recognition tools, with a test set validation (Ciosek et al., 2004b). In a subsequent study, the same research group performed the discrimination of five orange juice brands, with the same instrumental device. A variable selection was performed, by means of strategies based on PCA and PLS-DA scores. The validation was correctly performed with an external test set. 

Chemically sensitized field effect transistor in which the effect of the interaction between the analyte and the active coating is transformed into a change of the source-drain current. The interactions between the analyte and the coating are, from the chemical point of view, similar to those found in potentiometric ion-selective sensors. 

Bandodkar, A.J., Hung, V.W.S., Jia, W., Valdes-Ramlrez, G., Windmiller, J.R., Martinez, A.G., Ramirez, J., Chan, G., Kerman, K., Wang, J., 2013. Tattoo-based potentiometric ion-selective sensors for epidermal pH monitoring. Analyst 138,123-128. 

Ion-selective sensors for chloride are commercially available [103]. Both fundamental and practical information concerning the theory, design, and operation of chloride-selective electrodes is available from a recent textbook [57]. Sensor membranes for potentiometric chloride detection have been formed from Ag2 S (as ion... 

Electrochemical ion-selective sensors (ISSs), including potentiometric ion-selective electrodes (ISEs) and potentiometric or amperometric gas-selective sensors (GSSs), attracted the interest of clinical chemistry because they offer fast, reliable, inexpensive analytical results in service-free automated analyzers. In this way, the electrochemical sensors satisfy the present demands of central hospital laboratories and peripheral point-of-care medical service points, such as bedside, emergency or first-contact healthcare centers. 

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 ... 

Potentiometry—the measurement of electric potentials in electrochemical cells—is probably one of the oldest methods of chemical analysis still in wide use. The early, essentially qualitative, work of Luigi Galvani (1737-1798) and Count Alessandro Volta (1745-1827) had its first fruit in the work of J. Willard Gibbs (1839-1903) and Walther Nernst (1864-1941), who laid the foundations for the treatment of electrochemical equilibria and electrode potentials. The early analytical applications of potentiometry were essentially to detect the endpoints of titrations. More extensive use of direct potentiometric methods came after Haber developed the glass electrode for pH measurements in 1909. In recent years, several new classes of ion-selective sensors have been introduced, beginning with glass electrodes more or less selectively responsive to other univalent cations (Na, NH ", etc.). Now, solid-state crystalline electrodes for ions such as F , Ag", and sulfide, and liquid ion-exchange membrane electrodes responsive to many simple and complex ions—Ca , BF4", CIO "—provide the chemist with electrochemical probes responsive to a wide variety of ionic species. 

In general, any ion-selective potentiometric sensor can be used to monitor gases, provided that it is immersed in an electrolyte solution containing the ion sensed and whose activity changes on dissolution of the gas to be determined. Such a potentiometric cell, containing an indicating ion-selective sensor and a reference electrode immersed in an electrolyte, and... 

For the establishment of the receptor selectivity, different chemical interactions can be used. For example, the output of potentiometric sensors is strongly influenced by the equilibrium of the analyte with the sensitive layer of the chemosensor. Polymeric matrix membrane-based ion-selective electrodes are utilizing the concentration-dependent extraction of the analyte in the organic layer, while the analyte-dependent shift of potential of ion-selective sensors based on electrodes of the second kind can be described by the solubility product of the hardly soluble salt and the resulting Nemst equation of the electrochemical base reaction. Further equilibria can be predicated on ion exchanges, complexation, or adsorption effects. The interplay of analyte and receptor is determined by... 

Potentiometric ion-selective electrodes (ISEs) are one of the most important gronps of chemical sensors. The application of ISEs has evolved to a well-established rontine analytical technique in many fields, inclnding clinical and environmental analysis, physiology, and process control. The essential part of ISEs is the ion-selective membrane that is commonly placed between two aqueous phases, i.e the sample and inner solutions that contain an analyte ion. The membrane may be a glass, a crystalline solid, or a liquid (1). The potential difference across the membrane is measured with two reference electrodes positioned in the respective aqueous phases... 

Promethazine sensing devices based on MIPs include an MIP-based potentiometric sensor which was reported to be applicable in the concentration range of 5.0 X 10" - 1.0 X 10 M, with an LOD 1.0 X 10 M [409] and an MIP-modified carbon phase electrode with two linear response ranges of 4 x 10 -lx 10 M and 1 x 10 - 1 X 10" M and a detection limit of 2.8 x 10 M [381]. Propranolol detection has also been reported through MIP-based phosphorescent probes using tetrabromobisphenol A and diphenylmethane 4,4 -diisocyanate as functional monomers in tetrahydrofuran [380], and an MIP-based ion-selective sensor with a narrow linearity range of 10 -10" M [360]. 

Szigeti, Z., A. Malon, T. Vigassy, V. Csokai, A. Griin, K. Wygladacz, N. Ye et al. 2006. Novel potentiometric and optical silver ion-selective sensors with subnanomolar detection limits. Anal. Chim. Acta 572 1-10. 

An older general review by Stefan et al. [2] considers mathematical modeling for data processing (including a variety of chemometric methods such as linear and nonlinear partial least squares, fuzzy neural networks, and multivariate analysis of variance), designs for electrochemical sensor arrays as well as applications in environmental, food and clinical analysis. Arrays of potentiometric ion-selective electrodes, piezoelectric crystal sensors, and voltammetric biosensors, as well as the electronic nose gas-phase sensor arrays are reviewed. 

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. 

Sources of Error. pH electrodes are subject to fewer iaterfereaces and other types of error than most potentiometric ionic-activity sensors, ie, ion-selective electrodes (see Electro analytical techniques). However, pH electrodes must be used with an awareness of their particular response characteristics, as weU as the potential sources of error that may affect other components of the measurement system, especially the reference electrode. Several common causes of measurement problems are electrode iaterferences and/or fouling of the pH sensor, sample matrix effects, reference electrode iastabiHty, and improper caHbration of the measurement system (12). 

The sensor is an ammonium ion-selective electrode surrounded by a gel impregnated with the enzyme mease (Figme 6-11) (22). The generated ammonium ions are detected after 30-60 s to reach a steady-state potential. Alternately, the changes in the proton concentration can be probed with glass pH or other pH-sensitive electrodes. As expected for potentiometric probes, the potential is a linear function of the logarithm of the urea concentration in the sample solution. 

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. 

The disadvantages described above in terms of the irreversibility of the polyion response stimulated further research efforts in the area of polyion-selective sensors. Recently, a new detection technique was proposed utilizing electrochemically controlled, reversible ion extraction into polymeric membranes in an alternating galvanostatic/potentiostatic mode [51]. The solvent polymeric membrane of this novel class of sensors contained a highly lipophilic electrolyte and, therefore, did not possess ion exchange properties in contrast to potentiometric polyion electrodes. Indeed, the process of ion extraction was here induced electrochemically by applying a constant current pulse. 

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