Neutral carrier electrodes

2 Neutral Carrier Electrodes hi addition to charged liquid ion exchangers, liquid-membrane electrodes often rely on the use of complex-forming neutral carriers. Much effort has been devoted to the isolation or synthesis of compounds containing cavities of molecular dimensions. Such use of chemical recognition principles has made an enormous impact upon widespread acceptance of ISEs. The resulting neutral carriers can be natural macrocyclic molecules or synthetic crown 

FIGURE 5-11 The recognition process occurring at the TDMAC/PVC membrane/sample interface used for measurements of heparin. (Reproduced with permission from reference 26.) 

Many other cyclic and noncyclic organic carriers with remarkable ion selectivities have been used successfiilly as active hosts of various liquid membrane electrodes. These include the 14-crown-4-ether for lithium (30) 16-crown-5 derivatives for sodium bis-benzo-18-crown-6 ether for cesium the ionophore ETH 1001 [(R,R)-AA -bisd l-ethoxycarbonyl)undecyl-A,yVl-4,5-tctramcthyl-3,6-dioxaoctancdiamide] for calcium the natural macrocyclics nonactin and monensin for ammonia and sodium (31), respectively the ionophore ETH 1117 for magnesium calixarene derivatives for sodium (32) and macrocyclic thioethers for mercury and silver (33). 

1 Neutral Carrier Electrodes In addition to charged liquid ion 

A host of carriers, with a wide variety of ion selectivities, have been proposed for this task. Most of them have been used for the recognition of alkali and alkaline metal cations (e.g., clinically relevant electrolytes). A classical example is the cyclic depsipeptide valinomycin (Fig. 5.13), used as the basis for the widely used ISE for potassium ion (38). This doughnut-shaped molecule has an electron-rich pocket in the center into which potassium ions are selectively extracted. For example, the electrode exhibits a selectivity for K+ over Na+ of approximately 30,000. The basis for the selectivity seems to be the fit between the size of the potassium ion (radius 1.33 A) and the volume of the internal cavity of the macrocyclic molecule. The hydrophobic sidechains of valinomycin stretch into the lipophilic part of the membrane. In addition to its excellent selectivity, such an electrode is well behaved and has a wide working pH range. Strongly acidic media can be employed because the electrode is 18,000 times more responsive to K+ than to H+. A Nernstian response to potassium ion activities, with a slope of 59mV/pK+, is commonly observed 

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NADH, 121, 122, 180 Nafion coating, 118, 123, 124, 126 Nanometer electrodes, 116, 128 Nernst equation, 3, 15, 80 Nernstian behavior, 143 Nernst Planck equation, 5 Neuronal sensors, 188 Neurotransmitters, 40, 116, 124 Neutral carrier electrodes, 154 Nickel, 123... 

Potassium Wine, fish neutral carrier electrode... 

Sodium Soup stock, dried milk, infant formulations, canned food Na" neutral carrier electrode Na" glass electrode... 

Urea Milk Enzyme urease+ NH3 gas electrode Bacterial cell + NH neutral carrier electrode... 

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. 

Methods of sulfate determination used in common practice suffer from essential disadvantages (time consumption, laboriousness, low sensitivity, etc.). For this reason, creation of sulfate-selective electrode suitable for direct potentiometric determination of this ion, has been attempted for a long time. Nowadays, nearly a dozen of sulfate-selective electrodes based on charged or neutral carriers of different stmcture have been described. Flowever, no known receptors for sulfate ions are available commercially. 

The ammonium ion concentration may be monitored with a cation selective glass electrode or an neutral carrier based ion-selective electrode The pH may... 

However, there seems to be some drawback in the solubility or dispersibility of ion-sensing material in silicone rubber. This is mainly because silicone rubber does not contain a large quantity of plasticizer as the membrane solvent, in which neutral carriers can be dissolved easily, unlike in plasticized-PVC ion-sensing membranes. This issue is serious, especially with silicone-rubber membranes containing neutral carriers that show high crystallinity. Valinomycin, a typical ionophore, seems applicable to silicone-rubber-based K" -selec-tive electrodes [7,8,12-14]. Conventional crown-ether-based neutral carriers are also quite soluble in silicone rubber. 

FIG. 5 Potential response of silicone-rubber-membrane Na -selective electrodes based on neutral carriers (5) (O), (2) ( ), and bis(12-crown-4) (A)- (From Ref. 22.)... 

Selectivity coefficients values for K - and Na -ISFETs with the optimized ion-sen-sing membranes encapsulating valinomycin and bis(12-crown-4) are summarized in Fig. 9. The selectivity coefficient for with respect to Na in the K -ISFET is 2 x 10 " and that for Na with respect to in the Na -ISFET is 3 x 10. The selectivity coefficient values are similar to those for the ISFETs and ion-selective electrodes with the previous membrane materials containing the same neutral carriers. The high sensitivity and selectivity for the neutral-carrier-type ISFETs based on sol-gel-derived membranes can last for at least 3 weeks. 

The Na -selective electrodes based on silicone-rubber membranes modified chemically by (8) and (9), were also investigated for Na assay in control serum and urine [22]. The found values for the Na concentrations in both of the serum and urine samples are in good agreement with their corresponding actual values with a relative standard deviation of about 1%. These results suggest that the Na -selective electrodes based on silicone-rubber membranes modified chemically by calix[4]arene neutral carrier (8) are reliable on assay in human body fluid. 

Often, however, the PBP model can be used to describe the influence of key membrane parameters on the selectivity with a simplified equation after making certain assumptions. It is here given for cation-selective electrodes based on neutral carriers [30] ... 

R. Eugster, P.M. Gehrig, W.E. Morf, U.E. Spichiger, and W. Simon, Selectivity-modifying influence of anionic sites in neutral-carrier-based membrane electrodes. Anal. Chem. 63, 2285-2289 (1991). 

P.C. Meier, W.E. Morf, M. Laubli, and W. Simon, Evaluation of the optimum composition of neutral-carrier membrane electrodes with incorporated cation-exchanger sites. Anal. Chim. Acta 156,1—8 (1984). 

U. Schefer, D. Ammann, E. Pretsch, U. Oesch, and W. Simon, Neutral carrier based Ca-2+-selective electrode with detection limit in the sub-nanomolar range. Anal. Chem. 58, 2282-2285 (1986). 

J. Pick, K. Toth, E. Pungor, M. Vasak, and W. Simon, A potassium-selective silicone-rubber membrane electrode based on neutral carrier, Anal Chim Acta 64, 477-480 (1973). 

D. Ammann, R. Bessig, Z. Cimerman, U. Fiedler, M. Guggi, W. E. Morf, M. Oehme, H. Osswald, E. Pretsch and W. Simon, Synthetic neutral carriers for cations, in Ion and Enzyme Electrodes in Biology and Medicine (ed. M. Kessler, L. C. Clark, D. W. Lubbers, I. A. Silver and W. Simon), Urban Schwarzenberg, MUnchen (1976), p. 22. 

W. E. Morf and W. Simon, Ion-selective electrodes based on neutral carriers,... 

Neutral Carrier-Based Cation-Selective Electrodes... 

Thus, the system comprising membrane, solution 2 of constant composition (internal filling solution), and electrode 2 (internal reference electrode) constitutes an ion selective electrode. The electrically neutral carrier antibiotics of the valinomycin group and related lipid-soluble compounds can serve as the active components of highly selective liquid... 

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... 

A series of ion-selective membrane electrodes based on neutral carrier solvent polymeric membranes has been designed for the potentiometric determination of ion activities (for reviews see Refs. 52, 65). Systems with analytically relevant selectivities for Li+, Na+, K+, NHJ, Ca2+, and Ba2+, are available. In agreement with the treatment given in Sections III and IV, the ions preferred in potentiometric studies may be transported preferentially through the same membranes in electrodialytic experiments. So far, selective carrier transports have been realized for Li+, Na+, K+, and Ca2+. 

They are classified by membrane material into glass membrane electrodes, crystalline (or solid-state) membrane electrodes, and liquid membrane electrodes. Liquid membrane electrodes are further classified into liquid ion-exchange membrane electrodes and neutral carrier-based liquid membrane electrodes. Some examples are shown in Fig. 5.36 and Table 5.3. If the membrane is sensitive to ion i of charge Z and the activities of i in the sample and internal solutions are equal to (i) and a2(i), respectively, the membrane potential, m, which is developed across the membrane, is... 

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