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and 1991, respectively. He has been working in the field of chemical sensors since 1970. Further topics of his interest are spectroscopic databases, automatic spectra interpretation, and modeling of structure−property relationships. He has published over 180 papers and 7 books. Current activities in the fields of chemical sensors and computer-aided analytical chemistry are documented on the web page http://www/ceac.ethz.ch/pretsch/. His e-mail address is pretsch@ org.chem.ethz.ch.

Selectivities of solvent polymeric membrane ion-selective electrodes (ISEs) are quantitatively related to equilibria at the interface between the sample and the electrode membrane. However, only correctly determined selectivity coefficients allow accurate predictions of ISE responses to real-world samples. Moreover, they are also required for the optimization of ionophore structures and membrane compositions. Best suited for such purposes are potentiometric selectivity coefficients as defined already in the 1960s. This paper briefly reviews the basic relationships and focuses on possible biases in the determination of selectivity coefficients. The traditional methods to determine selectivity coefficients (separate solution method, fixed interference method) are still the same as those originally proposed by IUPAC in 1976. However, several precautions are needed to obtain meaningful data. For example, errors arise when the response to a weakly interfering ion is also influenced by the primary ion leaching from the membrane. Wrong selectivity coefficients may be also obtained when the interfering agent is highly preferred and the electrode shows counterion interference. Recent advances show how such pitfalls can be avoided. A detailed recipe to determine correct potentiometric selectivity coefficients unaffected by such biases is presented.

A new procedure for the determination of selectivity coefficients of neutral carrier-based cation-selective electrodes is established that avoids exposure to the preferred ion prior to the measurement of discriminated ions. The method is, therefore, unbiased by the presence of preferred ions in the membrane that otherwise could mask the response to discriminated ion solutions. It is generally applicable as long as a series of considerations are met and can only be applied once for a given membrane. Careful studies with a series of sodium-, silver-, and calcium-selective electrodes reveal that Nernstian response slopes can now be obtained for even highly discriminated cations. Specifically, a 1,3-bridged calix-[4]arene derivative as introduced by Yamamoto and Shinkai indeed yields an extraordinary sodium selectivity of log K Na,K pot

The influence of ionic sites on the behavior of charged carrierbased ion-selective liquid membrane electrodes is described by theory and experiments for cationand for anion-selective electrodes. The cation exchanger potassium tetrakis [3,5-bis-(trifluoromethyl)phenyl]borate proved to be a beneficial additive for nitrite-selective electrodes. On the other hand, the anion exchanger tridodecylmethylammonium chloride improved the potentiometric properties of cation-selective electrodes. By the incorporation of a defined amount of these sites, the selectivity was enhanced, the emf functions became theoretical, the electrode resistance was lowered, and the long-term stability improved. The optimal molar ratio of additive to ionophore was in the range of 0.3-0.6 for the ionophores studied. The theory and the experiments show clearly that ionic sites should be used not only with neutral ionophores but also with charged ones. ISE membranes without ionic additives should be avoided, since otherwise inherent ionic impurities could have a decisive influence on the response characteristics.

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The potentiometric response mechanism of a previously reported polymer membrane-based electrode sensitive to the polyanion heparin is established. Based on transport and extraction studies, the heparin response is attributed to a nonequilibrium change in the phase boundary potential at the sample/membrane interface. While true equilibrium polyion response, obtained for low heparin concentrations only after very long equilibration times (> 20 h), yields the expected Nernstian response slope of < 1 mV/decade, the observed large and reproducible EMF response to clinically relevant heparin concentrations (approximately 10(-7) M) during typical measurement periods (2-5 min) is ascribed to a steady-state kinetic process defined by the flux of the polyion both to the surface and into the bulk of the polymer membrane. A model describing this nonequilibrium response is presented. With this model, the uniqueness of the polymer membrane composition (e.g., very low plasticizer content, strictly controlled cationic site concentration, etc.) required to achieve analytically useful heparin response becomes clear. Practical working conditions and limitations of the sensor are discussed. To support the generality of the steady-state model proposed, corresponding EMF response data for a newly developed membrane electrode sensitive to a polycationic protein (protamine) are also presented. It is shown that the protamine-responsive membrane electrode appears to operate via the exact same kinetic mechanism as the heparin sensing system.

The influence of the composition of the internal electrolyte solution on the response of Pb 2+ -and Ca 2+ -selective membrane electrodes is investigated. It is shown that the lower detection limit is improved by generating, in the membrane, ionic gradients that lead to a flux of primary ions toward the inner reference electrolyte solution. If the ion flux is too strong, it may cause analyte depletion at the membrane surface and, as a consequence, apparent super-Nernstian response. Such electrodes are not adequate to measure low analyte activities but can be used to determine unbiased selectivity factors. The results are interpreted in terms of a steady-state model, introduced in the companion paper, that describes the influence of concentration gradients generated by ion-exchange and coextraction processes on both sides of the membrane.