Recognition of Inorganic Anions by Hydrogen Bonding Ionophores and Their Use for Ion-Selective Potentiometry

(1)为了从理论上支持用于实际样品的新型离子选择电极的发展，对表面上解释“非能斯特”平衡响应的模型进行了扩展。它现在还考虑了由一对阳离子和一对阴离子控制的反应。以前的工作只考虑了具有相同电荷符号的两个离子的响应。(2)作为模型的应用，我们研究了基于卟啉的氟离子选择电极的响应。这些电极的异常响应是多年未被理解的，可以用初级离子和次级离子络合物的不同化学计量比来解释。(3)利用明显的“非能斯特”响应模型，测定了基于带正电荷的离子载体的钙离子选择电极的热力学参数。这些参数被用来合理地解释这种ISE在长期实验中的实验寿命和选择性变化。建立了解释这些选择性变化的定量模型。(4)作为对ISES理论的进一步贡献，提出了第一个基于带电离子载体和附加离子中心的ISES选择性的通用模型。它允许合理地优化这些ISE的选择性。

(1) To support the development of new ion-selective electrodes for real-life samples from a thereotical side, the model explaining apparently "non-Nernstian" equilibrium responses was extended. It now also takes into account responses governed by a pair of a cation and an anion. Previous work had only taken into account responses governed by two ions of the same charge sign.(2) As an application of the model for apparently "non-Nernstian" responses, the responses of porphyrin-based fluoride ISEs were investigated. The unusual responses of those electrodes, which had not been understood for many years, could be explained by different stoichiometries of the complexes of the primary and the secondary ion.(3) Taking advantage of the model for apparently "non-Nernstian" responses, thermodynamic parameters of Ca2+ selective electrodes based on an ionophore with a positive charge were determined. These parameters were used to rationalize the experimental lifetime and selectivity changes of this ISE in long-term experiments. A quantitative model to explain these selectivity changes was developed.(4) As a further contribution to the theory of ISEs, the first general model explaining the selectivity of ISEs based on charged ionophores and added ionic sites was presented. It allows to rationally optimize the selectivity of these ISEs.