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The water uptake of plasticized poly(vinyl chloride) solid-contact calcium-selective electrodes

机译：增塑聚氯乙烯固体接触式钙选择电极的吸水率

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摘要

A hyphenated method based on FTIR-ATR and electrochemical impedance spectroscopy has been applied to simultaneously measure the water uptake, changes in the bulk resistance and potential of plasticized poly(vinyl chloride) (PVC) based Ca~(2+)-selective coated-wire (CaCWE) and solid-contact electrodes (CaSCISEs). Most of the water uptake of the ion-selective membranes (ISMs) used in both electrode types took place within the first 9h in 10~(-3)M CaCl_2 showing good correlation with the stabilization of the individual electrode potentials. The bulk resistance of the ISMs of the CaCWEs and the CaSCISEs with poly(3-octylthiophene) (POT) as the solid-contact (SC) increased most during the first 18h in 10~(-3)M CaCl_2. The increase in the resistance was found to be related to the exchange of K~+ for Ca~(2+) in the ISM and the formation of the Ca~(2+)-ionophore (ETH 5234) complex having a lower diffusivity than the free K~+ ions. In contrary to previously published results on silicone rubber based SCISEs and poly(methyl methacrylate):poly(n-decyl methacrylate) membranes containing POT, the plasticized PVC-based CaSCISEs with POT as the SC had a higher water uptake than the CaCWEs. The CaSCISEs had a detection limit of 2×10~(-8)M Ca~(2+) and a good potential reproducibility of 148.9±1.0mV in 10~(-4)M CaCl~2.
机译：已采用基于FTIR-ATR和电化学阻抗谱的联用方法同时测量吸水率，增塑聚氯乙烯（PVC）基Ca〜（2 +）-选择性涂层-导线（CaCWE）和固体接触电极（CaSCISE）。两种电极类型中使用的离子选择膜（ISMs）的大部分吸水发生在10〜（-3）M CaCl_2中的前9h内，显示出与各个电极电位的稳定性良好的相关性。在10〜（-3）M CaCl_2的前18h内，以聚（3-辛基噻吩）（POT）为固体接触（SC）的CaCWE和CaSCISE的ISM的整体电阻最大。发现电阻的增加与ISM中Ca〜（2+）的K〜+交换以及形成扩散度低于其的Ca〜（2 +）-离子载体（ETH 5234）络合物有关游离的K〜+离子。与先前发表的关于基于硅橡胶的SCISE和包含POT的聚（甲基丙烯酸甲酯）：聚（甲基丙烯酸正癸酯）膜的结果相反，以POT作为SC的增塑PVC基CaSCISE具有比CaCWE更高的吸水率。 CaSCISEs的检出限为2×10〜（-8）M Ca〜（2+），在10〜（-4）M CaCl〜2中具有良好的电位重现性148.9±1.0mV。

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