Ion Transfer Voltammetry in Polyurethane Thin Films Based on Functionalised Cationic [6]Helicenes for Carbonate Detection,Electroanalysis

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Ion Transfer Voltammetry in Polyurethane Thin Films Based on Functionalised Cationic [6]Helicenes for Carbonate Detection
Electroanalysis ( IF 2.7 ) Pub Date : 2018-03-08 , DOI: 10.1002/elan.201800080
Zdeňka Jarolímová ₁ , Johann Bosson ₂ , Geraldine M. Labrador ₂ , Jérôme Lacour ₂ , Eric Bakker ₁

Affiliation

We explore here molecular ion-to-electron redox probes based on cationic diaza, azaoxa, and dioxa [6]helicenes and their derivatives as ion-to-electron transducers for the electrochemical detection of anions. These cationic [6]helicenes exhibit reversible and reproducible oxidation/reduction behavior and facilitate the anion transfer of Gaussian shape into polymeric thin layer sensing films. Films composed of bis(2-ethylhexyl) sebacate (DOS), polyurethane (PU), tetrakis(4-chlorophenyl)borate tetradodecylammonium salt (ETH 500) and [6]helicenes were interrogated by cyclic voltammetry. Even though the peak separation of 90 mV is larger than ideal, the observed peak width at half maximum of 130 mV and the linear relationship between current and scan rate are near theoretical values, confirming a surface confined process. A Nernstian shift of the peaks with increasing carbonate concentration is obtained in the presence of carbonate ionophore VII incorporated into the thin sensing film. The concentration of carbonate was determined in an unfiltered sample of the Arve river (flowing from Chamonix to Geneva) and compared to a reference method (automatic titrator with potentiometric detection). The results suggested that cationic diaza [6]helicene functionalized with two bromine atoms is an attractive molecular ion-to-electron transducer for anion-selective electrodes.

中文翻译：

基于官能化阳离子 [6] 螺旋的聚氨酯薄膜中的离子转移伏安法用于碳酸盐检测

我们在此探索基于阳离子重氮、氮杂和二氧杂环己烷 [6] 螺旋烯的分子离子-电子氧化还原探针及其衍生物作为用于阴离子电化学检测的离子-电子传感器。这些阳离子 [6] 螺旋烯表现出可逆和可重复的氧化/还原行为，并促进高斯形状的阴离子转移到聚合物薄层传感膜中。由双（2-乙基己基）癸二酸酯（DOS）、聚氨酯（PU）、四（4-氯苯基）硼酸十四烷基铵盐（ETH 500）和[6]螺旋烯组成的薄膜通过循环伏安法进行了研究。尽管 90 mV 的峰间距大于理想值，但观察到的 130 mV 半峰宽和电流与扫描速率之间的线性关系接近理论值，证实了表面受限过程。在碳酸盐离子载体 VII 并入薄传感膜的情况下，随着碳酸盐浓度的增加，峰的能斯脱位移是获得的。碳酸盐浓度是在未过滤的 Arve 河（从夏蒙尼流向日内瓦）样品中测定的，并与参考方法（带电位检测的自动滴定仪）进行比较。结果表明，用两个溴原子官能化的阳离子二氮杂 [6] 螺旋烯是一种用于阴离子选择性电极的有吸引力的分子离子-电子转换器。碳酸盐浓度是在未过滤的 Arve 河（从夏蒙尼流向日内瓦）样品中测定的，并与参考方法（带电位检测的自动滴定仪）进行比较。结果表明，用两个溴原子官能化的阳离子二氮杂 [6] 螺旋烯是一种用于阴离子选择性电极的有吸引力的分子离子-电子转换器。碳酸盐浓度是在未过滤的 Arve 河（从夏蒙尼流向日内瓦）样品中测定的，并与参考方法（带电位检测的自动滴定仪）进行比较。结果表明，用两个溴原子官能化的阳离子二氮杂 [6] 螺旋烯是一种用于阴离子选择性电极的有吸引力的分子离子-电子转换器。

更新日期：2018-03-08

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