Baatout Zeineb, Jebnouni Achref, Sakly Nawfel, Teka Safa, Mohamed Nuzaiha, Osman Sayda, Soury Raoudha, El Oudi Mabrouka, Alsaqri Salman Hamdan, Jaballah Nejmeddine Smida, Majdoub Mustapha
Laboratory of Interfaces and Advanced Materials, Faculty of Sciences, University of Monastir, Monastir 5000, Tunisia.
Medical Surgical Nursing Department, College of Nursing, University of Hail, Hail 55476, Saudi Arabia.
Polymers (Basel). 2025 Jul 15;17(14):1937. doi: 10.3390/polym17141937.
This work represents the first use of a phosphonium salt-functionalized β-Cyclodextrin polymer (β-CDP) as a highly selective sensing membrane for monitoring the safety of drinking water against perchlorate ions (ClO) using electrochemical impedance spectroscopy (EIS). Structural confirmation via H NMR, C NMR, P NMR, and FT-IR spectroscopies combined with AFM and contact angle measurements demonstrate how the enhanced solubility of modified cyclodextrin improves thin film quality. The innovation lies in the synergistic combination of two detection mechanisms: the "Host-Guest" inclusion in the cyclodextrin cavity and anionic exchange between the bromide ions of the phosphonium groups and perchlorate anions. Under optimized functionalization conditions, EIS reveals high sensitivity and selectivity, achieving a record-low detection limit (LOD) of ~10 M and a wide linear range of detection (10 M-10 M). Sensing mechanisms at the functionalized transducer interfaces are examined through numerical fitting of Cole-Cole impedance spectra via a single relaxation equivalent circuit. Real water sample analysis confirms the sensor's practical applicability, with recoveries between 96.9% and 109.8% and RSDs of 2.4-4.8%. Finally, a comparative study with reported membrane sensors shows that β-CDP offers superior performance, wider range, higher sensitivity, lower LOD, and simpler synthesis.
这项工作首次使用了一种鏻盐功能化的β-环糊精聚合物（β-CDP）作为高选择性传感膜，通过电化学阻抗谱（EIS）监测饮用水中高氯酸根离子（ClO）的安全性。通过核磁共振氢谱（H NMR）、核磁共振碳谱（C NMR）、核磁共振磷谱（P NMR）和傅里叶变换红外光谱（FT-IR）结合原子力显微镜（AFM）和接触角测量进行结构确认，证明了改性环糊精溶解度的提高如何改善薄膜质量。创新之处在于两种检测机制的协同结合：环糊精腔内的“主-客”包合作用以及鏻基团的溴离子与高氯酸根阴离子之间的阴离子交换。在优化的功能化条件下，EIS显示出高灵敏度和选择性，实现了创纪录的低检测限（LOD）约为10 M以及宽检测线性范围（10 M - 10 M）。通过单弛豫等效电路对科尔-科尔阻抗谱进行数值拟合，研究了功能化传感器界面处的传感机制。实际水样分析证实了该传感器的实际适用性，回收率在96.9%至109.8%之间，相对标准偏差（RSD）为2.4 - 4.8%。最后，与已报道的膜传感器进行的对比研究表明，β-CDP具有卓越的性能、更宽的范围、更高的灵敏度、更低的检测限以及更简单的合成方法。
