Phosphonium Salt-Functionalized β-Cyclodextrin Film for Ultrasensitive and Selective Electrochemical Impedance Spectroscopy Detection of Perchlorate in Drinking Water.

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 (ClO4-) using electrochemical impedance spectroscopy (EIS). Structural confirmation via 1H NMR, 13C NMR, 31P 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 ~10-12 M and a wide linear range of detection (10-11 M-10-4 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.