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- Title
Electrofluorochromic Detection of Cyanide Anions Using a Nanoporous Polymer Electrode and the Detection Mechanism.
- Authors
Ding, Guoqiang; Lin, TingTing; Zhou, Rui; Dong, Yuliang; Xu, Jianwei; Lu, Xuehong
- Abstract
An electrofluorochromic (EFC) conjugated copolymer ( PEFC) containing carbazole and benzothiadiazole (BTD) moieties is synthesized through Suzuki coupling followed by electrochemical polymerization, resulting in a nanoporous EFC polymer electrode. The electrode exhibits high sensitivity and selectivity in the EFC detection of cyanide anions (CN−) in largely aqueous electrolyte (67 vol % water) because electrochemical oxidation of PEFC leads to significant fluorescence quenching, and the presence of different concentrations (1 to 100 μ M) of CN− in the electrolyte can weaken the oxidative quenching to substantially different extents. Although PEFC is hydrophobic in the neutral state, it is converted to radical cation/dication states upon oxidation, rendering the PEFC some hydrophilicity. Moreover, its nanoporous morphology provides a large surface area and short diffusion distance, facilitating the movement of CN− in the electrolyte into the PEFC film to interact with receptors. Density functional theory calculations show that the noncovalent interaction between electron-deficient BTD and nucleophilic CN− is energy favorable in the oxidized states in both aqueous and organic media, suggesting that the specific π−-π+ interaction plays the main role in the CN− detection.
- Subjects
ANIONS; IONS; POLYMER electrodes; CYANIDES; FLUOROPHORES
- Publication
Chemistry - A European Journal, 2014, Vol 20, Issue 41, p13226
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201403133