Calixarenes and cyclodextrins as off- and on-fluorescence probes for carbazole.

Abstract

Absorption and fluorescence spectra of the nitrogen polycyclic aromatic hydrocarbon carbazole (CZL) were analyzed with native cyclodextrins (CD;α,β,γ); derivatizedCD(hydroxypropyl-β-cyclodextrin,HPCD; methyl-β-cyclodextrin,MeCD) and p-sulfonated calixarenes (SCAn, with n = 6 and 8) macrocycles. The results showed a slight increase in the absorbance ofCZLwithCD, but the mixture ofCZLwithSCAshowed lower absorption than the sum of the individual spectra. Also, changes in fluorescence were observed by adding the macrocycles, quenching withSCA, and significant increases withCD. The higher fluorescence enhancement was withHPCDrationalized as a complex formation with 1:1 stoichiometry, with an average value for the association constant (K_A) of (12 ± 1) x 10²M^-1, and a quantum yield ratio between the complexedCZLand freeCZL(Φ^CZL-HPCD/Φ^CZL) of (1.56 ± 0.02) at neutral pH and 25.0 °C. These increases in fluorescence were used as an on-fluorescence switch to develop a supramolecular analytical method forCZLin aqueous samples. The best analytical parameters were inHPCD(LOD = 1.41 ± 0.01 ng mL^-1). The method was validated in aqueous samples of river and tap water with recoveries between 96%-104%. The proposed supramolecular method is quick, direct, selective and represents an alternative and low-cost analysis method.