Highly selective fluorescent sensing of fenitrothion using per-6-amino-β-cyclodextrin:Eu(III) complex

A unique, efficient, highly sensitive and selective fluorescent chemosensor for fenitrothion has been reported for the first time using per-6-amino-β-cyclodextrin:Eu(III) complex. Among the various pesticides, the sensitivity response is found to be in the order, fenitrothion ⋙ quinalphos > methylparathion > parathion > methylparaoxon > paraoxon > fenchlorphos > profenofos > malathion. A detection limit as low as 1 × 10−12 M for fenitrothion sensing is realized with a 2.4% relative standard deviation (RSD) of three consecutive runs. The per-6-amino-β-cyclodextrin:Eu(III):pesticide complexes and their sensing mechanism are evidenced from emission, NMR, FT-IR, binding constant measurement, Job's plot, ICD spectra, ESI-MS, lifetime measurements and molecular modeling studies. The proposed sensing is a consequence of Absorption Energy Transfer Emission (AETE) process as a result of better encapsulation of fenitrothion inside the cavity of per-6-amino-β-cyclodextrin:Eu(III) complex. The remarkable sensitivity and selectivity of fenitrothion compared to other OPs, is attributed to a more deeper binding and tighter fit of fenitrothion inside the CD cavity, which is evident from binding constant values and molecular modeling studies. This tighter fit ensures the replacement of two coordinating water molecules on Eu(III) ion, which may have contributed to the more selective sensing of fenitrothion.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► A highly selective and sensitive fluorescent chemosensor for fenitrothion is reported for the first time using per-6-amino-β-cyclodextrin:Eu(III) complex. ► The sensitivity response is in the order, fenitrothion ⋙ quinalphos > methylparathion > parathion > methylparaoxon > paraoxon > fenchlorphos > profenofos > malathion. ► A detection limit as low as 1 × 10−12 M for fenitrothion sensing is realized with a 2.4% relative standard deviation (RSD) of three consecutive runs. ► Absorption Energy Transfer Emission (AETE) is responsible for the observed sensing.