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Indirect Approach for CN– Detection: Development of “Naked-Eye” Hg2+-Induced Turn-Off Fluorescence and Turn-On Cyanide Sensing by the Hg2+ Displacement Approach

Shaily,, Kumar, Ajay, Ahmed, Naseem
Industrial & engineering chemistry process design and development 2017 v.56 no.22 pp. 6358-6368
color, colorimetry, cyanides, fluorescence, fluorometry, mercury, pH, process design, stoichiometry
The coumarin-thiol-based colorimetric and fluorimetric chemosensor (E)-7-(diethylamino)-3-((2-mercaptophenylimino)methyl)-2H-chromen-2-one 1a was designed, synthesized, and evaluated for anion detection through the metal displacement mechanism. Chemosensor 1a exhibited a high sensitivity and selectivity to Hg²⁺ ion detection in HEPES-buffered solution [20 mM, 3:7 CH₃CN/H₂O (v/v), pH 7.0] with a 1:1 binding stoichiometry and a 5.549 × 10⁵ M–¹ binding constant. The fluorescence intensity of chemosensor 1a was selectively quenched by Hg²⁺, and an obvious color change from yellowish green to orange was observed by the naked eye. Moreover, a solution of the in situ generated 1a + Hg²⁺ complex displayed a high selectivity to CN– through the Hg²⁺ displacement approach. The gradual addition of CN– to the resultant solution of the 1a + Hg²⁺ complex induced its fluorescence recovery with a detection limit of 31 nM. This reversibility in fluorescence suggests the promising applicability of chemosensor 1a as an “on–off–on” naked-eye sensor.