A simple fluorophore-imine ensemble for colorimetric and fluorescent detection of CN- and HS- in aqueous solution.

Colorimetric and fluorescent detection of cyanide and hydrogen sulfide ions has been effected using a simple organic probe in H2O:DMSO (20:80, v/v) medium. The probe exhibits a colour change from pale-yellow to red upon addition of these analytes under normal light and fluorescent change from green to red under UV lamp. Other competitive ions show no observable colour or fluorescence change. The binding constants of cyanide and hydrogen sulfide ions with the probe determined using fluorescence titration data are found to be 2.1 × 104 and 1.6 × 104 M-1, respectively. The probe fluorimetrically detects the analytes in a wide pH range (4-10). 1H and 13C NMR studies suggest that the probe senses cyanide ion through deprotonation and nucleophilic addition mechanism and hydrogen sulfide ion via deprotonation mechanism. Detection limits of cyanide and hydrogen sulfide are determined to be 0.15 and 1 µM, respectively. The practical utility of the probe has been demonstrated by same dual mode detection of cyanide in food materials like bitter almond, cassava flour and sprouting potato.

Rational design and application of a fluorogenic chemodosimeter for selective detection of cyanide in an aqueous solution via excimer formation.

A new quinone-benzothiazole imine based chemodosimeter (R) was rationally designed, synthesized and characterized using NMR and mass spectral techniques. The receptor colorimetrically senses cyanide in aq. HEPES buffer: DMF (2:8 v/v) solution with an instantaneous colour change from yellow to bluish green. An enhancement of fluorescence intensity at 429 nm with excimer formation is also observed after addition of cyanide to the receptor, which is accompanied with a colour change from yellow to blue under UV lamp. Nucleophilic addition of cyanide to imine C-atom inhibits intra-molecular charge transfer (ICT) transition, which is responsible for the excimer formation. This chemical reaction is confirmed by 1H NMR titration. The receptor binds with two equivalents of cyanide with a binding constant of 5.55 × 104 M-1. The limit of detection (LOD) of cyanide by the receptor is found to be as low as 69 nM, which is much lower than the acceptable limit of cyanide in drinking water as set by the WHO (1.9 µM). Electrochemical studies support the termination of ICT transition upon addition of cyanide ion. Theoretical studies substantiate experimental findings and excimer formation. The receptor fluorometrically detects cyanide present in tap water and food materials such as cassava flour, almond and potato.

Selective chromogenic detection of cyanide in aqueous solution - Spectral, electrochemical and theoretical studies.

A bisimidazole ensemble (R) possessing naphthoquinone as signaling unit is synthesized and characterized using 1H and 13C NMR and LC-MS spectral techniques. Anion sensing behaviour of the receptor has been investigated using electronic and fluorescence spectral techniques. The receptor exhibits a striking colour change from yellow to brown selectively with cyanide in aqueous HEPES buffer-DMSO (1:1 v/v) medium with a detection limit of 1 µM. Job's continuous variation method suggests that the stoichiometry of the interaction is 1:2 (R:CN-). The binding constant for receptor-cyanide complex was found to be 8.7 × 102 M-1. The mechanism of detection of cyanide occurs via deprotonation of imidazole N-H protons, which is well supported by electrochemical study. DFT based theoretical calculations shows that the energy gap between HOMO and LUMO decreases from 3.3086 (in R) to 1.7799 eV (in R + CN-), which is responsible for the red-shift observed in the UV-Vis spectrum of R upon addition of cyanide ions. The present quinone-bisimidazole based receptor shows few advantages over similar bisimidazoles reported elsewhere.