3-Hydroxy-2-naphthoic hydrazide as a probe for fluorescent detection of cyanide and aluminium ions in organic and aquo-organic media and its application in food and pharmaceutical samples.

The commercially available fluorophore, 3-hydroxy-2-naphthoic hydrazide (RS2), has rationally been selected for the study, which displays a rapid fluorescent response and high sensitivity for CN- and Al(III) ions in neat DMSO and H2O-DMSO (1:1 v/v) media. The addition of CN- to RS2 triggers an enhancement in fluorescence at 505 nm (green fluorescence), while the addition of Al(III) increases the fluorescence of the probe with a blue-shift of emission maximum by 25 nm (bluish-green fluorescence). The probe's action was investigated by 1H NMR titrations that indicate deprotonation of OH and NH moieties by these ions. 27Al NMR of RS2-Al(III) complex suggests an octahedral geometry for the complex. The sensitivity of the fluorescent-based assays in aq. DMSO medium, 0.8 µM for CN- and 1.9 µM for Al(III) ions are far below the limits in the World Health Organization guidelines for drinking water. RS2 detects Al(III) by the chelation-enhanced fluorescence (CHEF) mechanism. Besides, RS2 was successfully applied to detect CN- and Al(III) ions in food materials and pharmaceutical samples, respectively.

2-Aminophenols based Schiff bases as fluorescent probes for selective detection of cyanide and aluminium ions - Effect of substituents.

Three Schiff base based probes are designed and synthesized by facile condensation of a commercially available fluorophore 2,6-diformyl-4-tert-butylphenol with 4-nitro-2-aminophenol (KP1), 2-aminophenol (KP2) and 4-tert-butyl-2-aminophenol (KP3) and are characterized using various spectral techniques. The probes exhibit high selectivity and sensitivity CN- and Al(III) ions with striking fluorescent signaling responses in H2O-DMSO (1:1, v/v) medium. The mechanism of the probes' detection of CN involves deprotonation of the phenolic OH group(s) followed by nucleophilic addition of CN- onto imine C-atom. The 1H NMR chemical shifts of the OH protons of 2-aminophenol moiety exhibits a linear correlation with the Hammett's substituent constants (σp), yielding a positive reaction constant (ρ). In KP1, the electron-withdrawing nitro substituent polarizes the imine bond to a larger extent than in KP2, resulting in easier addition of CN- to imine C-atom. The electron releasing tert-Bu substituent in KP3 produces the opposite effect leading to a sluggish addition reaction. The separately populated HOMO and LUMO in KP1 and a relatively lower HOMO-LUMO energy gap indicate substantial intramolecular charge transfer (ICT) character, leading to weak fluorescence emission. The large reduction in HOMO-LUMO energy gap, in KP1, upon addition of cyanide is responsible for the greater enhancement in fluorescence with blue shift upon addition of CN-. Formation of tetrahedral Probe-Al(III) complex prevents the isomerization of imine bond, leading to enhancement in fluorescence and contribution from chelation enhanced fluorescence. As these probes show very low limits of detection of these ions, their practical utility has also been demonstrated.