Selective Turn-On Fluorescence Sensing of Cyanide Using the Pyridoxal Platform of a Ni(II) Complex

Cyanide is a very toxic pollutant to aquatic life and the environment. Analytical methods for the quantitative assay of cyanide, which are rapid, sensitive (low limit of detection), and cost-effective, are in great demand. Colorimetric and fluorometric methods are ideally suited for this purpose. In this report, we describe a Ni(II) complex containing a pyridoxal platform for the rapid and sensitive fluorometric estimation of cyanide. The square-planar Ni(II) complex, [Ni(L)(N₃)]·3H₂O, where the ligand LH = 4-[(2-dimethylamino-ethylimino)-methyl]-5-hydroxymtheyl-2-methyl-pyridin-3-ol, a Schiff base formed between pyridoxal and (2-dimethylamino)ethyl amine, was synthesized and characterized by various spectroscopic techniques as well as by single-crystal X-ray structure determination. The complex was found to selectively bind CN^- in the presence of other biologically important anions such as F^-, Cl^-, Br^-, I^-, OAc^-, S^2-, NO₃ ^-, PO₄ ^3-, SO₄ ^2-, and H₂PO₄ ^- in tris-HCl/NaCl buffer [pH = 7.4], and it can be monitored by fluorescence turn-on or by UV-visible spectroscopy. The binding constant of the complex with CN^- was estimated to be 2.046 × 10¹⁴ M^-2 and the limit of detection (LOD) was 9 nM, the LOD being considerably lower than the maximum permissible level of cyanide ions (1.9 μM) in drinking water, as recognized by the World Health Organization (WHO). The effects of pH and temperature on the sensing are also investigated. The Ni(II) complex is also found to bind to calf-thymus DNA very strongly, and the apparent binding constant (K _app) was determined to be 1.33 × 10⁷ M^-1 by the fluorescence quenching of the ethidium bromide-DNA adduct by the complex.