Supersensitive Detection of Anions in Pure Organic and Aqueous Media by Amino Acid Conjugated Ellman's Reagent.

Abstract

The last few decades witnessed a remarkable advancement in the field of molecular anion receptors. A variety of anion binding motifs have been discovered, and large number of designer molecular anion receptors with high selectivity are being reported. However, anion detection in an aqueous medium is still a formidable challenge as evident from only a miniscule of synthetic systems available in the literature. We, herein, report 5,5'-dithio-bis(2-nitrobenzoic acid) (Ellman's reagent) appended with amino acids as supersensitive anion sensors that can detect F- and H2PO4- ions in both aqueous as well as organic media. Interestingly, the sensors showed a dual response to anions, viz., chromogenic response in organic medium and electrochemical response in aqueous solutions. Various spectroscopic techniques such as UV-vis and 1H NMR are used to investigate the binding studies in acetonitrile, whereas electrochemical methods such as cyclic voltammetry (CV) and differential pulse voltammetry (DPV) are employed to explore the anion binding in water. The host-guest complex stoichiometry and binding constants are calculated using the BindFit software. The geometry of host-guest complex has been optimized by the density functional theory (DFT) method. These molecules are versatile sensors since these function in both water and acetonitrile with extremely low limit of detection (LOD) up to 0.07 fM and limit of quantification (LOQ) up to 0.23 fM. To our knowledge, the present system is the first example of a sensor that can detect the lowest concentration of anions in water quantitatively. The minimalistic design strategy presented here opens up the innumerable possibilities for designing dual anion sensors in a one fell swoop.