title: Selective anion sensing based on tetra-amide calix[6]arene derivatives in solution and immobilized on gold surfaces via self-assembled monolayers.
abstract: Two anion receptors, 1 and 2, based on the calix[6]crown-4 architecture were synthesized and characterized by NMR (1H, 13C, COSY), UV-vis, and MALDI-MS. 1H NMR measurements demonstrate that receptors 1 and 2 exhibit the highest binding affinity for fluoride ions compared to other anions including Cl-, Br-, NO3-, HSO4-, H2PO4-, and AcO-. The binding constants of 1 with F- and AcO- are 326 (+/-32) and 238 (+/-23) M-1, whereas those of 2 with F- and AcO- are 222 (+/-25) and 176 (+/-21) M-1. The fluorescent titration of 2 with various anions such as Cl-, Br-, NO3-, HSO4-, and H2PO4- led to essentially no change in excimer emission and a slight enhancement of monomer emission. In contrast, a dramatic change was observed in the fluorescence spectra upon the addition of F- and AcO- to 2. Self-assembled monolayers (SAMs) of 1 were formed on gold surfaces and characterized by reductive desorption and other techniques. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy were used to monitor anion recognition by the SAM-modified gold electrodes. The gold electrodes modified by SAMs of 1, upon binding with the F- anion, exhibit a dramatic increase in charge-transfer resistance (Rct) values. This is due to the repulsion between the negatively charged electrode surfaces and the negatively charged Fe(CN)6(3-/4-) redox probe in the electrolyte solution. In contrast, smaller increases in Rct values were observed in the cases of other monovalent anions investigated.
authors.affiliation: Department of Chemistry, Clemson University, Clemson, South Carolina 29634, USA.
authors.forename: Sheng
authors.initials: S
authors.lastname: Zhang
authors.forename: Amit
authors.initials: A
authors.lastname: Palkar
authors.forename: Luis
authors.initials: L
authors.lastname: Echegoyen