Molecular Recognition of Protonated Polyamines at Calix[4]Crown-5 Self-Assembled Monolayer Modified Electrodes by Impedance Measurements

Abstract

Molecular recognition of protonated aliphatic polyamines has been studied at calix[4]crown-5 self-assembled monolayer modified gold electrodes by electrochemical impedance spectroscopic (EIS) experiments. The energy of complex formation between the calix [4]crown-5 molecule and a series of alkyl ammonium ions was shown by molecular modeling and EIS experiments to depend on the number of amine groups in the alkyl chain as well as the number of methylene groups between the amine groups. The structures of complexes formed between the crown ether on the lower rim of calix[4]arene and protonated amines were determined by minimizing the complex formation energies. The adducts thus formed on the SAM rendered the electron transfer from the electrode to the probe (Fe(CN)63-/4- pair) easier or more difficult depending on the number of ammonium groups and their arrangement in linear alkyl chains. Analytical procedures have been developed to detect protonated spermidine (a recognized cancer marker) in simulated urine, blood, erythrocyte, and cerebrospinal fluids.