Synthesis of thiol derivatives of azobenzocrown ethers. The preliminary studies on recognition of alkali metal ions by gold nanoparticles functionalized with azobenzocrown and lipoic acid.

The article presents the synthesis of novel 13- and 16-membered azobenzocrown derivatives with peripheral thiol moieties and preliminary studies assessing their possible application in plasmonic sensors based on gold nanoparticles. The effect of the length of the chain connecting the macrocycle with the thiol group and the effect of the presence of the additional functional compound, i.e. lipoic acid, on the sensor response was analyzed. Colloidal gold nanoparticles modified with a 16-membered crown with a thiol group on oxyethylene (compound 12) or oxybutylene (compound 13) linker was found to have good properties, allowing for detection of potassium ions in aqueous solutions at concentrations 8-20 mM for bifunctionalized nanogold and 4-26 mM for less stable, colloidal gold modified only with thiol derivatives of azobenzocrowns. The response towards potassium cations of bifunctionalized nanogold modified with compound 13 was more stable in time than for the system incorporating compound 12. Compound 13, obtained with the highest yield among all presented thiol derivatives of azobenzocrowns, was selected for further, more detailed, studies.