Selective fluorescent sensor for mercury ions in aqueous media using a 1,4-dihydropyridine derivative

Novel 1,4-dihydropyridine (DHP) derivatives containing 3 carboxylic acid units are synthesized via cyclotrimerization of N-substituted beta-aminoacrylates followed by basic hydrolysis of the triester. These DHP derivatives are readily soluble in aqueous media buffered at pH 8.0 and the solutions give blue fluorescent signals with quantum yields of 7-23%. One of these compounds, bearing a p-methoxyphenyl N-substituted group, shows specific fluorescent quenching with the mercuric ion (Hg2+). The fluorescent signal of the DHP derivative decays over a period of minutes to hours depending on the Hg2+ concentration, which implies that the sensing mechanism involves chemical reaction between the Hg2+ ion and the DHP compound. The H-1 NMR and MS data suggest that Hg2+ mediates the oxidation of the DHP ring into a pyridinium ring. The event is useful for fluorescent detection of Hg2+ at the micromolar level within 30 min, with a detection limit of 0.2 mu M in aqueous medium. (c) 2012 Elsevier Ltd. All rights reserved.