Abstract

A new macromolecule possessing two dansyl moieties and based on 2-[4-(2-aminoethylthio)butylthio]ethanamine was prepared as a fluorescent sensor and its mercury sensing properties toward various transition metal, alkali, and alkali earth ions were investigated. The designed compound exhibited pronounced Hg2+-selective ON-OFF type fluorescence switching upon binding. The new compound provided highly selective sensing to Hg2+ in acetonitrile-water solvent mixtures with a detection limit of 2.49 x 10-7 M or 50 ppb. The molecular modeling results indicated that ions-recognition of the sensor originated from a self assembly process of the reagent and Hg2+ to form a helical wrapping structure with the favorable electrostatic interactions of Hg2+coordinated with sulfur, oxygen, nitrogen atoms and aromatic moieties.

Highlights

  • Mercury is a highly toxic and hazardous environmental contaminant, even at low levels [1]

  • Many fluorescent mercury ionophores have been designed for Hg2+-sensing such as calixarene [9], hydroxyquinolines [10,11], azines [12], cyclams [13,14,15], diazacrown ethers [16]

  • Dioxocyclams [17], diazatetrathia crown ethers [18], and most of these studies have shown that nitrogen, oxygen and sulfur atoms present in the ionophores can promote the coordination of Hg2+

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Summary

Introduction

Mercury is a highly toxic and hazardous environmental contaminant, even at low levels [1]. Moon and coworkers [10] prepared a fluorescence sensor based upon 8-hydroxyquinoline (Figure 1a) as a Hg2+fluorescence sensor with the detection limit of 5 × 10-6 M This sensor system displayed moderate sensitivity to Cu2+ ions. A diametrically disubstituted bis(anthrylmethyl) derivative of 1,8-dimethylcyclam (Figure 1c) presented by Youn and co-workers [20] exhibited pronounced Hg2+ and Cd2+ selective fluorogenic behaviors and the sensor provided a detection limit of 3.8 × 10-6 M for Hg2+. Song and co-workers [17] prepared a fluorescence sensor based upon the dioxocyclam moiety They observed that the dioxocyclam derivative bearing anthrylacetamide moieties (Figure 1d) exhibited both Hg2+ and Cu2+ sensing with a detection limit of 7.8 × 10-6 M for Hg2+. Compound 4 offers sufficiently low detection limits for the determination of sub-micromolar concentrations hazardous Hg2+ ions found in environmental and biological samples such as edible fish [24]

Results and Discussion
Molecular modeling studies
Sensitivity studies
Selectivity studies
General
Synthesis of compound 4
Computational modeling of complex structure with mercury
Conclusions

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