Selective sensing of Hg2+ by a proton-ionizable calix[4]arene fluoroionophore

A fluorogenic derivative of a calix[4]arene with two proton-ionizable N-(phenyl)sulfonyl carboxamide-containing side arms in the 1,3-positions on the lower rim is employed for the selective sensing of Hg(2+) at low concentration levels in water/MeCN (1:1, v/v) solutions containing Pb(2+) and Cd(2+). All three metal ions quench the fluorescence of the ligand in pure MeCN. However, in water/MeCN mixed solvent, the recognition of such cations occurs differently as only Hg(2+) complexation quenches the fluorescence of the calixarene. Experiments carried out in the presence of an acid and a bulky non-complexing cation shows that the quenching of the calixarene fluorescence upon Hg(2+) addition is likely due to proton displacement from the proton-ionizable side arms of the ligand. The system may be employed as a simple tool for the selective and efficient mercury sensing in mixed water/organic solvent.