Probing phosphate ion via the europium(III)-modulated fluorescence of gold nanoclusters

Fluorescent gold nanoclusters (Au-NCs) were synthesized by a one-pot method using 11-mercaptoundecanoic acid as a reducing and capping reagent. It is found that the red fluorescence of the Au-NCs is quenched by the introduction of Eu(III) at pH 7.0, but that fluorescence is restored on addition of phosphate. The Au-NCs were investigated by transmission electron microscopy and fluorescence photographs. The effect of pH on fluorescence was studied in the range from pH 6 to 10 and is found to be strong. Based on these findings, we have developed an assay for phosphate. Ions such as citrate, Fe(CN)₆ ³⁻, SO₄ ²⁻, S₂O₈ ²⁻, Cl⁻, HS⁻, Br⁻, AcO⁻, NO₂ ⁻, SCN⁻, ClO₄ ⁻, HCO₃ ⁻, NO₃ ⁻, Cd²⁺, Ba²⁺, Zn²⁺, Mg²⁺, and glutamate do not interfere, but ascorbate and Fe³⁺ can quench Au-NCs fluorescence. The fluorescent nanocluster probe responds to phosphate in the range from 0.18 to 250 μM, and the detection limit is 180 nM. The probe also responds to pyrophosphate and ATP.

Off/on fluorescence sensor for phosphate based on Eu³⁺-modulated Au NCs thanks to the competition of oxygen-donor atoms from phosphate with those from the carboxylate groups was developed