Determination of Hg2+ and Cu2+ ions by dual-emissive Ag/Au nanocluster/carbon dots nanohybrids: Switching the selectivity by pH adjustment

Abstract

An innovative dual-emissive ratiometric nanohybrid probe comprised of red-emitting a (Ag/Au)@insulin nanoclusters (NCs) and blue-emitting carbon dots (CDs) was designed for sensitive and selective ratiometric determination of Hg²⁺ and Cu²⁺ ions.The fluorescence intensity of CDs (λ_ex = 340 nm; λ_em = 420 nm) was unaffected in the presence of the metal ions tested, whereas the red emitting NCs (λ_ex = 340 nm; λ_em = 640 nm) was strongly quenched by both Cu²⁺ and Hg²⁺ ions. Interestingly, the selectivity of the probe toward these two ions was simply switched by controlling the pH of probe solution without using any chelating agent. The probe selectively responded to Hg²⁺ ions at acidic condition (pH = 4.0), Cu²⁺ ions at basic condition (pH = 10.0), and Hg²⁺-Cu²⁺ mixtures at pHs within this range. The respective detection limitsfor determination of Cu²⁺ and Hg²⁺ ions at their specific pH conditions were estimated as 5 nM and 7 nM, over linear ranges of 20-600 nM and 20-2000 nM, respectively. The fabricated ratiometric probe also showed distinguished fluorescence color changes to visual detection of these ions. Finally, the probe was successfully applied to determination of Hg²⁺ and Cu²⁺ ions in tap and mineral water samples.

Keywords: Bimetallic nanoclusters; Carbon dots; Detection of Hg(2+)and Cu(2+); Fluorescence; Nanohybrid probe; Ratiometric; pH control.