N-Doped carbon dots with pH-sensitive emission, and their application to simultaneous fluorometric determination of iron(III) and copper(II)

Mikrochim Acta. 2019 Dec 7;187(1):30. doi: 10.1007/s00604-019-4017-1.

Abstract

Simultaneous fluorometric determination of iron(III) and copper(II) without the use of any masking agent or additional treatment is achieved by using N-doped carbon dots (NCDs). The NCDs were hydrothermally prepared, have strongest excitation/emission peaks at 320/406 nm and a 47% quantum yield. Excitation-tunable emission is found to depend on solution pH values. This supports the involvement of surface states in the origin of the excitation dependent nature. The NCDs were employed as a fluorescent probe for the simultaneous determination of Fe(III) with a linear response in the 3-60 μM concentration range and a 0.31 μM detection limit (LOD). The probe also responds linearly to Cu(II) in the 0.5-15 μM concentration range and with a 56 nM LOD. With the addition of Cu(II), the absorption spectra of NCDs presented a clear decrease in the intensity at 312 nm followed by an increase at 360 nm. This is not observed in the presence of Fe(III). The fluorescence lifetime of NCDs (5.8 ns) is reduced by Fe(III) but not by Cu(II). Thus, the two metal ions can be simultaneously detected without the need for any reagents. The probe was employed to quantify Fe(III) and Cu(II) in spiked water, serum, and urine samples. Graphical abstract Schematic representation of hydrothermal synthesis of highly fluorescent N-doped carbon dots with novel pH dependent emission and their application for the simultaneous determination of Cu(II) and Fe(III) with individual ion discrimination.

Keywords: Dual metal detection; Ferric ion; Fluorescence lifetime; Hydrothermal method; Individual ion discrimination; Inner filter effect; Real sample analysis; Serum and urine analysis; pH dependent excitation tuneable emission.