Carbon nanospheres with dual-color emission and their application in ratiometric pyrophosphate sensing

Abstract

Herein, we employ pH-dependent solubility equilibrium to develop the one-pot aqueous synthesis of dual-color emission fluorescent carbon nanosphere (DFCSs) with novel physicochemical properties. Unexpectedly, some of the DFCSs have a regular nanosphere shape, containing uniform carbon dots (∼20 nm) on their surface. This may be attributed to the change in the surface composition of the carbon nanospheres under the strong alkaline conditions (pH 13), which results in dual-wavelength emission by single-wavelength excitation. Interestingly, the fluorescence intensities of the two emission peaks of the DFCSs at 315/410 nm can be simultaneously quenched upon the addition of Co²⁺ due to the strong coordination between Co²⁺ and the O-containing luminescent groups from the carbon dots and DFCSs. Also, the results demonstrate that one Co²⁺ simultaneously combines with two chromophoric groups. Furthermore, the quenched DFCSs exhibit high sensitivity for pyrophosphate (PPi) in the range of 0.075–200.0 μM through a fluorescence recovery process, which can be attributed to the stronger Co²⁺–OP bond. This results in the removal of Co²⁺ from the surface of DFCSs–Co²⁺ system via competitive adsorption interactions. Meanwhile, this sensor shows high selectivity for PPi over mercapto amino acid and phosphate in aqueous solution. These results indicate the DFCSs can act as a dual-signal PPi-selective sensor via a ratiometric competitive mechanism.