Phosphorimetric determination of 4-nitrophenol using mesoporous molecular imprinting polymers containing manganese(II)-doped ZnS quantum dots.

Mesoporous molecularly imprinted polymers (MIPs) containing mangnanese-doped ZnS quantum dots (Mn-ZnS QDs) were prepared for specific recognition and detection of 4-nitrophenol (4-NP). The Mn-ZnS QDs display orange room-temperature phosphorescence with excitation/emission peaks at 295/590 nm and a decay time of 2.0 ms. In the presence of 4-NP, the orange phosphorescence is strongly reduced. Phosphorescence drops linearly in the 0.1-100 μM 4-NP concentration range, and the detection limit is 60 nM. The detection limit is far lower than the maximally allowed 4-NP concentrations in surface water and drinking water as specified by the U.S. Environmental Protection Agency. The intraday (n = 5) and interday (n = 6) spiked recovery rates were 96.0-104.5% and 97.9-107.9%, respectively, with relative standard deviations of 0.7-4.8% and 1.8-7.5% respectively. These MIPs integrated the characteristic features of phosphorimetry and molecular imprinting. Potential interference by competitive substances, background fluorescence or scattered light are widely reduced. Graphical abstract Schematic presentation of the synthesis of phosphorescent molecularly-imprinted polymers. A novel probe with manganese-doped ZnS quantum dots (Mn-ZnS QDs) and 3-aminopropyl-triethoxysilane (APTES) as functional monomers and tetraethoxysilane (TEOS) as crosslinking agent was prepared for selective phosphorescence detection of 4-nitrophenol (4-NP).