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We have developed a selective upconversion switching method for the ratiometric fluorescence detection of nitrite using upconversion nanoparticles (UCNPs) and an efficient nitrite reaction. The green emission (λ(em) = 539 nm) of NaYF4:Yb(3+),Er(3+) nanoparticles can be selectively quenched by the neutral red (NR) dye due to the spectral overlap between the emission at 539 nm and the absorption of NR, while its red emission (λ(em) = 654 nm) remains unchanged. Nitrite reacts specifically and strongly with NR to form diazonium salt and lose the diazonium group, which sharply decreases the absorption of NR. Thus, the green emission of NaYF4:Yb(3+),Er(3+) can be recovered by increasing the amount of nitrite, leading to visible color changes from red to orange-yellow and finally green under excitation at 980 nm. The increase in the ratio of emission intensities (I539/I654) is quantitatively correlated to the concentration of nitrite ions. Moreover, the developed method has been successfully applied to nitrite detection in real samples such as drinking water, natural water and meat foods. In particular, the upconversion sensors can efficiently avoid background optical interference and thus show potential for the detection of nitrite salts in complex samples.

To convert the binding events on molecularly imprinted polymers (MIPs) into physically detectable signals and to extract the templates completely are the great challenges in developing MIP-based sensors. In this paper, a core-shell nanostructure was employed in constructing the MIP chemosensor for the improvements of template extraction efficiency and imprinted sites accessibility. Vinyl-substituted zinc(II) protoporphyrin (ZnPP) was used as both fluorescent reporter and functional monomer to synthesize atrazine-imprinted polymer shell at silica nanoparticle cores. The template atrazine coordinates with the Lewis acid binding site Zn of ZnPP to form a complex for the molecular imprinting polymerization. These imprinted sites are located in polymer matrix of the thin shells (~8 nm), possessing better accessibility and lower mass-transfer resistance for the target molecules. The fluorescence properties of ZnPP around the imprinted sites will vary upon rebinding of atrazine to these imprinted sites, realizing the conversion of rebinding events into detectable signals by monitoring fluorescence spectra. This MIP probe showed a limit of detection (LOD) of about 1.8 μM for atrazine detection. The core-shell nanostructured MIP method not only improves the sensitivity, but also shows high selectivity for atrazine detection when compared with the non-molecular imprinted counterparts.