Fluorescent metal-organic frameworks (MOFs) have received great attention in sensing application. Here, we report the exploration of fluorescent MIL-53(Al) for highly selective and sensitive detection of Fe(3+) in aqueous solution. The cation exchange between Fe(3+) and the framework metal ion Al(3+) in MIL-53(Al) led to the quenching of the fluorescence of MIL-53(Al) due to the transformation of strong-fluorescent MIL-53(Al) to weak-fluorescent MIL-53(Fe), allowing highly selective and sensitive detection of Fe(3+) in aqueous solution with a linear range of 3-200 μM and a detection limit of 0.9 μM. No interferences from 0.8 M Na(+); 0.35 M K(+); 11 mM Cu(2+); 10 mM Ni(2+); 6 mM Ca(2+), Pb(2+), and Al(3+); 5.5 mM Mn(2+); 5 mM Co(2+) and Cr(3+); 4 mM Hg(2+), Cd(2+), Zn(2+), and Mg(2+); 3 mM Fe(2+); 0.8 M Cl(-); 60 mM NO2(-) and NO3(-); 10 mM HPO4(2-), H2PO4(-), SO3(2-), SO4(2-), and HCOO(-); 8 mM CO3(2-), HCO3(-), and C2O4(2-); and 5 mM CH3COO(-) were found for the detection of 150 μM Fe(3+). The possible mechanism for the quenching effect of Fe(3+) on the fluorescence of MIL-53(Al) was elucidated by inductively coupled plasma-mass spectrometry, X-ray diffraction spectrometry, and Fourier transform infrared spectrometry. The specific cation exchange behavior between Fe(3+) and the framework Al(3+) along with the excellent stability of MIL-53(Al) allows highly selective and sensitive detection of Fe(3+) in aqueous solution. The developed method was applied to the determination of Fe(3+) in human urine samples with the quantitative spike recoveries from 98.2% to 106.2%.

Detection of intracellular Zn(2+) has gained great attention because of its biological significances. Here we show the fabrication of silica-coated S(2-)-enriched Mn-doped ZnS quantum dots (SiO(2)-S-Mn-ZnS QDs) by enriching S(2-) with a silica shell on the surface of Mn-doped ZnS QDs via a sol-gel process for imaging intracellular Zn(2+) ions. The developed probe gave a good linearity for the calibration plot (the recovered PL intensity of the SiO(2)-S-Mn-ZnS QDs against the concentration of Zn(2+) from 0.3 to 15.0 μM), excellent reproducibility (1.2% relative standard deviation for 11 replicate measurements of Zn(2+) at 3 μM), and low detection limit (3s; 80 nM Zn(2+)). The SiO(2)-S-Mn-ZnS QDs showed negligible cytotoxicity, good sensitivity, and selectivity for Zn(2+) in a photoluminescence turn-on mode, being a promising probe for photoluminescence imaging of intracellular Zn(2+).

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