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This work reports a spectrofluorimetric method for selective and sensitive determination of sulfide ion in aqueous solution. The ultra-small zinc sulfide quantum dots (QDs) doped with manganese (ZnS:Mn) were synthesized by using a simple and fast procedure based on the co-precipitation of nanoparticles in aqueous solution in the presence of 2-mercaptoethanol, as capping agent. The nanoparticles have exhibited two strong fluorescent emissions at about 424 and 594 nm. Luminescent surface-capped ZnS:Mn QDs, with particle size below 5 nm, have been applied for determination of sulfide anions in water samples. Under the optimum conditions, the fluorescence intensity of ZnS:Mn QDs is linearly proportional to the sulfide ion concentration in the range 1.2×10(-6) to 2.6×10(-5) mol L(-1) with a detection limit as 3.3×10(-7) mol L(-1). The relative standard deviation for five replicate measurements (for 8.0×10(-6) mol L(-1) of S(2-)) was obtained to be 2.6%. It was founded that the interference of the other anions was negligible on the quantitive determination of sulfide ion., (Copyright © 2013 Elsevier B.V. All rights reserved.)

This work reports a new experimental methodology for the synthesis of ultra small zinc sulfide and iron doped zinc sulfide quantum dots in aqueous media. The nanoparticles were obtained using a simple procedure based on the precipitation of ZnS in aqueous solution in the presence of 2-mercaptoethanol as a capping agent, at room temperature. The effect of Fe(3+) ion concentration as dopant on the optical properties of ZnS was studied. The size of quantum dots was determined to be about 1nm, using scanning tunneling microscopy. The synthesized nanoparticles were characterized by X-ray diffraction, UV-Vis absorption and photoluminescence emission spectroscopies. The presence and amount of iron impurity in the structure of Zn((1-x))Fe(x)S nanocrystals were confirmed by atomic absorption spectrometry. A blue shift in band-gap of ZnS was observed upon increasing incorporation of Fe(3+) ion in the iron doped zinc sulfide quantum dots. The photoluminescence investigations showed that, in the case of iron doped ZnS nanoparticles, the emission band of pure ZnS nanoparticles at 427nm shifts to 442nm with appearance of a new sharp emission band around 532nm. The X-ray diffraction analysis indicated that the iron doped nanoparticles are crystalline, with cubic zinc blend structure, having particle diameters of 1.7±022nm. Finally, the interaction of the synthesized nanoparticles with bovine serum albumin was investigated at pH 7.2. The UV-Vis absorption and fluorescence spectroscopic methods were applied to compare the optical properties of pure and iron doped ZnS quantum dots upon interaction with BSA. It was proved that, in both cases, the fluorescence quenching of BSA by the quantum dots is mainly a result of the formation of QDs-BSA complex in solution. In the steady-state fluorescence studies, the interaction parameters including binding constants (K(a)), number of binding sites (n), quenching constants ( [Formula: see text] ), and bimolecular quenching rate constants (k(q)) were determined at three different temperatures and the results were then used to evaluate the corresponding thermodynamic parameters ΔH, ΔS and ΔG., (Copyright © 2011 Elsevier B.V. All rights reserved.)