High-efficient mercury removal from environmental water samples using di-thio grafted on magnetic mesoporous silica nanoparticles.

In this work, magnetic di-thio functionalized mesoporous silica nanoparticles (DT-MCM-41) were prepared by grafting dithiocarbamate groups within the channels of magnetic mesoporous silica nanocomposites. The functionalized nanoparticles exhibited proper magnetic behavior. They were easily separated from the aqueous solution by applying an external magnetic field. The results indicated that the functionalized nanoparticles had a potential for high-efficient removal of Hg(2+) in environmental samples. The maximum adsorption capacity of the sorbent was 538.9 mg g(-1), and it took about 10 min to achieve the equilibrium adsorption. The resulted adsorption capacity was higher than similar works for adsorption of mercury. It can be due to the presence of di-thio and amine active groups in the structure of sorbent. The special properties of MCM-41 like large surface area and high porosity also provided a facile accessibility of the mercury ions into the ligand sites. The complete removal of mercury ions was attained with dithiocarbamate groups in a wide range of mercury concentrations. The recovery studies were also applied for the river water, seawater, and wastewater samples, and the values were over of 97 %.

Design of a surface-immobilized 4-nitrophenol molecularly imprinted polymer via pre-grafting amino functional materials on magnetic nanoparticles.

In order to resolve the low adsorption capacity of the surface molecularly imprinting methods, an approach was developed for the preparation of magnetic imprinted polymers by pre-grafting the amino functional material, 3-aminopropyltriethoxysilane (APTES), on the surface of the silica coated magnetic substrate. APTES was used for amino functionalization of the silica coated Fe3O4 nanoparticles. Amino groups were used for immobilization of the template molecules on the magnetic surface and additionally to react with the terminal vinyl groups of cross-linker, ethylene glycol dimethacrylate (EGDMA), by the Michael addition reaction. In this way, the imprinting sites of the analytes formed on the substrate were increased. The sorbent was synthesized in the presence of 4-nitrophenol (4-NP) and EGDMA as the template and cross-linker, respectively. Different parameters affecting the adsorption, such as pH, desorption solvent type and adsorption time were evaluated and optimized. The prepared magnetic molecularly imprinted polymer (MMIP) showed high adsorption capacity and proper selectivity for the template molecule. The kinetic adsorption curve indicated that 90 min was sufficient to achieve the adsorption equilibrium for MMIP. The maximum adsorption capacity was 129.1 mg g(-1). The experiments exhibited a linear range of 10-3000 µg L(-1) for 4-NP with the correlation coefficient (R(2)) of 0.997. The results of the real sample analysis confirmed the applicability of the proposed MMIP for quantitative analysis of 4-NP in the aqueous samples.

Magnetic solid phase extraction using gold immobilized magnetic mesoporous silica nanoparticles coupled with dispersive liquid-liquid microextraction for determination of polycyclic aromatic hydrocarbons.

An efficient magnetic sorbent was introduced for solid phase extraction by incorporation of the gold nanoparticles into the hexagonal lattice of magnetic MCM-41. For the effective incorporation of the gold nanoparticles, magnetic MCM-41 was functionalized with 3-aminopropyltriethoxysilane (APTES), which then interacted with Au atoms through the amine groups. Furthermore, to achieve high pre-concentration factors (PFs), the method was coupled with dispersive liquid-liquid microextraction (DLLME) procedure. Polycyclic aromatic hydrocarbons (PAHs) were used as the model compounds to evaluate the extraction performance of the proposed method. The π-system of PAH compounds and immobilized Au atoms on the surface of the sorbent can cause the electron donor-acceptor interactions. The parameters affecting extraction recovery such as types of the disperser and extraction solvents, pH of the sample solution, and the extraction time were optimized. Under the optimized conditions, the high PFs were obtained in the range 5519-6271 for the target analytes. The kinetic adsorption illustrated that 5 min was sufficient to achieve adsorption equilibrium for PAHs. The evaluations also showed a linearity range 0.01-50 µg L(-1) with the detection limit in the range 0.002-0.004 µg L(-1) for the PAHs. The applicability of the method for the analysis of PAHs in real samples was justified by the extraction of PAHs from seawater samples. The results indicated good recovery efficiencies ranging from 91.4 to 104.2%.

Magnetic molecularly imprinted nanoparticles based on grafting polymerization for selective detection of 4-nitrophenol in aqueous samples.

In this study, an analytical procedure for the selective extraction and detection of 4-nitrophenol (4-NP) was investigated by using of molecularly imprinted polymer on the surface of magnetic nanoparticles (MNPs). The magnetic nanoparticles were modified by tetraethyl orthosilicate (TEOS) and 3-methacryloxypropyl trimethoxysilane (MPTS) before imprinting. The magnetic molecularly imprinted polymer (MMIP) was polymerized at the surface of modified MNPs by using of methacrylic acid (MAA) as functional monomer, 4-NP as template and ethylene glycol dimethacrylate (EGDMA) as cross-linker. Experimental design by the Taguchi method was used for the optimization of synthesis procedure of imprinted polymer. The resulting MMIP showed high adsorption capacity, proper selectivity and fast kinetic binding for the template molecule. It was characterized by Fourier transform infrared (FT-IR) analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods. The maximum adsorption capacity of MMIP was obtained as 57.8mgg(-1) and it took about 2h to achieve the equilibrium state. The adsorption curve of MMIP was also fitted with the Freundlich isotherm equation. The assay exhibited a linear range of 25-1000µgL(-1) for 4-NP with the correlation coefficient (R(2)) of 0.995. The method was also examined for the analysis of 4-NPs in seawater. For recovery evaluation, the seawater samples were spiked at two concentration levels of 50 and 100µgL(-1) of 4-NPs and the recovery values were in the range of 79.3-99.8%. The relative standard deviations (RSD) for the recoveries were less than 5.2%.