Magnetic Solid-Phase Extraction of N,N-Diethyl-m-Toluamide From Baby Toilet Water Prior to its HPLC-UV Detection.

Fe3O4@MIL-100 (MIL, Material Institut Lavoisier) core-shell magnetic microspheres were prepared and applied as the sorbent for the magnetic solid phase extraction (MSPE) of N,N-diethyl-m-toluamide (DEET) in baby toilet water for the first time. The synthesized magnetic metal-organic frameworks were characterized by transmission electron microscope, infrared spectroscopy and thermogravimetric analysis. The functionalized magnetic microparticles showed excellent dispersibility in aqueous solution. The MSPE conditions were investigated in detail. Under the optimized conditions, an MSPE-high performance liquid chromatography method for the determination of DEET was developed. The method was linear in the concentration range from 5 to 500 µg L-1 for DEET in baby toilet water and good linearity (r2 > 0.9998) was obtained for the calibration curve. The limit of detection was 1.5 µg L-1. Both the intra-day and inter-day precisions (relative standard deviations) were <3%.

Removal of the insect repellent N,N-diethyl-m-toluamide (DEET) by laccase-mediated systems.

Numerous efforts have been made to remove emerging trace organic contaminants, such as pharmaceuticals and personal care products (PPCPs). This study examined the removal of N,N-diethyl-m-toluamide (DEET) by Trametes versicolor laccase and its laccase-mediator systems. Experimental results showed that DEET was poorly removed by laccase alone. The poor removal efficiency of DEET by laccase may be attributed to the presence of strong withdrawing electron group (-CO-N [CH2-CH3]2) in the chemical structure of DEET. Experimental results also indicated that DEET might be indirectly oxidized by laccase-mediator systems. More than 50% initial DEET amount was removed by laccase in the presence of a redox mediator, such as 2,2'-azino-bis[3-ethylbenzothiazoline-6-sulphonic acid] (ABTS) or 1-hydroxybenzotriazole (HBT). However, laccase activity was considerably decreased in the presence of a redox mediator (ABTS or HBT). Further studies on identification of degradation byproducts and degradation pathways are recommended.

Tuning the hydrophobicity of mesoporous silica materials for the adsorption of organic pollutant in aqueous solution.

The ability of various as-prepared and organically modified MCM-41 and HMS mesoporous silica materials to behave as efficient adsorbents for organic pollutants in aqueous solution was investigated by using different surface functionalization procedures, so as to adjust their hydrophilic/hydrophobic balance. The hydrophilic and organophilic properties of the parent silica materials and their corresponding surface functionalized counterparts were studied by using water and toluene adsorption isotherms. Their quantification was determined by the hydrophobic static index value (HI(static)), as well as by the silanol and organic group densities after the functionalization step. A clear correlation could be found between the HI(static) values and either the superficial silanol density, or the amount of organic moieties grafted or incorporated to the silica materials. For the highly organically functionalized samples, the residual superficial silanol groups (<50%) are sufficiently isolated from each other so as to prevent the water capillary condensation within the pores, thereby leading to an increased hydrophobic character of the resulting mesoporous silica. Those hydrophobic samples, for which the water liquid meniscus formation within the mesopores was minimized or avoided, exhibited a storage capacity for an organic pollutant (N,N-diethyl-m-toluamide, DEET) in aqueous solution more than 20 times higher than that of the corresponding unmodified sample, independently of the silica nature (MCM-41 or HMS). For all calcined and silylated samples, the DEET maximum adsorption capacities determined by the Langmuir model could be correlated with the silica surface coverage by trimethylsilyl groups and thus with the remaining silanol amount.

Incorporation of single-wall carbon nanotubes into an organic polymer monolithic stationary phase for mu-HPLC and capillary electrochromatography.

Single-wall carbon nanotubes (SWNT) were incorporated into an organic polymer monolith containing vinylbenzyl chloride (VBC) and ethylene dimethacrylate (EDMA) to form a novel monolithic stationary phase for high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The retention behavior of neutral compounds on this poly(VBC-EDMA-SWNT) monolith was examined by separating a mixture of small organic molecules using micro-HPLC. The result indicated that incorporation of SWNT enhanced chromatographic retention of small neutral molecules in reversed-phase HPLC presumably because of their strongly hydrophobic characteristics. The stationary phase was formed inside a fused-silica capillary whose lumen was coated with covalently bound polyethyleneimine (PEI). The annular electroosmotic flow (EOF) generated by the PEI coating allowed peptide separation by CEC in the counterdirectional mode. Comparison of peptide separations on poly(VBC-EDMA-SWNT) and on poly(VBC-EDMA) with annular EOF generation revealed that the incorporation of SWNT into the monolithic stationary phase improved peak efficiency and influenced chromatographic retention. The structures of pretreated SWNT and poly(VBC-EDMA-SWNT) monolith were examined by high-resolution transmission electron microscopy, Raman spectroscopy, scanning electron microscopy, and multipoint BET nitrogen adsorption/desorption.