Application of boehmite as a fiber coating for headspace solid-phase microextraction of chlorophenols from aqueous samples.

In this paper, the extraction of chlorophenols from water samples was carried out using high surface area boehmite nanoparticles as a sorbent. The surfactant-free process employed to make the nano-boehmite used in this work was simple, green, and efficient. The proposed approach was based on headspace solid-phase microextraction, followed by GC-ECD for the determination of analytes. In situ derivatization of analytes was performed with acetic anhydride in a basic medium. Various effective parameters, including the amount of derivatization reagent, ionic strength, desorption temperature and time, extraction temperature, equilibrium time, and extraction time were studied. Under optimal conditions, the linear dynamic range was 0.05-5.0 µg L-1 for 2,4-dichlorophenol and 2,6-dichlorophenol and 0.003-0.1 µg L-1 for 2,4,6-trichlorophenol. A low limit of detection (0.75 × 10-3-15 × 10-3 µg L-1), and relative standard deviations for real samples (RSDs) <10% were obtained. The precision (as intra- and inter-day RSDs) was between 1.2 and 9.8%. In comparison to commercial fibers (CAR-PDMS, 85 µm), this fiber showed a greater extraction efficiency. Various water samples were subjected to extraction by the proposed method. The recoveries ranged from 90 to 110%.

Determination of desipramine in biological samples using liquid-liquid-liquid microextraction combined with in-syringe derivatization, gas chromatography, and nitrogen/phosphorus detection.

A method was established for the determination of desipramine in biological samples using liquid-liquid-liquid microextraction followed by in-syringe derivatization and gas chromatography-nitrogen phosphorus detection. The extraction method was based on the use of two immiscible organic solvents. n-Dodecane was impregnated in the pores of the hollow fiber and methanol was placed inside the lumen of the fiber as the acceptor phase. Acetic anhydride was used as the reagent for the derivatization of the analyte inside the syringe barrel. Parameters that affect the extraction efficiency (composition of donor and acceptor phase, ionic strength, sample temperature, and extraction time) as well as derivatization efficiency (amount of acetic anhydride and reaction time and temperature) were investigated. The limit of detection was 0.02 µg/L with intra and interday RSDs of 2.6 and 7.7%, respectively. The linearity of the method was in the range of 0.2-20 µg/L (r(2) = 0.9986). The method was successfully applied to determine desipramine in human plasma and urine.

An effective configuration for automated magnetic micro solid-phase extraction of phenylurea herbicides from water samples followed by high-performance liquid chromatography.

In this study, a new automated magnetic micro solid-phase extraction was introduced. A Tygon tube was folded and fixed around the pole of a cylindrical magnet. Nanosized magnetic sorbents modified with diphenyldichlorosilane were uniformly immobilized on one side of the inner wall of the tube. Sample solution and desorption solvent were passed through the tube using a peristaltic pump. Four phenylurea herbicides (tebuthiuron, monolinuron, isoproturon, and monuron) were used as the model compounds to evaluate the method performance. HPLC-UV was used to separate and quantify the analytes. The effective parameters influencing the performance of the extraction process (i.e., extraction and desorption flow rates, eluent and sample volumes, type of eluent and sample ionic strength) were investigated. The limit of detection was 0.04 µg L-1 for all studied compounds. Calibration curves were linear in the range of 0.1-500 µg L-1 with a determination coefficient between 0.9988 and 0.9999. Intra-day, inter-day and batch-to-batch precisions expressed as relative standard deviation were less than 7%. Several environmental water samples were investigated to assess the applicability of the method for real sample analysis.

Mesoporous carbon-zirconium oxide nanocomposite derived from carbonized metal organic framework: A coating for solid-phase microextraction.

In this paper, a mesoporous carbon-ZrO2 nanocomposite was fabricated on a stainless steel wire for the first time and used as the solid-phase microextraction coating. The fiber was synthesized with the direct carbonization of a Zr-based metal organic framework. With the utilization of the metal organic framework as the precursor, no additional carbon source was used for the synthesis of the mesoporous carbon-ZrO2 nanocomposite coating. The fiber was applied for the determination of BTEX compounds (benzene, toluene, ethylbenzene and m, p-xylenes) in different water samples prior to gas chromatography-flame ionization detection. Such important experimental factors as synthesis time and temperature, salt concentration, equilibrium and extraction time, extraction temperature, desorption time and desorption temperature were studied and optimized. Good linearity in the concentration range of 0.2-200µgL(-1) and detection limits in the range of 0.05-0.56µgL(-1) was achieved for BTEX compounds. The intra- and inter-day relative standard deviations were in the range of 3.5-4.8% and 4.9-6.7%, respectively. The prepared fiber showed high capability for the analysis of BTEX compounds in different water and wastewater samples with good relative recoveries in the range of 93-107%.

A simple approach for the preparation of simazine molecularly imprinted nanofibers via self-polycondensation for selective solid-phase microextraction.

A novel molecularly imprinted sol-gel material based on polysiloxane nanofiber was introduced as a solid-phase microextraction coating on a stainless steel wire for the extraction of simazine. The nanostructured molecularly imprinted fiber was prepared by a simple single step method at room temperature, using methyltriethoxysilane as the sol-gel precursor and simazine as the template molecule. The fiber was applied for the extraction of simazine in different water samples followed by gas chromatography and mass spectrometry detection. The extraction capacity of the molecularly imprinted fiber was 8 ng, and it had better extraction efficiency than the non-imprinted fiber and commercial fibers (PDMS and PA). The fiber had also a good selectivity for simazine and its analogous compounds. Important parameters affecting the extraction and desorption efficiency, such as salt concentration, stirring rate, pH of sample solution, extraction time and temperature, temperature and time of desorption, were investigated. The intra- and inter-day relative standard deviations were in the range of 4.3-7.6%. The fiber-to-fiber reproducibility was 7.7-8.5%. The method showed a good linearity (r(2)> 0.9980) in the range of 0.02-20 µg L(-1) with the detection limit of 0.005 µg L(-1). The relative recoveries were also in the range of 94-97% for different water samples.