Microextraction of organophosphorus pesticides on a screw coated with PAN/calcined ZnMgAl-LDH electrospun nanofibers.

The present research is an attempt to expand the recently reported microextraction on screw method. For this purpose, polyacrylonitrile/calcined ZnMgAl-LDH nanofiber was fabricated by the electrospinning technique on the surface of a screw. It was applied to the extraction of organophosphorus pesticides (OPP) from agricultural samples. The separation and determination of OPPs were carried out by gas chromatography-mass spectrometry. The characterization of the fabricated nanofiber was performed utilizing Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction instruments. Effective parameters on the extraction efficiency of the analytes including sample pH, ionic strength, sample flow rate and number of cycles, type, volume, and flow rate of desorption solvent were optimized by one-variable-at-a-time method. Under optimized conditions, the limits of detection were 0.03 and 0.07 µg L-1 for diazinon and chlorpyrifos, respectively. This method showed wide linearity in the range 0.10-1000 µg L-1 for diazinon and 0.25-1000 µg L-1 for chlorpyrifos with R2 > 0.996. The intra- and inter-day precisions (RSD%, n = 3) were ≤ 6.4% and ≤ 7.7%, respectively. Also, RSD% values less than 11.1% were obtained for screw-to-screw reproducibility. The applicability of the method for the extraction and determination of the analytes in complex agricultural environments such as cabbage, potato, tomato, cucumber, and beetroot was investigated. The results led to acceptable relative recoveries in the range 81.0-108.2%.

Microextraction on a screw for determination of trace amounts of hexanal and heptanal as lung cancer biomarkers.

Solid phase microextraction on a screw was utilized for the extraction of hexanal and heptanal as lung cancer biomarkers from urine samples. Reduced graphene oxide (rGO) was coated on the surface of a stainless-steel set screw by electrophoretic deposition method. The screw was located inside a glass cover, and the created channel acted as the sample solution flow pass. A 5 mL glass syringe was connected to a syringe pump to direct the sample and the eluent through the channel. The extraction procedure was followed by gas chromatography/mass spectrometry (GC/MS) for separation and determination of the extracted aldehydes. The effective parameters on the extraction efficiencies of the analytes were identified and optimized. Under the optimal extraction conditions, the extraction time was as short as 10 min. The calibration curves indicated good linearity (R2 > 0.97) within the concentration range of 1.0-50 µg L-1. The obtained limits of detection (LODs) for hexanal and heptanal were down to 0.4 and 0.3 µg L-1, respectively. Considering the repeatability, simplicity, and eco-friendliness of this simple extraction method, it can be efficiently used for preconcentration of aldehydes in different samples.

Carbon fibers modified with polypyrrole for headspace solid phase microextraction of trace amounts of 2-pentyl furan from breath samples.

This study introduces micrometric carbon strands as a suitable fiber for headspace solid phase microextraction. Compared to previous supports, carbon fibers have mechanical flexibility, wide thermal expansion, and a large surface area, which is an important factor in headspace solid phase microextraction. The electrophoretic technique was applied to modify the surface of stainless steel and carbon fibers with polypyrrole. Modified carbon fibers were used for extraction of 2-pentylfuran (2-PF) as a model analyte from patients' breath and coffee samples. 2-PF belongs to the furan family, which was suggested as a biomarker for Aspergillus fumigatus and was classified as a possible carcinogen. 2-PF can be found in many heat-processed foods and drinks. The separation and detection of the analyte was performed by gas chromatography coupled to mass spectrometry. The effective factors in the extraction performance of the analyte by carbon fiber supports were investigated and optimized. Under optimized extraction conditions (temperature, 20 °C; time, 15 min; desorption temperature, 200 °C; desorption time, 2 min; salt concentration, 10% w/v; and stirring rate, 700 rpm), the limit of detection was calculated as 0.05 ng mL-1, whereas repeatability and fiber-to-fiber reproducibility (RSD %) was found to be in the range of 3.2-4.1%. The experimental results showed that the proposed fiber had greater extraction performance for 2-pentylfuran.

Microextraction on a screw.

For the first time, a rapid, efficient, simple, and inexpensive approach for solid phase microextraction on a screw (MES) was developed. MES is a miniaturized form of solid-phase extraction without any backpressure. In this system, analytes were adsorbed on the surface of micro channels of a screw that was coated by polypyrrole (PPy). Based on this procedure, the analytes are adsorbed on the solid phase and then eluted by a desorption solvent. The MES method followed by gas chromatography-mass spectrometry (MES-GC-MS) was applied for the rapid extraction and determination of six polycyclic aromatic hydrocarbons (PAHs) (as model analytes) in well water samples. Several parameters affecting the extraction procedure, including the sampling flow rate, the number of the loading/desorption cycles of the sample, and the volume of the desorption solvent, were evaluated and optimized. Under optimum conditions, the detection limits for the PAHs varied between 0.5 and 1 µg L-1 and linear ranges varied between 2 and 600 µg L-1. The results showed good correlation coefficients (R > 0.99) for all of the analytes in the studied calibration range. The relative recovery (RR%) of the desired MES-GC-MS method for the studied PAHs was between 83.0 and 104.0% and the interday and intraday precision (n = 5 days), expressed as relative standard deviation (RSD %), were between 3.9-6.2% and 6.2-8.9%, respectively. To evaluate the matrix effect, the developed method was also applied for preconcentration and determination of the selected PAHs in real water samples, and good results were obtained.