Functionalized carbon nanotube-polyaniline composite coating for on-line microextraction on a screw coupled with high performance liquid chromatography to determine opium alkaloids.

A novel and efficient on-line microextraction on a screw coupled with high-performance liquid chromatography with an ultraviolet-visible detector was developed to extract and determine trace quantities of five opium alkaloids. All detections of the analytes were achieved at 210 nm. The surface of the screw grooves was electrochemically coated with the carbon nanotubes-COOH/polyaniline composite. The surface characterization was assessed by Fourier transform infrared spectroscopy and field emission scanning electron microscopy. The prepared screw was inserted into a cartridge of a guard column, and then the constructed microextraction on a screw device was placed in the loop of a six-port HPLC injection valve. The parameters affecting the extraction efficiency of the analytes were optimized using the one variable-at-a-time method. The effective parameters for the extraction efficiency of the analytes, including sample volume, extraction time, sampling flow rate, desorption solvent type, ionic strength, and pH were investigated and optimized. Under optimal conditions, the detection limits were 3-10 µg L-1, and the linear dynamic ranges were 10-2000 µg L-1 with a coefficient of determination greater than 0.9940. The inter-day and intra-day (n = 3) relative standard deviations were less than 7% and 5%, respectively. The proposed method was simple and reproducible, with an acceptable relative recovery (90-108%) for determining opium alkaloids in water and urine samples.

Electrophoretically deposited sulfonated poly(styrene-co-divinylbenzene) on a screw for microextraction of cationic dyes from aqueous solutions.

In the present work, a novel solid-phase microextraction on a screw (MES) was employed to extract cationic dyes (malachite green, methylene blue, and rhodamine B) from food samples and fish breeding pool water. The sulfonated poly(styrene-co-divinylbenzene) was electrophoretically deposited on the surface of the grooves of a screw. Then the screw was placed inside a silicon tube as a holder to create a channel to run a test solution through it. The extracted dyes on the coated screw were eluted by a suitable eluent. High-performance liquid chromatography with an ultraviolet/visible detector was utilized for the separation and analysis of the analytes. The effective parameters of the analyte extraction efficiency were optimized. Under optimum conditions, the limits of detection were 0.15 µg/L, and calibration curves were linear in the range of 0.50-250.00 µg/L, with coefficients of determination > 0.989 for all studied dyes. The relative standard deviations of intra and inter-day (n = 3) were in the range of 2.8%-7.0% and 7.0%-9.5%, respectively. The MES was applied as a simple and repeatable method with acceptable relative recoveries (82.0%-103.0%) for the determination of cationic dyes in grape nectar, ice pop, jelly powder, and fish breeding pool water.

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%.

Application of HKUST-1 metal-organic framework as coating for headspace solid-phase microextraction of some addictive drugs.

In the present study, a copper-based metal-organic framework (HKUST-1) was used first time for preconcentration trace amounts of addictive drugs in biological samples. HKUST-1 was synthesized and coated onto the surface of stainless steel wire. The prepared coating was used in headspace solid-phase microextraction method coupled with gas chromatography-mass spectrometry for preconcentration and determination of some addictive drugs in biological fluids. Prepared coating shows good extraction efficiency due to large surface area, and π-π stacking interaction with selected analytes. Under optimum conditions, the method was validated with a reasonable determination coefficient (R2  > 0.9961) and suitable linear dynamic range (0.5-1000 µg L-1 ). Also, the limits of detections were obtained in the range of 0.1-0.4, 0.2-0.6, and 0.4-0.7 µg L-1 for water, urine, and plasma samples, respectively. The limits of quantification of present method were obtained in the range 0.5-1.3, 0.7-1.5, and 1.0-1.9 µg L-1 in water, urine, and plasma samples, respectively. The intra-day and inter-dye single fiber and fiber to fiber relative standard deviations were observed in the range 3.0-13.9% and 3.5-12.3%, respectively. Finally, the present method was applied for the determination of the drugs in biological samples.

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.