Synthesis and characterization of MoS2-COOH/gly/Mn nanocomposite as an efficient adsorbent for Ultra-trace determination of trifluralin herbicide.

The world is confronting a severe water crisis. To clean up water from heavy metals, microorganisms, chemicals, and other types of pollutants, nanocomposites have been receiving great attention specifically due to the high surface area affording to work effectually even at low concentrations. In this research, we synthesized a new amino acid-modified MoS2 nanocomposite by chemically immobilizing Mn (II). The synthesized absorbent MoS2-COOH/gly/Mn was identified by thermogravimetric analysis (TGA), nitrogen adsorption measurement, X-ray diffraction (XRD), analysis of energy dispersive X-ray mapping (EDAX and MAP), field emission scanning electron microscopy (FE-SEM), and Fourier Transform Infrared spectrometry (FT-IR). The nanocomposite was employed as an adsorbent through the solid phase microextraction (SPME) method while trifluralin herbicide was chosen as a model compound. For the monitoring of trifluralin molecules, we employed an ion mobility spectrometry apparatus featuring a corona discharge ionization source. The SPME method's effectiveness was examined by investigating the stirring rate and extraction time as two crucial parameters, aiming to achieve trace analysis of trifluralin. Under the optimized condition of the trifluralin extraction, the coefficient (R2) and linear dynamic range (LDR) correlation were obtained at 0.9961 and 0.5-10 µg L-1, respectively. Relative recovery values the described approach were obtained in the span of 96-97% for agricultural wastewater samples. The quantification (LOQ) and limit of detection (LOD) were calculated at 0.5 and 0.15 µg L-1, respectively. The proposed nanocomposite absorbent has the capability to be applied as an efficient material for the extraction of trifluralin herbicide from different solutions.

In situ growth of copper-based metal-organic framework on a helical shape copper wire as a sorbent in stir-bar sorptive extraction of fenthion followed by corona discharge ion mobility spectrometry.

In this paper, a helical copper wire, coated with copper-benzene-1,4-dicarboxylic acid metal-organic framework (Cu-BDC) was used as a sorbent for stir-bar sorptive extraction of fenthion from water and fruit samples. The homogenous coating was fabricated through two simple and fast steps. The chemical conversion of copper substrate to copper hydroxide nanotubes (Cu(OH)2 NTs) was performed in an alkaline solution and then Cu-BDC was formed through a neutralization reaction. Corona discharge ion mobility spectrometry in positive mode was applied for the detection of fenthion. To improve the sensitivity of the method, some synthesis and extraction parameters affecting the extraction efficiency such as benzene-1,4-dicarboxylic acid concentration, ionic strength, sample pH, stirring rate, extraction temperature, and extraction time were investigated. The linear dynamic range between 0.5 and 80 µg L-1 and detection limit of 0.1 µg L-1 were obtained under optimal conditions. The intra- and inter-day relative standard deviations were less than 6.4 and 8.6%, respectively. The applicability of the method was examined for the analysis of different samples (i.e., well water, agricultural wastewater, and orange). The recovery for the determination of fenthion in spiked samples varied from 88 to 111%.

Electrochemically prepared three-dimensional reduced graphene oxide-polyaniline nanocomposite as a solid-phase microextraction coating for ethion determination.

Here, a three-dimensional reduced graphene oxide-polyaniline nanocomposite was synthesized and applied as a sorbent for solid-phase microextraction of ethion from water samples followed by negative corona discharge ionization ion mobility spectrometry. The nanocomposite was synthesized via a fast and facile two-step electrochemical method. The prepared sorbent was characterized by Fourier transform infrared spectroscopy, field emission scanning electron microscopy and thermogravimetric analysis. The main experimental parameters in the preparation of the fiber including concentration of graphene oxide, electrodeposition time, aniline concentration, and electropolymerization time were investigated. Also, parameters affecting the extraction process (i.e., salt addition, sample stirring rate, solution pH, extraction temperature and extraction time) were studied. Under the optimal conditions, the linearity and limit of detection were found to be 1.0-70 and 0.4 µg L-1, respectively. The method presented good precision (intra-day and inter-day, n = 3), ranged from 1.7 to 4.7%. The analyte recovery obtained using spiked real water samples were in the range of 84-98%.

Mg-Al-CO3 layered double hydroxide reinforced polymer inclusion membrane as an extractant phase for thin-film microextraction of cyanide from environmental water samples.

In this paper, a flexible and efficient nano-reinforced polymer inclusion membrane (PIM) was fabricated and used for cyanide (CN-) extraction from water samples. Aliquat 336 (a liquid anion exchanger) was embedded in poly(vinyl chloride) (PVC) support as the extractant. Mg-Al-CO3 layered double hydroxide (LDH) with high surface area and anion exchange ability was applied to promote the extraction efficiency of PIM. A PIM comprising 56% PVC, 40% Aliquat 336, and 4% Mg-Al-CO3 LDH showed the best extraction efficiency. A single beam ultraviolet-visible spectrophotometer was used for the detection of cyanide. Surface morphology of the PIM was studied by field emission scanning electron microscopy. The experimental parameters influencing the extraction process were investigated and optimized. The intra- and inter-day relative standard deviations at two different concentrations were in the range of 2.8-7.6%. The dynamic range of the method was in the range of 5-500 µg L-1, and the detection limit was 1.4 µg L-1. The LDH reinforced PIM showed proper characteristics for the extraction of cyanide from real water and wastewater samples with recoveries between 82 and 115%.

Direct molecular imprinting technique to synthesize coated electrospun nanofibers for selective solid-phase microextraction of chlorpyrifos.

Molecularly imprinted-electrospun nanofibers based on the use of poly(vinyl alcohol) were fabricated and used as a new sorbent for solid-phase microextraction of chlorpyrifos. The molecularly imprinted nanofibers were prepared by electrospinning and direct molecular imprinting of polymeric nanofibers. Poly(vinyl alcohol) was used as the functional and electrospun polymer. Chlorpyrifos was used as a template molecule, and glutaraldehyde as the cross-linker. Detection was performed by ion mobility spectrometry equipped with a secondary electrospray ionization source. The molecularly imprinted fiber has a selectivity and extraction efficiency better than the fiber fabricated using the conventional method of encapsulating MIP particles in electrospun nanofibers. Parameters affecting the extraction efficiency such as ionic strength, stirring rate, extraction time, and temperature were evaluated. The dynamic range of the method was in the range of 0.5-200 µg L-1 with the limit of detection of 0.1 µg L-1. The intra- and inter-day relative standard deviations of the method were 4 and 9%, respectively. The fiber-to-fiber reproducibility for three different fibers is 5%. The spiking recoveries from spiked apple, cucumber, and water samples were in the range of 82-112%. Graphical abstract Molecularly imprinted-electrospun nanofibers were fabricated based on the direct molecular imprinting technique and used as a new SPME fiber coating for selective extraction of chlorpyrifos from fruits and water samples prior its determination by secondary electrospray ionization-ion mobility spectrometry.

Thin film nanofibers containing ZnTiO3 nanoparticles for rapid evaporation of extraction solvent: application to the preconcentration of chlorpyrifos prior to its quantification by ion mobility spectrometry.

Thin film nanofibers containing ZnTiO3 nanoparticles were used for rapid and efficient evaporation of solvents as used to extract analytes by dispersive liquid-liquid microextraction (DLLME). The method is referred to as thin film evaporation (TFE). A combination of DLLME and TFE was applied to the extraction and preconcentration of the pesticide chlorpyrifos (as a model compound) prior to analysis by ion mobility spectrometry. The ZnTiO3 nanoparticles were placed on polyacrylonitrile nanofibers which increases the porosity and surface area in the TFE process, thus causing fast and complete evaporation of solvents. The effects of sample pH value, extraction solvent and its volume, disperser solvent and volume, centrifugation time, evaporation time, and desorption temperature were optimized. The relative standard deviations of intra- and inter-day analyses were found to be 3% and 7%, respectively. The method has a linear dynamic range that covers the 0.10-3.0 µg.L-1 chlorpyrifos concentration range, the limit of detection is 0.04 µg.L-1, and the enrichment factor is up to 5400 in case of spiked samples. Some spiked field samples were analyzed and the relative recoveries ranged between 99 and 111%. When applied along with ion mobility spectrometry, the interferences caused by solvent are found to be reduced in the ionization source. This makes it possible to select a variety of solvents as needed for sample extraction. Graphical abstract Schematic presentation of dispersive liquid-liquid microextraction (DLLME) combined with thin film evaporation (TFE) for rapid vaporization of extraction solvent: Application to the pre-concentration of chlorpyrifos prior to its quantification by corona discharge-ion mobility spectrometry (CD-IMS).

Sol-gel/nanoclay composite as a sorbent for microextraction in packed syringe combined with corona discharge ionization ion mobility spectrometry for the determination of diazinon in water samples.

In this work, the microextraction in packed syringe technique combined with corona discharge ion mobility spectrometry was used for determining diazinon in water samples. A new porous composite of nanoclay and polysiloxane was prepared using a sol-gel process. An amount of 2.0 mg of the sorbent was packed in a 250 µL syringe and used for extraction. A volume of 2 mL of the sample was passed through the sorbent bed, and the entrapped analyte was eluted by 25 µL of methanol. Important parameters influencing the extraction performance were investigated. Under optimum experimental conditions, the detection limit for diazinon was 0.07 ng/mL. The intra- and inter-day relative standard deviations were 5.0 and 12.3%, respectively. The calibration curve was linear in the concentration range from 0.2 to 20.0 ng/mL (r2  = 0.999). The applicability of the method was demonstrated by analyzing spiked real water samples and the spiking recoveries were in the range of 95 to 106%.

Chemically modified halloysite nanotubes as a solid-phase microextraction coating.

Halloysite nanotubes were modified in three simple steps including etching, hydroxylation and amino grafting. The sol-gel technique was used for the chemical bonding of the modified halloysite nanotubes (MHNTs) to fused-silica support. The MHNTs, as a novel adsorbent was applied as a SPME coating. Diazinon, parathion and fenthion were selected as the model compounds to study the extraction efficiency of the coating. Gas chromatography-corona discharge ion mobility spectrometry was applied for the analysis of the extracted analytes. The parameters influencing the extraction efficiency of the method, such as stirring rate, salt effect, extraction temperature and time were optimized. The results showed that the MHNTs fiber had better extraction efficiency than the commercial SPME (PA, PDMS, and PDMS-DVB), bare silica, silica-based HNTs and HNTs-titanium dioxide fibers. The limits of detection were found to be in the range of 0.01-0.03 µg L-1. The limits of quantification were in the range of 0.03-0.07 µg L-1. Also, a good linearity in the range of 0.03-3.0, 0.07-2.0 and 0.03-3.0 µg L-1, was found for diazinon, fenthion and parathion, respectively. The method precision was lower than 7.0 and 8.7% as the intra- and inter-day relative standard deviations, respectively. Agricultural wastewater, cucumber and apple were chosen as the real samples. The spiking recovery values were between 84 (±9) and 97% (±6). The results showed that the method was applicable and suitable for real samples analysis.

Halloysite nanotubes-titanium dioxide as a solid-phase microextraction coating combined with negative corona discharge-ion mobility spectrometry for the determination of parathion.

Halloysite nanotubes-titanium dioxide (HNTs-TiO2) as a biocompatible environmentally friendly solid-phase microextraction (SPME) fiber coating was prepared. HNTs-TiO2 was chemically coated on the surface of a fused-silica fiber using a sol-gel process. Parathion as an organophosphorus pesticide was selected as a model compound to investigate the extraction efficiency of the fiber. The extracted analyte was detected by negative corona discharge-ion mobility spectrometer (NCD-IMS). The effective parameters on the extraction efficiency, such as salt effect, extraction temperature and extraction time were investigated and optimized. The extraction efficiency of HNTs-TiO2 fiber was compared with bare-silica (sol-gel based coating without HNTs-TiO2), HNTs, carbon nanotubes and commercial SPME fibers (PA, PDMS, and PDMS-DVB). The HNTs-TiO2 fiber showed highest extraction efficiency among the studied fibers. The intra- and inter-day relative standard deviations were found to be 4.3 and 6.3%, respectively. The limit of detection and limit of quantification values were 0.03 and 0.1 µg L(-1), respectively. The dynamic range of the method was in the range of 0.1-25 µg L(-1). The spiking recoveries were between 85 (±9) and 97 (±6). The SPME-HNTs-TiO2 combined with NCD-IMS was successfully applied for the determination of parathion in apple, strawberry, celery and water samples.

Carbon nanotubes@silicon dioxide nanohybrids coating for solid-phase microextraction of organophosphorus pesticides followed by gas chromatography-corona discharge ion mobility spectrometric detection.

A high efficiency solid-phase microextraction (SPME) fiber coated with porous carbon nanotubes-silicon dioxide (CNTs-SiO2) nanohybrids was synthesized and applied for the determination of some organophosphorus pesticides (OPPs) in vegetables, fruits and water samples. Gas chromatography-corona discharge ion mobility spectrometry was used as the detection system. Glucose, as a biocompatible compound, was used for connecting CNT and SiO2 during a hydrothermal process. The electrospinning technique was also applied for the fiber preparation. The parameters affecting the efficiency of extraction, including stirring rate, salt effect, extraction temperature, extraction time, desorption temperature and desorption time, were investigated and optimized. The developed CNTs@SiO2 fiber presented better extraction efficiency than the commercial SPME fibers (PA, PDMS, and PDMS-DVB). The intra- and inter-day relative standard deviations were found to be lower than 6.2 and 9.0%, respectively. For water samples, the limits of detection were in the range of 0.005-0.020 µg L(-1) and the limits of quantification were between 0.010 and 0.050 µg L(-1). The results showed a good linearity in the range of 0.01-3.0 µg L(-1) for the analytes. The spiking recoveries ranged from 79 (± 9) to 99 (± 8). The method was successfully applied for the determination of OPPs in real samples.

Sol-gel/nanoclay composite as a solid-phase microextraction fiber coating for the determination of organophosphorus pesticides in water samples.

A novel solid-phase microextraction (SPME) fiber coated with a sol-gel/nanoclay composite was prepared by the sol-gel technique involving the hydrolysis reaction of alkoxysilanes and the subsequent condensation reaction with hydroxyl groups of the nanoclay on a stainless steel wire. A method based on direct immersion SPME and gas chromatography-corona discharge ion mobility spectrometry was developed for the determination of four organophosphorus pesticides in aqueous samples. The effect of different experimental parameters on the extraction efficiency of the method was investigated. The sol-gel/nanoclay fiber showed higher extraction performance for the organophosphorus pesticides compared with Ppy/nanoclay, sol-gel coating, and three commercial fibers (polydimethylsiloxane (PDMS), PDMS/divinylbenzene (DVB), and polyacrylate (PA)). Limits of detection (LOD) and quantitation (LOQ) of the method were in the range of 0.003-0.012 and 0.01-0.02 µg L(-1), respectively. The calibration curves were linear in a concentration range from 0.01 to 2.0 µg L(-1) (r (2) > 0.995). The relative standard deviations for intra- and inter-day precision were 3.3-5.6 and 6.4-8.4 %, respectively. Fiber-to-fiber reproducibility for three prepared fibers was 7.4-10.2 %. Finally, the method was successfully applied for the extraction of the studied compounds from water samples. The relative recovery obtained for the spiked real-water samples were 86-104 %.

Selective extraction and analysis of pioglitazone in cow plasma using a molecularly imprinted polymer combined with ESI ion mobility spectrometry.

A method based on ESI ion mobility spectrometry as a detection technique after treatment with a molecularly imprinted polymer is described for the analysis of pioglitazone. In addition to the molecularly imprinted polymer separation methodology, the positive ion mobility spectrum and the reduced mobility values for pioglitazone are reported for the first time. The method was exhaustively validated in terms of sensitivity, imprinting factor, enrichment factor, and sorption capacity. A linear dynamic range of 0.10-20.00 µg/mL and an RSD below 6% were obtained for the analysis of this compound. The average recovery for the analysis of spiked samples was calculated to be about 91%. The method was also used to determine pioglitazone in cow plasma, and the results were compared with those obtained using HPLC. The satisfactory results evidence a convenient method for the analysis of the target compound in real samples without using any additional derivatization methods.

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.

Hollow fiber-based liquid-liquid-liquid microextraction combined with electrospray ionization-ion mobility spectrometry for the determination of pentazocine in biological samples.

A new method based on liquid-liquid-liquid microextraction combined with electrospray ionization-ion mobility spectrometry (LLLME-ESI-IMS) was used for the determination of pentazocine in urine and plasma samples. Experimental parameters which control the performance of LLLME, such as selection of composition of donor and acceptor phase, type of organic solvent, ionic strength of the sample, extraction temperature and extraction time were studied. The limit of detection and relative standard deviation of the method were 2 ng/mL and 5.3%, respectively. The linear calibration ranged from 10 to 500 ng/mL with r(2)=0.998. Pentazocine was successfully determined in urine and plasma samples without any significant matrix effect.