Combination of online hollow fiber liquid phase microextraction with smartphone-based sensing for in situ formaldehyde assay in fabric and wastewater samples.

A miniaturized analytical methodology was introduced based on the combination of a direct and online hollow fiber microextraction method with smartphone color detection. The method was used for the determination of formaldehyde (target analyte) in fabric and wastewater samples. In this regard, two reagents including ammonium acetate buffer and acetylacetone were added to the formaldehyde samples to create a colored compound. The colored compound was extracted from the sample by using the hollow fiber liquid-phase microextraction method, the extracted phase was not taken out of the extraction box and was directly transferred into a specially designed detection cell, and a smartphone was applied for in-situ color sensing and data readout. This combination gathered the advantages of both state-of-the-art microextraction techniques and smartphone sensing. Formaldehyde, as a carcinogenic compound widely used in paint and clothing industries, was selected as a model test. Factors affecting extraction efficiency were investigated and optimized, including the type of organic solvents, reagent concentration, salt, pH, stirring speed, reaction temperature, and extraction time. The linear region of the method under optimal conditions was 40-1500 µg L-1 for wastewater samples and 0.3-11.2 mg kg-1 for fabrics. The limit of detection and limit of qualification were 13 and 40 µg L-1, respectively. The relative standard deviations for concentrations of 100 and 1000 µg L-1 were 6% and 4%, respectively. To evaluate the application of the method for real samples, types of fabric and two samples of oil refinery wastewater were selected. The relative recovery in real samples was 84-98%. The results of the analytical parameters of the method show that the developed method can be used as an efficient method to determine formaldehyde in real samples.

Development of a colorimetric sensor based on the coupling of a microfluidic paper-based analytical device and headspace microextraction for determination of formaldehyde in textile, milk, and wastewater samples.

A user-friendly, cost-effectively, portable, and environmentally friendly colorimetric sensor for the quantitative determination of formaldehyde was developed based on the combining of microfluidic paper-based analytical device (µPAD), headspace microextraction (HSME), and digital image colorimetry. Coupling HSME and µPAD led to enhancements in selectivity and sensitivity of the sensor through sample cleanup and analyte enrichment. To construct the µPAD-HSME device, two pieces of paper as the sample and detection zone were placed facing each other so that a small common and sealed space was created between them. The color change occurred when the analyte in the gaseous form crossed this gap and reached the detection zone. Colorimetric sensing in the detection zone was performed based on the Hantzsch reaction. The color change in the detection zone was recorded by a smartphone and digital images were processed using image analysis software based on the RGB model. The influence of some key variables on the sensitivity of the method including derivatization reagent composition, sample volume, extraction temperature, and extraction time was studied and optimized. The linear dynamic range of the method was obtained in two ranges of 0.10-0.75 and 0.75-5.0 mg L-1 with a limit of detection of 0.03 mg L-1. The recoveries were in the range 80-126% for the quantification of formaldehyde in textile, milk, and wastewater samples.

Evaluating cottonwood seeds as a low-cost biosorbent for crystal violet removal from aqueous matrics.

In this study, cottonwood seeds (CWS) were introduced as a novel, green, and low-cost biosorbents for the removal of crystal violet (CV) dye from aqueous solutions. To illustrate the characteristics of CWS, surface morphology, Fourier-transform infrared spectroscopy, field emission scanning electron microscopes, and energy dispersive X-ray spectroscopy techniques were employed. Important adsorption variables (i.e., equilibrium time, solution pH, CWS amount, CV concentration, and temperature) were systematically studied. Maximum CV dye adsorption was observed at pH 10 using 20 mg of the adsorbent. Different adsorption isotherms were investigated, and the results were more accurately consistent with the Langmuir model (R2 = 0.992). The maximum capacity of adsorption was 153.85 mg g-1 at 60 min. The kinetic data were examined by different models and a pseudo-second-order model supplied the best correlation between experimental data. Investigated thermodynamic parameters at different temperatures illustrated that the CV adsorption procedure was spontaneous and endothermic with an increase in entropy. The percentage removal and the relative standard deviations for the real sample analysis were in the range of 89-98% and 4.9-9.5%, respectively. High adsorption capacity and low equilibrium time demonstrated that CWS is an impressive biosorbent for dye pollutants uptakes from aqueous solutions and real industrial wastewater samples.

A novel, green, available, and low-cost cottonwood seeds were introduced for the removal of crystal violet from aqueous media. In terms of adsorption capacity and contact time, cottonwood seeds show excellent performance compared to the other low-cost biosorbents previously reported for the adsorption of the organic dye from wastewater. The use of cottonwood seeds to remove environmental pollutants has not been introduced yet.

Synthesis and characterization of g-C3N4-modified zeolite and its application as a methyl violet 6b cationic dye sorbent.

This paper reports a novel, low-cost, and facile approach to prepare a hybrid material consisting of zeolite, Fe3O4, and graphitic carbon nitride as a sorbent to remove methyl violet 6b (MV) from aqueous solutions. To improve the performance of the zeolite for the removal of MV, graphitic carbon nitride (with different C-N bonds and conjugated π region) was used. Also, to perform an easy and fast separation of sorbent from aqueous media, magnetic nanoparticles were incorporated into the sorbent. The prepared sorbent was characterized by different analytical techniques such as X-ray diffraction analysis, Fourier transform infrared, field emission scanning electron microscopy, and energy-dispersive X-ray analysis. The effects of four parameters of initial pH, initial concentration of MV, contact time, and the adsorbent amount on the removal process were investigated and optimized by the central composite design method. The removal efficiency of MV was modeled as a function of the experimental parameters. Affording to the proposed model, the values of 10 mg, 28 mg L-1, and 2 min were selected as optimum condition for adsorbent amount, initial concentration, and contact time, respectively. Under this condition, the optimal removal efficiency was 86% ± 2.8 which were close to the predicted value of the model (89%). Therefore, the model could fit and predict the data. The maximal adsorption capacity of sorbent derived from Langmuir's isotherm was 384.6 mg g-1. The applied composite can efficiently remove MV from various wastewater samples (paint, textile industries, pesticide production wastewater samples, and municipal wastewater).

Electroanalytical Sensor Based on Gold-Nanoparticle-Decorated Paper for Sensitive Detection of Copper Ions in Sweat and Serum.

The growth of (bio)sensors in analytical chemistry is mainly attributable to the development of affordable, effective, portable, and user-friendly analytical tools. In the field of sensors, paper-based devices are gaining a relevant position for their outstanding features including foldability, ease of use, and instrument-free microfluidics. Herein, a multifarious use of filter paper to detect copper ions in bodily fluids is reported by exploiting this eco-friendly material to (i) synthesize AuNPs without the use of reductants and/or external stimuli, (ii) print the electrodes, (iii) load the reagents for the assay, (iv) filter the gross impurities, and (v) preconcentrate the target analyte. Copper ions were detected down to 3 ppb with a linearity up to 400 ppb in standard solutions. The applicability in biological matrices, namely, sweat and serum, was demonstrated by recovery studies and by analyzing these biofluids with the paper-based platform and the reference method (atomic absorption spectroscopy), demonstrating satisfactory accuracy of the novel eco-designed analytical tool.

A novel nanocomposite based on covalent organic polymer and nanocellulose for thin-film microextraction of imipramine from biological samples.

A novel covalent organic polymer was prepared using 1,5-diaminonaphthalene as a linker and cyanuric chloride as a node. A thin-film nanocomposite of 1,5-diaminonaphthalene covalent organic polymer and cellulose nanocrystalline was then fabricated via filtering and casting method. The effect of incorporation of various amounts of 1,5-diaminonaphthalene covalent organic polymer and cellulose nanocrystalline was studied to obtain an efficient nanocomposite thin-film with a large number of polar functional groups and high mechanical stability. Field emission scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectrometry, and thermogravimetric analysis techniques were applied for the characterization of physicochemical properties of the prepared materials. Imipramine was determined in the biological samples using thin-film microextraction followed by gas chromatography flame ionization detection. Parameters affecting the extraction efficiency of imipramine were investigated. Under the optimized conditions, the limit of detection was 0.5 ng/mL. Film-to-film reproducibility for three different films fabricated under the same conditions (at three concentration levels) varied between 8.9 and 9.7%. The linear dynamic range covered more than three orders of magnitude (2-5000 ng/mL) with a determination coefficient of 0.9985. The method was successfully applied for preconcentration and determination of imipramine in biological samples with spiking recoveries between 78 and 93%.

Covalent triazine-based framework-grafted functionalized fibrous silica sphere as a solid-phase microextraction coating for simultaneous determination of fenthion and chlorpyrifos by ion mobility spectrometry.

A novel covalent triazine-based framework (CTF)-grafted phenyl-functionalized fibrous silica nanosphere, KCC-1 (named as RS-2) was synthesized via a simple and effective Friedel-Crafts approach. The microporous CTF with fluorene backbone was coupled and grown uniformly on the surface of phenyl-functionalized KCC-1 to prepare a hybrid extended porous framework. The prepared materials were characterized, and FE-SEM and TEM images revealed a flower-like structure for RS-2. The synthesized RS-2 showed excellent thermal stability, so the weight loss was about 30% at 800 °C. RS-2 was applied as a new coating in the solid-phase microextraction procedure to extract chlorpyrifos and fenthion pesticides from water, wastewater, and fruit samples, before determining by corona discharge-ion mobility spectrometry. Some experimental factors affecting the extraction yield of the analytes, including ionic strength, stirring rate, sample pH, extraction temperature, and extraction time, were investigated. Under optimum conditions, the linear dynamic ranges were 0.1-10 µg L-1 and 1.0-70 µg L-1, and the limits of detection were 0.05 and 0.55 µg L-1 for chlorpyrifos and fenthion, respectively. The proposed method showed recovery values in the range 86-117% with a precision of 3.0-7.1% for real samples. Covalent triazine-based framework (CTF)-grafted phenyl-functionalized fibrous silica nanosphere (named as RS-2) was synthesized. RS-2 was applied as a sorbent for solid-phase microextraction (SPME) of chlorpyrifos and fenthion from fruit and water samples followed by corona discharge ionization ion mobility spectrometry (CD-IMS).

Solvent holder-assisted liquid-phase microextraction using nano-structure biomass-derived carbonaceous aerogel combined with ion mobility spectrometry for simultaneous determination of ethion and chlorpyrifos.

A biomass-derived sponge-like carbonaceous aerogel was prepared through a two-step procedure, including hydrothermal carbonization and freeze-drying process. The aerogel was employed as the solvent holder for liquid-phase microextraction of organophosphorus pesticides, ethion, and chlorpyrifos (as the model compounds), prior to determination by secondary electrospray ionization-ion mobility spectrometry. The carbonaceous aerogel is an appropriate candidate to be used as the solvent holder due to some properties such as three-dimensional structure, porous nature, and very low density. So, the aerogel, including extraction solvent, can tumble on the top of the sample solution, without loss of solvent during its agitation. A comparison of the extraction efficiency was performed at similar conditions between the proposed method and single-drop microextraction, as well as hollow-fiber solvent bar microextraction. Different parameters affecting the extraction efficiency, such as stirring rate, salt concentration, temperature, and extraction time were investigated by using the response surface methodology. The linear dynamic range was in the ranges 1-30 and 1-70 µg L-1 with regression coefficients of 0.9973 and 0.9956 for ethion and chlorpyrifos, respectively. The limit of detection was 0.09 and 0.21 µg L-1 for ethion and chlorpyrifos, respectively. The method was used for extracting analytes from environmental water and vegetable samples, with the spiking recoveries in the range 80-121%. Graphical abstract Schematic representation of three-dimensional biomass-derived carbonaceous aerogel as the solvent holder in solvent bar microextraction (as a mode of the liquid-phase microextraction method). It was used for the extraction of two kinds of organophosphorus pesticides prior to the determination by ion mobility spectrometry.

Combining gold nanoparticle-based headspace single-drop microextraction and a paper-based colorimetric assay for selenium determination.

A novel method combining headspace single-drop microextraction with a paper-based colorimetric assay was developed. Headspace single-drop microextraction using a microdrop containing unmodified gold nanoparticles (AuNPs) as both the extractant and the colorimetric probe was used for the sensitive and selective determination of Se(IV). The method relies on the color change of the microdrop solution caused by the adsorption of in situ-generated hydrogen selenide on the surface of AuNPs. Following extraction, the microdrop was spotted onto cellulose paper, and scanometric-assisted digital image analysis was used for selenium quantification. The analytical variables affecting the method sensitivity, including the drop volume, the concentrations of KBH4, HCl, and AuNP solutions, and the extraction time, were studied. Under the optimal conditions, a linear correlation between the colorimetric signal and Se(IV) concentration in the range from 15-100 µg L-1 with a limit of quantification of 12 µg L-1 was achieved. The repeatability of the method was studied by the calculation of intraday and interday precision for the standard solutions at concentrations of 20 and 70 µg L-1. The batch-to-batch reproducibility of the AuNPs synthesized under the same conditions was also assessed. The relative standard deviations were less than 7%. The method provided satisfactory results for the determination of selenium in real samples.

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.

Porous magnetized carbon sheet nanocomposites for dispersive solid-phase microextraction of organophosphorus pesticides prior to analysis by gas chromatography-ion mobility spectrometry.

Carbon sheets were attached to magnetite (Fe3O4) nanoparticles. The resulting nanocomposite is shown to be a viable sorbent for use in magnetic dispersive solid-phase microextraction of three organophosphorus pesticides. The sorbent was synthesized via the sol-gel process followed by calcination and was characterized by an X-ray diffractometer, field emission scanning electron microscopy and energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and Raman spectrometry techniques. The affecting parameters in the adsorption and desorption steps were assessed and optimized via response surface methodology. Following desorption with dichloromethane, the OPPs were quantified by gas chromatography along with ion mobility spectrometry detection. Under optimized conditions, the limits of detection were 1.00, 0.46 and 0.85 µg L-1 for fenthion, malathion and chlorpyrifos, respectively. Response is linear in the concentration range of 2-500 µg L-1 for fenthion and malathion, and 2-1000 µg L-1 for chlorpyrifos with the determination coefficient larger than 0.9969. The intra-day and inter-day precision were from 3 to 9% and 5 to 16%, respectively. The enrichment factor was greater than 142 for all the studied pesticides. The sorbent was used for analyze spiked water and vegetable samples and gave relative recovery higher than 82%. Graphical abstract A flowchart of the synthesis of porous magnetized carbon sheet nanocomposites and the process of the magnetic dispersive solid-phase microextraction (MD-µ-SPE) of three organophosphorus pesticides prior to analysis by gas chromatography-ion mobility spectrometry (GC-IMS).

Magnetic Polyamide Nanocomposites for the Microextraction of Benzophenones from Water Samples.

In this article, the influence of the monomers on the extraction efficiency and the effect of the addition of surfactants during the synthesis have also been considered. The sorption capacity of the resulting nanocomposites has been evaluated, in the dispersive micro-solid phase extraction format, by determining that of six benzophenones in water using ultra performance liquid chromatography (UPLC) combined with photodiode array detection. Under the optimum conditions, the limits of detection were in the range of 0.5⁻4.3 ng/mL and the repeatability, expressed as the relative standard deviation (RSD), varied between 1.5% and 5.6%. The proposed method has been applied for the analysis of real water samples, providing relative recoveries in the interval of 84⁻105.

Comparison of three different dispersive liquid-liquid microextraction modes performed on their most usual configurations for the extraction of phenolic, neutral aromatic, and amino compounds from waters.

In this work we seek clues to select the appropriate dispersive liquid-liquid microextraction mode for extracting three categories of compounds. For this purpose, three common dispersive liquid-liquid microextraction modes were compared under optimized conditions. Traditional dispersive liquid-liquid microextraction, in situ ionic liquid dispersive liquid-liquid microextraction, and conventional ionic liquid dispersive liquid-liquid microextraction using chloroform, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-hexyl-3-methylimidazolium hexafluorophosphate as the extraction solvent, respectively, were considered in this work. Phenolic, neutral aromatic, and amino compounds (each category included six members) were studied as analytes. The analytes in the extracts were determined by high-performance liquid chromatography with UV detection. For the analytes with polar functionalities, the in situ ionic liquid dispersive liquid-liquid microextraction mode mostly led to better results. In contrast, for neutral hydrocarbons without polar functionalities, traditional dispersive liquid-liquid microextraction using chloroform produced better results. In this case, where dispersion forces were the dominant interactions in the extraction, the refractive index of solvent and analyte predicted the extraction performance better than the octanol/water partition coefficient. It was also revealed that none of the methods were successful in extracting hydrophilic analytes (compounds with the log octanol/water partition coefficient <2). The results of this study could be helpful in selecting a dispersive liquid-liquid microextraction mode for the extraction of various groups of compounds.

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%.

Automated solid-phase extraction of phenolic acids using layered double hydroxide-alumina-polymer disks.

The application of layered double hydroxide-Al2 O3 -polymer mixed-matrix disks for solid-phase extraction is reported for the first time. Al2 O3 is embedded in a polymer matrix followed by an in situ metal-exchange process to obtain a layered double hydroxide-Al2 O3 -polymer mixed-matrix disk with excellent flow-through properties. The extraction performance of the prepared disks is evaluated as a proof of concept for the automated extraction using sequential injection analysis of organic acids (p-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, gallic acid) following an anion-exchange mechanism. After the solid-phase extraction, phenolic acids were quantified by reversed-phase high-performance liquid chromatography with diode-array detection using a core-shell silica-C18 stationary phase and isocratic elution (acetonitrile/0.5% acetic acid in pure water, 5:95, v/v). High sensitivity and reproducibility were obtained with limits of detection in the range of 0.12-0.25 µg/L (sample volume, 4 mL), and relative standard deviations between 2.9 and 3.4% (10 µg/L, n = 6). Enrichment factors of 34-39 were obtained. Layered double hydroxide-Al2 O3 -polymer mixed-matrix disks had an average lifetime of 50 extractions. Analyte recoveries ranged from 93 to 96% for grape juice and nonalcoholic beer samples.

Hydrazide functionalized magnetic nanoparticles for specific extraction of N-terminal serine and threonine peptides.

In this study, we present hydrazide functionalized magnetic nanoparticles as a sorbent prepared by a new and facile method. Scanning electron microscope and Fourier transform infrared were used for characterizing the synthesized nanoparticles. The ability of the sorbent to extract N-terminal serine and threonine peptides was evaluated. The peptides were modified by oxidation of the hydroxyl group in the 1,2-amino alcohol structure before extraction. These aldehyde-forms of peptides were specifically bonded to the hydrazide groups of the sorbent. The formed hydrazone bonds were cleaved in the presence of hydroxylamine reagent. Finally, the oximated peptides were released and quantified with a high-performance liquid chromatography-diode array spectroscopy. The effects of experimental parameters including extraction time, elution time and elution volume on extraction efficiency were also investigated. The required time for the extraction process to reach equilibrium and elution time was only 8 h. The adsorption efficiency of the sorbent was 79 and 77% for peptides with N-terminal serine and threonine, respectively. The sorbent showed good specificity for extracting the peptides. In addition, the extraction efficiency of the sorbent remained constant in the presence of a non-N-terminal serine and threonine peptide as interference.

Plasmid DNA purification by zirconia magnetic nanocomposite.

A zirconia magnetic nanocomposite was prepared by a co-precipitation method in one step. The synthesized nanocomposite was characterized by scanning electron microscopy, energy-dispersive X-ray and Fourier transform infrared spectroscopy. The nanocomposite was applied for the adsorption/desorption of tobacco plant DNA (as a model). Experimental parameters controlling adsorption efficiency, including pH of binding solution, extraction time, the amount of nanocomposite and ionic strength, were optimized. To obtain high desorption efficiency, the effects of pH, the ionic strength of elution buffer and desorption time were investigated. The nanocomposite provided the adsorption capacity of 53.5 mg g-1 for DNA. The adsorption and desorption efficiency of the sorbent was found to be greater than 98 and 81%, respectively. The zirconia magnetic nanocomposite was used for the purification of plasmid DNA (pDNA) from Escherichia coli cell culture. The yield and purity of pDNA obtained by the method were compared to those obtained by the phenol-chloroform solvent extraction and a commercial kit.

Octadecylsilane/Nylon-6 composite as a thin-film microextraction sorbent for the determination of bisphenol A in water samples.

We report on the fabrication of a thin-film composite for the extraction of bisphenol A from aqueous solutions. Nylon-6, C18 particles, and polyethylene glycol were used to prepare the thin film sorbent. Bisphenol A was used as a model compound to evaluate the extraction efficiency of the sorbent. High-performance liquid chromatography with UV detection was used for the analysis. The extraction yield of the sorbent was compared with other thin films fabricated using different sorbents including nanoclay, LiChrolut EN, and multiwalled carbon nanotubes. Experimental parameters affecting the extraction performance (extraction time, desorption condition, sample stirring, and ionic strength of the sample solution) were investigated. The detection limit and the dynamic range of the method were 0.05 and 0.15-50 µg/L, respectively. The relative standard deviation of the method at two concentration levels (0.5 and 20 µg/L) was less than 7.2%. Finally, a polycarbonate baby bottle, river water, and wastewater samples were analyzed by the method.

Anticodeine aptamer immobilized on a Whatman cellulose paper for thin-film microextraction of codeine from urine followed by electrospray ionization ion mobility spectrometry.

A combination of thin-film microextaction based on an aptamer immobilized on modified Whatman cellulose paper followed by electrospray ionization ion mobility spectrometry has been developed for the analysis of codeine in urine samples. The immobilization is based on the covalent linking of an amino-modified anticodeine aptamer to aldehyde groups of the oxidized cellulose paper. The covalent bonds were examined by infrared spectroscopy and elemental analysis. The effect of the extraction parameters, including the elution conditions (solvent type and volume), extraction time, and extraction temperature, on the extraction efficiency were investigated. Under the optimized conditions, the linear dynamic range was found to be 10-300 ng/mL with a detection limit of 3.4 ng/mL for codeine in urine. The relative standard deviation was 6.8% for three replicate measurements of codeine at 100 ng/mL in urine. Furthermore, the samples were analyzed with a standard method for the analysis of codeine using high-performance liquid chromatography with ultraviolet detection. The comparison of the results validates the accuracy of the proposed method as an alternative method for the analysis of codeine in urine 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 %.