Evaluation of polypyrrole/silver/polyethylene glycol nanocomposite sorbent for electroenhanced direct-immersion solid-phase microextraction of carvacrol and thymol from medicinal plants

The unique features of nanostructured polypyrrole, conductivity enhancement effect of silver nanoparticles and high polar adsorptivity of polyethylene glycol were merged into polypyrrole/silver/polyethylene glycol (PPy/Ag/PEG) nanocomposite. It was synthesized and simultaneously coated on the surface of a stainless-steel fiber using an amended electropolymerization procedure. Before coating, the fiber substrate was made porous and sticky by allocating platinum dots on the surface of the stainless-steel fiber using the electrophoretic method. The prepared fiber was applied for the extraction of carvacrol and thymol (the most important antioxidants in medicinal plants) through an electroenhanced direct-immersion solid-phase microextraction (EE-DI-SPME) sampling strategy, followed by GC-FID quantification. To achieve the best efficiency, the effectual experimental variables including pH of sample solution, applied voltage, extraction temperature and time, stirring rate, and ionic strength were investigated. Under the optimal experimental conditions, the calibration curves were linear over the range of 0.5–30 µg mL^?1 for thymol and 0.01–30 µg mL^?1 for carvacrol. The detection limits (3S_b) and relative standard deviation (RSD%, n?=?6) were obtained to be 0.15, 0.003 µg mL^?1 and 10.2, 8.7% for thymol and carvacrol, respectively. The results demonstrated the priority of the proposed fiber compared with polypyrrole and polyacrylate fibers, in terms of extraction efficiency, durability and stability. The developed method was successfully employed for the analysis of thymol and carvacrol in medicinal plants.     

A new porous-layer activated-charcoal-coated fused silica fiber: Application for determination of BTEX compounds in water samples using headspace solid-phase microextraction and capillary gas chromatography

Summary Extra-fine powdered activated charcoal has been used as stationary phase (coating layer) in solid-phase microextraction (SPME). The efficiency and reliability of the prepared device have been investigated for the extraction of some volatile organic compounds such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) from the headspace of water samples. Monitoring of the extracted compounds and further quantitative analysis of the real samples have been performed by capillary GC-FID. Effects of several factors such as temperature, addition of salt, and stirring speed on extraction efficiency and exposure time have been studied. Under optimum conditions, extraction recoveries for these compounds from 50 mL water were >95%. The calibration graphs were linear in the range 5 to 10⁴ pg mL⁻¹ and the detection limit for each BTEX compound was 1.5–2 pg mL⁻¹. The results obtained by use of this porous layer activated charcoal (PLAC)-coated fiber have also been compared with results reported in the literature by use of a polydimethylsiloxane (PDMS)-coated fiber. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Comparative study of direct immersion and headspace single drop microextraction techniques for BTEX determination in water samples using GC-FID

In the present work the determination of benzene, toluene, ethylbenzene and o-xylene (BTEX) in environmental sample solutions using gas chromatography with flame ionisation detection (GC-FID) combined with three different sampling techniques, such as; direct single drop microextraction (DI-SDME), headspace single drop microextraction (HS-SDME) and ultrasonic assisted HS-SDME, were compared. In all of these techniques, for the determination of BTEX, the experimental parameters such as organic solvent effect, extraction time, agitation speed and salting effect were optimised. At their optimised conditions of operation the detection limits, times of extraction and precision for the three techniques are established. A detailed comparison of the analytical performance characteristics of these techniques for final GC-FID determination of BTEX in water samples was given. The technique provided a linear range of 50–20000?ng?mL^–1 for DI-SDME and 10–20000?ng?mL^–1 for HS-SDME methods, good repeatability (RSDs <4.72–7.74% for DI-SDME and 1.80–7.05% for HS-SDME (n?=?5), good linearity (r?≥?0.9978) and limits of detection (LODs) in the range of 0.006–10?ng?mL^?1 for DI-SDME, 0.1–3?ng?mL^–1 for HS-SDME methods (S/N?=?3). Then the optimised techniques were also applied to real samples (river and waste waters) containing BTEX and similar precision (RSD?<?8.2,?n?=?3) was obtained.     

Preparation of an ionic liquid-mediated carbon nanotube-poly(dimethylsiloxane) fiber by sol–gel technique for determination of polycyclic aromatic hydrocarbons in urine samples using head-space solid-phase microextraction coupled with gas chromatography

A novel ‘ionic liquid-mediated multi-walled carbon nanotube (MWCNT)-poly(dimethylsiloxane) (PDMS)’ hybrid coating was prepared by the covalent functionalization of MWCNTs with hydroxyl-terminated PDMS using the sol–gel technique. The prepared fiber was successfully used for the separation and determination of trace amounts of polycyclic aromatic hydrocarbon compounds (PAHs) in four urine samples using head-space solid-phase microextraction coupled to gas chromatography-flame ionization detection. The proposed fiber has high thermal stability and long durability and it can be used more than 210 times without any significant change in its sorption properties. The effects of important parameters such as the exposure time, sampling temperature, sample ionic strength and stirring rate on the extraction efficiency have been studied and optimized. Under the optimal conditions, the method detection limits (S/N = 3) were in the range of 0.0005–0.004 ng mL^?1 and the limits of quantification (S/N = 10) between 0.002 and 0.01 ng mL^?1. The relative standard deviations for one fiber (repeatability, n = 5) were 4.9–7.5 % and for the fibers obtained from different batches (reproducibility, n = 3), 6.1–8.9 %. The developed method was successfully applied to determine trace levels of PAHs in real urine samples. The obtained relative recoveries for the spiked samples with 0.05 ng mL^?1 of each of the PAH compounds were 89.3–107.2 %.     

Application of Sol–Gel Based Poly(ethylene glycol)/Multiwalled Carbon Nanotubes Coated Fiber for SPME of Methyl tert-Butyl Ether in Environmental Water Samples

In this research, the sol–gel technology was applied for the preparation of solid-phase microextraction fibers for extracting of methyl tert-butyl ether (MTBE) from environmental water samples. For this purpose, two different polymers such as poly(ethylene glycol) (PEG) and combination of PEG and multiwall carbon nanotubes (MWCNTs) were prepared using sol–gel technology as coating procedure for the fibers. The pre-concentration process followed by GC–FID determination was used and the results evidenced that pre-concentration factor for PEG/CNTs fiber was approximately five times higher than PEG. Parameters affecting the extraction efficiency such as temperature, extraction time, stirring speed and salt effect for each fiber were investigated and optimized. On the optimal conditions, the linear range for MTBE with PEG and PEG/CNT fibers were 10–3,000 and 1–1,000 ng mL^?1 and the detection limits (S/N = 3) were 1.0 and 0.3 ng mL^?1, respectively. The sol–gel PEG/CNTs fiber has good performance and therefore relatively better figures of merit and experimental results such as thermal stability (up to 320 °C), average of life time (over 150 times) and repeatability (RSD < 4) in comparison to conventional PDMS/Carboxen fiber, which was already reported for determination of MTBE.     

Determination of BTEX in Water Samples with an SPME Hollow Fiber Coated Copper Wire

A piece of copper wire coated with a polypropylene hollow fiber membrane was used as an SPME fiber and its efficiency for extraction of BTEX compounds from the headspace of water samples prior to GC analysis was evaluated. Under optimum extraction conditions, limits of detection for benzene, toluene, ethylbenzene, m-p-xylene, and o-xylene were found to be 0.11, 0.22, 0.26, 0.37, and 0.26 μg L^?1, respectively. Low detection limits, wide linear dynamic ranges, good reproducibility (RSD% <4), high fiber capacity and higher mechanical durability are some of the most important advantages of the new fiber.     

Electrodeposition of a copolymer nanocomposite for the headspace solid-phase microextraction of benzene,toluene, ethylbenzene and xylenes

In this study, polyaniline-co-poly(o-toluidine)/graphene oxide nanosheets composite was electrodeposited on the surface of a stainless steel wire as a new coating for headspace solid-phase microextraction of benzene, toluene, ethylbenzene and xylenes (BTEX) with gas chromatography–mass spectrometry. The characteristics of the new coating were evaluated by the scanning electron microscopy and Fourier transform infrared spectroscopy. To study the coating performance, the influence of various parameters such as deposition potential and time, concentration of the monomers and GONSs, desorption temperature and time, extraction temperature and time and ionic strength on BTEX extraction efficiency was investigated. At the optimum conditions, the linear ranges and detection limits (S/N?=?3) were found 0.01–50 and 0.001–0.05 ng mL^?1, respectively. The intra-day and inter-day relative standard deviations (RSDs) at 0.5 ng mL^?1 concentration level (n?=?5) using a single-fiber were from 5.4 to 8.3 and 7.5 to 10.3%, respectively. The fiber-to-fiber RSDs % (n?=?3) was between 8.4 and 12.5%. Finally, the development method was applied to the analysis of various real samples.     

Preparation of a New Solid‐Phase Microextraction Fiber by Coating Silylated Nanoporous Silica on a Copper Wire

LUS‐1 typed nanoporous silica particles were synthesized and silylated with hexamethyldisilazane and investigated as a highly porous fiber coating for solid‐phase microextraction (SPME). The pore size distribution of the prepared Sil‐LUS‐1 was still typical of MCM‐41 and centered at 3 nm with a specific surface area of 720 m²g^?1. The SPME fiber was prepared by liming the material on a copper wire. The extraction efficiency of the new fiber was compared with a commercial PDMS fiber for headspace extraction and GC‐MS analysis of phenol, 4‐nitrophenol, 2,4‐dichlorophenol and 4‐chlorophenol in water samples. Due to the high porosity of the prepared fiber it showed a higher sensitivity and better selectivity for the extraction of the target compounds. For optimization of different factors affecting the extraction efficiency, a simplex optimization method was used. The relative standard deviation for the measurements by one fiber was better than 7% for five replicates and the fiber‐to‐fiber reproducibility was about 10% for five fabricated fibers. Detection limits in the range of 0.002 to 0.026 μg mL^?1 were obtained for the phenolic compounds. The fiber was successfully applied for the determination of phenolic compounds in natural water samples.     

A Hexagonally Ordered Nanoporous Silica-Based Fiber Coating for SPME of Polycyclic Aromatic Hydrocarbons from Water Followed by GC�CMS

A highly porous fiber coating material was prepared and functionalized with 3-amino propyl triethoxysilane (APTES) on hexagonally ordered nanoporous silica (SBA-15). Applicability of this coating was assessed employing a laboratory made solid-phase microextraction (SPME) device and gas chromatography?Cmass spectrometry for the simultaneous sampling and determination of trace polycyclic aromatic hydrocarbons (PAHs) from aqueous sample solutions. A one at the time optimization strategy was applied to investigate and optimize important extraction parameters such as extraction temperature, extraction time, ionic strength and sonication time. In the optimum conditions, the relative standard deviations for deionized water, spiked with selected PAHs were between 3.3 and 7.7% (n = 3), and detection limits for the studied compounds were 4.2 and 26.1 pg mL^?1. No significant change was observed in the extraction efficiency of the new SPME fiber, over 50 extractions. The proposed method was successfully applied to the extraction and determination of PAHs in the waste water samples.     

Preparation and application of NiTi alloy coated with ZrO(2) as a new fiber for solid-phase microextraction

In this study a NiTi alloy was applied as an SPME support due to its superelasticity and shape memory properties. This new metallic support was coated with ZrO(2) by electrodeposition using chronoamperometry. It was then evaluated for extraction of three classes of compounds from gaseous samples: alcohols, BTEX and trihalomethanes (THM). For the optimization of the parameters affecting the extraction efficiency of the target compounds, the univariate approach was used. Five fibers were electrodeposited to evaluate the reproducibility of the coating procedure, resulting in a relative standard deviation lower than 11.9%. The repeatability for one fiber (n=6) was lower than 8.5%. The detection limits were lower than 28.1, 20.8 and 0.18 microgL(-1) for alcohols, BTEX and THM, respectively, and the correlation coefficients were higher than 0.996. Taking into account the amount extracted per unit volume, the NiTi-ZrO(2) fiber showed a better extraction profile in comparison with the commercial fibers 7 microm PDMS, 85 microm PA and 30-50 microm DVB/CAR/PDMS. The new SPME fiber has a lifetime of over 300 extractions. Thus, it is a promising alternative for low-cost analysis, as it is robust, and easily and inexpensively prepared.     

Separation and determination of benzene, toluene, ethylbenzene and o-xylene compounds in water using directly suspended droplet microextraction coupled with gas chromatography-flame ionization detector

The directly suspended droplet microextraction (DSDME) technique coupled with the capillary gas chromatography-flame ionization detector (GC-FID) was used to determine BTEX compounds in aqueous samples. The effective parameters such as organic solvent, extraction time, microdroplet volume, salt effect and stirring speed were optimized. The performance of the proposed technique was evaluated for the determination of BTEX compounds in natural water samples. Under the optimal conditions the enrichment factors ranged from 142.68 to 312.13, linear range; 0.01-20 μg mL⁻¹, limits of detection; 0.8-7 ng mL⁻¹ for most analytes. Relative standard deviations for 0.2 μg mL⁻¹ of BTEX in water were in the range 1.81-2.47% (n = 5). The relative recoveries of BTEX from surface water at spiking level of 0.2 μg mL⁻¹ were in the range of 89.87-98.62%.     

Nano-structured lead dioxide as a novel stationary phase for solid-phase microextraction

The first study on the high efficiency of nano-structured lead dioxide as a new fiber for solid-phase microextraction (SPME) purposes has been reported. The size of the PbO2 particles was in the range of 34-136 nm. Lead dioxide-based fibers were prepared via electrochemical deposition on a platinum wire. The extraction properties of the fiber to benzene, toluene, ethylbenzene, and xylenes (BTEX) were examined using headspace solid-phase microextraction (HS-SPME) mode coupled to gas chromatography-flame ionization detection (GC-FID). The results obtained proved the suitability of proposed fibers for the sampling of organic compounds from water. The extraction procedure was optimized by selecting the appropriate extraction parameters, including preparation conditions of coating, salt concentration, time and temperature of adsorption and desorption and stirring rate. The calibration graphs were linear in a concentration range of 0.1-100 microg l(-1) (R2 > 0.994) with detection limits below 0.012 microg l(-1) level. Single fiber repeatability and fiber-to-fiber reproducibility were less than 10.0 and 12.5%, respectively. The PbO2 coating was proved to be very stable at relatively high temperatures (up to 300 degrees C) with a high extraction capacity and long lifespan (more than 50 times). Higher chemical resistance and lower cost are among the advantages of PbO2 fibers over commercially available SPME fibers. Good recoveries (81-108%) were obtained when environmental samples were analyzed.     

Modified Pencil Lead as a New Fiber for Solid-Phase Microextraction

The efficiency of modified pencil lead as a new fiber for solid-phase microextraction (SPME) has been investigated. Modified pencil lead fibers have been prepared by use of several activation processes, for example heating at 600 °C in the stream of inert gas (He), heating under reflux with concentrated H₂SO₄ , fusing with NaOH at 400 °C, and activation at 600 °C with water vapor for 60 min. The fibers were used for extraction of trace amounts of polycyclic aromatic hydrocarbons (PAH) from aqueous samples. Monitoring of extracted compounds and quantitative analysis of model samples were performed by capillary GC–FID. The results obtained prove the suitability of the proposed fibers for sampling organic compounds from water. Effects on extraction efficiency of factors such as temperature, salting out, stirring speed, and exposure time were studied. Under optimum conditions and using one fiber for extraction of naphthalene as a typical compound, a relative standard deviation of 5.3% (n=7) was achieved. The calibration plot was linear in the range 50–10,000 pg mL^–1 (r=0.9997) and the detection limit was 25 pg mL^–1 (S/N=3). This fiber is very stable at high temperature, inexpensive, and can be prepared simply.     

Self-doped polyaniline as new polyaniline substitute for solid-phase microextraction

This work is a first study on extraction efficiency and thermal stability of nano-structured self-doped polyaniline (SPAN) as a coating of solid-phase microextraction (SPME) fibers. SPAN-based fibers were prepared using electrochemical deposition on platinum wires. The particle sizes of prepared nano-structure were in the range of 50–100 nm. Extraction properties of the fiber to 1,4-dioxane were examined using headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-flame ionization detection (GC-FID). The results have proved higher thermal stability of the proposed fiber compared to common PANI fiber. The SPAN coating was proved to be very stable at relatively high temperatures (up to 350 °C) with high extraction capacity and long lifespan (more than 50 times). Therefore, it can be a good substitute of polyaniline (PANI) as a SPME coating. The extraction procedure was optimized by selecting the appropriate extraction parameters including extraction time, extraction temperature, salt concentration, stirring rate and headspace volume. Calibration graph was linear in the concentration range of 1–100 ng mL⁻¹ (R² > 0.993) with detection limit of 0.1 ng mL⁻¹. Single fiber and fiber-to-fiber repeatability were lower than 6.0% and 10.4%, respectively. Different water samples were analyzed as real samples and good recoveries (98–120%) were obtained.     

Cobalt oxide nanoparticles as a novel high-efficiency fiber coating for solid phase microextraction of benzene,toluene, ethylbenzene and xylene from aqueous solutions

In this work cobalt oxide nanoparticles were introduced for preparation of a novel solid phase microextraction (SPME) fiber coating. Chemical bath deposition (CBD) technique was used in order for synthesis and immobilization of the Co₃O₄ nanomaterials on a Pt wire for fabrication of SPME fiber. The prepared cobalt oxide coating was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The fiber was evaluated for the extraction of benzene, toluene, ethylbenzene and xylene (BTEX) in combination with GC–MS. A simplex optimization method was used to optimize the factors affecting the extraction efficiency. Under optimized conditions, the proposed fiber showed extraction efficiencies comparable to those of a commercial polydimethylsiloxane (PDMS) fiber toward the BTEX compounds. The repeatability of the fiber and its reproducibility, expressed as relative standard deviation (RSD), were lower than about 11%. No significant change was observed in the extraction efficiency of the new SPME fiber after over 50 extractions. The fiber was successfully applied to the determination of BTEX compounds in real samples. The proposed nanostructure cobalt oxide fiber is a promising alternative to the commercial fibers as it is robust, inexpensive and easily prepared.     

Determination of BTEX in urine samples using cooling/heating-assisted headspace solid-phase microextraction

Excessive and uncontrolled exposures of the workers to benzene, toluene, ethylbenzene and xylene (BTEX) have currently raised great concerns among industrial hygienist all over the world. Therefore, the effective monitoring of such exposures is assumed to be of prime importance. A cold fiber solid-phase microextraction device based on a cooling capsule as a cooling unit and CO₂ as a coolant was applied to quantitatively analyze BTEX in aqueous samples. A gas chromatography with flame ionization detection was recruited to analyze the target analytes, which had been identified according to their retention times. Several factors such as coating temperature, extraction time and temperature, sample volume and sodium content were optimized. Two modes of extraction, i.e., headspace (HS) and headspace cold fiber (HS-CF) in SPME, were investigated and compared under optimized conditions. The results revealed that HS-CF-SPME has the most appropriate outcome for the extraction of BTEX from aqueous samples. Under the optimized conditions, the calibration curves were linear within the range of 0.2–500 ng ml^?1 and the detection limits were between 0.02 and 0.07 ng ml^?1.The intraday relative standard deviations was lower than about 10%. The method was successfully applied to the determination of BTEX in urine samples with good recovery.     

High extraction efficiency for polar aromatic compounds in natural water samples using multiwalled carbon nanotubes/Nafion solid-phase microextraction coating

A novel solid-phase microextraction (SPME) fiber coated with multiwalled carbon nanotubes (MWCNTs)/Nafion was developed and applied for the extraction of polar aromatic compounds (PACs) in natural water samples. The characteristics and the application of this fiber were investigated. Electron microscope photographs indicated that the MWCNTs/Nafion coating with average thickness of 12.5 μm was homogeneous and porous. The MWCNTs/Nafion coated fiber exhibited higher extraction efficiency towards polar aromatic compounds compared to an 85 μm commercial PA fiber. SPME experimental conditions, such as fiber coating, extraction time, stirring rate, desorption temperature and desorption time, were optimized in order to improve the extraction efficiency. The calibration curves were linear from 0.01 to 10 μg mL⁻¹ for five PACs studied except p-nitroaniline (from 0.005 to 10 μg mL⁻¹) and m-cresol (from 0.001 to 10 μg mL⁻¹), and detection limits were within the range of 0.03–0.57 ng mL⁻¹. Single fiber and fiber-to-fiber reproducibility were less than 7.5 (n = 7) and 10.0% (n = 5), respectively. The recovery of the PACs spiked in natural water samples at 1 μg mL⁻¹ ranged from 83.3 to 106.0%.     

On-Fiber Derivatization of SPME Extracts of Phenol, Hydroquinone and Catechol with GC-MS Detection

A gas chromatography-mass spectrometry (GC-MS) method for the simultaneous determination of phenol (PHE), hydroquinone (HQ) and catechol (CAT) in urine was developed and validated. The method was based on the acidic hydrolysis of conjugated phenolic compounds and further extraction of analytes using solid-phase microextraction (SPME). Analytes were extracted by submersing the polar polyacrylate coated fiber (85 μm) into urine (adjusted to pH 3.0 with glacial acetic acid) for 20 min with magnetic stirring. The extracted compounds on the fiber were exposed to hexamethyldisilazane reagent in the vapor phase for 20 min to yield the corresponding trimethysililylated derivates. This on-fiber derivatization procedure allowed the formation of more amenable compounds for GC analysis, without adversely affecting the lifetime of the fiber. The MS was operated in the selected ion monitoring mode (SIM). The limits of detection were 0.3 μg mL⁻¹ for PHE, 0.15 μg mL⁻¹ for HQ and 0.02 μg mL⁻¹ for CAT. Inter and intra-assay precisions were also verified (coefficient of variation < 8%) with the use of deuterated internal standards. This method of GC-MS analysis can be readily utilized to monitor PHE and its metabolites (HQ and CAT) in urine samples.     

Headspace Solid‐Phase Microextraction (HS‐SPME) for the Determination of Benzene,Toluene, Ethylbenzene,and Xylenes (BTEX) in Foundry Molding Sand

Abstract

The use of headspace solid‐phase microextraction (HS‐SPME) to determine benzene, toluene, ethylbenzene, and xylenes (BTEX) in foundry molding sand, specifically a “green sand” (clay‐bonded sand) was investigated. The BTEX extraction was conducted using a 75 µM Carboxen‐polydimethylsiloxane (CAR‐PDMS) fiber, which was suspended above 10 g of sample. The SPME fiber was desorbed in a gas chromatograph injector port (280°C for 1 min) and the analytes were characterized by mass spectrometry. The effects of extraction time and temperature, water content, and clay and bituminous coal percentage on HS‐SPME of BTEX were investigated. Because green sands contain bentonite clay and carbonaceous material such as crushed bituminous coal, a matrix effect was observed. The detection limits for BTEX were determined to be ≤0.18 ng g^?1 of green sand.     

Selective extraction of catecholamines by packed fiber solid‐phase using composite nanofibers composing of polymeric crown ether with polystyrene

For the first time, electrospun composite nanofibers comprising polymeric crown ether with polystyrene (PCE‐PS) have been used for the selective extraction of catecholamines – dopamine (DA), norepinephrine (NE) and epinephrine (E) – prior to their analysis by high‐performance liquid chromatography–electrochemical detection. Using a minicartridge packed with PCE‐PS composite nanofibers, the target compounds were extracted effectively from urine samples to which diphenylborinic acid 2‐aminoethyl ester was added as a complexing reagent. The extracted catecholamines could be liberated from the fiber by the addition of acetic acid. A good linearity was observed for catecholamines in the range of 2.0–200 ng mL^?1 (NE, E and DA). The detection limits of catecholamines (signal‐to‐noise ratio = 3) were 0.5 ng mL^?1 (NE), 0.2 ng mL^?1 (E) and 0.2 ng mL^?1 (DA), respectively. Under the optimized conditions, the absolute recoveries of the above three catecholamines were 90.6% (NE), 88.5% (E) and 94.5% (DA). The repeatability of extraction performance was from 5.4 to 9.2% (expressed as relative standard deviation). Our results indicate that the proposed method could be used for the determination of NE, E and DA in urine. Copyright © 2014 John Wiley & Sons, Ltd.