Simultaneous determination of methadone and tramadol in serum samples by ultrasonic-assisted micro solid phase extraction and gas chromatography-mass spectrometry.

Ultrasonic-assisted dispersive micro solid phase extraction (UA-DMSPE) is proposed as a fast and easy technique for the extraction and preconcentration of methadone and tramadol from serum samples. Different sorbents including carbon nanotubes, oxidized carbon nanotubes, and TiO2 nanoparticles were compared to extract methadone and tramadol. The best performance was obtained using oxidized carbon nanotubes due to the strong affinity between the drugs and carbon nanotube adsorbents. Final analysis of drugs performed by using gas chromatography-mass spectrometric detection. Different parameters affecting the extraction efficiency, such as the sample volume, amount of adsorbent, desorption solvent type and volume, centrifugation time, and speed were investigated and optimized. The striking features of this technique are correlated to its speed and the small volumes of sample (about 1 mL), desorption solvent (about 50 µL), and adsorbent (about 0.001 g) for analysis of drugs, and finally, milder centrifugation conditions relative to the previously reported adsorbent. The optimal parameters were achieved as follows: pH value was set at 9, the sample volume was adjusted to 1200 µL, the amount of adsorbent used was 1 mg, the extraction time was set at 5 min, and the volume of the desorption solvent was adjusted to 50 µL. The limits of detections (0.5 and 0.8 ng mL-1) and quantifications (1.5 and 2.5 ng mL-1) were obtained for methadone and tramadol, respectively. The developed method also showed good repeatability, relative standard deviation (RSD) of 9.49 % and 7.47 % (n = 5), for the spiked aqueous solution at the concentration level of 10, 50, and 100 ng mL-1 for analytes, and linearity, R ≥ 0.9809. The results showed that UA-DMSPE is a quick, relatively inexpensive, and environmentally friendly alternative technique for the extraction of opiate drugs from serum samples.

PLA/CS-ZnO bionanocomposite for rapid catalytic reduction of nitrophenol compounds as a heterogeneous nanocatalyst.

In this research, a high efficiency and environmentally friendly method to reduce nitrophenol compounds such as 4-nitrophenol (4-NP), 2,4,6-trinitrophenol (2,4,6-TNP) and 2,4-dinitrophenol (2,4-DNP) was used in the presence of poly(lactic acid)/chitosan-ZnO ( PLA/CS-ZnO) bionanocomposite. Using FT-IR, SEM, XRD and UV-Vis techniques, PLA/CS-ZnO bionanocomposite was identified after synthesis. Also, the mechanical properties of the bionanocomposite were investigated using the stress-strain curve. The mentioned bionanocomposite showed a very good efficiency in reducing nitrophenol compounds to aminophenolic compounds, so that under optimal conditions, 100% conversion and selectivity in the reduction of 4-NP, 2,4,6-TNP and 2,4-DNP to 4-aminophenol (4-AP), 2,4,6-triaminophenol (2,4,6-TAP) and 2,4-diaminophenol (2,4-DAP) were observed. UV-Vis absorption spectrum at different times were used to evaluate the progress of the reaction. Furthermore, after the reaction, PLA/CS-ZnO was recovered and used for the next cycle. The results showed that the bionanocomposite can perform ten consecutive cycles without a significant decrease in efficiency. The comparison of catalytic activity with other catalysts showed that the bionanocomposite synthesized in the present research has a higher efficiency in reduction of nitrophenol compounds.

Polybutylene succinate/modified cellulose bionanocomposites as sorbent for needle trap microextraction.

In this work, different polybutylene succinate/modified cellulose bio-nanocomposites were synthesized by solving the casting method and then used as a new sorbent for needle trap microextraction of some polycyclic aromatic hydrocarbons from the water samples in headspace mode. The surface of cellulose nanocrystalline was modified using aminosilane groups to improve the dispersion of nanoparticles in the polybutylene succinate matrix. The characterization of synthesized nanocomposites, were performed using TGA, SEM, BET analysis and FT-IR spectroscopy. Adding modified nanocrystalline cellulose to a polybutylene succinate matrix increased the surface area, and thermal and mechanical stabilities. The significant parameters of the sorbent extraction process, including the amount of modified cellulose nanoparticles, the extraction time, and temperatures and salt content, were studied and optimized. Under the optimized extraction conditions (extraction time of 25 min, and extraction temperature of 50 °C), an analytical method for selected polycyclic aromatic hydrocarbons with low detection limits (0.75-1 ng L-1) and the quantification limit (3-5 ng L-1), good repeatability (3-7% at 20 ng L-1), and reproducibility (9%-14%, n = 3) was developed. The linearity of the method was obtained in the range of 5-1000 ng L-1 with R2 > 0.9996. The enrichment factor was obtained for the spiked real aqueous samples (at 50 ng L-1) in the range of 276-311. Also, the performance of the developed method was studied via the extraction of selected analytes in real water samples, and the relative recovery values were found to be in the range of 98-103%.

Modified activated carbon derived from chestnut oak shells as a new sorbent for the needle-trap extraction.

In this study, an acid-treated-activated carbon was prepared from chestnut oak shell carbonization followed by modification with hydrochloric acid/nitric acid and then used as a new sorbent for headspace needle-trap extraction of chlorophenol compounds from aqueous solutions. Different techniques, including scanning electron microscopy, nitrogen adsorption-desorption analysis, and Fourier transform-infrared spectroscopy were used for the characterization of the sorbents. The effects of some experimental parameters, including the temperature, pH, sorbent amount, and time of extraction were optimized. The developed method is fast and sensitive, providing low and sub ng/L detection limits. The limits of detection and quantification were in the range of 0.75-5 and 5-15 ng/ml, respectively, and the equilibrium time was 20 min. Wide linearity in the range of 15-2000 ng/L with R2  > 0.9993 was obtained. Repeatability of the method was accessed at 50, 100, and 200 ng/L concentration levels and RSD% of 5%-12% was achieved. The introduced method was applied for analyzing real water samples containing spiked chlorophenols, and the relative recovery values were found to be in the range of 84%-99% at the concentration levels of 50, 100 and 200 ng/L.

Electrospun decyl-3-methylimidazolium mono bromate/polyamide nanofibers as solid-phase microextraction coating.

In the current study, electrospun-based ionic liquid (IL) doped polyamide (PA) nanofibers were prepared and used as the coating material of solid phase microextration device in the fiber geometry. Addition of IL, decyl-3-methylimidazolium mono bromate, increased the conductivity of the PA solution facilitating the electrospining process. The scanning electron microscopy images of decyl-3-methylimidazolium mono bromated/polyamide nanofibers showed the decreased diameter of the nanofibers in the range of 35-160nm compared to the PA nanofiber. The factors affecting the structure of nanofibers (e.g. ratio of decyl-3-methylimidazolium mono bromate to PA, coating time and applied voltage) were studied. In addition, influential parameters of extraction/desorption performance such as ionic strength, extraction time, and desorption time and temperature were studied. The limit of detections and limit of quantifications were obtained in the range of 0.75-0.9 and 2-5ngL-1, respectively, demonstrating high efficiency of the prepared nanofiber. The developed method also showed good repeatability, RSD 4-9% (n=3), for the spiked aqueous solution at concentration level 150ngL-1 of chlorobenzenes, and linearity,R=0.996, in the range of 5-5000ngL-1.

Electrospun magnetic polybutylene terephthalate nanofibers for thin film microextraction.

A thin film microextraction method using elecrospun magnetic polybutylene terephthalate nanofibers is developed and implemented to isolate some selected triazines. Due to the high mechanical stability of these nanofibers, they are repeatedly used under harsh magnetic stirring and ultrasonic conditions without any damage and structure degradation. The presence of magnetic nanoparticles within the nanofiber structure increases the extraction efficiency while the fibers could be collected by an external magnet. The synthesized nanocomposite showed strong affinity toward the selected analytes. Apart from the concentration of magnetic nanoparticles within the nanocomposite network, the effect of different parameters on the extraction and desorption processes including the sample pH, extraction time, sample volume, type of desorption solvent, solvent volume, and desorption time were optimized. Eventually, the detection limits were in the range of 0.02-0.05 ng/mL, while the limits of quantification were between 0.1 and 0.2 ng/mL. The linear dynamic range was 0.1-100 ng/mL, and the relative standard deviations were 4-9% (n = 3). The developed method was extended to the real water samples, and the relative recoveries were in the range of 86-103%, indicating that the prepared sorbent is suitable for extraction of triazines from environmental samples.

Improvement of solid-phase microextraction efficiency by the application of a carbon-nanotubes-based ternary microextraction fiber composite.

In this study, a novel technique is proposed for preparation of an efficient and unbreakable metal-wire-supported solid-phase microextraction fiber. A sol-gel film was deposited on electrophoretically deposited carbon nanotubes on a stainless-steel wire. The applicability of the fiber was evaluated through the extraction of some aromatic pollutants as model compounds from the headspace of aqueous samples in combination with gas chromatography and mass spectrometry. The parameters affecting the structure and extraction efficiency of the fiber (including the type of solvent, time, and potential for electrophoretic deposition) and the parameters affecting the extraction efficiency (such as coating type, salt content, extraction temperature, and time) were investigated. The results showed that the film thickness will be increased by increasing the potential and time duration. Finally, the characterization of the deposited film was accomplished by scanning electron microscopy and thermogravimetric analysis. After the optimization of the extraction parameters, the limit of detection of less than 20 pg/mL was achieved, and the calibration curves were all linear (r2  ≥ 0.9737), in the range from 50 to 500 pg/mL. The solid-phase microextraction fiber has a high mechanical strength; good stability and long service life, making it potentially applicable in the extraction of trace polycyclic aromatic hydrocarbons from aqueous samples.

Composite Magnetic Nanoparticles (CuFe2O4) as a New Microsorbent for Extraction of Rhodamine B from Water Samples.

In this work, novel composite magnetic nanoparticles (CuFe2O4) were synthesized based on sol-gel combustion in the laboratory. Next, a simple production method was optimized for the preparation of the copper nanoferrites (CuFe2O4), which are stable in water, magnetically active, and have a high specific area used as sorbent material for organic dye extraction in water solution. CuFe2O4 nanopowders were characterized by field-emission scanning electron microscopy (SEM), FTIR spectroscopy, and energy dispersive X-ray spectroscopy. The size range of the nanoparticles obtained in such conditions was estimated by SEM images to be 35-45 nm. The parameters influencing the extraction of CuFe2O4 nanoparticles, such as desorption solvent, amount of sorbent, desorption time, sample pH, ionic strength, and extraction time, were investigated and optimized. Under the optimum conditions, a linear calibration curve in the range of 0.75-5.00 µg/L with R2 = 0.9996 was obtained. The LOQ (10Sb) and LOD (3Sb) of the method were 0.75 and 0.25 µg/L (n = 3), respectively. The RSD for a water sample spiked with 1 µg/L rhodamine B was 3% (n = 5). The method was applied for the determination of rhodamine B in tap water, dishwashing foam, dishwashing liquid, and shampoo samples. The relative recovery percentages for these samples were in the range of 95-99%.

A flow injection µ-solid phase extraction system based on electrospun polyaniline nanocomposite.

In this study, a fast and sensitive flow injection µ-solid phase extraction (FI-µ-SPE) technique based on an electrospun polyaniline (PANI) nanocomposite in conjunction with gas chromatography-mass spectrometry (GC-MS) was developed. The PANI-based nanocomposite was synthesized by electrospinning of a solution containing polyvinyl alcohol (PVA)/PANI. The majority of PVA template was subsequently removed from the whole PVA/PANI nanofibers blend by exposing the electrospun nanocomposite to hot water. The homogeneity, porosity and characterization of the electrospun nanofibers were investigated by the scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. Due to the polar-oriented nature of the prepared nanofibrous nitrogen-containing sorbent, its capability was examined by FI-µ-SPE of some selected triazines, as model compounds, from aquatic media. After optimizing the extraction conditions, the intraday relative standard deviation values for a double distilled water spiked with the selected triazines were in range of 8.9-9.5% (n=3) while the limits of detection were between 0.03-0.09 ng mL(-1). The linearity of the method was in the concentration range of 0.1-500 ng mL(-1). The proficiency of the developed method was validated by analyzing paddy, well and tap water samples and the relative recovery values were found to be in the range of 83-95% under the optimized conditions.

Polybutylene terephthalate-nickel oxide nanocomposite as a fiber coating.

A highly efficient polybutylene terephthalate (PBT)-based nanocomposite containing nickel oxide nanoparticles was synthesized by electrospinning technique and used as a fiber coating for solid phase microextraction. The influential morphological parameters and capability of the prepared nanocomposite including the NiO content, the coating time, the PBT concentration and applied voltage were considered for optimization. The applicability of the synthesized fiber coating was examined by headspace solid phase micro extraction and gas chromatography mass spectrometry detection of some volatile organic compounds in aqueous samples. Among the synthesized nanocomposites and pristine PBT nanofibers, the fiber coating with 14% of NiO nanoparticles doping level exhibited the highest extraction efficiency. In addition, important parameters influencing the extraction/desorption process were investigated and optimized. The detection limits were less than 5 ng L(-1) using the selected ion monitoring mode. The inter-day and intra-day precisions of the developed method under optimized conditions were below 11%. The method showed a linearity in the range of 10-1000 ng L(-1) with the correlation coefficient greater than 0.9987. The optimized method was applied to the sampling of some volatile organic compounds from real water samples. The developed method is convenient, rapid, simple, easy and inexpensive and offers high sensitivity and sufficient reproducibility.

Roles of inorganic oxide nanoparticles on extraction efficiency of electrospun polyethylene terephthalate nanocomposite as an unbreakable fiber coating.

In the present work, the roles of inorganic oxide nanoparticles on the extraction efficiency of polyethylene terephthalate-based nanocomposites were extensively studied. Four fiber coatings based on polyethylene terephthalate nanocomposites containing different types of nanoparticles along with a pristine polyethylene terephthalate polymer were conveniently electrospun on stainless steel wires. The applicability of new fiber coatings were examined by headspace-solid phase microextraction of some environmentally important volatile organic compound such as benzene, toluene, ethylbenzene and xylene (BTEX), as model compounds, from aqueous samples. Subsequently, the extracted analytes were transferred into a gas chromatography by thermal desorption. Parameters affecting the morphology and capability of the prepared nanocomposites including the type of nanoparticles and their doping levels along with the coating time were optimized. Four types of nanoparticles including Fe3O4, SiO2, CoO and NiO were examined as the doping agents and among them the presence of SiO2 in the prepared nanocomposite was prominent. The homogeneity and the porous surface structure of the SiO2-polyethylene terephthalate nanocomposite were confirmed by scanning electron microscopy indicating that the nanofibers diameters were lower than 300 nm. In addition, important parameters influencing the extraction and desorption process such as temperature and extraction time, ionic strength and desorption conditions were optimized. Eventually, the developed method was validated by gas chromatography-mass spectrometry. Under optimized conditions, the relative standard deviation values for a double distilled water spiked with the selected volatile organic compounds at 50 ng L(-1) were 2-7% (n=3) while the limits of detection were between 0.7 and 0.9 ng L(-1). The method was linear in the concentration range of 10 to 1,000 ng L(-1) (R(2)>0.9992). Finally, the developed method was applied to the analysis of Kalan dam and tap water samples and the relative recovery values were found to be in the range of 86-102%.

Electrospun polyamide-polyethylene glycol nanofibers for headspace solid-phase microextration.

A solution of polyamide (PA) containing polyethylene glycol (PEG) as a side low-molecular-weight polymer was electrospun. After synthesizing the PA-PEG nanofibers, the constituent was subsequently removed (modified PA) and confirmed by Fourier transform infrared spectroscopy. The scanning electron microscopy images showed an average diameter of 640 and 148 nm for PA and PA-PEG coatings, respectively, while the latter coating structure was more homogeneous and porous. The extraction efficiencies of PA, PA-PEG, and the modified PA fiber coatings were assayed by headspace solid-phase microextraction of a number of chlorophenols from real water samples followed by their determination by gas chromatography with mass spectrometry. To prepare the most appropriate coatings, the amounts and the flow rate of the electrospinning solution were investigated. Various extraction parameters, such as the salt content, desorption condition, extraction temperature, and time were optimized. The limits of detection of the method were in the range of 0.8-25 ng/L, while the RSDs at two concentration levels of 200 and 80 ng/L were between 2.1 and 12.2%. The analysis of real water samples led to relative recoveries between 85 and 98% with a linearity of 8-1500 ng/L.

A chitosan-polypyrrole magnetic nanocomposite as µ-sorbent for isolation of naproxen.

An extracting medium based on chitosan-polypyrrole (CS-PPy) magnetic nanocomposite was synthesized by chemical polymerization of pyrrole at the presence of chitosan magnetic nanoparticles (CS-MNPs) for micro-solid phase extraction. In this work, magnetic nanoparticles, the modified CS-MNPs and different types of CS-PPy magnetic nanocomposites were synthesized. Extraction efficiency of the CS-PPy magnetic nanocomposite was compared with the CS-MNPs and Fe3O4 nanoparticles for the determination of naproxen in aqueous samples, via quantification by spectrofluorimetry. The scanning electron microscopy images obtained from all the prepared nanocomposites revealed that the CS-PPy magnetic nanocomposite possess more porous structure. Among different synthesized magnetic nanocomposites, CS-PPy magnetic nanocomposite showed a prominent efficiency. Influencing parameters on the morphology of CS-PPy magnetic nanocomposite such as weight ratio of components was also assayed. In addition, effects of different parameters influencing the extraction efficiency of naproxen including desorption solvent, desorption time, amount of sorbent, ionic strength, sample pH and extraction time were investigated and optimized. Under the optimum condition, a linear calibration curve in the range of 0.04-10 µg mL(-1) (R(2)=0.9996) was obtained. The limits of detection (3Sb) and limits of quantification (10Sb) of the method were 0.015 and 0.04 µg mL(-1) (n=3), respectively. The relative standard deviation for water sample spiked with 0.1 µg mL(-1) of naproxen was 3% (n=5) and the absolute recovery was 92%. The applicability of method was extended to the determination of naproxen in tap water, human urine and plasma samples. The relative recovery percentages for these samples were in the range of 56-99%.

Electrospun modified silica-polyamide nanocomposite as a novel fiber coating.

In the present work, a new solid phase microextraction (SPME) fiber coating based on modified silica-polyamide (PA) nanocomposite was electrospun on a stainless steel wire. Four modified silica-PA nanocomposites together with PA were fabricated by dispersing several typical modified silica nanoparticles in PA polymer solution prior to electrospinning. The surface characteristic of PA nanofibers and modified silica-PA nanocomposites was investigated using scanning electron microscopy (SEM). The homogeneity and the porous surface structure of the modified silica-PA nanocomposites were confirmed by SEM, showing nanofibers diameters lower than 170 nm. The applicability of the new fiber coating was examined by headspace SPME of some selected chlorobenzenes (CBs), as model compounds, from aqueous samples. Subsequently, the extracted analytes were transferred into a gas chromatography (GC) by thermal desorption. Influencing parameters on the morphology of nanocomposites such as type of modified silica nanoparticles and the weight ratio of components were optimized. In addition, effects of different parameters influencing the extraction efficiency including extraction temperature, extraction time, ionic strength, desorption temperature, and desorption time were investigated and optimized. Eventually, the developed method was validated by gas chromatography-mass spectrometry (GC-MS). At the optimum conditions, the relative standard deviation values for a double distilled water spiked with the selected CBs at 100 ng L(-1) were 4-12% (n=3) and the limit of detection for the studied compounds was between 5 and 30 ng L(-1). The calibration curves of analytes were investigated in the range of 50-1000 ng L(-1) and correlation coefficients (R(2)) between 0.9897 and 0.9992 were obtained.

A novel magnetic poly(aniline-naphthylamine)-based nanocomposite for micro solid phase extraction of rhodamine B.

A novel Fe3O4-poly(aniline-naphthylamine)-based nanocomposite was synthesized by chemical oxidative polymerization process as a magnetic sorbent for micro solid phase extraction. The scanning electron microscopy images of the synthesized nanocomposite revealed that the copolymer posses a porous structure with diameters less than 50nm. The extraction efficiency of this sorbent was examined by isolation of rhodamine B, a mutagenic and carcinogenic dye, from aquatic media in dispersion mode. Among different synthesized polymers, Fe3O4/poly(aniline-naphthylamine) nanocomposite showed a prominent efficiency. Parameters including the desorption solvent, amount of sorbent, desorption time, sample pH, ionic strength, extraction time and stirring rate were optimized. Under the optimum condition, a linear spiked calibration curve in the range of 0.35-5.00µgL(-1) with R(2)=0.9991 was obtained. The limits of detection (3Sb) and limits of quantification (10Sb) of the method were 0.10µgL(-1) and 0.35µgL(-1) (n=3), respectively. The relative standard deviation for water sample with 0.5µgL(-1) of RhB was 4.2% (n=5) and the absolute recovery was 92%. The method was applied for the determination of rhodamine B in dishwashing foam, dishwashing liquid, shampoo, pencil, matches tips and eye shadows samples and the relative recovery percentage were in the range of 94-99%.

Aniline-silica nanocomposite as a novel solid phase microextraction fiber coating.

A new unbreakable solid phase microextraction (SPME) fiber coating based on aniline-silica nanocomposite was electrodeposited on a stainless steel wire. The electropolymerization process was carried out at a constant deposition potential, applied to the corresponding aqueous electrolyte containing aniline and silica nanoparticles. The scanning electron microscopy (SEM) images showed the non-smooth and the porous surface structure of the prepared nanocomposite. The applicability of the new fiber coating was examined by headspace-solid phase microextraction (HS-SPME) of some environmentally important polycyclic aromatic hydrocarbons (PAHs), as model compounds, from aqueous samples. Subsequently, the extracted analytes were transferred into a gas chromatography (GC) by thermal desorption. Parameters affecting the synthesizing and extraction processes including the voltage of power supply, the weight ratio of components, the time of electrodeposition, extraction time and temperature, the ionic strength, and desorption temperature and time were optimized. Eventually, the developed method was validated by gas chromatography-mass spectrometry (GC-MS). At the optimum conditions, the relative standard deviation (%RSD) values for a double distilled water spiked with the selected PAHs at 40 ng L(-1) were 6-13% (n=3) while the limit of detection (LOD) results were between 1 and 3 ng L(-1). The calibration graphs were linear in the concentration range from 20 to 4000 ng L(-1) (R(2)>0.995). Finally the developed method was applied to the analysis of Kalan dam, rain and tap water samples and the relative recovery values were found to be in the range of 76-109%, under optimized conditions. In addition, the synthesis of the nanocomposite coating was carried out conveniently while it is rather inexpensive, easy, simple, rapid and highly durable and can be used frequently.