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

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

Multiwall carbon nanotube- zirconium oxide nanocomposite hollow fiber solid phase microextraction for determination of polyaromatic hydrocarbons in water, coffee and tea samples.

The purpose of this study was to evaluate the application of hollow fiber solid-phase microextraction (HF-SPME) followed by HPLC-UV to determine the ultra-trace amounts of polycyclic aromatic hydrocarbons (PAHs) as model analytes in complex coffee and tea samples. HF-SPME can be effectively used as an alternative to the direct immersion SPME (DI-SPME) method in complex matrices. The DI-SPME method suffers from serious limitation in dirty and complicated matrices with low sample clean-up, while the HF-SPME method has high clean-up and selectivity due to the high porosity of hollow fiber that can pick out analyte from complicated matrices. As a hollow fiber sorbent, a novel multiwall carbon nanotube/zirconium oxide nanocomposite (MWCNT/ZrO2) was fabricated. The excellent adsorption of PAHs on the sorbent was attributed to the dominant roles of π-π stacking interaction and hydrophobic interaction. Under the optimized extraction conditions, the wide linear range of 0.1-200 µg L-1 with coefficients of determination better than 0.998 and low detection limits of 0.033-0.16 µg L-1 with satisfactory precision (RSD < 6.6%) were obtained. The relative recoveries obtained by spiking the PAHs in water, coffee and tea samples were in the range of 92.0-106.0%. Compared to other methods, MWCNT/ZrO2 hollow fiber solid phase microextraction demonstrated a good capability for determination of PAHs in complex coffee and tea samples.

Determination of phthalate esters in drinking water and edible vegetable oil samples by headspace solid phase microextraction using graphene/polyvinylchloride nanocomposite coated fiber coupled to gas chromatography-flame ionization detector.

In the current study, a graphene/polyvinylchloride nanocomposite was successfully coated on a stainless steel substrate by a simple dip coating process and used as a novel headspace solid phase microextraction (HS-SPME) fiber for the extraction of phthalate esters (PEs) from drinking water and edible vegetable oil samples. The prepared SPME fibers exhibited high extractability for PEs (due to the dominant role of π-π stacking interactions and hydrophobic effects) yielding good sensitivity and precision when followed by a gas chromatograph with a flame ionization detector (GC-FID). The optimization strategy of the extraction process was carried out using the response surface method based on a central composite design. The developed method gave a low limit of detection (0.06-0.08µgL(-1)) and good linearity (0.2-100µgL(-1)) for the determination of the PEs under the optimized conditions (extraction temperature, 70±1°C; extraction time, 35min; salt concentration, 30% w/v; stirring rate, 900rpm; desorption temperature, 230°C; and desorption time, 4min) whereas the repeatability and fiber-to-fiber reproducibility were in the range 6.1-7.8% and 8.9-10.2%, respectively. Finally, the proposed method was successfully applied to the analysis of PEs in drinking water and edible oil samples with good recoveries (87-112%) and satisfactory precisions (RSDs<8.3%), indicating the absence of matrix effects in the proposed HS-SPME method.

Hollow fiber liquid phase microextraction followed by high performance liquid chromatography for determination of ultra-trace levels of Se(IV) after derivatization in urine, plasma and natural water samples.

In the present work, a simple and high sensitive method based on hollow fiber liquid phase microextraction (HF-LPME) was developed followed by high performance liquid chromatography (HPLC) for determination of ultra-trace amounts of Se(IV) after derivatization in biological and natural water samples. Se(IV) was complexed with o-phenylenediamine to form piazselenol. The formed piazselenol was extracted into 20 microL of 1-octanol located in the lumen of a hollow fiber and the solution was injected into HPLC-UV for analysis. Using the Taguchi method, an orthogonal array design (OAD), OA(16) (4(5)) was employed to optimize the HF-LPME of piazselenol. The effect of five experimental factors (each factor at four levels) including the volume of the organic phase, extraction time, pH of the solution, stirring rate and ionic strength on the extraction efficiency of piazselenol was studied and optimized. The maximum extraction efficiency of piazselenol was obtained at 20 microL of 1-octanol as the extracting solvent, 30 min extraction time, pH 2, stirring rate of 500 rpm and 30% (w/v) NaCl. Under the optimum conditions, preconcentration factors up to 130 were achieved and the relative standard deviation (%RSD) of the method was <3.7% for different concentrations of Se(IV). The calibration curves were obtained in the ranges of 0.2-100 and 0.05-10 microgL(-1) for the 11 and 50 mL of the sample volumes with reasonable linearity, respectively (r(2)> 0.995). The limits of detection (LOD) were 0.1 and 0.02 microgL(-1) for the 11 and 50 mL sample volumes, respectively (S/N - 3). Finally, the applicability of the proposed method was evaluated by the extraction and determination of Se(IV) in the plasma, urine and water samples.

Taguchi OA16 orthogonal array design for the optimization of cloud point extraction for selenium determination in environmental and biological samples by tungsten-modified tube electrothermal atomic absorption spectrometry.

Orthogonal array design (OAD) was applied for the first time to optimize cloud point extraction (CPE) conditions for Se(IV) determination by electrothermal atomic absorption spectrometry (ETAAS) in environmental and biological samples. Selenium was reacted with o-phenylenediamine to form piazselenol in an acidic medium (pH 2). Using Triton X-114, as surfactant, piazselenol was quantitatively extracted into small volume (about 30 microL) of the surfactant-rich phase after centrifugation. Five relevant factors, i.e. surfactant concentration, pH, ionic strength, equilibrium time and temperature were selected and the effects of each factor were studied at four levels on the extraction efficiency of Se(IV) and optimized. The statistical analysis revealed that the most important factors contributing to the extraction efficiency are ionic strength, pH and percent of surfactant. Based on the results obtained from the analysis of variance (ANOVA), the optimum conditions for extraction were established as: pH 6; vial temperature=50 degrees C; extraction time=7 min and 0.3% (w/v) of Triton X-114. The method was permitted to obtain a detection limit of 0.09 ng mL(-1) and two linear calibration ranges from 0.6 to 1.0 and 1.0 to 80.0 ng mL(-1) Se. The precision (%RSD) of the extraction and determination for the six replicates of Se at 20 ng mL(-1) was better than 3.6% and the enrichment factor of 63.5 was achieved. The studied analyte was successfully extracted and determined with high efficiency using cloud point extraction method in water and biological matrices.

Extraction of essential oil from Pimpinella anisum using supercritical carbon dioxide and comparison with hydrodistillation.

Supercritical fluid extraction (SFE) of essential oil from Pimpinella anisum, using carbon dioxide as a solvent is presented in this work. An orthogonal array design OA9 (3(4)) was applied to select the optimum extraction condition. The effects of pressure, temperature, dynamic extraction time and methanol volume on the extraction efficiency were investigated by the three-level orthogonal array design. Results show that pressure has a significant effect on the extraction efficiency. The extract obtained from P. anisum by using supercritical fluid extraction was compared with the essential oil obtained by hydrodistillation, considering both quantity and quality of the product. SFE products were found to be of markedly different composition, compared with the corresponding hydrodistilated oil. The total amount of extractable substances obtained in SFE (7.5%) is higher than that obtained by hydrodistillation (3.1%) and SFE is faster than hydrodistillation method.

Simultaneous preconcentration and determination of U(VI), Th(IV), Zr(IV) and Hf(IV) ions in aqueous samples using micelle-mediated extraction coupled to inductively coupled plasma-optical emission spectrometry.

A simple cloud point extraction method followed by inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for simultaneous preconcentration and determination of trace amounts of U(VI), Th(IV), Zr(IV) and Hf(IV) ions in aqueous samples. The metal ions in 50 ml of aqueous solution (containing 0.1 M sodium acetate, pH 6.0) were formed complexes with dibenzoylmethane (DBM). Then, Triton X-114 (0.2%, w/v) was added to the solution. By increasing the temperature of the solution up to 50 degrees C, a phase separation occurred. After centrifugation at 4000 rpm for 6 min, the surfactant-rich phase (sediment phase) was diluted with 1.0 ml of 20:80 (v/v) of methanol/1 M HNO(3). The metal ions were then determined using ICP-OES. Finally, the main factors affecting the cloud point extraction were evaluated and optimized. Under optimized conditions, enhancement factors in the range of 37.0-43.6 were obtained. The calibration graphs were linear in the range of 0.5-1500 microg l(-1) for Th and Zr, 0.5-500 microg l(-1) for Hf and 2.5-1240 microg l(-1) for U with correlation coefficients (r(2)) better than 0.9926. The detection limits were between 0.1 and 1.0 microg l(-1) and the R.S.D. values for seven replicates were lower than 6.1%.