Electrospun polyethylene terephthalate/graphene oxide nanofibrous membrane followed by HPLC for the separation and determination of tamoxifen in human blood plasma.

An electrospun polyethylene terephthalate/graphene oxide nanofibrous mat was fabricated and used as an effective and novel membrane for the solid-phase extraction of tamoxifen in human blood plasma samples before detection by high-performance liquid chromatography. The membrane was characterized by some identification techniques, such as FTIR spectroscopy, X-ray diffraction, and scanning electron microscopy. The effective variables of the extraction procedure including desorption condition (type and volume of the eluent), adsorbent dose, pH of sample solution, salt concentration, and sample loading time were investigated and their optimum values were obtained using one factor at a time methodology. Under the optimized conditions, the results showed wide linear concentration range of 5-2000 ng/mL with a determination coefficient of 0.992. The limits of detection and limits of quantification were 1.3 and 5.0 ng/mL, respectively. The intra-day and inter-day precisions were 3.4 and 4.6%, respectively. The method was successfully applied to determination of tamoxifen in the blood plasma samples and satisfactory relative recoveries (92.6-98.3 %) were achieved.

Application of response surface method for optimization of dispersive liquid-liquid microextraction of water-soluble components of Rosa damascena Mill. essential oil.

Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) was applied for the determination of Rose water constituents. The effective parameters such as volume of extraction and disperser solvents, temperature, and salt effect were inspected by a full factorial design to identify important parameters and their interactions. It showed that salt addition had no effect on the efficiency. Next, a central composite design was applied to obtain optimum point of the important parameters. The optimal condition was obtained as 37.0 microL for extractor, 0.42 mL for disperser and temperature for 48 degrees C. The main components that were extracted at the optimum point were benzeneethanol (24.87%), geraniol (23.07%), beta-citronellol (22.38%), nerol (8.48%), eugenol (5.98%) and linalool (5.62%).

Solid-phase extraction combined with dispersive liquid-liquid microextraction-ultra preconcentration of chlorophenols in aqueous samples.

The solid-phase extraction (SPE) joined with the dispersive liquid-liquid microextraction (DLLME) has been developed as an ultra preconcentration technique for the determination of chlorophenols in water samples. Chlorophenols (CPs) were employed as model compounds to assess the extraction procedure and were determined by gas chromatography-electron-capture detection (GC-ECD). In solid-phase extraction-dispersive liquid-liquid microextraction (SPE-DLLME), CPs were adsorbed from a large volume of aqueous samples (100 mL) into 100 mg functionalized styrene-divinylbenzene polymer (PPL) sorbent. After the elution of the desired compounds from the sorbent by using acetone, DLLME technique was performed on the obtained solution. Some important extraction parameters, such as sample solution flow rate, breakthrough volume, sample pH, type and volume of the elution solvent as well as the salt addition, were studied and optimized. The new method (SPE-DLLME) provided an ultra enrichment factor (4390-17,870) for 19 CPs. The calibration graphs were linear in the range of 0.001-20 microg L(-1) and the limits of detection (LODs) ranged from 0.0005 to 0.1 microg L(-1). The relative standard deviations (RSDs, for 10.0 microg L(-1) of MCPs, 5.00 microg L(-1) of DCPs, 0.200 microg L(-1) of TCPs, 0.100 microg L(-1) of TeCPs and PCP) with and without the internal standard varied from 1.1 to 6.4% (n=7) and 2.5-9.7% (n=7), respectively. The relative recoveries of the well, tap and river water samples, spiked with different levels of CPs, were 71-110%, 73-115% and 88-121%, respectively.

A rapid and simple determination of caffeine in teas, coffees and eight beverages.

Caffeine was extracted and preconcentrated by the simple, fast and green method of dispersive liquid-liquid microextraction (DLLME) and analysed by gas chromatography-nitrogen phosphorus detection (GC-NPD). The influence of main parameters affecting the extraction efficiency investigated and optimised. Under the optimal conditions, the method was successfully applied to determination of caffeine in different real samples including five types of tea (green, black, white, oolong teas and tea bag), two kinds of coffee (Nescafe coffee and coffee), and eight beverages (regular Coca Cola, Coca Cola zero, regular Pepsi, Pepsi max, Sprite, 7up, Red Bull and Hype).The limit of detection (LOD) and limit of quantification (LOQ) were 0.02 and 0.05 µg mL(-1), respectively. Linear dynamic range (LDR) was 0.05-500 µg mL(-1) and determination coefficient (R(2)) was 0.9990. The relative standard deviation (RSD) was 3.2% (n=5, C=1 µg mL(-1)).

Determination of volatile components of saffron by optimised ultrasound-assisted extraction in tandem with dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

In the present research, a combined extraction method of ultrasound-assisted extraction (UAE) in conjunction with dispersive liquid-liquid microextraction (DLLME) was applied to isolation and enrichment of saffron volatiles. The extracted components of the saffron were separated and determined by gas chromatography-mass spectrometry (GC-MS) technique. The mixture of methanol/acetonitrile was chosen for the extraction of the compounds and chloroform was used at the preconcentration stage. The important parameters, such as composition of extraction solvent, volume of preconcentration solvent, ultrasonic applying time, and salt concentration were optimised by using a half-fraction factorial central composite design (CCD). Under the optimal conditions, the linear dynamic ranges (LDRs) were 10-10,000mgL(-)(1). The determination coefficients (R(2)) were from 0.9990 to 0.9997. The limits of detection (LODs) and limits of quantification (LOQs) for the extracted compounds were 6-123mgL(-)(1) and 20-406mgL(-)(1), respectively. The relative standard deviations (RSDs) were 2.48-9.82% (n=3). The enhancement factors (EFs) were 3.6-41.3.

Determination of volatile components of green, black, oolong and white tea by optimized ultrasound-assisted extraction-dispersive liquid-liquid microextraction coupled with gas chromatography.

Ultrasound assisted extraction (UAE) followed by dispersive liquid-liquid microextraction (DLLME) was used for extraction and preconcentration of volatile constituents of six tea plants. The preconcentrated compounds were analyzed by gas chromatography-mass spectrometry (GC-MS). Totally, 42 compounds were identified and caffeine was quantitatively determined. The main parameters (factors) of the extraction process were optimized by using a central composite design (CCD). Methanol and chloroform were selected as the extraction solvent and preconcentration solvent, respectively .The optimal conditions were obtained as 21 in for sonication time; 32°C for temperature; 27 L for volume of extraction solvent and 7.4% for salt concentration (NaCl/H(2)O). The determination coefficient (R(2)) was 0.9988. The relative standard deviation (RSD %) was 4.8 (n=5), and the enhancement factors (EFs) were 4.0-42.6.

Optimized ultrasound-assisted emulsification microextraction for simultaneous trace multielement determination of heavy metals in real water samples by ICP-OES.

Ultrasonic-assisted emulsification microextraction (USAEME) combined with inductively coupled plasma-optical emission spectrometry (ICP-OES) was used for preconcentration and determination of aluminum, bismuth, cadmium, cobalt, copper, iron, gallium, indium, nickel, lead, thallium and zinc in real water samples. Ammonium pyrrolidine dithiocarbamate (APDC) and carbon tetrachloride (CCl(4)) were used as the chelating agent and extraction solvent, respectively. The effective parameters (factors) of the extraction process such as volume of extraction solvent, pH, sonication time, and concentration of chelating agent were optimized by a small central composite design (CCD). The optimum conditions were found to be 98 µL for extraction solvent, 1476 mg L(-1) for chelating agent, 3.8 for pH and 9 min for sonication time. Under the optimal conditions, the limits of detection (LODs) for Al, Bi, Cd, Co, Cu, Fe, Ga, In, Ni, Pb, Tl and Zn were 0.13, 0.48, 0.19, 0.28, 0.29, 0.27, 0.27, 0.38, 0.44, 0.47, 0.52 and 0.17 µg L(-1), respectively. The linear dynamic range (LDR) was 1-1000 µ gL(-1) with determination coefficients of 0.991-0.998. Relative standard deviations (RSDs, C=200 µg L(-1), n=6) were between 1.87%-5.65%. The proposed method was successfully applied to the extraction and determination of heavy metals in real water samples and the satisfactory relative recoveries (90.3%-105.5%) were obtained.

Ultra-preconcentration and determination of thirteen organophosphorus pesticides in water samples using solid-phase extraction followed by dispersive liquid-liquid microextraction and gas chromatography with flame photometric detection.

An ultra-preconcentration technique composed of solid-phase extraction (SPE) and dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-flame photometric detection (GC-FPD) was used for determination of thirteen organophosphorus pesticides (OPPs) including phorate, diazinon, disolfotane, methyl parathion, sumithion, chlorpyrifos, malathion, fenthion, profenphose, ethion, phosalone, azinphose-methyl and co-ral in aqueous samples. The analytes were collected from large volumes of aqueous solutions (100 mL) into 100 mg of a SPE C(18) sorbent. The effective variables of SPE including type and volume of elution solvent, volume and flow rate of sample solution, and salt concentration were investigated and optimized. Acetone was selected as eluent in SPE and disperser solvent in DLLME and chlorobenzene was used as extraction solvent. Under the optimal conditions, the enrichment factors were between 15,160 and 21,000 and extraction recoveries were 75.8-105.0%. The linear range was 1-10,000 ng L(-1) and limits of detection (LODs) were between 0.2 and 1.5 ng L(-1). The relative standard deviations (RSDs) for 50 ng L(-1) of OPPs in water with and without an internal standard, were in the range of 1.4-7.9% (n=5) and 4.0-11.6%, respectively. The relative recoveries of OPPs from well and farm water sat spiking levels of 25 and 250 ng L(-1) were 88-109%.

Bifunctional ultrasound assisted extraction and determination of Elettaria cardamomum Maton essential oil.

A new hyphenated extraction method composed of ultrasound assisted extraction (UAE)-optimized ultrasound assisted emulsification microextraction (USAEME) was developed for the extraction and preconcentration of the essential oil of Elettaria cardamomum Maton. The essential oil was analyzed by gas chromatography-mass spectrometry (GC-MS) and optimization was performed using gas chromatography-flame ionization detection (GC-FID). Ultrasound played two different roles in the extraction of the essential oil. First, as a source of sufficient energy to break the oil-containing glands in order to release the oil, and second as an emulsifier to disperse the organic phase within water. The effective parameters (factors) of USAEME including volume of extraction solvent (C(2)H(4)Cl(2)), extraction temperature and ultrasonic time were optimized by using a central composite design (CCD). The optimal conditions were 120 µL for extraction solvent volume, 32.5 °C for temperature and 10.5 min for ultrasonic time. The linear dynamic ranges (LDRs) were 0.01-50 mg L(-1) with the determination coefficients in the range of 0.9990-0.9999. The limits of detection (LODs) and the relative standard deviations (RSDs) were 0.001-0.007 mg L(-1) and 3.6-6.3%, respectively. The enrichment factors were 93-98. The main components of the extracted essential oil were α-terpenyl acetate (46.0%), 1,8-cineole (27.7%), linalool (5.3%), α-terpineol (4.0%), linalyl acetate (3.5%).

Optimized ultrasonic assisted extraction-dispersive liquid-liquid microextraction coupled with gas chromatography for determination of essential oil of Oliveria decumbens Vent.

Ultrasonic assisted extraction-dispersive liquid-liquid microextraction (UAE-DLLME) coupled with gas chromatography (GC) was applied for extraction and determination of essential oil constituents of the plant Oliveria decumbens Vent. Scanning electron microscopy (SEM) was used to see the effect of ultrasonic radiation on the extraction efficiency. By comparison with hydrodistillation, UAE-DLLME is fast, low cost, simple, efficient and consuming small amount of plant materials (∼1.0 g). The effects of various parameters such as temperature, ultrasonication time, volume of disperser and extraction solvents were investigated by a full factorial design to identify significant variables and their interactions. The results demonstrated that temperature and ultrasonication time had no considerable effect on the results. In the next step, a central composite design (CCD) was performed to obtain the optimum levels of significant parameters. The obtained optimal conditions were: 0.45 mL for disperser solvent (acetonitrile) and 94.84 µL for extraction solvent (chlorobenzene). The limits of detection (LODs), linear dynamic range and determination coefficients (R(2)) were 0.2-29 ng mL(-1), 1-2100 ng mL(-1) and 0.995-0.998, respectively. The main components of the essential oil were: thymol (47.06%), carvacrol (23.31%), gamma-terpinene (18.94%), p-cymene (8.71%), limonene (0.76%) and myristicin (0.63%).

Optimization of dispersive liquid-liquid microextraction coupled with inductively coupled plasma-optical emission spectrometry with the aid of experimental design for simultaneous determination of heavy metals in natural waters.

In this study, dispersive liquid-liquid microextraction (DLLME) combined with inductively coupled plasma optical emission spectrometry (ICP-OES) was developed for simultaneous preconcentration and trace determination of chromium, copper, nickel and zinc in water samples. Sodium diethyldithiocarbamate (Na-DDTC), carbon tetrachloride and methanol were used as chelating agent, extraction solvent and disperser solvent, respectively. The effective parameters of DLLME such as volume of extraction and disperser solvents, pH, concentration of salt and concentration of the chelating agent were studied by a (2(f-1)) fractional factorial design to identify the most important parameters and their interactions. The results showed that concentration of salt and volume of disperser solvent had no effect on the extraction efficiency. In the next step, central composite design was used to obtain optimum levels of effective parameters. The optimal conditions were: volume of extraction solvent, 113 µL; concentration of the chelating agent, 540 mg L(-1); and pH, 6.70. The linear dynamic range for Cu, Ni and Zn was 1-1000 µg L(-1) and for Cr was 1-750 µg L(-1). The correlation coefficient (R(2)) was higher than 0.993. The limits of detection were 0.23-0.55 µg L(-1). The relative standard deviations (RSDs, C=200 µg L(-1), n=7) were in the range of 2.1-3.8%. The method was successfully applied to determination of Cr, Cu, Ni and Zn in the real water samples and satisfactory relative recoveries (90-99%) were achieved.

Optimization of dispersive liquid-liquid microextraction and improvement of detection limit of methyl tert-butyl ether in water with the aid of chemometrics.

Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry-selective ion monitoring (GC-MS-SIM) was applied to the determination of methyl tert-butyl ether (MTBE) in water samples. The effect of main parameters affecting the extraction efficiency was studied simultaneously. From selected parameters, volume of extraction solvent, volume of dispersive solvent, and salt concentration were optimized by means of experimental design. The statistical parameters of the derived model were R(2)=0.9987 and F=17.83. The optimal conditions were 42.0 µL for extraction solvent, 0.30 mL for disperser solvent and 5% (w/v) for sodium chloride. The calibration linear range was 0.001-370 µg L(-1). The improved detection limit with the aid of chemometrics was 0.3 ng L(-1). The relative standard deviation (RSD) with n=9 for 0.1 mg L(-1) MTBE in water with and without internal standard was 2.7% and 3.1%, respectively. Under the optimal conditions, the relative recoveries of spiked MTBE in different water samples were in the range of 100-105%.