Ultrasound-assisted Surfactant-enhanced Emulsification Microextraction Research Articles

Ultrasound-assisted surfactant-enhanced emulsification microextraction and determination of caffeine and theophylline in human plasma and cocoa powder

Ultrasound-assisted surfactant-enhanced emulsification microextraction and determination of caffeine and theophylline in human plasma and cocoa powder

Vortex and Ultrasound-Assisted Surfactant-Enhanced Emulsification Microextraction for the Determination of Pesticide Residues in Honey using Gas Chromatography–Mass Spectrometry

A novel sample pre-treatment technique based on vortex and ultrasound-assisted surfactant-enhanced emulsification microextraction followed by gas chromatographic–mass spectrometric detection has been developed to determine the selected pesticide residues in honey samples. The key parameters which have affected extraction efficiency were investigated and optimized. Under optimal conditions, the extraction recovery was 90–101% and the enrichment factors were 173–191. The concentration ranges of detection and quantification limits were from 0.03 to 0.9 ng/g and from 0.1 to 3 ng/g, respectively, in honey samples. The relative standard deviation was <5% for intra-day (n = 6) and <8% for inter-day precision (n = 4). Target pesticides were observed in 25% of the samples. The results of this study showed that the residues of such pesticides as bifenthrin, fenpyroximate and thiamethoxam were more than the maximum amount in some honey samples, which causes serious harm to human health.

Ultrasound-assisted surfactant-enhanced emulsification microextraction using a magnetic ionic liquid coupled with micro-solid phase extraction for the determination of cadmium and lead in edible vegetable oils

A novel ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) using a magnetic ionic liquid (MIL) coupled with micro-solid phase extraction was developed for the preconcentration of cadmium and lead in edible vegetable oils prior to analysis by graphite furnace atomic absorption spectrometry. MIL [C4mim] [FeCl4] was used as the extractant, non-ionic surfactant Triton X-100 as the emulsifier and Fe3O4 nanoparticles as the sorbent, while ultrasound was applied to assist the dispersion of the extractant and accelerate the mass transfer process. By mixing Fe3O4 nanoparticles with the MIL after UASEME, the phase separation time was shortened and the separation can be simplified by applying an external magnetic field. Under the optimized conditions, the proposed method was validated and the results demonstrated that the method can produce satisfactory linearity, sensitivity, reproducibility and recovery for the analytes. Finally, the method was successfully applied for the determination of Cd and Pb in edible vegetable oil samples.

Application of Ultrasound-Assisted Surfactant-Enhanced Emulsification Microextraction Based on Solidification of Floating Organic Droplets and High Performance Liquid Chromatography for Preconcentration and Determination of Alprazolam and Chlordiazepoxide in Human Serum Samples.

An improved microextraction method is proposed on the basis of ultrasound-assisted surfactant-enhanced emulsification and solidification of a floating organic droplet procedure combined with high performance liquid chromatography for the preconcentration and quantification of alprazolam (ALP) and chlordiazepoxide (CHL) present in a number of human serum samples. Several parameters affecting the extraction efficiency were investigated by the Plackett -Burman factorial design as the screening design. Then the response surface methodology based on the Box-Behnken design was used to optimize the effective parameters in the proposed procedure. The limits of detection for the proposed method were found to be 3.0 and 3.1 ng mL-1 for CHL and ALP, respectively. The calibration curves obtained for the method were linear in the ranges of 10.0-3,500.0 and 10.0-3,000.0 ng mL-1 for CHL and ALP, respectively, with a good determination coefficient. The recoveries of the drugs in the spiked human serum samples were above 93.0%. The developed method was successfully applied to the analysis of these studied drugs in human serum samples. The pre-treatment of the serum samples was performed using acetonitrile to remove the proteins. The proposed procedure was an accurate and reliable one for the determination and preconcentration of these drugs in blood samples.

Development of Manual Shaking and Ultrasound-Assisted Surfactant-Enhanced Emulsification Microextraction for Analysis of Organophosphorus Pesticides in Aqueous Samples

A novel, rapid and efficient manual shaking and ultrasound-assisted surfactant-enhanced emulsification microextraction (M-UASEME) combined with gas chromatography-flame photometric detection (GC-FPD) was developed for the extraction and determination of eight organophosphorus pesticides (OPPs) in tap water and honey samples. The main parameters that affected the extraction efficiency were investigated and optimized. Under the optimum conditions, the relative standard deviation (RSD, n = 6) ranged from 2.4 to 9.3%. Limits of detection (LOD) were varied between 0.005 and 0.05 µg L-1. Good linearity was obtained in a range of 0.5-50.0 µg L-1 for all analytes with the correlation coefficients (r) > 0.9964. Finally, the developed method was successfully applied to determine the eight pesticide residues in real samples. The recoveries of the target analytes in samples were between 82.4 and 96.7%.

Ultrasound-Assisted Surfactant-Enhanced Emulsification Micro-Extraction Followed by HPLC for Determination of Preservatives in Water, Beverages and Personal Care Products.

An ultrasound-assisted surfactant-enhanced emulsification micro-extraction (UASEME) procedure has been developed for pre-concentration of benzoic acid (BA) and paraben preservatives, including methylparaben, ethylparaben, propylparaben and butylparaben, prior to high-performance liquid chromatography-ultraviolet (HPLC-UV) analysis. Separations were performed on a Lichrospher RP-18 endcapped 5 µm, using an isocratic mobile phase of 40% acetonitile, at a flow rate of 1 mL min-1 The selected UASEME conditions comprised the use of 10 mL sample extract, 125 µL 1-octanol as extraction solvent and 0.05 mmol L-1 Tween 20 as emulsifier, 0.5% sodium chloride, ultrasonication time of 6 min and centrifugation time of 10 min. Method performance demonstrated wide linear range between 0.5 and 7,000 µg L-1 (R2>0.9903) and limits of detection between 0.03 and 10 µg L-1, which providing the enrichment factors of 15-184. The method precision (relative standard deviation) was <7%. The developed UASEME coupled with HPLC-UV has been successfully applied to determine four paraben preservatives in various sample matrices such as water, beverages and personal care products. The recoveries in the range of 70-138.1% were obtained. However, BA could not be determined in real sample extracts.

Optimization of modified dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the simultaneous preconcentration and determination of nitrazepam and midazolam drugs: An experimental design.

A simple, sensitive, and rapid microextraction method, namely, ultrasound-assisted surfactant-enhanced emulsification microextraction based on the solidification of floating organic droplet method coupled with high-performance liquid chromatography was developed for the simultaneous preconcentration and determination of nitrazepam and midazolam. The significant parameters affecting the extraction efficiency were considered using Plackett-Burman design as a screening method. To obtain the optimum conditions with consideration of the selected significant variables, a Box-Behnken design was used. The microextraction procedure was performed using 29.1 μL of 1-undecanol, 1.36% (w/v) of NaCl, 10.0 μL of sodium dodecyl sulfate (25.0 μg mL(-1)), and 1.0 μL of Tween80 (25.0 μg mL(-1)) as an emulsifier in an extraction time of 20.0 min at pH 7.88. In order to investigate the validation of the developed method, some validation parameters including the linear dynamic range, repeatability, limit of detection, and recoveries were studied under the optimum conditions. The detection limits of the method were 0.017 and 0.086 ng mL(-1) for nitrazepam and midazolam, respectively. The extraction recovery percentages for the drugs studied were above 91.0 with acceptable relative standard deviation. The proposed methodology was successfully applied for the determination of these drugs in a number of human serum samples.

Ionic-liquid-based, manual-shaking- and ultrasound-assisted, surfactant-enhanced emulsification microextraction for the determination of three fungicide residues in juice samples

A novel manual-shaking- and ultrasound-assisted surfactant-enhanced emulsification microextraction method was developed for the determination of three fungicides in juice samples. In this method, the ionic liquid, 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, instead of a volatile organic solvent was used as the extraction solvent. The surfactant, NP-10, was used as an emulsifier to enhance the dispersion of the water-immiscible ionic liquid into an aqueous phase, which accelerated the mass transfer of the analytes. Organic dispersive solvent typically required in common dispersive liquid-liquid microextraction methods was not necessary. In addition, manual shaking for 15 s before ultrasound to preliminarily mix the extraction solvent and the aqueous sample could greatly shorten the time for dispersing the ionic liquid into aqueous solution by ultrasound irradiation. Several experimental parameters affecting the extraction efficiency, including type and volume of extraction solvent, type and concentration of surfactant, extraction time, and pH, were optimized. Under the optimized conditions, good linearity with the correlation coefficients (γ) higher than 0.9986 and high sensitivity with the limit of detection ranging from 0.4 to 1.6 μg/L were obtained. The average recoveries ranged from 61.4 to 86.0% for spiked juice, with relative standard deviations from 1.8 to 9.7%. The proposed method was demonstrated to be a simple, fast, and efficient method for the analysis of the target fungicides in juice samples.

Ultrasound Assisted Surfactant Enhanced Emulsification Microextraction and Spectrofluorimetry for Determination of Oxadiazon in Agricultural Water Samples

In this work, an environmentally friendly sample pre-treatment method, Ultrasound Assisted Surfactant Enhanced Emulsification Microextraction (UASEME) followed with spectrofluorimetry was performed for determination of oxadiazon residues in water samples. After the determination of the most suitable extraction solvent and its volume, other parameters such as type and concentration of surfactant, pH, extraction time and ionic strength were optimized. Under the best conditions for extraction recovery, 50µL of chlorobenzene was chosen as extraction solvent and Tween 20 in concentration of 0.06 mmol/L as emulsifier and 2 min was the required time for quantitative analysis, without ionic strength and pH adjustment. Limit of detection and relative standard deviation were calculated as 0.05µg/L and 3.2% respectively. The procedure was applied successfully for assessing matrix effect in real water samples with relative recovery 96-104% with the precision in the range of 2.9-3.4%. The results demonstrate that UASEME procedure as reported is reliable, rapid and easy to use for analysis of oxadiazon in water samples.

Extraction and determination of sulfonylurea herbicides in water and soil samples by using ultrasound-assisted surfactant-enhanced emulsification microextraction and analysis by high-performance liquid chromatography

An ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) with low-density extraction solvents was developed for the extraction of sulfonylurea herbicides from water and soil samples prior to high-performance liquid chromatography coupled with ultraviolet detection (HPLC–UV). In this technique, a surfactant was used as emulsifier which could enhance the dispersion of water-immiscible extraction solvent into aqueous phase and was favorable for the mass-transfer of the analytes from aqueous phase to organic phase. The target analytes were extracted into an extraction phase (Aliquat-336 in1-octanol) and dispersed in an aqueous solution. After extraction and phase separation, the organic solvent on top of the solution was withdrawn into a syringe and 20µL of it was injected into a HPLC instrument for analysis. Influential factors in extraction were investigated and optimized. Under optimum experimental conditions, calibration curve was linear in the concentration range from 1 to 100µg/L, with coefficients of estimation (R2 values) varying from 0.9928 to 0.9952, and satisfactory repeatabilities (4.7<RSDs%<6.1) were attained. High preconcentration factors were achieved ranging from 103 to 153. Applicability of the method to the extraction of sulfonylurea herbicides from different types of complicated matrices, such as water and soil samples, was studied. The obtained results indicated that the proposed method is efficient, fast and inexpensive for extraction and determination of sulfonylurea herbicides in environmental aqueous and soil samples.

Alternative Green Preconcentration Approach Based on Ultrasound-Assisted Surfactant-Enhanced Emulsification Microextraction and HPLC for Determination of Benzimidazole Anthelmintics in Milk Formulae

An alternative green microextraction method based on ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) using a low-density extraction solvent coupled with HPLC has been developed for preconcentration and determination of six benzimidazole anthelmintics, namely, oxfendazole, albendazole, mebendazole, flubendazole, fenbendazole, and niclosamide. The separation was achieved within 12 min, using an Inertsil® C18 column (4.6 × 150 mm, 5.0 µm), with a gradient mobile phase of acetonitrile and 0.1 % (v/v) formic acid. Under the optimum UASEME conditions using Tergitol® TMN-6 and 1-octanol as emulsifier and extraction solvent, respectively, linearity was in the range of 0.5–5,000 μg L−1 with the coefficients of determination (R 2) ranging from 0.9959 to 0.9999. Enrichment factors were obtained up to 89, corresponding to limits of detection ranging from 0.50 to 6.00 µg L−1. Intra-day (n = 8) and inter-day (n = 3 × 3) precisions were obtained with relative standard deviations for retention time and peak area of lower than 2 and 15 %, respectively. The proposed method was successfully applied to determine the target benzimidazoles in milk formulae.

Ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of Cd and Ni in tea and water samples

A microextraction method based on ultrasound-assisted surfactant-enhanced emulsification using solidification of a floating organic droplet (UASEME-SFO) was evaluated for simultaneous determination of Cd and Ni in water and tea samples followed by flame atomic absorption spectrometry. In the UASEME-SFO technique, Triton X-100 was used as an emulsifier to accelerate the emulsification of the extraction solvent into a sample solution and hasten the mass transfer of the analytes. Analytes form a complex and are extracted into 1-dodecanol which was used as an extraction solvent. Some parameters such as type and volume of the extraction solvent, the type and concentration of the surfactant, ultrasound extraction time, reagent concentration, centrifuge conditions and salt concentration were investigated. Under optimum conditions, calibration curves were linear in the range of 0.3–100 and 0.6–180 μg L−1 with detection limits of 0.11 and 0.20 μg L−1 for Cd and Ni, respectively. The accuracy of the method was confirmed by parallel analyses using the certified reference material of water and tea samples. The recoveries of the analytes in tea leaves, tea infusions and water samples were in the range of 96.5–105.1%.

Determination of Phenolics in Water and Arthrospira (Spirulina) platensis by Concentrated Sulfuric Acid and Ultrasound-Assisted Surfactant-Enhanced Emulsification Microextraction and High Performance Liquid Chromatography

A novel, practical, and environmentally friendly technique, termed concentrated sulfuric acid cleanup and ultrasound-assisted surfactant-enhanced emulsification microextraction (CSAC-UASEM), was combined with HPLC for the preconcentration and determination of five phenolics in water and Arthrospira (Spirulina) platensis samples. The main advantages include that the concentrated sulfuric acid is used to decrease macromolecular interferences prior to microextraction and, unlike dispersive liquid–liquid microextraction procedures, no dispersive organic solvent is required. Chloroform and sodium dodecyl sulfate were used as the extraction solvent and emulsifier, respectively. The algal cell preparation and CSAC-UASEM procedure parameters, including selection of cleanup method, ultrasound power, cell cytocylasis time, type and volume of extraction solvent, extraction temperature, ultrasound-extracted time, and sample pH, were optimized. At the fortification levels of 1.0 and 10.0 µg/L, the enrichment factors of analytes were in the range of 201.38 to 269.24. The percent extraction ranged from 71.57% to 107.42% in environmental Arthrospira-350, -793, and -834 samples, whereas the range was from 74.17% to 106.72% in water samples. The limits of detection (at S/N = 3) were 0.02 to 0.04 µg/L (except for 4-bromobisphenol A of 0.10 µg/L). These values indicate an approximately ten-fold improvement compared with the values reported by other techniques. In summary, the CSAC-UASEM sample preparation technique has great potential in the routine determination of trace phenolics in environmental waters and aquatic biological samples.

A hydroxyl functionalized ionic liquid-based ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of herbicides in water samples

This paper describes a hydroxyl functionalized ionic liquid (FIL), 1-hydroxyl hexyl-3-methylimidazoliumbis[(trifluoromethyl)sulfonyl] imide [HHyMIMTf2N] used for the extraction and preconcentration of 7 herbicides from water samples by ultrasound-assisted surfactant-enhanced emulsification microextraction.

Development and validation of an ultrasound-assisted surfactant-enhanced emulsification microextraction method for liquid chromatographic determination of carbamate residues in fruit juices

A microextraction procedure based on ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) was optimized and validated for preconcentration of carbamate pesticides prior to fast determination using high-performance liquid chromatography (HPLC) with monolithic column. The nonionic surfactant (Tween 20) was used as an emulsifier, and chloroform was selected as an extraction solvent. The experimental parameters affecting the extraction efficiency, such as the kind, concentration, and volume of surfactant, the kind of extraction solvent and its volume, salt addition, ultrasonic extraction time, and centrifugation time, were optimized. Under the selected UASEME and HPLC conditions, separation of five carbamate pesticides (carbofuran, carbaryl, isoprocarb, methiocarb, and promecarb) was achieved within 10 min. The linearity of the method was obtained in the wide range of 2–5000 μg L−1, with correlation coefficients of 0.9931–0.9970. The limits of detection were in the range of 0.4–7.0 μg L−1. The relative standard deviations (n = 5) were less than 0.59% and 4.86% for retention time and peak area, respectively. The enrichment factors of the developed UASEME method were in the range of 33–166. The fruit juice samples (at fortified levels of 0.25, 0.50, and 1.00 mg L−1) were successfully analyzed, and the relative recoveries were obtained in the range of 81–115%.

Determination of Cobalt in Food and Water Samples by Ultrasound-assisted Surfactant-enhanced Emulsification Microextraction and Graphite Furnace Atomic Absorption Spectrometry

A novel method based on ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) has been developed for the preconcentration of cobalt prior to its determination by graphite furnace atomic absorption spectrometry. In the UASEME technique, chloroform was used as the extraction solvent, sodium dodecyl sulfate was adopted as emulsifier, and ultrasound was applied to assist emulsification. There is no need of using organic dispersive solvent which is typically required in conventional dispersive liquid–liquid microextraction method. Several parameters that affect the extraction efficiency, such as the kind and volume of the extraction solvent, the type and concentration of the surfactant, pH of sample solution, concentration of the chelating agent, and extraction time and temperature were investigated and optimized. Under the optimal conditions, the linearity of calibration curve was in the range of 0.1–5 ng mL−1 with a correlation coefficient (R 2) of 0.9992. An enrichment factor of 58 was achieved with a sample volume of 5.0 mL. The detection limit of this method for Co was 15.6 ng L−1, and the relative standard deviation (RSD) was 4.3 % at 1.0 ng mL−1 concentration level of Co. The accuracy of the developed method was evaluated by analysis of the certified reference materials GBW07605 tea leaf and GBW10015 spinach. The method was successfully applied to determine trace cobalt in food and water samples with satisfactory results.

Ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of carbamates in wines by ultra-high performance liquid chromatography–tandem mass spectrometry

A new sensitive multiresidue method based on ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) has been developed for the detection, confirmation and quantification of twenty five carbamates in wine samples. The separation was achieved in 5.5min, using a Zorbax Eclipse plus RRHD C18 column (50mm×2.1mm, 1.8μm), with a mobile phase of water and methanol, both of them with 0.01% formic acid. The analytes were detected in positive mode with multiple reaction monitoring mode. Ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME), using a low-density extraction solvent has been optimized for the satisfactory extraction of carbamates and clean-up of extracts. The matrix effect was studied, showing that the proposed procedure provides very clean extracts. Under optimum conditions, recoveries for fortified wine samples ranged from 74 to 102%, with relative standard deviations lower than 6%. Limits of quantification ranged from 0.15 to 0.92μgl−1, showing the high sensitivity of this fast and simple method and its compliance with current requirements.

Ultrasound-assisted surfactant-enhanced emulsification microextraction based on the solidification of a floating organic droplet used for the simultaneous determination of six fungicide residues in juices and red wine

A novel ultrasound-assisted surfactant-enhanced emulsification microextraction technique based on the solidification of a floating organic droplet followed by high performance liquid chromatography with diode array detection was developed for simultaneous determination of six fungicide residues in juices and red wine samples. The low-toxicity solvent, 1-dodecanol, was used as an extraction solvent. For its low density and proper melting point near room temperature, the extractant droplet was collected easily by solidifying it at a low temperature. The surfactant, Tween 80, was used as an emulsifier to enhance the dispersion of the water-immiscible extraction solvent into an aqueous phase, which hastened the mass-transfer of the analytes. Organic dispersive solvent typically required in common dispersive liquid–liquid microextraction methods was not used in the proposed method. Some parameters (e.g., the type and volume of extraction solvent, the type and concentration of surfactant, ultrasound extraction time, salt addition, and volume of samples) that affect the extraction efficiency were optimized. The proposed method showed a good linearity within the range of 5μgL−1–1000μgL−1, with the correlation coefficients (γ) higher than 0.9969. The limits of detection for the method ranged from 0.4μgL−1 to 1.4μgL−1. Further, this simple, practical, sensitive, and environmentally friendly method was successfully applied to determine the target fungicides in juice and red wine samples. The recoveries of the target fungicides in red wine and fruit juice samples were 79.5%–113.4%, with relative standard deviations that ranged from 0.4% to 12.3%.

Ultrasound-assisted surfactant-enhanced emulsification microextraction with solidification of floating organic droplet followed by high performance liquid chromatography for the determination of strobilurin fungicides in fruit juice samples

A novel method, ultrasound-assisted surfactant-enhanced emulsification microextraction with solidification of floating organic droplet (UASEME-SFOD), has been developed for the extraction of four strobilurin fungicides (kresoxim-methyl, picoxystrobin, pyraclostrobin and trifloxystrobin) in fruit juices. In the UASEME-SFOD technique, Tween 80 was used as emulsifier, and 1-undecanol was used as extraction solvent without using any organic dispersive solvent. Several parameters that affect the extraction efficiency, such as the kind and volume of extraction solvent, the type and concentration of the surfactant, extraction time, extraction temperature and salt addition were investigated and optimized. Under the optimum extraction condition, the method yields a linear calibration curve in the concentration range from 5 to 10,000 ng mL(-1) for the targeted analytes with the correlation coefficient ranging from 0.9991 to 0.9998. The enrichment factors were in the range between 95 and 135, and the limits of detection of the method were 2-4 ng mL(-1). The fruit juice samples were successfully analyzed using the proposed method, and the relative recoveries at fortified levels of 50 and 100 ng mL(-1) were in the range of 82.6-97.5%.

Preconcentration and Simultaneous Analysis of Benzimidazole Anthelmintics in Milk Samples by Ultrasound-Assisted Surfactant-Enhanced Emulsification Microextraction and High-Performance Liquid Chromatography

The proposed ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) coupled with high-performance liquid chromatography-photodiode array detection (HPLC-PDA) has been developed for the preconcentration and simultaneous analysis of five benzimidazole anthelmintics. Dichloromethane (extraction solvent) and Triton X-114 (emulsifier) was used for extraction of the target analytes. The parameters affecting the extraction efficiency were investigated and optimized. Under the optimum conditions, linearity was in the range from 10 to 150 μg L−1 with good coefficients of determination (R2) higher than 0.994. Preconcentration factors were obtained up to 60, corresponding to limits of detection range of 1.8 − 3.6 μg L−1. Intra-day (n = 5) and inter-day (n = 4 × 3) precisions were obtained with relative standard deviation of retention time and peak area below 0.8 and 9.2 %, respectively. Good recoveries for the spiked target anthelmintics at different concentrations (e.g., 20, 50, and 100 μg L−1) of milk samples were obtained in 72.5–113.5 %. The results demonstrated that the proposed UASEME-HPLC-PDA can be used as an alternative powerful method for the simultaneous determination of the target analytes in milk samples.