Ultrasound-assisted Emulsification Microextraction Research Articles

Combination of Ultrasound-Assisted Extraction and Ultrasound-Assisted Emulsification Microextraction for Separation and Enrichment of Permethrin and Deltamethrin Residues in Spinach Samples

Combination of Ultrasound-Assisted Extraction and Ultrasound-Assisted Emulsification Microextraction for Separation and Enrichment of Permethrin and Deltamethrin Residues in Spinach Samples

Development of an Ultrasound-Assisted Emulsification Microextraction Method for the Determination of Volatile Compounds in Wines

A fast and simple method based on ultrasound-assisted emulsification microextraction (USAEME) was developed for the analysis of volatile compounds in wines. A full factorial 24 screening design was built to investigate the main factors affecting the extraction of volatile components, namely the volume of extraction solvent, sonication time, salt content, and pH. Then, the factors with significant effects were optimized using an I-optimal design. The optimal value for all the variables studied was reached under the following experimental conditions: volume of extraction solvent 200 μL and salt content 5% m/v. The suitability of the optimized method was evaluated, resulting in very good linearity with coefficients of determination (R2) higher than 0.995 in all cases, while repeatability was lower than 8.4% except for d-limonene and p-cymene. Recoveries higher than 82% were observed for the groups of ethyl esters, acetate esters, alcohols, and terpenoid alcohols (linalool, α-terpineol). The recovery of acids ranged from 70.5% to 88.9%, whereas the three monoterpenes studied (d-limonene, γ-terpinene, p-cymene) were not extracted satisfactorily. The proposed method was effectively applied for the analysis of volatile compounds in laboratory-scale fermentations with selected strains of Saccharomyces cerevisiae.

Multi-response optimization of a deep eutectic solvent‑based microextraction method for the simultaneous extraction of twenty organochlorine pesticides for monitoring in various water samples

This study investigates the application of a relatively hydrophobic deep eutectic solvent (DES) for ultrasound-assisted emulsification-microextraction of twenty organochlorine pesticides from environmental water samples before determination by gas chromatography equipped with a micro-electron capture detection. To find the highest global extraction efficiency, the central composite design combined with the desirability function (DF) approach was utilized for multi-response optimization of effective parameters, including DES volume, pH, salt concentration, and sonication time. DES was prepared by combining choline chloride as a hydrogen bond acceptor and 1-phenylethanol as a hydrogen bond donor in a mole ratio 1:4. The optimum conditions corresponding to 0.888 in the DF were pH 10.10, DES volume of 73 µL, salt concentration of 17.44% (w/v), and sonication time of 7.36 min. The analytical performance of the method was evaluated under optimum conditions and a wide linear range (0.05–30 ng/mL) with good linearity (R2 > 0.9967), low limit of detection (3.5–33 pg/mL), high enrichment factors (151.1–616.3), and good extraction recoveries (27.2–98.6%) were obtained. The potential of using the method to determine OCPs in four real water samples was proved through high relative recoveries values. The Green Analytical Procedure Index (GAPI) tool was used to evaluate the method's greenness, which confirms the superior eco-friendship of the method compared to other methods.

A natural hydrophobic deep eutectic solvent-based microextraction method integrated with a spectrofluorimetric technique for the determination of daclatasvir as a direct-acting hepatitis C antiviral drug in plasma samples

An ultrasound-assisted emulsification microextraction method based on a natural hydrophobic deep eutectic solvent (USAEME-HDES) was developed for extraction and preconcentration of daclatasvir, a hepatitis C virus inhibitor, from plasma samples prior to spectrofluorimetric measurement. To make the deep eutectic solvent (DES) compatible with the fluorescence device, fatty acids were used as components of DES that can simultaneously act as hydrogen bond donors (HBD) and hydrogen bond acceptors (HBA). Various parameters, such as the solvent effect on the fluorescence spectrum and the composition and ratio of DES, were investigated and optimized. Other parameters, including pH, DES volume, sonication time, and NaCl concentration, were investigated and optimized using the central composite design combined with the desirability function. Under optimal conditions, compared to other methods, this method had a wide linear range (5–600 ng/mL) with a good coefficient of determination (0.9985) and a low limit of detection (1.42 ng/mL). Drug analysis results in the plasma samples showed that the method has good accuracy. Finally, the Green Analytical Procedure Index (GAPI) tool was used to evaluate the greenness of the method, which demonstrates our method's superior eco-friendship in comparison to other reported methods.

The comparison of two microextraction methods for the determination of safranal from Iranian saffron

In this study, safranal as the main component of the pleasant aroma of saffron was extracted and analyzed by two liquid-phase microextraction based methods, namely ultrasound-assisted emulsification microextraction and solidified floating organic drop microextraction. These methods are fast, simple, low-cost, environmentally friendly and efficient procedures that have been developed for the determination of safranal from aqueous samples. Extracted safranal was determined by high pressure liquid chromatography and the performance of the above mentioned methods was compared accurately. A narrow neck glass tube was used for the simple and rapid collection of the low-density organic phase from the sample surface after its centrifugation. A dynamic range over 0.1 to 5 μg mL−1 of safranal and limit of detection of 20 ng mL−1 were obtained for ultrasound-assisted emulsification microextraction. In addition, the dynamic range for solidified floating organic drop microextraction was between 0.02 to 5 μg mL−1 as well as a limit of detection of 3 ng mL−1 was obtained. Furthermore, the enrichment factor and recovery percent were 38 and 101±4.6% in ultrasound-assisted emulsification microextraction besides 252 and 25.2 ± 5.8% in solidified floating organic drop microextraction. The applicability of the proposed methods was evaluated by the extraction and determination of safranal from different Iranian saffron samples and finally, the results were validated by the ISO 3632 procedure.

Hydrophobic deep eutectic solvent‐based microextraction method for the simultaneous extraction of two benzodiazepines from saliva samples before determination by 96‐well microplates‐based spectrophotometer with the aid of chemometrics

AbstractIn this study, a 96‐well microplates‐based spectrophotometer with the aid of the partial least squares (PLS) approach was used for the simultaneous determination of more common benzodiazepines, clonazepam, and nitrazepam, in human saliva samples. For this purpose, a hydrophobic deep eutectic solvent (DES) based on choline chloride and 1‐phenylethanol in the mole ratio of 1:4 was prepared and utilized in the ultrasound‐assisted emulsification‐microextraction (USAEME) method followed by back‐extraction to retrieve the drugs from the DES phase to 200 μL of 0.1 M NaOH solution. Central composite design (CCD) in combination with the desirability function was used for multi‐response optimization of different parameters and the optimum values were found to be: pH 2.06; DES volume, 247.1 μL; NaCl, 1.55% (w/v); sonication time, 5.33 min. The DES‐based USAEME method showed wide linear ranges of 0.1–6 and 0.2‐8 μg/mL and good limits of detection of 0.02 and 0.05 μg/mL for clonazepam and nitrazepam, respectively. Furthermore, the method was successfully used for determining the drugs in human saliva samples.

Ultrasound-assisted Emulsified Microextraction Followed by High Performance Liquid Chromatography for Permethrin

Ultrasound assisted emulsification microextraction (UAEME) as a new sample preparation method was optimized for the determination of permethrin in urine samples. Also, deep eutectic solvent was used as the extracting solvent instead of organic solvents in this method. In order to determine the optimal values, six main parameters were studied in different levels. Totally, 105 runs were performed using the one-variable-at-a-time method followed by high-performance liquid chromatography with a UV detector. Under the optimum conditions, the calibration curve for permethrin was linear in the concentration range of 5 to 500 μgL‑1 for urine samples. The accuracy and reproducibility of the introduced method were determined using the relative recovery (RR%) and relative standard deviation (RSD%) tests on the fortified urine samples. RR% and RSD% were found to be 96.3–101.7 % and 3.2–7.6 %, respectively. The limit of quantification and also the limit of detection were obtained 5 and 1 μg/L, respectively. In the present study, the DES-UA-EME technique was successfully developed for the extraction of permethrin from urine samples and subsequent quantification by high-performance liquid chromatography.In comparison to the other sample preparation methods, the proposed technique has the advantages of shorter extraction time, simplicity, and applicability in laboratories with less equipment

Simultaneous determination of low molecule benzotriazoles and benzotriazole UV stabilizers in wastewater by ultrasound-assisted emulsification microextraction followed by GC\u2013MS detection

A rapid, sensitive, economically and ecologically friendly method based on one-step ultrasound-assisted emulsification microextraction and in situ derivatization followed by gas chromatography–mass spectrometry for simultaneous determination of low molecular benzotriazoles and benzotriazole-based ultraviolet filters was developed. The optimized method allows quantification of benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole; 5-chlorobenzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzortriazole and 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole in municipal and industrial (dairy) wastewater. The method was validated using real influent and effluent wastewater and samples at various stages of the purification process. Relative recoveries obtained using wastewater as sample matrix were between 77 and 137%, method limits of detection from 0.001 to 0.035 µg/L, method limits of quantification from 0.003 to 0.116 µg/L, the repeatability expressed by the coefficient of variation did not exceed 12%. The use of the method for the determination of tested compounds in municipal and industrial wastewater showed their presence in most of the tested samples, in concentrations from LoD to 6.110 µg/L. The conducted studies of samples from municipal wastewater treatment plant located in north-east Poland showed that the effectiveness of benzotriazole removal by this plant wasfrom 29 to 84%. The load of tested compounds released into the environment by this facility ranges from 2 to 269 mg/day/1000 inhabitants.

Ultrasound-Assisted Emulsified Microextraction Based on Deep Eutectic Solvent for Trace Residue Analysis of Metribuzin in Urine Samples

Deep eutectic solvent was used as extraction solvent to develop and optimize a new sample preparation method for the determination of metribuzin in urine samples. In order to determine the optimal values of the effective factors in the deep eutectic solvent-based ultrasound assisted emulsification microextraction method, six effective parameters were selected. The design of experiments was performed using the onevariable- at-a-time method. Totally, 96 experimental runs were performed, and the samples were analyzed using high-performance liquid chromatography with a UV detector. Under the optimum conditions, the calibration curve for metribuzin was linear in the concentration range of 5 to 500 μg L-1 for urine samples. The accuracy and reproducibility of the introduced method were determined using the relative recovery (RR %) and relative standard deviation (RSD %) tests on the fortified urine samples. RR % and RSD % were found to be 96.3 – 101.7 % and 3.2 – 7.6 %, respectively. The limit of quantification and the limit of detection were obtained 5 and 0.8 μg L-1, respectively.

Deep eutectic solvent based ultrasound assisted emulsification microextraction for preconcentration and voltammetric determination of aflatoxin B1 in cereal samples.

A new and simple deep eutectic solvent based ultrasound-assisted emulsification microextraction (DES-UAEME) procedure has been developed for preconcentration and voltammetric determination of aflatoxin B1 (AFB1) in cereal products. The method is based on the acetonitrile-based extraction of AFB1 from homogenized cereal samples followed by a DES-UAEME procedure for subsequent differential pulse voltammetry (DPV) determination in a microcell. A DES composed of choline chloride and urea (ChCl-Ur) was used as the extraction solvent and electrolyte for DPV detection. Various parameters affecting the extraction efficiency of AFB1 were evaluated and optimized. Under optimum conditions the calibration graph was linear in the range of 0.2-80.0 μg L-1 (R2 = 0.9966) and the limit of detection (3Sb) was estimated to be 0.05 μg L-1. The intra-day and inter-day precision (RSD%) for determination of 5.0 μg L-1 AFB1 were 3.4% and 3.9%, respectively. The proposed method was also successfully applied for preconcentration and determination of AFB1 in different cereal samples and good relative recoveries were obtained over a range of 94 to 104%.

Spectrophotometric determination of lamotrigine in plasma samples: Ultrasound-assisted emulsification-microextraction based on a hydrophobic deep eutectic solvent followed by back-extraction.

In this study, sensitive detection of lamotrigine in human plasma samples was realized at a low cost approach through ultrasound-assisted emulsification-microextraction based on using a hydrophobic deep eutectic solvent followed by back-extraction (USAEME-DES-BE) method. After extraction, detection and quantification of lamotrigine were done by spectrophotometry in the UV region. The hydrophobicity of the deep eutectic solvent not only eliminates the need of the third solvent as an emulsifying agent but also helps to retrieve lamotrigine from the DES by back-extraction to another aqueous phase. The back extraction process allowed the drug to be measured in the UV region. Central composite design in combination with a desirability function approach was applied for the optimization of the USAEME-DES-BE procedure. Essential factors in the method efficiency were discussed, such as back-extraction solution, time of back-extraction, the ratio of DES components, pH, the volume of DES, salt concentration, and sonication time. The method exhibited a wide dynamic linear range from 0.5 to 10µgmL-1 and a limit of detection of 0.15μgmL-1. The established method was successfully applied to determine lamotrigine in human plasma samples with satisfactory relative recoveries.

Deep eutectic solvent-based ultrasound-assisted emulsification microextraction for the rapid determination of benzotriazole and benzothiazole derivatives in surface water samples

This work describes a simple and environmental-friendly method for the simultaneous determination of five benzotriazole derivatives (BTRs) and four benzothiazole derivatives (BTs) that are frequently found in surface water. The target analytes were efficiently extracted from water samples using a “green” deep eutectic solvent (DES) as the extraction solvent based- ultrasound-assisted emulsification microextraction (DES-USAEME), and their determination were performed by ultrahigh-performance liquid chromatography and electrospray ionization (+)-quadrupole time-of-flight mass spectrometry (UHPLC-ESI(+)-QToF-MS). The DES was composed of a mixture of choline chloride and phenol (molar ratio 1:2). The DES-USAEME factors were optimized by a Box-Behnken Design coupled response surface methodology. The developed method was validated, providing limits of quantitation (LOQs; 02 μg L−1), high precisions (1–8%), and satisfactory mean spiked recoveries (72–104 %). Relatively high total concentrations of the target analytes were found in samples collected from a reservoir (47.2–101.3 μg L−1), which may have been released from tire-wear particles and scrap tires from buses and old tires that were strung alongside the shuttle boats to prevent the boats from coming into contact with each other or from impacting against the dock during docking. This is the first study on the occurrence of BTRs and BTs in reservoir samples.

Simultaneous Determination of Lamotrigine and Carbamazepine in Plasma Using Ultrasound-Assisted Emulsification Microextraction-High Performance Liquid Chromatography

A simple, fast and efficient method based on ultrasound-assisted emulsification microextraction (USAEME) followed by HPLC has been developed for simultaneous determination of Carbamazepine (CBZ) and Lamotrigine (LTG) in biological samples. The influence of different parameters affecting the USAEME procedure was evaluated to optimize the efficiency of the process. At these conditions, validation of the proposed method was performed based on European medicines agency guidelines. The proposed method showed good linearity in plasma samples ranging from 0.25 to 6 µg/mL and 0.13 to 6 µg/mL (R2 ≥ 0.99) for CBZ and LTG, respectively. The precision of the proposed method was evaluated for repeatability which was ≤12% (n = 5). The detection limits of 0.06 and 0.05 µg/mL were obtained for CBZ and LTG, respectively. The proposed method can be applied as an effective technique for therapeutic drug monitoring of CBZ and LTG in plasma of epileptic patients.

Emulsification-assisted micro-solid-phase extraction using a metal-organic framework as sorbent for the liquid chromatography-tandem mass spectrometric analysis of polar herbicides from aqueous samples

Two miniaturized sample preparation techniques, ultrasound-assisted emulsification microextraction (USAEME) and micro-solid-phase extraction (μ-SPE) have been integrated for the pre-concentration of four polar chlorophenoxy acid (CPA) herbicides from environmental aqueous samples. An metal-organic framework, MIL-101(Cr), characterized by its high porosity and large surface area, was explored as a sorbent. Despite the simplicity and convenience of μ-SPE, its use can potentially be limited by a long equilibration time, especially when applied to polar analytes. However, as demonstrated in this work, this drawback can be overcome by employing 1-octanol as a medium during the USAEME step to concentrate, and transport the polar herbicides through the polypropylene membrane of the μ-SPE device, onto the MIL-101(Cr). After μ-SPE, the herbicides were desorbed using 125 μL of organic solvent, and analyzed by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Under the most favorable conditions, wide calibration ranges with good linearity (r2 ≥ 0.995) are attained for all the herbicides. The limits of detection of the method range between 7.20 and 58.1 ng L−1 while the limits of quantification (LOQs) range between 24.0 and 194 ng L−1. The LOQs determined are lower than the guidelines set by the World Health Organization for the respective herbicides. USAEME-μ-SPE-UHPLC-MS/MS also shows good repeatability, with relative standard deviations ≤ 15.2%. Enrichment factors are between 21 and 70. The method was applied to the analysis of tap and reservoir waters, in which satisfactory relative recoveries ranging between 64.4% and 106% were obtained. The MIL-101(Cr) exhibited superior extraction capability in comparison to activated carbon and multi-walled carbon nanotubes.

Simple Approach Based On Ultrasound-Assisted Emulsification Microextraction For Determination Of β-Sitosterol In Dietary Supplements And Selected Food Products

A novel method based on ultrasound-assisted emulsification microextraction (USAEME) was proposed for the determination of β-sitosterol (β-SIT) in dietary supplements and selected food products using liquid chromatography coupled with UV. Mostly, USAEME is used for preconcentration analytes from water samples. The influences on the extraction efficiency were studied. Hexane was used as extraction solvent. Parameters such as volume of extraction solvent, temperature, ionic strength, effect of sonication were checked. Under optimum conditions, β-SIT was quantitatively extracted achieving enrichment factor (EF) equals 97. The limit of detection (LOD) and quantification (LOQ) of the β-SIT for the preconcentration of 5 mL sample volume were 0.013 µg mL−1 and 0.04 µg mL−1, respectively. The calibration curve was linear within the concentration range of 0.04–12.44 µg mL−1. The coefficient of estimation was 0.9979 ± 0.0014. The relative standard deviations were 4.65% (at n = 5, intraday) and 5.21% (at n = 15, interday). Recovery value was 99.84 ± 3.37%. The new prescribed methodology has been applied to determine this phytosterol in supplements, vegetables (broccoli, black olives, romaine lettuce, pea) and fruits (bananas, apples, mandarins, lemons). To the best of our knowledge, this is the first time that USAEME has been applied to isolate β-SIT from methanol samples obtained from real samples.

Ionic liquid-based ultrasound-assisted emulsification microextraction for the determination of ranitidine in water samples and pharmaceutical preparations

A new extraction method is proposed for the isolation of the histamine H2 receptor antagonist ranitidine (RNT) from aqueous samples.

Rapid and Sensitive Analysis of Hormones and Other Emerging Contaminants in Groundwater Using Ultrasound-Assisted Emulsification Microextraction with Solidification of Floating Organic Droplet Followed by GC-MS Detection

Ultrasound-assisted emulsification microextraction with solidification of floating organic droplet (USAEME-SFOD) has been applied to isolate hormones and other emerging contaminants from groundwater samples. Simultaneously with the extraction process, derivatization in the matrix was carried out using acetic anhydride. Quantification of studied organic pollutants was done through gas chromatography mass spectrometry (GC-MS). Hormones included β-estradiol (E2), estrone (E1), and diethylstilbestrol (DES). Other compounds belonged to groups of pharmaceuticals (diclofenac (DIC)), antiseptics (triclosan (TRC)), preservatives (propylparaben (PP) and butylparaben (BP)), sunscreen agents (benzophenone (BPH), and 3-(4-methylbenzylidene)camphor (3MBC)), repellents (N,N-diethyltoluamide (DEET)), industrial chemicals (bisphenol A (BPA), 4-t-octylphenol (4OP), 4-n-nonylphenol (4NP)). A non-toxic and inexpensive 1-undecanol was successfully used as the extraction solvent. Volume of extractant and derivatization agent, ionic strength, and time of extraction were optimized. Very low limits of detection (LoD) ranging from 0.01 to 5.9 ng/L were obtained. Recoveries ranged from 90% to 123%, with relative standard deviation being lower than 17%. The developed procedure was used to determine target compounds in groundwater collected at municipal waste landfills as well as in groundwater from wells distant from sources of pollution.

Reverse ultrasound-assisted emulsification-microextraction of macrolides from chicken fat followed by electrophoretic determination

A new microextraction methodology, called reverse ultrasound-assisted emulsification-microextraction (R-USAEME) was developed to extract Tilmicosin (TILM) and Tylosin (TYL) from chicken fat samples, prior to their determination by capillary electrophoresis with UV-detection. The R-USAEME was based on the use of an aqueous ionic liquid ([Bmim]Cl) solution with sodium tartrate and sodium phosphate as extractant, applying an ultrasound probe (91 W; 7.5 min). A good linearity was obtained in a range from 35 to 200 μg kg−1 with relative standard deviations (RSDs) lower than 13% using matrix-matched calibration on five chicken fat samples. The quantification limits (LOQs), ranged from 17.4 to 55.0 μg kg−1 and from 22.1 to 47.0 μg kg−1 for TILM and TYL respectively. The obtained recoveries were between 73 and 117%. The analytical parameters clearly showed the applicability of the method for the extraction and quantification of macrolides in this complex biological sample.

Determination of toxic heavy metals in rice samples using ultrasound assisted emulsification microextraction combined with inductively coupled plasma optical emission spectroscopy

A straightforward and efficient method was developed by ultrasound assisted emulsification microextraction (USAEME) combined with inductively coupled plasma optical emission spectroscopy (ICP/OES) to trace some toxic heavy metal ions in eight select farmed and four select imported rice samples. In this study, carbon tetrachloride (CCl4) and 1-(2-pyridylazo)2-naphthol (PAN) were used as the extraction solvent and complexing reagent, respectively. The extraction parameters were optimized by means of a central composite design (CCD). Detection and quantification limits were set to be between 0.02 and 0.08 µg L−1 and 0.07–0.30 µg L−1, respectively. The accuracy of our method was further verified against two certified reference materials namely NCS ZC73029 and NIES No 10-b. While no trace of contaminations was found in some rice samples (Tarom, Hashemi, Sadri, Khazar and one imported sample), others such as Kazemi, Jamshidi, Dom Siah, Guilanehand and three of the imported samples were considerably polluted.

A metal-organic framework of type MIL-101(Cr) for emulsification-assisted micro-solid-phase extraction prior to UHPLC-MS/MS analysis of polar estrogens.

A seamless two-step extraction procedure integrating ultrasound-assisted emulsification microextraction (USAEME) and vortex-assisted micro-solid-phase extraction (μ-SPE) was developed. A highly porous metal-organic framework of type MIL-101(Cr) is used as the sorbent, and ultra-high-performance liquid chromatography in combination with tandem mass spectrometry is used for detection. The steroid hormones estrone 17β-estradiol, estriol, and 17α-ethynylestradiol were extracted from water samples by using this method. These steroids are polar and do not pass through the polypropylene membrane that is conventionally used in μ-SPE. In the method presented here, 1-octanol is used in USAEME to extract and pre-concentrate the steroids. This facilitates the transfer to the MIL-101(Cr) phase retained by the membrane in the subsequent μ-SPE step. MIL-101(Cr) was characterized by various methods, and the parameters affecting the overall extraction efficiency were optimized. Under the most favorable conditions, the limits of detection are between 0.95 and 23ngL-1. Good intra-day and inter-day precisions were obtained, with relative standard deviations of ≤ 9.9%. Enrichment factors are between 34 and 52. The method was applied to genuine environmental water samples in which estrone was detected. Relative recoveries ranged between 85.4% and 120.8%. Graphical abstract Schematic of the emulsification-assisted micro-solid-phase extraction (μ-SPE). By emulsifying 1-octanol in the water sample, polar estrogens dissolved in the solvent can easily pass the hydrophobic polypropylene membrane and then are adsorbed onto the unmodified MIL-101(Cr) held within the μ-SPE device.