Composition Of Supported Liquid Membrane Research Articles

Optimized three‐phase hollow fiber liquid‐phase automated microextraction and its application in ultra‐trace analysis of three pyrethroids in water and fruit samples using high‐performance liquid chromatography‐diode array detection

AbstractIn the present manuscript, an automated three‐phase hollow fiber liquid‐phase microextraction followed by high‐performance liquid chromatography‐diode array detection is applied for the extraction and determination of three pyrethroids, deltamethrin, fenpropathrin, and permethrin in water and fruit samples. N‐dodecane was selected as a supported liquid membrane (SLM) and its polarity was adjusted by trioctylphosphine oxide one‐variable‐at‐a‐time method was used in order to achieve optimal hollow fiber liquid‐phase microextraction parameters such as type of organic acceptor phase, the composition of SLM, ionic strength of sample solution, extraction time, length of hollow fibers and stirring speed. Under the optimal conditions, the calibration curves for the three pyrethroids were plotted, and figures of merit of the proposed method were calculated. The linear dynamic ranges were in the range of 0.9–200, 0.75–200, and 1.5–200 μg/L for deltamethrin, fenpropathrin, and permethrin, with the coefficient of determination better than 0.998. The limits of detection were in the range of 0.3, 0.25, and 0.5 and the limits of quantification were in the range of 0.9, 0.75, and 1.5 μg/L for deltamethrin, fenpropathrin, and permethrin, respectively. The precision of the method was evaluated in terms of relative standard deviation at two different concentration levels 10 and 50 μg/L. The results of real sample analysis in cucumber exhibited high sensitivity, excellent sample clean‐up, favorable repeatability, and suitable accuracy.

Effect of Aliquat®336 on supported liquid membrane on electromembrane extraction of non-steroidal anti-inflammatory drugs

Up to now, most electromembrane extraction methods describe the use of pure organic solvents or mixtures as supported liquid membrane. However, the need to incorporate carriers in the supported liquid membrane to achieve the extraction of high polar compounds, seems to indicate that the presence of certain additives in the organic solvent may improve the extraction yield. For this reason, some studies have tried to enhance electrokinetic migration in different ways, modifying either the supported liquid membrane or even the donor solution. In this work, it has been studied and optimized an electromembrane extraction of five widely used non-steroidal anti-inflammatory drugs: salicylic acid, ketoprofen, naproxen, diclofenac and ibuprofen. The thickness and porosity of the support, the supported liquid membrane composition, the donor and acceptor phase pH, the voltage, the extraction time and the electrode configuration were optimized. supported liquid membrane was modified by adding different amounts of Aliquat®336, a cationic carrier commonly used in electromembrane extraction procedure for anionic compounds. The results compared with those obtained in the same extraction conditions using the pure organic solvent as supported liquid membrane, showed better extraction recoveries. The highest recoveries were achieved using a pH 5 donor phase and an acceptor phase at pH 12. The recoveries were within the range of 39 and 53% after 12 min extraction, using a voltage of 80 V, a stirring speed of 400 rpm and 1-nonanol modified with Aliquat®336 2.5% (w/v) as support liquid membrane. Detection and quantitation limits were within 0.02–1.0 ng mL−1 and 0.05–3.0 ng mL−1, respectively.The selected analytes were extracted by electromembrane extraction using a home-made device designed with a flat configuration. The analyses were carried out by high performance liquid chromatography with diode array and fluorescence detection and finally, applied to the analysis of human urine samples.

Supported liquid membrane based loading technique for thermal ionization mass spectrometry: an application to plutonium isotopic composition and concentration determination

Supported liquid membrane (SLM) was prepared by immobilizing the extractant tricaprylmethyl ammonium chloride (Aliquat-336) into the microporous poly(propylene) membrane. The formed SLM with optimize composition was found be selective toward Pu4+ ions over UO22+ and Am3+ ions in a wide range of high acid concentrations (3–7 mol L−1 HNO3). The composition of SLM was optimized by using varying proportions of Aliquat-336 with solvents/diluents such as dioctyl phthalate (DOP), 2-nitrophenyl octyl ether and tris(2-ethylhexyl) phosphate. Among these diluents, DOP was found to be stable and causing uniform distribution of the extractant on the membrane. The surface morphology was characterized by atomic force microscopy. Stability and change in physical structure of SLM was characterized by capillary flow porometry. The Pu pre-concentrated in SLM was used to find out isotopic composition and concentration of the plutonium with help of thermal ionization mass spectrometry. The SLM was found to be stable and amenable to routine analyses.

Extraction and determination of trace amounts of three anticancer pharmaceuticals in urine by three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents followed by high-performance liquid chromatography.

An automated three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents followed by high-performance liquid chromatography with UV-Vis detection method was applied for the extraction and determination of exemestane, letrozole, and paclitaxel in water and urine samples. n-Dodecane was selected as the supported liquid membrane and its polarity was justified by trioctylphosphine oxide. Acetonitrile was used as an organic acceptor phase with desirable immiscibility having n-dodecane. All the effective parameters of the microextraction procedure such as type of the organic acceptor phase, the supported liquid membrane composition, extraction time, pH of the donor phase, hollow fiber length, stirring rate, and ionic strength were evaluated and optimized separately by a one variable at-a-time method. Under the optimal conditions, the linear dynamic ranges were 1.8-200 (R2 =0.9991), 0.9-200 (R2 =0.9987) and 1.2-200μg/L (R2 =0.9983), and the limits of detection were 0.6, 0.3, and 0.4μg/L for exemestane, letrozole, and paclitaxel, respectively. To evaluate the capability of the proposed method in the analysis of biological samples, three different urinary samples were analyzed under the optimal conditions. The relative recoveries of the three pharmaceuticals were in the range of 91-107.3% for these three analytes.

Rapid ionic liquid-supported nano-hybrid composite reinforced hollow-fiber electromembrane extraction followed by field-amplified sample injection-capillary electrophoresis: An effective approach for extraction and quantification of Imatinib mesylate in human plasma

The focus of this study is development of a new, convenient, rapid and sensitive electromembrane extraction approach (based on an ionic liquid-supported MWCNTs/ZnO reinforced hollow fiber, for the first time) as an off-line sample clean-up/preconcentration method coupled with capillary electrophoresis (CE-UV) using field-amplified sample injection (FASI) for quantification of Imatinib mesylate in human plasma. The nano-hybrid sorbent, coated by 1-octyl-3-methylimidazolium bromide ionic liquid ([OMIm]Br) in this research, was prepared by a feasible basic catalyzed sol-gel method. Then, it was immobilized (supported by capillary forces and sonication) in pores of a segment of a polypropylene hollow fiber membrane as the extraction unit after dispersing in 2-nitrophenyl octyl ether (NPOE) solvent and subsequently served as the supported liquid membrane (SLM) composition. Significant variables affecting the proposed method were evaluated and optimized to achieve the maximum extraction performance. Optimal conditions were obtained by NPOE with 4mgmL−1 nano-sorbent as the SLM composition, 105V as the driving force, pH 2 and 1.8 of the donor and acceptor phases, respectively, an extraction time of 15min and an agitation rate of 800rpm. The developed method was validated according to FDA guidelines. Regarding the validation results, the method is proved to be linear (R2=0.998) over concentrations ranging from 25 to 1500ngmL−1 (LOD=6.24ngmL−1). The mean RSD values for intra- and inter-day precision studies were 6.83 and 7.71%, respectively and the mean recoveries ranged between 98 and 106%. Finally, the validated method was successfully applied for sensitive, selective and rapid determination of Imatinib in patient’s plasma samples.

Direct coupling of electromembrane extraction to mass spectrometry - Advancing the probe functionality toward measurements of zwitterionic drug metabolites

A triple-flow electromembrane extraction (EME) probe was developed and coupled directly to electrospray-ionization mass spectrometry (ESI-MS). Metabolic reaction mixtures (pH 7.4) containing drug substances and related metabolites were continuously drawn (20 μL/min) into the EME probe in one flow channel, and mixed inside the probe with 7.5 μL min−1 of 1 M formic acid as make-up flow from a second flow channel. Following this acidification, the drug substances and their related metabolites were continuously extracted by EME at 400 V, across a supported liquid membrane (SLM) comprising 2-nitrophenyl octyl ether (and for some experiments containing 30% triphenyl phosphate (TPP)), and into 20 μL min−1 of formic acid as acceptor phase, which was introduced through a third flow channel. The acceptor phase was pumped directly to the MS system, and the ion intensity of extracted analytes was followed continuously as function of time. The triple-flow EME probe was used for co-extraction of positively charged parent drugs and their zwitterionic drug metabolites (hydroxyzine and its carboxylic acid metabolite cetirizine; and vortioxetine and its carboxylic acid metabolite Lu AA34443). While the zwitterionic metabolites could not be extracted at pH 7.4, it was shown that by acidifying the sample solution the zwitterionic metabolites could be extracted effectively. Various extraction parameters like make-up flow, extraction voltage and SLM composition were optimized for simultaneous extraction of parent drugs and metabolites. It was found that TPP added to the SLM improved extraction efficiencies of certain drug metabolites. Finally the optimized and characterized triple-flow EME probe was used for online studying the in-vitro metabolism of hydroxyzine and vortioxetine by rat liver microsomes. Due to the automated pre-extraction acidification of the rat liver microsomal solutions, it was possible to continuously monitor formation of the zwitterionic drug metabolites. As the triple-flow EME probe allowed modification of the pH of the sample without changing the pH in the bulk sample, the system can potentially be used for direct analysis of various kinds of chemical reactions that have to be run at pH conditions unfavorable for direct analyte extractions.

A glass capillary based microfluidic electromembrane extraction of basic degradation products of nitrogen mustard and VX from water

In this work, a glass capillary based microfluidic electromembrane extraction (μ-EME) was demonstrated for the first time. The device was made by connecting an auxillary borosilicate glass tubing (O.D. 3mm, I.D. 2mm) perpendicular to main borosilicate glass capillary just below one end of the capillary (O.D. 8mm, I.D. 1.2mm). It generated the distorted T-shaped device with inlet ‘1’ and inlet ‘2’ for the introduction of sample and acceptor solutions, respectively. At one end of this device (inlet ‘2’), a microsyringe containing acceptor solution along with hollow fiber (O.D. 1000μm) was introduced. This configuration creates the micro-channel between inner wall of glass capillary and outer surface of hollow fiber. Sample solution was pumped into the system through another end of glass capillary (inlet ‘1’), with a micro-syringe pump. The sample was in direct contact with the supported liquid membrane (SLM), consisted of 20% (w/w) di-(2-ethylhexyl)phosphate in 2-nitrophenyl octyl ether immobilized in the pores of the hollow fiber. In the lumen of the hollow fiber, the acceptor phase was present. The driving force for extraction was direct current (DC) electrical potential sustained over the SLM. Highly polar (logP=−2.5 to 1.4) basic degradation products of nitrogen mustard and VX were selected as model analytes. The influence of chemical composition of SLM, extraction time, voltage and pH of donor and acceptor phase were investigated. The model analytes were extracted from 10μL of pure water with recoveries ranging from 15.7 to 99.7% just after 3min of operation time. Under optimized conditions, good limits of detection (2–50ngmL−1), linearity (from 5–1000 to 100–1000ngmL−1), and repeatability (RSDs below 11.9%, n=3) were achieved. Applicability of the proposed μ-EME was proved by recovering triethanolamine (31.3%) from 10μL of five times diluted original water sample provided by the Organization for the Prohibition of Chemical Weapons during 28th official proficiency test.

Selective electromembrane extraction based on isoelectric point: Fundamental studies with angiotensin II antipeptide as model analyte

For the first time, selective isolation of a target peptide based on the isoelectric point (pI) was achieved using a two-step electromembrane extraction (EME) approach with a thin flat membrane-based EME device. In this approach, step #1 was an extraction process, where both the target peptide angiotensin II antipeptide (AT2 AP, pI=5.13) and the matrix peptides (pI>5.13) angiotensin II (AT2), neurotensin (NT), angiotensin I (AT1) and leu-enkephalin (L-Enke) were all extracted as net positive species from the sample (pH 3.50), through a supported liquid membrane (SLM) of 1-nonanol diluted with 2-decanone (1:1v/v) containing 15% (v/v) di-(2-ethylhexyl)-phosphate (DEHP), and into an aqueous acceptor solution (pH 1.80). In step #1, the cathode was located in the acceptor solution. Following step #1 (and prior to step #2), the pH of the acceptor solution was adjusted to pH 5.25, and the anode was located in the acceptor solution. Step #2 was a clean-up process to remove the matrix peptides with pI>5.13 (net positively charged) from the acceptor solution pH 5.25. During step #2, the target peptide was not net positively charged. This suppressed complex formation with negatively charged DEHP, and the target remained in the acceptor solution. The acceptor solution pH, the SLM composition, the extraction voltage, and the extraction time during the clean-up process (step #2) were important factors influencing the separation performance. An acceptor solution pH of 5.25 for the clean-up process slightly above the pI value (pH 5.13) was found to be optimal. Under the optimal conditions, 73% of AT2 AP (RSD 13%) and 48% of L-Enke (RSD 5%) were found in the solution after this two-step EME process, whereas the other three positively charged peptides were not detected. The observations above indicated that two-step EME may have a future potential for the fractionation of peptides and other ampholytic compounds based on their isoelectric points.

Automated hollow fiber microextraction based on two immiscible organic solvents for the extraction of two hormonal drugs

In this research, a rapid efficient and automated instrument based on hollow fiber liquid-phase microextraction (HF-LPME) followed by high performance liquid chromatography (HPLC) with UV–vis detection was applied for the preconcentration and determination of two hormonal drugs (megestrol acetate and levonorgestrel) in water and urinary samples. n-Dodecane was used as the supported liquid membrane (SLM) and methanol was used as the acceptor phase in the hollow fiber lumen. The effects of different parameters such as fiber length, extraction time, stirring rate, and ionic strength on the extraction efficiency were investigated using modified simplex and central composite design as the screening and optimization methods, respectively. The composition effect of SLM and type of acceptor phase were optimized separately. For adjustment of the SLM composition, trioctylphosphine oxide (TOPO) was chosen. Under optimized condition, the calibration curves were linear (r2>0.997) in the range of 0.5–200μgL−1. LOD for both of the drugs were 0.25μgL−1. The applicability of this technique was examined by analyzing drugs in water and urine samples. The relative recoveries of the drugs were in the range of 86.2–102.3% that show the capability of the method for the determination of the drugs in various matrices.

Voltage-step pulsed electromembrane as a novel view of electrical field-induced liquid-phase microextraction

In the present work, the effect of application of voltage steps on extraction efficiency of pulsed electromembrane extraction (PEME) was investigated for the first time. The effects of voltage variations including initial and final voltages, number of steps between the initial and final voltages as well as their time durations were studied on the extraction efficiencies of three different classes of analytes. These classes include amitriptyline (AMI) and nortriptyline (NOR) as more hydrophobic analytes, diclofenac (DIC) and mefenamic acid (MEF) as acidic drugs and salbutamol (SB) and terbutaline (TB) as hydrophilic compounds. It was anticipated that the application of high voltages is not necessary at the beginning of the extraction, since large amounts of target analytes exist around the supported liquid membrane (SLM)/sample solution interface. So, they could be easily transferred into the acceptor phase utilizing lower voltages. Results showed that the benefits of voltage-step PEME (VS-PEME) are more obvious in systems with low electrical resistance (regarding the SLM composition). Efficiencies of VS-PEME for extraction of AMI and NOR (96% and 89% for AMI and NOR, respectively) were comparable with those achieved from applying a constant voltage (95% for AMI and 83% for NOR). However, recoveries from the VS-PEME of DIC and MEF (53% and 44% for DIC and MEF, respectively) were significantly higher than those from the application of a constant voltage (33% for DIC and 31% for MEF). Also, recoveries obtained from the VS-PEME for SB and TB were approximately 3 orders of magnitude greater than those from a constant voltage. Moreover, it was demonstrated that in all cases analytes could effectively be extracted at the beginning of extraction by applying low voltages.

A selective electromembrane extraction of uranium (VI) prior to its fluorometric determination in water

A novel method for the selective electromembrane extraction (EME) of U6+ prior to fluorometric determination has been proposed. The effect of extraction conditions including supported liquid membrane (SLM) composition, extraction time and extraction voltage were investigated. An SLM composition of 1% di-2-ethyl hexyl phosphonic acid in nitrophenyl octyl ether (NPOE) showed good selectivity, recovery and enrichment factor. The best performance was achieved at an extraction potential of 80 volts and an extraction time of 14minutes Under the optimized conditions, a linear range from 1 to 1000ngmL−1 and LOD of 0.1ngmL−1 were obtained for the determination of U6+. The EME method showed good performance in sample cleanup and the reduction of the interfering effects of Mn2+, Zn2+, Cd2+, Ni2+, Fe3+, Co2+, Cu2+, Cl− and PO43− ions during fluorometric determination of uranium in real water samples. The recoveries above 54% and enrichment factors above 64.7 were obtained by the proposed method for real sample analysis.

Electromembrane extraction combined with gas chromatography for quantification of tricyclic antidepressants in human body fluids

Recent advances in electromembrane extraction (EME) methodology calls for effective and accessible detection methods. Using imipramine and clomipramine as model therapeutics, this proof-of-principle work combines EME with gas chromatography analysis employing a flame ionization detector (FID). The drugs were extracted from acidic aqueous sample solutions, through a supported liquid membrane (SLM) consisting of 2-nitrophenyl octyl ether (NPOE) impregnated on the walls of the hollow fiber. EME parameters, such as SLM composition, type of ion carrier, pH and the composition of donor and acceptor solutions, agitation speed, extraction voltage, and extraction time were studied in detail. Under optimized conditions, the therapeutics were effectively extracted from different matrices with recoveries ranging from 90 to 95%. The samples were preconcentrated 270–280 times prior to GC analysis. Reliable linearity was also achieved for calibration curves with a regression coefficient of at least 0.995. Detection limits and intra-day precision (n=3) were less than 0.7ngmL−1 and 8.5%, respectively. Finally, method was applied to determination and quantification of drugs in human plasma and urine samples and satisfactory results were achieved.

Electromembrane extraction of amino acids from body fluids followed by capillary electrophoresis with capacitively coupled contactless conductivity detection

Electromembrane extraction (EME) proved to be a simple and rapid pretreatment method for analysis of amino acids and related compounds in body fluid samples. Body fluids were acidified to the final concentration of 2.5 M acetic acid and served as donor solutions. Amino acids, present as cations in the donor solutions, migrated through a supported liquid membrane (SLM) composed of 1-ethyl-2-nitrobenzene/bis-(2-ethylhexyl)phosphonic acid (85:15 (v/v)) into the lumen of a porous polypropylene hollow fiber (HF) on application of electric field. The HF was filled with 2.5 M acetic acid serving as the acceptor solution. Matrix components in body fluids were efficiently retained on the SLM and did not interfere with subsequent analysis. Capillary electrophoresis with capacitively coupled contactless conductivity detection was used for determination of 17 underivatized amino acids in background electrolyte solution consisting of 2.5 M acetic acid. Parameters of EME, such as composition of SLM, pH and composition of donor and acceptor solution, agitation speed, extraction voltage, and extraction time were studied in detail. At optimized conditions, repeatability of migration times and peak areas of 17 amino acids was better than 0.3% and 13%, respectively, calibration curves were linear in a range of two orders of magnitude ( r 2 = 0.9968–0.9993) and limits of detection ranged from 0.15 to 10 μM. Endogenous concentrations of 12 amino acids were determined in EME treated human serum, plasma, and whole blood. The method was also suitable for simple and rapid pretreatment and determination of elevated concentrations of selected amino acids, which are markers of severe inborn metabolic disorders.