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In the present work, the impact of dilution and filtration of biological samples (plasma and urine) using ultra‐centrifugal filters were analytically assessed as pretreatment steps before the electromembrane extraction. Pseudoephedrine, lidocaine, propranolol, and ketoconazole were chosen as the basic model drugs. They were analyzed by using high‐performance liquid chromatography coupled with an ultraviolet‐visible detector after the extraction process. In this way, the type of filter and sample dilution order were evaluated in addition to the method's figures of merit. Hence, purification of the biological samples via ultra‐centrifugal filters results in a successful electromembrane extraction procedure in the presence of high applied voltages (≥300 V). It brings notable augmentation in the extraction recoveries. As a result, a reduction in the amount of electrical current of the extraction system (17.0–30.0 µA for plasma and 23.0–33.0 µA for urine) and acceptable repeatability (4.6–12.9%) were observed. In the water, linearity was attained between 25.0 and 1000.0 ng/mL; besides, limits of quantification were in the range of 10.0–25.0 ng/mL, and limits of detection were between 3.0 and 7.5 ng/mL.

Amphetamine and its related derivatives have stimulant and hallucinogenic properties. Illegal use of these drugs is an increasing global problem resulting in significant public health and legal problems. Deaths have been reported after intake of these drugs due to overdose. It is important to determine the type and concentration of illicit drugs in biological samples. These compounds are found in complex matrices at low concentration levels. The microextraction techniques are dominant sample preparation procedure and they are widely accepted as the most labor-intensive part of the bioanalytical process. For this purpose, a survey of recent published advances in microextraction procedures for quantification of amphetamines in biological samples found in the different databases from 2008 to date will be conducted.

The current study presents for the first time a combination of the gel electromembrane extraction (GEL-EME) and switchable hydrophilicity solvent-based homogeneous liquid-liquid microextraction (SHS-HLLME) methods which can be used as an efficient hyphenated extraction procedure. This coupled method, which was followed by GC-FID, was applied for quantification of antidepressants (desipramine, clozapine, and citalopram) in biological and wastewater samples. The effective parameters of both GEL-EME and SHS-HLLME procedures were optimized. Using an agarose gel membrane, analytes were extracted from 7.0 mL of the sample solution to 500 µL of the aqueous acceptor solution. The maximum extraction of analytes of interest was obtained under the optimized conditions (pH of acceptor solution, 5.0; pH of gel membrane, 5.0; pH of sample solution, 7.0, voltage value, 30 V; and extraction time, 30 min). Then, the acceptor solution was transferred to the extraction cell and the SHS-HLLME procedure was conducted again under the optimized conditions. Dipropylamine (50 µL) was selected as an extraction solvent. The introduced technique exhibited good linearities with coefficients of determinatin (R2) higher than 0.983 and an acceptable linear range of 5.0–1000 ng/mL. Accordingly, the limit of detection was ≤ 1.0 ng/mL (S/N = 3) for all analytes, and the high enrichment factors were obtained in the range of 178.7–194.8. Moreover, the corresponding repeatability was from 4.0 to 8.7% (n = 3). The proposed method was successfully utilized to determine trace levels of the drugs in human serum, wastewater, and breast milk samples.

Introducing new membranes with green chemistry approach seems to be a great challenge for the development of a practical method in separation science. In this regard, for the first time, polyacrylamide gel as a new membrane in electromembrane extraction (EME) was used for the extraction of three model basic drugs (pseudoephedrine (PSE), lidocaine (LID), and propranolol (PRO)), followed by HPLC-UV. In comparison with conventional EME, in this method neither organic solvent nor carrier agents were used for extraction of mentioned drugs. Different variables for fabrication of polyacrylamide gel and extraction process were evaluated. Polyacrylamide gel (containing 12% (w/v) acrylamide, and 3.0% (w/w) bisacrylamide) with 2 mm thickness at pH = 1.5 was fabricated as membrane. The drugs were extracted from aqueous samples, through a polyacrylamide gel membrane, to an aqueous acceptor phase on membrane. Under the optimized extraction conditions (Voltage: 85 V, extraction time: 28 min, acceptor phase's pH: 4.0, and donor phase’s pH: 7.0) limits of quantification and detection were in the ranges of 1.0–20.0 ng mL−1 and 0.3–6.0 ng mL−1, respectively. Applying the proposed method to determine and quantify intended drugs in breast milk, and wastewater samples have revealed acceptable results.

In the current study, for the first time, the sugaring-out effect was assessed in a conventional electromembrane extraction (EME) system. Utilizing the sugars in the donor solution as green additives can result in production of a pioneering and influential EME mode. Sugaring-out assisted electromembrane extraction was combined with high-performance liquid chromatography (HPLC) to enhance the extraction of four basic model drugs (pseudoephedrine, lidocaine, propranolol, and ketoconazole). In this mode of EME, not only the transfer of analytes through the supported liquid membrane (SLM) was improved, but also the whole extraction system became more stable than the conventional one in the same voltage. The type and concentration of sugars were optimized in addition to the common experimental parameters influencing the EME, and figures of merit were also studied. Under the optimum conditions, repeatability (RSD%) was obtained in the range of 2.8–6.9% in the water, while RSD value was obtained in the range of 8.2–11.8% (n = 3) for conventional EME with the same state. The linearity range was also in the interval of 5.0–1000.0 n g m L - 1 and limits of quantification and detection were in the ranges of 5.0–10.0 n g m L - 1 and 1.5–3.0 n g m L - 1 , respectively, in the introduced EME. Extraction recoveries in the range of 41.2 and 80.8% were obtained resulting in enrichment factors in the range of 96–189. In light of such factor, new suggested EME mode was assessed in the real biological samples including human plasma and urine in order to prove the sugaring-out efficiency in EME systems.

Introducing a new approach to a methodology is an interesting task and represents a hot topic in the field of sample preparation. This work is the first study to introduce rotating electrode electro membrane extraction (REEME) as an efficient and inexpensive method. In this new approach to EME, the acceptor phase (AP) was agitated using a rotating electrode that was connected to a modulated speed rotator. The aim of this set up was to enhance the extraction efficiency by increasing analyte mass transfer from supported liquid membrane (SLM) to the AP and reducing the thickness of the double-layer in the inner side of the SLM. Box–Behnken design and response surface methodology were applied to find optimal experimental conditions for the extraction of a few model basic drugs including verapamil, haloperidol, and rivastigmine. Under the optimized conditions (organic solvent in the SLM: 2-ethyl hexanol, stirring rate of AP: 64 rpm, stirring rate of sample solution: 1400 rpm, potential difference: 170 V, extraction time: 16 min, acceptor phase's pH: 2.0, and donor phase's pH: 5.0), limits of detection and quantification were in the ranges of 2.0–3.0 ng mL−1 and 6.0–10.0 ng mL−1, respectively. To understand the influence of agitation of the AP on extraction efficiency, a comparative study was carried out between conventional EME and REEME methods. The results showed that, the extraction efficiency of REEME was higher than that of EME. Finally, the proposed method was successfully applied to determine concentrations of model drugs in wastewater and urine samples.

Simultaneous extraction of acidic and basic analytes from a sample is seen to be a challenging task. In this work, a novel and efficient electromembrane extraction (EME) method based on two separate cells was applied to simultaneously extract and preconcentrate two acidic drugs (naproxen and ibuprofen) along with a basic drug (ketamine). Once both cells were filled with the sample solution, basic drug was extracted from one cell with the other cell used to extract acidic drugs. The employed supported liquid membranes for the extraction of acidic and basic drugs were 2-ethyl hexanol and 1-octanol, respectively. Under an applied potential of 250 V in the course of the extraction process, acidic, and basic drugs were extracted from a 3.0 mL aqueous sample solution into 25 μL acceptor solutions. The pH values of the donor and acceptor solutions in the cathodic cell were 5.0 and 1.5, respectively, the corresponding values in the anodic cell were, however, 8.0 and 12.5, respectively. The rates of recovery obtained within 20 min of extraction time at a stirring rate of 750 rpm ranged from 45 to 54%. With correlation coefficients ranging from 0.990 to 0.996, the proposed EME technique provided good linearity over a concentration range of 20-1000 ng/mL. The LOD for all drugs was found to be 6.7 ng/mL, while reproducibility ranged from 7 to 12% (n = 5). Finally, applying the proposed method to determine and quantify the drugs in urine and wastewater samples, satisfactory results were achieved.

Extraction of polar acidic compounds is a challenging task in electromembrane extraction. In this study, gel-electromembrane extraction was employed for the extraction of phenolic acids as the polar acidic compounds from fruit juices. For this aim, the extraction of phenolic acids from the juice samples (4 mL, pH = 6.0) was carried out across the agarose gel membrane (concentration of agarose; 3% (w/v), pH of gel; 10.0, and thickness of membrane: 3 mm) into the acceptor solution (100 μL, pH = 12.0). Also, this extraction process was conducted by applying the optimum potential (25 V) for 15 min to the extraction system. Under the optimized condition, acceptable linearity (R2 ≥ 0.993) over a concentration range of 10.0–2500 ng mL−1 was achieved. The limits of detection were between 3.0 and 15.2 ng mL−1, while the corresponding repeatabilities ranged from 5.3 to 11.4% (n = 4). The recoveries achieved for the extraction of target compounds were ranged from 26.8 to 74.4%. The proposed method was used for the extraction of phenolic acids from orange, apple and kiwi juices, and the obtained relative recoveries in the range of 78.0–104.2% and RSDs in the range of 6.3 to 11.3% indicated successful extraction of phenolic acids.

In this study, electromembrane extraction from a flowing sample solution, termed continuous-flow electromembrane extraction, was developed and compared with conventional procedures for the determination of four basic drugs in real samples. Experimental parameters affecting the extraction efficiency were further studied and optimized. Under optimum conditions, linearity of continuous flow procedure was within 8.0–500 ng mL−1, while it was wider for conventional procedures (2.0–500 ng mL−1). Moreover, repeatability (%RSD) was found to range between 5.6 and 10.4% (n = 3) for the continuous-flow procedure, with a better repeatability than that of conventional procedures, 2.3–5.5% (n = 3). Also, for the continuous-flow procedure, the estimated detection limit (S/N = 3) was less than 2.4 ng mL−1 and extraction recoveries were within 8–10%, while the corresponding figures for conventional procedures were less than 0.6 ng mL−1 and 42–60%, respectively. Thus, the results showed that both continuous flow and conventional procedures were applicable for the extraction of model compounds. However, the conventional procedure was more convenient to use, and thus it was applied to determine sample drugs in real urine and wastewater samples. This article is protected by copyright. All rights reserved

Developing green methods for analyte extraction is one of the most important topics in the field of sample preparation. In this study, for the first time, agarose gel was used as membrane in electromembrane extraction (EME) without using any organic solvent, for the extraction of four model basic drugs (rivastigmine (RIV), verapamil (VER), amlodipine (AML), and morphine (MOR)) with a wide polarity window (log P from 0.43 to 3.7). Different variables playing vital roles in the proposed method were evaluated and optimized. As a driving force, a 25 V electrical field was applied to make the analyte migrate from sample solution with pH 7.0, through the agarose gel 3% (w/v) with 5 mm thickness, into an acceptor phase (AP) with pH 2.0. The best extraction efficiency was obtained with an extraction duration of 25 min. With this new methodology, MOR with high polarity (log P = 0.43) was efficiently extracted without using any carrier or ion pair reagents. Limits of detection (LODs) and quantification (LOQs) were in the ranges of 1.5–1.8 ng mL −1 and 5.0–6.0 ng mL −1 , respectively. Finally, the proposed method was successfully applied to determine concentrations of the model drugs in the wastewater sample.

In the present work, acidic and basic drugs were simultaneously extracted by a novel method of high efficiency herein referred to as two-step voltage dual electromembrane extraction (TSV-DEME). Optimizing effective parameters such as composition of organic liquid membrane, pH values of donor and acceptor solutions, voltage and duration of each step, the method had its figures of merit investigated in pure water, human plasma, wastewater, and breast milk samples. Simultaneous extraction of acidic and basic drugs was done by applying potentials of 150 V and 400 V for 6 min and 19 min as the first and second steps, respectively. The model compounds were extracted from 4 mL of sample solution (pH = 6) into 20 μL of each acceptor solution (32 mM NaOH for acidic drugs and 32 mM HCL for basic drugs). 1-Octanol was immobilized within the pores of a porous hollow fiber of polypropylene, as the supported liquid membrane (SLM) for acidic drugs, and 2-ethyle hexanol, as the SLM for basic drugs. The proposed TSV-DEME technique provided good linearity with the resulting correlation coefficients ranging from 0.993 to 0.998 over a concentration range of 1–1000 ng mL −1 . The limit of detections of the drugs were found to range within 0.3–1.5 ng mL −1 , while the corresponding repeatability ranged from 7.7 to 15.5% (n = 4). The proposed method was further compared to simple dual electromembrane extraction (DEME), indicating significantly higher recoveries for TSV-DEME procedure (38.1–68%), as compared to those of simple DEME procedure (17.7–46%). Finally, the optimized TSV-DEME was applied to extract and quantify model compounds in breast milk, wastewater, and plasma samples.

Simultaneous extraction of acidic and basic analytes from a sample is seen to be a challenging task. In this work, a novel and efficient electromembrane extraction (EME) method based on two separate cells was applied to simultaneously extract and preconcentrate two acidic drugs (naproxen and ibuprofen) along with a basic drug (ketamine). Once both cells were filled with the sample solution, basic drug was extracted from one cell with the other cell used to extract acidic drugs. The employed supported liquid membranes for the extraction of acidic and basic drugs were 2-ethyl hexanol and 1-octanol, respectively. Under an applied potential of 250 V in the course of the extraction process, acidic, and basic drugs were extracted from a 3.0 mL aqueous sample solution into 25 μL acceptor solutions. The pH values of the donor and acceptor solutions in the cathodic cell were 5.0 and 1.5, respectively, the corresponding values in the anodic cell were, however, 8.0 and 12.5, respectively. The rates of recovery obtained within 20 min of extraction time at a stirring rate of 750 rpm ranged from 45 to 54%. With correlation coefficients ranging from 0.990 to 0.996, the proposed EME technique provided good linearity over a concentration range of 20-1000 ng/mL. The LOD for all drugs was found to be 6.7 ng/mL, while reproducibility ranged from 7 to 12% (n = 5). Finally, applying the proposed method to determine and quantify the drugs in urine and wastewater samples, satisfactory results were achieved.