Supported Liquid Membrane Research Articles

Kinetic control aspects and mechanisms in oriented membrane processes for extraction and recovery of ascorbic acid compound.

Ascorbic acid comprises four enantiomers, with only one of them, L-ascorbic acid, recognized as vitamin C. The modern industries place significant importance on obtaining this compound in its purest form. The challenge is to recover L-ascorbic acid, which requires specific processes within these industries. To satisfy this condition, purification is needed, a process that requires large quantities of solvents and high energy consumption. To overcome these limitations, we conducted a study on the facilitated extraction of L-ascorbic acid using three affinity polymer membranes, including supported liquid membrane (SLM), polymer inclusion membrane (PIM), and grafted polymer membranes (GPM) with cholic acid as the extractive agent. Following the characterization of the membranes using IR spectroscopy and SEM techniques, we investigated various parameters associated with substrate diffusion through the organic membrane phase. Regarding the biologically active L-ascorbic acid, our research findings indicated that kinetic factors drove the mechanisms of the studied processes.

COSMO-RS screening of organic mixtures for membrane extraction of aromatic amines: TOPO-based mixtures as promising solvents

Aromatic amines are crucial in pharmaceuticals, but their synthesis is challenging due to unfavorable reaction equilibria and the use of costly, environmentally unfriendly methods. This study presents a membrane extraction (ME) process for in situ product removal (ISPR) of aromatic amines. Using a supported liquid membrane (SLM), -methylbenzylamine (MBA) and 1-methyl-3-phenylpropylamine (MPPA) were separated from isopropyl amine (IPA). COSMO-RS was employed to screen over 200 organic mixtures, identifying twelve mixtures based on trioctylphosphine oxide (TOPO), lidocaine, and menthol as solvent candidates, due to their hydrophobicity. These mixtures were analysed for critical solvent properties including density, viscosity, hydrophobicity, and hydrogen bonding interactions. ME tests showed TOPO-thymol had the highest solvent residual and selectivity. Moreover, TOPO-thymol demonstrated solute fluxes of 9.0±3.0 g/(m2 h) for MBA, 16.5±5.4 g/(m2 h) for MPPA, and 0.7±0.3 g/(m2 h) for IPA, with selectivity values of 12.4±0.8 for MBA/IPA and 22.8±1.4 for MPPA/IPA. Compared to undecane, which had lower selectivity values of 6.9±0.8 for MBA/IPA and 10.1±1.3 for MPPA/IPA, TOPO-thymol showed superior selectivity, indicating its promise as an extractant for ME applications.

Exploring Unusual Confined Chemistry: Excited-State Proton Transfer Reaction in Supported Liquid Membrane with Deep Eutectic Solvents.

Supported liquid membrane (SLM) incorporating ionic liquids (ILs) or deep eutectic solvents (DESs) offers a promising method for ion and (bio)chemical separations and CO2 capture. However, a molecular understanding of whether chemical reactions occur in these confined media is crucial. We report excited-state proton transfer (ESPT) reaction of a photoacid, HPTS, in various DES-based SLMs (pore size ∼280 nm) using steady-state and time-resolved fluorescence spectroscopy. Our findings reveal that, while the ESPT is unfavorable in bulk DESs, it occurs substantially in SLM-containing DESs. Time-resolved area normalized emission spectra (TRANES) show that ESPT time ranges from 2.6 to 7.5 ns and is greatly affected by changes in DES constituents. The results suggest that HPTS interacts with ordered DES structures formed by long-range interfacial effects in membrane pores, making it suitable for ESPT. Furthermore, it is found that the dynamics of solvent relaxation in confined DESs are significantly slower than in bulk liquids. This observation, together with a large red-edge excitation shift, supports the impact of long-range interfacial effects on the DES structure inside membrane pores. Given the task-specific properties of DESs, the incorporation of these solvents into SLM pores can be a useful strategy for investigating new chemical processes.

Real-time non-destructive monitoring of supported liquid membranes using electrochemical impedance spectroscopy

The degradation of supported liquid membranes (SLMs) due to membrane liquid leaching has been a hurdle for their implementation in resource recovery from waste streams. We present a novel approach utilizing four-electrode mode electrochemical impedance spectroscopy (EIS) for real-time, non-destructive monitoring of SLM degradation, providing detailed analysis of SLM's structural changes. We first showed that SLMs may be depicted as an electrical circuit of resistors and capacitors by EIS. The EIS then revealed that SLM degradation progressed over four different phases as a result of varying rates of thickness and area reduction of the SLM. To demonstrate the effectiveness of EIS-based diagnosis, we prepared SLMs designed for selective medium-chain fatty acid (MCFA) extraction in intact, partially, and completely degraded states, determined by the EIS. The intact SLM showed a high selectivity (∼50) for MCFAs over short-chain fatty acids. The selectivity decreased to ∼22 in the partially degraded SLMs, and less than 1 in the completely degraded SLM, indicating the clear linkage between the degree of degradation and the separation performance. Our four-electrode mode EIS method is expected to serve as a key tool for efficient SLM operation and stable SLM development.

A green and sensitive electromembrane extraction (EME) method for the determination of dialkylphosphates in maternal urine and amniotic fluid

Organophosphates compounds are extensively used pesticides, whose metabolites, dialkyl phosphates, are considered as bioindicators of human exposure. Recently, research has indicated that they can affect thyroid endocrine function. Pregnant women are a particularly vulnerable cohort to these effects due to concerns about prenatal exposure to environmental pollutants. For the first time an electromembrane microextraction method is proposed for the simultaneous determination of seven dialkylphosphate metabolites in maternal urine and amniotic fluid, which is compatible with mass spectrometry detection and achieves highly sensitive levels of quantitation. Dialkylphosphates were extracted from a 10 mL donor solution at pH 7 into a 50 µL acceptor solution at pH 12 using 1-octanol as the supported liquid membrane and applying 60 V for 10 min at 600 rpm. The obtained extracts were analysed by ion pair liquid chromatography coupled to a triple quadrupole mass spectrometer, using an Acquity UPLC® BEH C18 column (100 mm × 2.1 mm i.d., 1.7 µm particle size) at 30 °C. Under optimal extraction conditions, the preconcentration factors were achieved were up to 178-fold, allowing for high sensitivity levels, in the order of ng mL−1. The limits of quantitation were within 0.075 ng mL−1 (diethyl thiophosphate) and 1.67 ng mL−1 (dimethyl phosphate) in maternal urine samples and within 0.015 ng mL−1 (diethyl thiophosphate) and 0.5 ng mL−1 (dimethyl dithiophosphate) in amniotic fluid samples. The comparative study revealed a significant improvement in terms of analysis time, sensitivity, greenness, and practicality. Finally, the applicability of the method for the determination of selected dialkylphosphates was demonstrated in paired maternal urine and amniotic fluid samples. These results suggest potential placental transfer to the offspring.

Polymer-Based Extracting Materials in the Green Recycling of Rare Earth Elements: A Review.

Rare earth elements (REEs) are becoming increasingly important in the development of modern and green energy technologies with the demand for REEs predicted to grow in the foreseeable future. The importance of REEs lies in their unique physiochemical properties, which cannot be reproduced using other elements. REEs are sourced through mining, with global exploration of additional commercially viable mining sites still ongoing. However, there is a growing need for recycling of REEs due to the current supply of REEs not matching the growing demand, the environmental impact of REE mining and processing (the so-called "balance problem"), and the generation of large volumes of harmful electronic waste (e-waste). Industrial REE processing is mainly carried out by hydrometallurgy processes, particularly solvent extraction (SX) and ion exchange (IX) technologies. However, these methods have a significant environmental impact due to their intensive use of harmful and nonsustainable reagents. This Review highlights the development of approaches involving polymer-based extracting materials for REE manufacturing as more sustainable alternatives to current industrial REE processing methods. These materials include supported liquid membranes (SLMs), solvent impregnated resins (SIRs), macro and micro capsules, polymer inclusion membranes (PIMs), and micro polymer inclusion beads (μPIBs). Polymer-based extracting materials have the advantage of more economical regent usage while applying the same extractants used in commercial SX, enabling applications analogous to the current industrial process. These materials can be fabricated by a variety of methods in a diverse range of physical formats, with the advantages and disadvantages of each material type described and discussed in this Review along with their applications to REE processing, including e-waste recycling and mineral processing.

A Review on the Application of Deep Eutectic Solvents in Polymer-Based Membrane Preparation for Environmental Separation Technologies.

The use of deep eutectic solvents (DESs) for the preparation of polymer membranes for environmental separation technologies is comprehensively reviewed. DESs have been divided into five categories based on the hydrogen bond donor (HBD) and acceptor (HBA) that are involved in the production of the DESs, and a wide range of DESs' physicochemical characteristics, such as density, surface tension, viscosity, and melting temperature, are initially gathered. Furthermore, the most popular techniques for creating membranes have been demonstrated and discussed, with a focus on the non-solvent induced phase separation (NIPS) method. Additionally, a number of studies have been reported in which DESs were employed as pore formers, solvents, additives, or co-solvents, among other applications. The addition of DESs to the manufacturing process increased the presence of finger-like structures and macrovoids in the cross-section and, on numerous occasions, had a substantial impact on the overall porosity and pore size. Performance data were also gathered for membranes made for various separation technologies, such as ultrafiltration (UF) and nanofiltration (NF). Lastly, DESs provide various options for the functionalization of membranes, such as the creation of various liquid membrane types, with special focus on supported liquid membranes (SLMs) for decarbonization technologies, discussed in terms of permeability and selectivity of several gases, including CO2, N2, and CH4.

Electrochemical Extraction with Supported Liquid Membrane for Removing Copper from Synthetic Wastewater: Optimisation through Response Surface Methodology

In this study, copper was removed from an aqueous solution through electromembrane extraction (EME), a new approach that utilises a two-chamber electrochemical cell. It consists of two electrodes (stainless steel cathode and graphite anode) and a solid liquid membrane (SLM). SLM is composed of supporting polypropylene membrane impregnated with1-octanol as an organic solvent and bis(2-ethylhexyl) phosphate (DEHP) as a carrier. The effects of process parameters such as applied voltage, pH and copper concentration on the removal of copper were investigated. Response surface methodology (RSM) was applied to optimise these parameters and their interactions. Results indicated that pH has the major effect on the removal of copper, followed by applied voltage. The squared interaction term in the RSM model has the highest contribution (70.5%), followed by the linear term, thereby confirming the significant interaction among the variables. The optimum conditions include an applied voltage of 60V, pH of 5.18 and initial copper concentration of 5 ppm, which yield to a removal efficiency of 80% after 6 hours of operation. The findings demonstrate the use of electromembrane extraction as an efficient method for the removal of heavy metals and provide valuable insights for future application to other environmental and water treatment processes.

Membrane transport of rare earth metal ions N, N’-bisdioctylphosphorylmethyl-1,4-diaminobutane by the active transport mechanism

The method of membrane extraction for rare earth elements (REE) using the carrier N, N’-bisdioctylphosphorylmethyl-1,4-diaminobutane (DPDA-8) ions, leveraging an active transport mechanism, has been optimized. The distribution of DPDA-8 within the membrane pores was confirmed using scanning electron microscopy (SEM). Both light and heavy REE extractions from a simulated solution using DPDA-8 and trioctylphosphine oxide (TOPO) in 1,2-dichlorobenzene were explored. The influence of feed solution pH, carrier and anion concentration, supported liquid membrane (SLM) type and stability, and cell temperature, among other parameters, were meticulously examined. The results indicate a decrease in permeability with a decrease in feed solution pH attributed to competitive acid transport through the membrane. Additionally, the formation of H-complexes between carriers and perchloric or phosphoric acids was investigated using Fourier Transform Infrared (FTIR) spectroscopy and X-ray diffraction (XRD) techniques. Changes in the stretching bands of amino and phosphine oxide groups in DPDA-8 were monitored and characterized. XRD analysis of the crystal structures of salts DPDA-6·ClO4 and DPDA-12·H2PO4 revealed a two-dimensional layered supramolecular organization with varying anion positions relative to hydrophobic fragments. The DPDA-8 carrier demonstrated significantly higher permeability values compared to TOPO, with differences in permeability exceeding twofold for certain metals. FTIR spectroscopy identified the main coordination centers of DPDA-8 during the liquid–liquid extraction of specific REEs.

Supported liquid membrane with selective stripping for separative recovery of copper and zinc from plating wastewater

For separation and recovery of different but chemically similar metal from dilute wastewater with reduced process complexity and cost, a supported liquid membrane (SLM) system that utilizes a single carrier together with strip dispersion for selective stripping of coextracted metal ions was proposed to enable concurrent separation and recovery. This study aims to investigate the effectiveness of the proposed SLM system for separative recovery of copper and zinc from real plating wastewater. Solvent extraction experiments were conducted to understand the effect of feed pH and carrier concentration on organic phase migration to the aqueous phase. The effect of stirring speed on the SLM transport rate was studied using synthetic feed. Combined with the insights from our previous study, appropriate settings were identified and applied to the SLM system. The SLM system could recover 83.7% copper with 91.0% purity and 85.5% Zn with 99.3% purity from the plating wastewater in 30 h. The findings indicate the feasibility of using SLM with selective stripping for the concurrent separation and recovery of copper and zinc from a dilute aqueous waste stream predominantly containing these two metals.

Investigation of biodistribution by liquid-phase microextraction: Using a fatal diphenidol poisoning case

Liquid-phase microextraction (LPME) possesses a high potential to isolate organic substances from different sample matrices. In this work, LPME was applied for the first time to investigate the biodistribution of diphenidol in different biofluids, organs, and brain regions using a fatal poisoning case. Since the LPME of diphenidol hasn't been reported, the effect of supported liquid membrane (SLM), acceptor and donor phases, and extraction time on LPME performance was investigated first. The solvents of 2-nonanone and 2-nitrophenyl octyl ether (NPOE) were found to be stable and efficient SLMs for LPME of diphenidol from biofluids and tissue samples, respectively. At steady state, the LPME recoveries for different sample matrices were in the range of 87 %-91 %. Due to the clean-up capability of LPME and the relatively high concentration of diphenidol in the fatal poisoning case, the proposed LPME systems were validated with related sample matrices using HPLC-UV for the determination. The methods displayed good linearity (R² ≥ 0.9943), and the limits of detection were 0.30 mg L−1, 0.28 mg L−1, and 2.7 μg g−1 for blood, urine, and liver samples, respectively. Meanwhile, the precision (≤13%), accuracy (90–110%), and matrices effect (±15%) were satisfactory at low, medium, and high concentrations. In addition, the stability, carryover, and dilution integrity met the requirements of ASB Standard 036. Finally, the proposed method was successfully applied to evaluate the biodistribution of diphenidol in five different biofluids, five organs, and six brain regions from a fatal poisoning case. Generally, the distribution of diphenidol in biofluids was lower than that in the organs and brain regions, and the highest concentration of diphenidol was observed in the liver, which is very important for the selection of inspection samples in forensic toxicological analysis. Therefore, LPME was proved to be a powerful tool for the investigation of biodistribution and postmortem redistribution in the fields of forensics.

Mesoporous silica modified alumina improves pressure stability of supported ionic liquid membranes

Supported liquid membranes (including those containing ionic liquids) offer the opportunity for high selectivity for a target gas imparted by the properties of the functional liquid or liquid mixture, along with high flux resulting from gas permeation through a liquid rather than a solid. One disadvantage of supported liquid membranes is limitations on the transmembrane pressure (TMP) they can sustain. Liquids held in the pores of the support by capillary forces are prone to “blow-out” at relatively modest TMP values. Here, we modify anodic aluminum oxide (AAO) membranes with uniformly sized ∼6–8 nm diameter cylindrical silica mesopores to improve the blow-out TMP. This modification increases the feasible TMP for various ionic liquids from ∼4 bar to more than ∼20 bar. Additionally, the liquid in the membrane at depths where the AAO membrane has not been modified (i.e., greater than a few microns) is expelled from the large pores, reducing the effective thickness of the liquid in the membrane and increasing permeance. This approach is analogous to asymmetric polymeric membranes, which are the standard of the commercial membrane industry. These findings open up the opportunity for investigation and use of supported liquid membranes at much higher TMPs than has been previously possible.

An efficient microchip electromembrane extraction online with high-performance liquid chromatography for the measurement of nicotine in high consumption vegetables.

Nicotine, a highly addictive substance, is naturally produced in the Solanaceae family of plants, particularly tobacco. The presence of nicotine in plant foods has adverse effects on the lungs, kidneys, heart, and reproductive system. A novel three-phase microchip flat electromembrane coupled with online high-performance liquid chromatography (HPLC) was developed to analyze nicotine in tomato, mushroom, eggplant, bell pepper, and red pepper. The microchip was connected to the HPLC in online mode. All effective variables were optimized to achieve the best extraction response. The use of electric potential and 2-nitrophenyl octyl ether -5% di(2-ethylhexyl) phosphate as a modified supported liquid membrane (SLM) increased the sensitivity and selectivity. The optimal extraction voltage, extraction time, and ion balance were 40 V, 10 min and 0, respectively. The dynamic linear range was 0.5-1000 ng g-1. The obtained recovery, relative standard deviation, and enrichment factor were 98%, 7%, and 35, respectively. The limits of detection 0.4 ng g-1 and the limits of quantification were obtained 1.3 ng g-1. The highest (105.0 ng g-1) and lowest (3.4 ng g-1) concentrations of nicotine were obtained for eggplant and tomato, respectively. Selective electromembrane extraction of nicotine from the donor phase to the acceptor phase was performed by optimizing the main variables influencing the method mechanism. The new channel design in this analytical system and online injection increased efficiency, stability, and repeatability. The results revealed that this method is capable for the efficient determination of trace amount of nicotine in edible vegetables.

Electromembrane Extraction of Ofloxacin from Human Plasma and Its Quantification by Capillary Electrophoresis

Background: Application of electromembrane extraction coupled with capillary electrophoresis was studied for ofloxacin extraction from plasma samples. Methods: Ofloxacin migrated from acidic plasma samples through a thin layer of 1-octanol immobilized in the pores of a porous hollow fiber wall into a 10 µL acidic aqueous acceptor solution located inside the lumen of the fiber. Results: Under optimum conditions influencing electromigration (i.e., 20 min of the operation time, stirring speed of 750 rpm, donor phase pH at 4.0, acceptor pH at 3.0, and applied voltage of 30 V across the supported liquid membrane), ofloxacin was extracted from plasma samples with an enrichment factor of 100-fold corresponding to extraction percent of 24%. The calibration curve showed acceptable linearity in the range of 0.2-7.0 µg.mL-1 (R=0.9993). The limits of detection and quantification of 0.05 and 0.2 µg.mL-1 were obtained, respectively. The inter- and intra-day precision and accuracy were obtained below 8.65%. Conclusion: The validated method was successfully processed for the ofloxacin determination in the plasma samples of patients under ofloxacin therapy. There were no interfering peaks which indicates the great selectivity of the developed method.

The usability of green deep eutectic solvents in hollow fiber Liquid-Phase microextraction for the simultaneous extraction of analytes of different Natures: A comprehensive study

In the current study, a wide range of deep eutectic solvents (DESs) with different properties (hydrophilic, hydrophobic, ionic, and nonionic) were prepared in the initial phase. Subsequently, an assessment was conducted to evaluate some characteristics of the produced DESs, including their stability at room temperature and their capacity to extract three distinct types of analytes (anionic, cationic, and non-ionic) simultaneously through hollow fiber-liquid phase microextraction (HF-LPME) technique. To carry out the extraction procedure, the prepared DESs were inserted into the pores (as supported liquid membrane (SLM)) and lumen of hollow fiber membrane (HF) to apply two-phase and three-phase HF-LPME techniques. After a thorough evaluation, the three-phase HF-LPME technique (HF(3)-LPME) was chosen by using a mixture of menthol/TBAB-based hydrophobic DES (DES-35) as SLM and the mixture of malic acid/citric acid/water-based hydrophilic DES (DES-2) as an extraction solvent in the lumen of HF. All factors affecting the extraction recovery (including pH, extraction time, extraction temperature, stirring speed, and salt effect) were optimized utilizing the one-variable-at-a-time (OVAT) methodology. After applying the extraction procedure, all extracted samples were analyzed using the UV–Vis spectrometer and results were recorded at different wavelengths including 655 nm for Methylene blue, 550 nm for Amaranth, and 375 nm for Quercetin. The calibration graphs showed linearity in the range of 20.0–1500 µg/L, with a limit of detection of 6.2–15.1 µg/L and correlation coefficients higher than 0.9913 for the studied analytes. Moreover, the intra-day RSD, inter-day RSD, preconcentration factor (PF), enrichment factors (EF), and extraction recoveries (ER%) were obtained in the range of 3.1–4.8, 3.8–6.7, 125, 102.9–111.4, and 82.3–89.1 %, respectively. The use of the selected DES in the HF-LPME methodology resulted in an ecologically friendly strategy, as evidenced by the use of green metrics from the SPMS tool. The proposed strategy is also considered environmentally friendly due to its use of minimal solvents, waste reduction, and low energy consumption. The proposed technique effectively and simultaneously extractedmethylene blue, amaranth, and quercetin analytes in different real samples.

Continuous flow membrane microextraction as a clean method for detecting codeine and papaverine in biological samples using HPLC-UV

In this study, continuous-flow membrane microextraction (CFMME) was connected online with a high-performance liquid chromatography-UV detector (HPLC-UV) for the pre-concentration and high clean-up of papaverine and codeine in biological samples. The extraction cell was designed with donor and acceptor chambers separated by a sheet membrane. By adjusting the pH of the donor phase (10 mL, pH 11), the analyte molecules were extracted into the supported liquid membrane (SLM) (15 μL of 1-octanol). The donor solution was circulated through the donor chamber using a peristaltic pump and magnetically agitated by a bar stirrer placed near the membrane, enhancing the diffusion and convection flow of the targeted drugs from the donor solution to the SLM. Subsequently, by adjusting the acceptor solution to an acidic pH of 2 (100 μL), the drugs in ionic form were reversely extracted into the acceptor phase. The procedure exhibited desirable relative standard deviation (RSD%) of less than 3.70%, linear ranges of 7-600 ng mL-1 for codeine and 2.0-600 ng mL-1 for papaverine, and limits of detection of 2.0 ng mL-1 for codeine and 0.6 ng mL-1 for papaverine. The design of the extraction cell significantly improved the performance for determining targeted drugs in complex matrices such as plasma and urine.

Solvent Extraction of Gold(III) by 2-Ethylhexanol and Modeling of Facilitated Transport across a Supported Liquid Membrane

The solvent extraction of gold(III) by undiluted 2-ethylhexanol or dissolved in toluene from a HCl solution has been investigated in this paper. The numerical analysis of gold distribution data suggests the formation of HAuCl4·L and HAuCl4·2L (L = 2-ethylhexanol) species in the organic phase, with formation constants K11 = 38 and K12 = 309, respectively. The results derived from gold(III) distribution have been implemented in a solid-supported liquid membrane system. The influence of several variables on gold transport has been considered: feed and receiving phases’ stirring speeds, HCl and gold concentrations in the feed phase, and carrier concentration in the membrane phase as well as the presence of base metals (Fe, Cu, Ni) and platinum-group metals (PGMs) in the feed phase. Gold transport is influenced by the stirring speed of the feed phase and the variation in HCl and gold (feed phase) and carrier (membrane phase) concentrations. Also, diffusional resistances to mass transfer are estimated, and the contribution of each resistance to gold transport is estimated. Gold is recovered as zero-valent nanoparticles.

Fatty Alcohol-Assisted Electro-Driven Liquid Membrane Multi-Stage Extraction Technology for Selective Separation and Purification of 3,4-Dihydroxybenzaldehyde from Salvia miltiorrhiza Bge.

3,4-Dihydroxybenzaldehyde (DHB) is a highly effective water-soluble compound in the traditional Chinese medicine Salvia miltiorrhiza Bge. Which demonstrates clear therapeutic effects against a variety of diseases. Therefore, the development of a selective approach for the separation of 3,4-dihydroxybenzaldehyde is of great significance. In this study, electro-driven extraction combined with multi-stage extraction technology was employed for the first time to separate 3,4-dihydroxybenzaldehyde from S. miltiorrhiza Bge. Decoction (Recovery ≥ 46.09%). Five long-chain fatty alcohols were selected as the supported liquid membrane (SLM) in the electro-driven extraction. Factors influencing extraction efficiency, including pH, voltage, and extraction time, were optimized using a design of experiments. Under the optimal conditions, the linearity of 3,4-dihydroxybenzaldehyde ranged from 0.01 to 100 μg·mL−1), with limits of detection (LOD) and quantification (LOQ) of 5 and 17 ng·mL−1, respectively. The precision of electro-driven liquid membrane extraction for 3,4-dihydroxybenzaldehyde was below 8.42%. This paper reports novel electro-driven liquid membrane extraction for selectively isolating 3,4-dihydroxybenzaldehyde from S. miltiorrhiza Bge.

Solvent-free parallel artificial liquid membrane extraction for drugs of abuse in plasma samples using LC-MS/MS

BackgroundParallel artificial liquid membrane extraction (PALME) is a 96-well plate setup variant of liquid-phase microextraction. Basic or acidic analytes are extracted in neutral form from the sample, through a supported liquid membrane (SLM), and into aqueous acceptor. PALME is already considered a green extraction technique, but in the current conceptual work, we sought to make it even greener by replacing the use of organic solvents with essential oils (EO). PALME was combined with LC-MS/MS for analysis of plasma samples and multiple drugs of abuse with toxicological relevance (amphetamines, phenethylamines, synthetic cathinones, designer benzodiazepines, ayahuasca alkaloids, lysergic acid diethylamide, and ketamine). ResultsFourteen EO were compared to organic solvents frequently used in PALME. The EO termed smart & sassy yielded the best analyte recovery for all drugs studied and was thus selected as SLM. Then, factorial screening and Box-Behnken were employed to optimize the technique. The extraction time, concentration of base, sample volume, and percentage of trioctylamine significantly impacted analyte recovery. The optimum values were defined as 120 min, 10 mmol/L of NaOH, 150 μL, and 0%, respectively. Once optimized, validation parameters were 1–100 ng mL-1 as linear range, accuracy ±16.4%, precision >83%, 1 ng mL-1 as limit of quantitation, 0.1–0.75 ng mL-1 as limit of detection, matrix effect <20%, and recovery 20–106%. Additionally, EO purchased from different production batches were tested and achieved acceptable reproducibility. Data were in compliance with requirements set by internationally accepted validation guidelines and the applicability of the technique was proven using authentic samples. SignificanceIn this study, the use of an EO provided a solvent-free sample preparation technique suited to extract different classes of drugs of abuse from plasma samples, dismissing the use of hazardous organic solvents. The method also provided excellent sample clean-up, thus being a simple and efficient tool for toxicological applications that is in agreement with the principles of sustainable chemistry.

Comparison of the applicability of electromembrane extraction and liquid-phase microextraction for extraction of non-polar basic drugs from different biological samples: Using clozapine as the model analyte.

Understanding and comparing the applicability of electromembrane extraction (EME) and liquid-phase microextraction (LPME) is crucial for selecting an appropriate microextraction approach. In this work, EME and LPME based on supported liquid membranes were compared using biological samples, including whole blood, urine, saliva, and liver tissue. After optimization, efficient EME and LPME of clozapine from four biological samples were achieved. EME provided higher recovery and faster mass transfer for blood and liver tissue than LPME. These advantages were attributed to the electric field disrupting clozapine binding to interfering substances. For urine and saliva, EME demonstrated similar recoveries while achieving faster mass transfer rates. Finally, efficient EME and LPME were validated and evaluated combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS). The coefficient of determination of all methods was greater than 0.999, and all methods showed acceptable reproducibility (≤14%), accuracy (90%-110%), and matrix effect (85%-112%). For liver and blood with high viscosity and complex matrices, EME-LC-MS/MS provided better sensitivity than LPME-LC-MS/MS. The above results indicated that both EME and LPME could be used to isolate non-polar basic drugs from different biological samples, although EME demonstrated higher recovery rates for liver tissue and blood.