Liquid-phase Microextraction Technique Research Articles

Application of liquid-phase microextraction to the analysis of plant and herbal samples.

The analysis of plant and herbal samples is a challenging task for analytical chemists due to the complexity of the matrix combined with the low concentration of analytes. In recent years different liquid-phase microextraction (LPME) techniques coupled with a variety of analytical equipment have been developed for the determination of both organic and inorganic analytes. Over the past few years, the number of research papers in this field has shown a markedly growing tendency. Therefore, the purpose of this review paper is to summarise and critically evaluate research articles focused on the application of LPME techniques for the analysis of plant and herbal samples. Due to the complex nature of the samples, the direct application of LPME techniques to the analysis of plants has not often been done. LPME techniques as well as their modalities have been commonly applied in combination with other pretreatment techniques, including a solid-liquid extraction technique supported by mechanical agitation or auxiliary energies for plant analysis. Applications and the most important parameters are summarised in the tables. This review summarises the application of the LPME procedure and shows the major benefits of LPME, such as the low volume of solvents used, high enrichment factor, simplicity of operation and wide selection of applicable detection techniques. We can expect further development of microextraction analytical methods that focus on direct sample analysis with the application of green extraction solvents while fully automating procedures for the analysis of plant materials.

Hollow fiber–liquid phase microextraction method based on a new deep eutectic solvent for extraction and derivatization of some phenolic compounds in beverage samples packed in plastics

The present study describes a sensitive, efficient, and easy approach for isolation, enrichment, and derivatization some phenolic compounds in the beverage samples packed in plastic bottles. The sample preparation method is based on a hollow fiber–liquid phase microextraction technique using a deep eutectic solvent. The enriched analytes are determined by gas chromatography–mass spectrometry. For this purpose, a new deep eutectic solvent composed of 8–hydroxyquinoline and pivalic acid is synthesized and used as an extraction solvent. The solvent is mixed with chloroacetyl chloride as a derivatization agent and filled into a hollow fiber segment containing an iron wire within the lumen. The prepared stir bar (hollow fiber) is stirred into the sample solution in which sodium chloride is dissolved to increase ionic strength of the solution. Temperature of the solution is adjusted at 50 °C to improve efficiency of the extraction/derivatization procedure. Under optimum conditions, the introduced method indicated high enhancement (1652–3265) and enrichment (1085–1256) factors, low limits of detection (9–22 ng L−1) and quantification (29–76 ng L−1), good linearity (r2 ≥ 0.9950), and satisfactory repeatabilities. Finally, the proposed method was applied in analysis of the analytes in the various beverage samples packed in plastic packages.

Deep eutectic-based vortex-assisted/ultrasound-assisted liquid-phase microextractions of chromium species

In the present work, vortex-assisted liquid-phase microextraction (VA-LPME) and ultrasound-assisted liquid-phase microextraction (UA-LPME) techniques were used for the speciation of chromium (Cr3+/Cr6+) followed by their determination using flame atomic absorption spectrometry. 1-(2-Pyridylazo)-2-naphthol (PAN) was used as a chelating agent to form a hydrophobic complex with Cr3+; then, it was extracted by choline chloride–phenol mixture, as an extraction solvent. A solution of 1.0 mol L−1 ascorbic acid was used as a reducing agent to convert Cr6+ to Cr3+ (total chromium), and the concentration of Cr6+ was determined from the subtraction of Cr3+ form total chromium. The efficiency of two microextraction techniques was compared in terms of type and amount of extraction solvent, type and volume of extraction solvent, pH of solution, volume of tetrahydrofuran (THF), and extraction time. Based on the obtained results, the extraction recoveries of VA-LPME and UA-LPME techniques are 52% and 60%, respectively. Therefore, UA-LPME is superior technique than VA-LPME. By optimizing different parameters affecting the recovery percentage (RP) of Cr3+, the calibration curve was depicted in the concentration range of 1.5–375.0 ng mL−1 Cr3+ with a correlation coefficient of 0.9937. The limit of detection was 0.4 ng mL−1, and the relative standard deviation (RSD%) for seven replicate analyses of 50.0 µg L−1 of Cr3+ was 3.6%. Finally, the UA-LPME method was successfully applied for the determination of Cr species in different food and water samples.

Three-pesticide residue analysis in tomato using a fast pressure variation in-syringe dispersive liquid-phase microextraction technique coupled with gas chromatography-mass spectrometry by assisting experimental design

ABSTRACT In this study, an analytical procedure based on a pressure variation in-syringe dispersive liquid–phase microextraction method coupled with gas chromatography-mass spectrometry by using experimental design methods is introduced for determining diazinon, malathion and chloropyrifos in tomato samples. In the proposed method, chloroform is selected as an extraction solvent. The screening strategy is done by using Plackett–Burman design. The volume of extraction solvent, ionic strength, extraction time and pH are statistically significant, Optimal conditions for these variables were determined. The calibration curves were linear in the range of 10.0–200.0 μg Kg−1, 10.0–100.0 μg Kg−1, and 10.0–50.0 μg Kg−1, with determination coefficients of 0.9999, 0.9993 and 0.996 for diazinon, malathion and chloropyrifos respectively. The detection limits were found to be 6.3 μg Kg−1 for diazinon, 7.1 μg Kg−1 for malathion and 4.8 μg Kg−1for chlorpyrifos. The inter-day and intra-day precision (RSD%) were 2.88% and 8.66% for diazinon, 0.92% and 4.45% for malathion and 3.63% and 5.78% for chloropyrifos (n = 5, concentration = 20 μg Kg−1). The pressure variation in-syringe -DLLME method was used to determine OPPs for the first time in this study.

Hyphenated dispersive solid- and liquid-phase microextraction technique based on a hydrophobic deep eutectic solvent: application for trace analysis of pesticides in fruit juices.

Pesticides are extensively used worldwide to control plant pathogens and prevent agricultural product damage. However, they can pollute the environment and endanger human health. So far, a variety of sample preparation methods have been developed for the analysis of pesticide residues. A hyphenated solid-liquid microextraction method based on a new adsorbent of magnetic graphene oxide functionalized by (3-glycidyloxypropyl)trimethoxysilane and a deep eutectic solvent (choline chloride/4-chlorophenol (1:2)) was developed for extraction/preconcentration of trace levels of pesticides. The sorbent was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. In-syringe magnetic dispersive solid-phase extraction in tandem with dispersive liquid-liquid microextraction followed by gas chromatography was applied for the analysis of the selected pesticides. The main parameters governing sample preparation efficiency, including adsorbent dosage, desorption conditions, pH, extraction time, deep eutectic solvent volume, and salt concentration, were investigated. The linear ranges were 0.024-500 μg L-1 with 0.9971-0.9999 linearity factor (R2 ). The limits of detection and quantification were 0.006-0.038 and 0.024-0.126 μg L-1 , respectively. The relative standard deviations were 0.5-4.2% for intra-day analysis and 2.7-4.6% for inter-day analysis. Enrichment factors were in the range 210-540. The method was successfully applied for the determination of malathion, heptachlor epoxide, endrin, dichlorodiphenyltrichloroethane, azinphos ethyl, cypermethrin, and deltamethrin in fruit juice samples (apple, pineapple, cherry, peach, and red and green grape juices) and the recoveries were within the range 71-115%. © 2020 Society of Chemical Industry.

Hollow-fibre liquid-phase microextraction and gas chromatography-mass spectrometric determination of amphetamines in whole blood

Here, we present a fully validated method using a hollow-fibre liquid-phase microextraction technique for the determination by gas chromatography-mass spectrometry (GC–MS) of amphetamine (AMP), methamphetamine (MET), fenproporex (FEN), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA) and 3,4-methylenedioxyethylamphetamine (MDEA) in whole blood. The validation parameters presented successful values within those recommended by the Scientific Working Group for Forensic Toxicology (SWGTox) in the Standard Practices for Method Validation in Forensic Toxicology. The limits of detection ranged from 1 to 3 ng/mL, and the limits of quantification ranged from 2 to 5 ng/mL. The determination coefficients (r2) ranged from 0.990 to 0.997, and the method presented good intraday and interday accuracy (from 90.4% to 97.2%) and satisfactory recovery (from 68% to 110%). No carryover was observed. The heteroscedasticity was tested, and only AMP presented homoscedasticity. Weighting factors were applied to correct the linearity of MET (1/x2), MDA (1/x), FEN (1/x1/2), MDMA (1/x2) and MDEA (1/y). Dilution integrity was tested at ratios of 1:2, 1:5 and 1:10, and all maintained intraday precision (from 94.9% to 99.3%) and interday precision (from 89.4% to 94.9%). The validated method was applied to six real whole blood samples from individuals suspected of consuming ecstasy, and MDMA, MDA and amphetamine were successfully identified and quantified.

A novel switchable solvent liquid-phase microextraction technique based on the solidification of floating organic droplets: HPLC-FLD analysis of polycyclic aromatic hydrocarbon monohydroxy metabolites in urine samples

A novel switchable solvent liquid-phase microextraction technique, based on the solidification of floating organic droplets (SS-LPME-SFO), was developed for the pretreatment of aqueous samples.

Hollow fiber liquid-phase microextraction based on the use of a rotating extraction cell: A green approach for trace determination of rhodamine 6G and methylene blue dyes

In this work, a novel mode of hollow fiber liquid-phase microextraction (HF-LPME) technique namely rotating extraction cell solvent bar microextraction (REC-SBME) was introduced. The proposed method was applied for the preconcentration of methylene blue (MB) and rhodamine 6G (RG) in some real samples, including soft drink, lipstick, environmental water, and wastewater samples. In the extraction setup, two pieces of hollow fibers were fixed on a mechanical support and immersed in a rotating extraction cell containing the sample solution during the extraction process. The rotation of the extraction cell by using an electric motor led to an enhancement in the mass transfer of the dyes from the sample solution into the organic acceptor phase. In the developed procedure, the UV–Vis spectrophotometry and HPLC-UV/Vis were employed as detection methods for the analysis of the acceptor phase and the obtained results were compared. Optimization of the extraction factors affecting the method, including organic solvent type, sample solution pH, extraction time, rotational rate, the volume of sample and acceptor solutions, salt addition, and temperature was performed in order to obtain the best preconcentration factor. Linear dynamic range obtained by HPLC-UV/Vis and spectrophotometry was observed in the ranges of 2.5–1200 ng mL−1 for RG and 1.6–600 ng mL−1 for MB with R2 more than 0.9971. Also, relative standard deviation (RSD) values (n = 3) less than 3.8% were obtained. The good conformity of the obtained results makes UV–Vis spectrophotometric method an ideal tool for routine analysis of trace dyes in the complex matrices after REC-SBME.

Determination of selected antiretroviral drugs in wastewater, surface water and aquatic plants using hollow fibre liquid phase microextraction and liquid chromatography - tandem mass spectrometry

This work describes a simple and sensitive method for the simultaneous isolation, enrichment, identification and quantitation of selected antiretroviral drugs; emtricitabine, tenofovir disoproxil and efavirenz in aqueous samples and plants. The analytical method was based on microwave extraction and hollow fibre liquid phase microextraction technique coupled with ultra-high pressure liquid chromatography-high resolution mass spectrometry. A multivariate approach via a half-fractional factorial design was used focusing on six factors; donor phase pH, acceptor phase HCl concentration, extraction time, stirring rate, supported liquid membrane carrier composition and salt content. The optimal enrichment factors for emtricitabine, tenofovir disoproxil and efavirenz from aqueous phase were 78, 111 and 24, respectively. The analytical method yielded recoveries in the range of 86 to 111%, and quantitation limits for emtricitabine, tenofovir disoproxil and efavirenz in wastewater were 0.033, 0.10 and 0.53 μg L−1, respectively. The drugs were detected in most samples with concentrations up to 37.6 μg L−1 recorded for efavirenz in wastewater effluent. Roots of the water hyacinth plant had higher concentrations of the investigated drugs ranging from 7.4 to 29.6 μg kg−1. Overall, hollow fibre liquid phase microextraction proved to be an ideal tool for isolating and pre-concentrating the selected antiretroviral drugs from environmental samples.

Liquid phase microextraction techniques combined with chromatography analysis: a review

Sample pretreatment is the first and the most important step of an analytical procedure. In routine analysis, liquid–liquid microextraction (LLE) is the most widely used sample pre-treatment technique, whose goal is to isolate the target analytes, provide enrichment, with cleanup to lower the chemical noise, and enhance the signal. The use of extensive volumes of hazardous organic solvents and production of large amounts of waste make LLE procedures unsuitable for modern, highly automated laboratories, expensive, and environmentally unfriendly. In the past two decades, liquid-phase microextraction (LPME) was introduced to overcome these drawbacks. Thanks to the need of only a few microliters of extraction solvent, LPME techniques have been widely adopted by the scientific community. The aim of this review is to report on the state-of-the-art LPME techniques used in gas and liquid chromatography. Attention was paid to the classification of the LPME operating modes, to the historical contextualization of LPME applications, and to the advantages of microextraction in methods respecting the value of green analytical chemistry. Technical aspects such as description of methodology selected in method development for routine use, specific variants of LPME developed for complex matrices, derivatization, and enrichment techniques are also discussed.

New passive sampling device for effective monitoring of pesticides in water

The extensive use of pesticides promotes environmental contamination, mainly in surface and ground waters. However, they remain at very low concentration and present wide degradation level requiring the use of efficient devices for pesticides passive sampling. In this study, a new in situ passive sampling device was developed for monitoring and estimating time-weighted average (TWA) of pesticides in waters. The device was made with simple, recyclable and cheap materials. The sampling system involves the liquid phase microextraction technique with hollow fiber in two-phases mode. Pesticides determination was done by gas chromatography coupled to mass spectrometry. The method was optimized and validated for the determination of 29 pesticides in water, showing good linearity in the range between 0.012 and 40.00 μg L−1 with determination coefficients of R2 > 0,9649. Limit of detection (LOD) ranged from 0.009 to 0.557 μg L−1 and limit of quantification (LOQ) from 0.012 to 0.802 μg L−1. The recoveries of spiked pesticides in water samples were in the range from 96 to 130%. The method was applied to forty environmental water samples collected at São Francisco river basin, Brazil. The highest detection frequency was found for the pesticides 4,4-DDE, 4,4-DDD and propazine. They were detected in more than 20 percent of the samples.

A green dispersive liquid phase microextraction technique based on the solidification of switchable hydrophilic fatty acid for determination of polynuclear aromatic hydrocarbons in aqueous samples.

A green dispersive liquid phase microextraction approach based on the solidification of switchable hydrophilic fatty acid as an extraction phase has been developed for the determination of 16 priority polynuclear aromatic hydrocarbons (PAHs) in aqueous samples. In this study, the centrifugation step was omitted by the applying salting-out phenomenon. The influence of main variables on the efficiency of the procedure was studied by chemometric methods. Under optimal conditions, the completion time for extraction was less than 1 min, and the detector response was linear in the range of 0.1-250 μg L-1. Limit of detection and limit of quantitation were estimated as the concentration range of 0.01-0.14 μg L-1 and 0.03-0.47 μg L-1, respectively. The precision consists of repeatability and reproducibility, which were determined by calculating the relative standard deviation percent; their values were less than 7.2% and 10.5%, respectively. Applicability of the developed procedure was successfully evaluated for the analysis of PAHs in different water samples.

Selective Method for Determination and Microextraction of Imatinib at Trace Levels: A Possible Dose Monitoring Technique in Cancer Patients

Background: Imatinib (Gleevec) is an antineoplastic agent acting as tyrosine kinase inhibitor used for the treatment of cancer such as lymphoblastic leukemia. The dosage of the anticancer drugs plays a critical role in the survival of the patients. Therefore, each patient should be administered with a customized dosage of the antineoplastic agent. For this reason, patients’ plasma and urine samples should be monitored to obtain the necessary information regarding the toxicity of the drug. Objective: To determine the trace levels of imatinib, the trend solvent bar microextraction and hollow fiber liquid phase microextraction technique coupled with High-Performance Liquid Chromatography- Ultraviolet (HPLC-UV) detection were employed and optimized using Minitab. Method: In this method, pH gradient plays a critical role in obtaining the optimum results. Imatinib is a weak base so that the donor phase containing the drug was adjusted to 10.5 and the acceptor phase (free of drug) was adjusted to pH 2.8. N-octanol was used as the organic solvent to impregnate the pores of the hollow fiber so that the drug could enter the solvent bar. To enhance the results and shorten the time required, the other parameters such as stirring rate (750 rpm), time (20 min), temperature (25°C) and salt addition (14.2%) were optimized. Results: Under the optimum condition, the Limit Of Detection (LOD), Limit Of Quantification (LOQ), and Preconcentration Factor (PF) were obtained as 7.0 ng mL-1, 20.0 ng mL-1, and 107, respectively. The relative standard deviations of analysis were 4.9% within a day (n=3) and 5.7% between days (n=9). The calibration curves represented good linearity for urine and plasma samples with coefficient estimations higher than 0.99 with a linearity range of 20.0-6000.0 ng mL-1. Conclusion: Considering the results, it can be concluded that the present technique can be a great method in clinical applications, customized treatment and for clean validation in pharmaceutical industries. Keywords: Imatinib, solvent bar, hollow fiber, microextraction, HPLC, minitab, cancer.

Recent Modifications and Validation of QuEChERS-dSPE Coupled to LC-MS and GC-MS Instruments for Determination of Pesticide/Agrochemical Residues in Fruits and Vegetables: Review.

Fruits and vegetables constitute a major type of food consumed daily apart from whole grains. Unfortunately, the residual deposits of pesticides in these products are becoming a major health concern for human consumption. Consequently, the outcome of the long-term accumulation of pesticide residues has posed many health issues to both humans and animals in the environment. However, the residues have previously been determined using conventionally known techniques, which include liquid-liquid extraction, solid-phase extraction (SPE) and the recently used liquid-phase microextraction techniques. Despite the positive technological effects of these methods, their limitations include; time-consuming, operational difficulty, use of toxic organic solvents, low selective property and expensive extraction setups, with shorter lifespan of instrumental performances. Thus, the potential and maximum use of these methods for pesticides residue determination has resulted in the urgent need for better techniques that will overcome the highlighted drawbacks. Alternatively, attention has been drawn recently towards the use of quick, easy, cheap, effective, rugged and safe technique (QuEChERS) coupled with dispersive solid-phase extraction (dSPE) to overcome the setback challenges experienced by the previous technologies. Conclusively, the reviewed QuEChERS-dSPE techniques and the recent cleanup modifications justifiably prove to be reliable for routine determination and monitoring the concentration levels of pesticide residues using advanced instruments such as high-performance liquid chromatography, liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry.

Evaluation of a Hollow-Fiber Liquid-Phase Microextraction Technique for the Simultaneous Determination of PPI Drugs in Human Plasma by LC-DAD.

This study involved the development, validation and application of a three-phase hollow-fiber liquid-phase microextraction (HF-LPME) and liquid chromatography with diode array detection (LC-DAD) method for the simultaneous determination of the proton pump inhibitor (PPI) drugs omeprazole, pantoprazole and lansoprazole in human plasma. The evaluation of the HF-LPME parameters was crucial for the determination of the drugs and the conditions selected were: 1-octanol as solvent; phosphate buffer at pH 5 as donor phase; borate buffer at pH 10 as acceptor phase; extraction time of 15 min; stirring at 750 rpm and NaCl was added at 5% (w/v). Validation of the method according to US-FDA recommendations showed a good linear range (0.2-2.0 μg/mL) for all analytes, with a determination coefficient >0.9910. Precision was evaluated using intra- and inter-day assays, which showed relative standard deviations (RSD), <15% for all concentrations, with a limit of quantification (LOQ) of 0.2 μg/mL. Accuracy was also assessed at these concentration levels and was in the range from 80 to 130%. Finally, the sensitive, selective and reproducible HF-LPME/LC-DAD developed method was successfully applied to human plasma samples from patients undergoing therapy with the PPI drugs.

A highly selective and sensitive ultrasonic assisted dispersive liquid phase microextraction based on deep eutectic solvent for determination of cadmium in food and water samples prior to electrothermal atomic absorption spectrometry

A simple, fast, green, sensitive and selective ultrasonic assisted deep eutectic solvent liquid-phase microextraction technique was used for preconcentration and extraction of cadmium (Cd) in water and food samples by electrothermal atomic absorption spectrometry (ETAAS). In this technique, a synthesized reagent (Z)-N-(3,5-diphenyl-1H-pyrrol-2-yl)-3,5-diphenyl-2H-pyrrol-2-imine (Azo) was used as a complexing agent for Cd. The main factors effecting the pre-concentration and extraction of Cd such as effect of pH, type and composition of deep eutectic solvent (DES), volume of DES, volume of complexing agent, volume of tetrahydrofuran (THF) and ultrasonication time have been examined in detail. At optimum conditions the value of pH and molar ratio of DES were found to be 6.0 and 1:4 (ChCl:Ph), respectively. The detection limit (LOD), limit of quantification (LOQ), relative standard deviation (RSD) and preconcentration factor (PF) were observed as 0.023 ng L−1, 0.161 ng L−1, 3.1% and 100, correspondingly. Validation of the developed technique was observed by extraction of Cd in certified reference materials (CRMs) and observed results were successfully compared with certified values. The developed procedure was practiced to various food, beverage and water samples.

Liquid-phase microextraction of biomarkers: A review on current methods

ABSTRACTThe detection and quantification of biomarkers have gained more attention in the medical discipline to evaluating disease progression to manage medical treatment. Biomarkers range from gases to biological macromolecules. Because of the nanomolar range levels of typical biomarkers in plasma, blood, urine, exhalation samples, and other biological fluids as well as complex matrix of biological media, adequate sample preparation methods should be used for quantification of biomarkers. Biomarkers are discussed here generally classified mainly into two subgroups which arisen from disease or exposure compounds. The analytical method is critical for the validity/reliability of a biomarker. Accuracy, precision, reproducibility, recovery, sensitivity, and specificity all have high influence to the consistency with the limit and reference values concerned. In this paper, developments in well-established liquid-phase microextraction techniques for the clinical analysis of biological samples will be reviewed and discussed. This article presents an overview of microextraction methods for biological samples, focusing especially on biomarkers.

Methods of liquid phase microextraction for the determination of cadmium in environmental samples

Liquid phase microextraction (LPME) has been widely used in extraction and preconcentration systems as an excellent alternative to conventional liquid phase extraction. In this work, a critical review is presented on liquid phase microextraction techniques used in the determination of cadmium in environmental samples. LPME techniques are classified into three main groups: single-drop liquid phase microextraction (SDME), hollow fiber liquid phase microextraction (HF-LPME), and dispersive liquid-liquid microextraction (DLLME). Methods involving these liquid phase microextraction techniques are described, addressing advantages and disadvantages, samples, figures of merit, and trends.

High enrichment and ultra-trace analysis of aflatoxins in edible oils by a modified hollow-fiber liquid-phase microextraction technique.

An improved approach for the ultra-trace analysis of aflatoxins B1, B2, G1 and G2 in edible oils was developed for the first time by a hollow-fiber liquid-phase microextraction (HF-LPME) technique. Good linearity, low limits of detection, high enrichment factors and good repeatability were obtained, which ensured the application of the method for ultra-trace detection of AFTs in edible oils.

Deep eutectic liquid organic salt as a new solvent for carrier-mediated hollow fiber liquid phase microextraction of lead from whole blood followed by electrothermal atomic absorption spectrometry

In the present work, for the first time, a new carrier-mediated hollow fiber liquid phase microextraction (CM-HFLPME) technique was applied for the determination of lead in whole blood samples by means of ETAAS.