Simultaneous effervescence-assisted microextraction and magnetic adsorbent generation for rapid and cost-effective organochlorine pesticides analysis.

This study introduced an innovative magnetic effervescence-assisted microextraction method, streamlining the preparation of effervescent tablets through a one-pot method that blends a CO2 donor (Na2CO3) and an H+ donor (NaH2PO4) with bare magnetic particles (Fe3O4) and an adsorbent (hydroxylated multi-walled carbon nanotubes), followed by pressing. During the extraction process, the bare magnetic particles and adsorbent undergo in-situ self-assembly to create a magnetic adsorbent. The effervescence generates bubbles that enhance effective extraction and magnetism facilitates the easy separation of the magnetic adsorbent from the sample solution, completing the process within 4 min. Applied to organochlorine pesticide analysis in fruit juices and herbal extracts, the method exhibits excellent linearity (R2 > 0.993), sensitivity (detection limits: 0.010-0.125 ng/mL), accuracy (recoveries: 85.8-99.9%), and precision (RSDs < 9.7%) with GC-ECD. Overall, this approach stands out for its simplicity, cost-effectiveness, and suitability for on-site analysis, owing to its operational ease and independence from specialized equipment.

Modern automated microextraction procedures for bioanalytical, environmental, and food analyses.

Sample preparation frequently is considered the most critical stage of the analytical workflow. It affects the analytical throughput and costs; moreover, it is the primary source of error and possible sample contamination. To increase efficiency, productivity, and reliability, while minimizing costs and environmental impacts, miniaturization and automation of sample preparation are necessary. Nowadays, several types of liquid-phase and solid-phase microextractions are available, as well as different automatization strategies. Thus, this review summarizes recent developments in automated microextractions coupled with liquid chromatography, from 2016 to 2022. Therefore, outstanding technologies and their main outcomes, as well as miniaturization and automation of sample preparation, are critically analyzed. Focus is given to main microextraction automation strategies, such as flow techniques, robotic systems, and column-switching approaches, reviewing their applications to the determination of small organic molecules in biological, environmental, and food/beverage samples.

Menthol-assisted homogenous liquid-liquid microextraction for HPLC/UV determination of favipiravir as an antiviral for COVID-19 in human plasma.

Favipiravir is a promising antiviral agent that has been recently approved for treatment of COVID-19 infection. In this study, a menthol-assisted homogenous liquid-liquid microextraction method has been developed for favipiravir determination in human plasma using HPLC/UV. The different factors that could affect the extraction efficiency were studied, including extractant type, extractant volume, menthol amount and vortex time. The optimum extraction efficiency was achieved using 300 µL of tetrahydrofuran, 30 mg of menthol and vortexing for 1 min before centrifuging the sample for 5 min at 3467g. Addition of menthol does not only induce phase separation, but also helps to form reverse micelles to facilitate extraction. The highly polar favipiravir molecules would be incorporated into the hydrophilic core of the formed reverse micelle to be extracted by the non-polar organic extractant. The method was validated according to the FDA bioanalytical method guidelines. The developed method was found linear in the concentration range of 0.1 to 100 µg/mL with a coefficient of determination of 0.9992. The method accuracy and precision were studied by calculating the recovery (%) and the relative standard deviation (%), respectively. The recovery (%) was in the range of 97.1-103.9%, while the RSD (%) values ranged between 2.03 and 8.15 %. The developed method was successfully applied in a bioequivalence study of Flupirava® 200 mg versus Avigan® 200 mg, after a single oral dose of favipiravir administered to healthy adult volunteers. The proposed method was simple, cheap, more eco-friendly and sufficiently sensitive for biomedical application.

Reversed lipid micellar hollow-fiber liquid-phase microextraction of rotigotine in rat plasma.

A hollow fiber liquid phase microextraction (HF-LPME) based on a reversed lipid micelle as the extraction phase was proposed and combined with high performance liquid chromatography (HPLC) for the determination of rotigotine in biological matrix. In the proposed procedure, pieces of hollow fibers were fastened on a magnetic stir bar using a thread to provide better precision. Rotigotine was extracted from 5 mL of diluted plasma sample phase with pH 6 into reversed lipid micelle (5 mmol/L of dipalmitoyl phosphatidyl choline in n-octanol/water) impregnated in both the wall pores and the lumen of the hollow fiber. After the extraction at 900 rpm and room temperature for 30 min, the acceptor phase of reversed lipid micelle was collected for HPLC analysis. Various parameters affecting the extraction efficiency, such as type of surfactant and organic solvent, surfactant concentration, sample phase pH, salt amount, extraction time, stirring rate, and dilution factor of the plasma sample, were investigated and optimized. Furthermore, the formed reversed lipid micelle was characterized by fluorescence method. Under the optimal conditions, the linear range of rotigotine was between 2 ng/mL and 100 ng/mL with determination coefficient (r2) ≥ 0.9913. It is shown from results of method validation that the satisfactory accuracy (the relative errors between -8.5% and 3.3%), precision (the relative standard deviations from 3.8% to 8.9%), stability and matrix effect were obtained. The enrichment factor (EF) of the reversed lipid micelle-based HF-LPME for rotigotine reached 126. And the feasibility of the proposed method was confirmed by the application to the pharmacokinetic study of rotigotine in rat plasma.

In-syringe temperature-controlled liquid-liquid microextraction based on solidified floating ionic liquid for the simultaneous determination of triazine and phenylurea pesticide in vegetable protein drinks.

A novel in-syringe temperature-controlled liquid-liquid microextraction based on solidified floating ionic liquid (in-syringe TC-LLME-SFIL) combined with high performance liquid chromatography was developed for the simultaneous determination of monuron, chlorotoluron, atrazine, monolinuron, propazine and prometryn in commercial vegetable protein drinks. The samples were deproteinized by trichloroacetic acid and further cleaned up by solid phase extraction column. The ionic liquid tributyldodecylphosphonium tetrafluoroborate ([P4 4 4 12]BF4) was used as extraction solvent and dispersed into the depurated sample solution to form fine droplets with the assistance of heating and vortex. With the help of an ice bath, the ionic liquid phase solidified and floated on the surface of aqueous phase. After separation from the aqueous phase, the solidified ionic liquids were dissolved with acetonitrile and the resulting solution was analyzed by high performance liquid chromatography. Some extraction parameters, including type and amount of adsorbent, type and amount of ionic liquids, amount of NaCl, melting temperature and time of ionic liquid, vortex time, pH of sample solution, ice bath temperature and time, were investigated and optimized by single-factor experiment, Plackett-Burman design and Box-Behnken design. The results showed that good linearities (r ≥ 0.9994) were obtained in the concentration range of 7.8-1000.0 µg/L. The limits of detection and quantification were in the range of 0.25-2.59 µg/L and 0.82-8.63 µg/L, respectively. The spiked recoveries were 81.26-118.42% with the relative standard deviation (RSD, n = 3) lower than 8.17%. The present method was successfully applied to the simultaneous determination of triazine and phenylurea herbicides in vegetable protein drinks.

Gel electromembrane microextraction followed by ion chromatography for direct determination of iodine in supplements and fortified food samples: Green chemistry for food analysis.

In this study, a sensitive, selective, and environmentally friendly analytical method for direct extraction and preconcentration of iodine was developed. Iodine, as an iodate ion or iodide ion, was simultaneously extracted and preconcentrated by gel electromembrane microextraction (G-EME) and analyzed for total iodine by ion chromatography. The total iodine was determined by combining the peak areas of both iodate and iodide ions. Under the optimized conditions, linear calibration for iodine using a mixture of iodate and iodide ions was obtained from 10 to 100 µg L-1 (r2 > 0.996). The detection limit was 7.0 µg L-1. Recoveries of spiked iodine (as iodate) in the samples were greater than 90%. The method was applied for the determination of iodine in dietary supplements and fortified food samples, i.e., iodine-enriched eggs. Our developed method could be directly applied for the determination of iodine in different matrix samples including eggs without a pretreatment step.

A basic and effective liquid phase microextraction with a novel automated mixing system for the determination of cobalt in quince samples by flame atomic absorption spectrometry.

A new, green, and simple liquid-phase microextraction method namely sieve conducted two syringe-based pressurized liquid-phase microextraction methods was combined with flame atomic absorption spectrometry for the preconcentration and determination of cobalt. For this aim, a novel automated syringe mixing system was developed to be used in the developed extraction procedure. Two syringes were connected to each other by an apparatus having six holes to produce efficient dispersion of the extractant. The pressure created between the two syringes by the forward and backward movements of the syringe plungers created an efficient dispersion of the extractant. In the present study, ligand as complexing agent was synthesized in our laboratory. Limits of detection and quantification were determined to be 1.8 and 6.0 µg L-1, respectively. A 33.7-fold enhancement in detection power was obtained with the developed method. Method was effectively applied for the determination of cobalt in quince samples.

Determination of Polybrominated Diphenyl Ethers in Water Samples Using Effervescent-Assisted Dispersive Liquid-Liquid Icroextraction with Solidification of the Aqueous Phase.

An effective and sensitive method is necessary for the determination of polybrominated diphenyl ethers (PBDEs) pollutants in water. In this study, effervescent-assisted dispersive liquid-liquid microextraction with solidification of the aqueous phase (EA-DLLME-SAP), followed by Gas Chromatography-Tandem Mass Spectrometry (GC-MS-MS) quantitative analysis, was established for the preconcentration and determination of PBDEs in real environmental water samples. 1,1,2,2-Tetrachloroethane was used as the extractant and directly dispersed into the water phase of the aqueous samples with the aid of a large number of carbon dioxide bubbles generated via the acid-base reaction of acetic acid and sodium bicarbonate, which did not require the use of a dispersant during the extraction process. The key factors affecting the extraction recovery were optimized, and an internal standard was used for quantitative analysis, which gave good linearity ranges of 1-100 ng·L-1 (BDEs 28, 47, 99, and 100), 2-200 ng·L-1 (BDEs 153, 154, and 183) and 5-500 ng·L-1 (BDE 209) with limits of quantification in the range of 1.0-5.0 ng·L-1. The accuracy was verified with relative standard deviations < 8.5% observed in tap, lake, river and reservoir water samples with relative recoveries ranging from 67.2 to 102.6%. The presented method contributes to the determination of PBDEs in environmental water samples.

Green microfluidic liquid-phase microextraction of polar and non-polar acids from urine.

In this work, hippuric acid (log P = 0.5), anthranilic acid (log P = 1.3), ketoprofen (log P = 3.6), and naproxen (log P = 3.0) were simultaneously extracted by a green microfluidic device based on the principles of liquid-phase microextraction (LPME). Different deep eutectic solvents (DESs) were investigated as supported liquid membrane (SLM), and a mixture of camphor and menthol as eutectic solvents in the molar ratio 1:1 was found to be highly efficient for the simultaneous extraction of non-polar and polar acidic drugs. LPME was conducted for 6 min per sample. Urine sample was delivered to the system at 1 µL min-1, and target analytes were extracted exhaustively (75-100% recovery) across the DES SLM, and into pure aqueous phosphate buffer pH 11.0 delivered as acceptor at 1 µL min-1. The acceptor was analyzed with liquid chromatography-UV detection. Interestingly, the DES enabled extraction of both the polar and non-polar model analytes at the same time; all chemicals were green and non-hazardous, and the chemical waste was less than 1 mg per sample.

Determination of pyridaphenthion in soybean sprout samples by gas chromatography mass spectrometry with matrix matching calibration strategy after metal sieve linked double syringe based liquid-phase microextraction.

A novel analytical strategy for the trace determination of pyridaphenthion pesticide was developed in this study. Gas chromatography-mass spectrometry (GC-MS) was used for the accurate, feasible and precise determination of this analyte. Liquid phase microextraction (LPME) was performed with a metal sieve linked double syringe (MSLDS) system, which eliminated the need for a disperser solvent. In order to increase extraction efficiency for the analyte, all variable parameters were optimized and the system analytical performance of the proposed method was determined. Limit of detection and quantification (LOD and LOQ) values of pyridaphenthion were found to be 0.8 and 2.7 µg L-1, respectively. Compared to GC-MS system's analytical performance, the developed method provided approximately 273-folds improvement in the detection limit of the analyte. Applicability/accuracy of the developed analytical strategy was checked by recovery experiments carried out with soybean sprouts, and the results obtained were satisfactory.

Smartphone digital image colorimetry combined with solidification of floating organic drop-dispersive liquid-liquid microextraction for the determination of iodate in table salt.

Smartphone digital image colorimetry (SDIC), combined with solidification of floating organic drop-dispersive liquid-liquid microextraction (SFOD-DLLME), was proposed for the determination of iodate ions. A colorimetric box was designed to capture images of sample solutions. Factors affecting the efficiency of SDIC included type of phone, region of interest, position of camera, and distance between camera and sample solution. Optimum SFOD-DLLME conditions were achieved with 1-undecanol (500 µL) as the extraction solvent, ethanol (1.5 mL) as the disperser solvent within 20 s extraction time. Limit of detection (LOD) was found as 0.1 µM (0.2 µg g-1) and enrichment factors ranged between 17.4 and 25.0. Calibration graphs showed good linearity with coefficients of determination higher than 0.9954 and relative standard deviations lower than 5.6%. The proposed method was efficiently applied to determine iodate in table salt samples with percentage relative recoveries ranging between 89.3 and 109.3%.

A fast and selective gas liquid microextraction of semiochemicals for quantitative analysis in plants.

A trapping-based gas liquid microextraction (GLME) method coupled with gas chromatography-mass spectrometry (GC-MS) was utilized to qualitatively and quantitatively characterize semiochemicals in plants. The main GLME extraction efficiency associated parameters (heating temperature and extraction time) were optimized. The results obtained from GLME process were compared with those of steam distillation and ultrasonic extraction, and the recovery, peak number and reproducibility were evaluated by using Thuja koraiensis Nakai as a representative plant. Furthermore, the quantitative performances of the GLME in terms of sample amount, recoveries of spiked standards and correlation were systematically evaluated using standard addition method, which gave a good quantitative ability for all the compounds with squares of correlation coefficient (r2) of higher than 0.99. Finally, the contents of α-pinene, camphene, linalool, α-terpinenol, ß-caryophyllene, α-caryophyllene, and totarol in Thuja koraiensis Nakai samples were quantified, and their concentrations (SD, n = 3) were; 0.65 (0.06), 0.62 (0.05), 4.12 (0.15), 0.99 (0.08), 1.11 (0.07), 0.63 (0.04), and 21.91 (0.25) µg g-1, respectively. It was demonstrated that GLME is a powerful sample preparation technique for quantitative and qualitative analysis of plant semiochemicals.

Application of aeration-assisted homogeneous liquid-liquid microextraction procedure using Box-Behnken design for determination of curcumin by HPLC.

A simple, efficient, and rapid sample preparation method based on aeration-assisted homogeneous liquid-liquid microextraction was developed for determination of curcumin in food samples by high-performance liquid chromatography. The centrifuge step has been eliminated in this procedure. The effects of some variables, such as pH, volume of extraction solvent, extraction time, and salt effect, were studied through a Box-Behnken design method. Under the optimum conditions, calibration curves of curcumin were linear in the range of 0.08-4000 µg/mL with R2  = 0.997. Limit of detection and relative standard deviation were 0.019 µg/mL and 3.01%, respectively. The preconcentration factor achieved was 166. The proposed method was successfully applied to determination of curcumin in various food samples.

A Simple in Syringe Low Density Solvent-Dispersive Liquid Liquid Microextraction for Enrichment of Some Metal Ions Prior to Their Determination by High Performance Liquid Chromatography in Food Samples.

A simple and highly sensitive method is developed for the simultaneous determination of Ni2+, Cr2O72-, Co2+, and Hg2+ by using in syringe low density solvent-dispersive liquid liquid microextraction (ISLD-DLLME), followed by high performance liquid chromatography with a UV detector. The four metal ions were derivatized with pyrrolidine dithiocarbamate (PDC) based on complexation before their enrichment by ISLD-DLLME in which 1-octanol and methanol were used as the extraction solvent and the dispersive solvent, respectively. The extraction was performed in a commercially available syringe under vortex agitation. Phase separation was achieved without centrifugation, and the extraction phase was easily collected by moving the syringe plunger. Parameters affecting the extraction efficiency were studied and optimized. Under the optimum conditions, the four metal-PDC complexes were detected within 18 min, and ISLD-DLLME could increase the detection sensitivity in the range of 64-230 times compared to the direct HPLC analysis. The obtained limits of detection (LODs) were found to be in the range of 0.011-2.0 µg L-1. The applicability of the method is demonstrated for freshwater fish, shrimp, and shellfish samples. In addition, the results are in good agreement with those obtained by inductively-coupled plasma-optical emission spectrometry (ICP-OES).

Deep eutectic mixture membrane-based microextraction: HPLC-FLD determination of phenols in smoked food samples.

A novel approach for effective sample pretreatment of food was developed. This approach was based on in situ deep eutectic mixtures formation between analytes (hydrogen bond donors) and choline chloride (a hydrogen bond acceptor) supported in a hydrophilic porous membrane. By this action, the analytes were extracted and retained into the hydrophilic porous membrane. Finally, the hydrophilic porous membrane containing the analytes was transferred into an aqueous phase and back-extraction occurred due to deep eutectic mixture decomposition in the aqueous phase. The developed approach was applied to the HPLC-FLD determination of phenols (phenol, o-cresol, p-cresol, eugenol, isoeugenol and guaiacol) in smoked food samples. The limits of detection, calculated from a blank test based on 3σ, were 0.3 µg kg-1 for phenol, o-cresol, p-cresol; 0.6 µg kg-1 for eugenol, isoeugenol; and 1 µg kg-1 for guaiacol.

Rapid screening and characterization of natural antioxidants in Polygonum viviparum by an on-line system integrating the pressurised liquid micro-extraction, HPLC-DAD-QTOF-MS/MS analysis and antioxidant assay.

Rapid discovery of active ingredients from complex matrices is one of great challenges for modern drug development. Traditional methods often require many sample treatment steps, including an extraction step with exclusively dedicated solvents followed by repeated separation and activities assessment. This present work described an integrated analytical setup for natural antioxidants discovery in which the online extraction (OLE) of a solid sample is directly coupled to its analysis by high performance liquid chromatography-diode array detector-quadrupole time-of-flight tandem mass spectrometry and 2,2'-Azinobis-(3-ethylbenzthiazoline-6-sulphonate) (ABTS) antioxidant assay (OLE-HPLC-DAD-QTOF-MS/MS-ABTS). This developed approach makes sample extraction, chromatographic separation and chemical detection, and antioxidant assay integrated into a single HPLC injection and was successfully applied for the rapid discovery of natural antioxidant bioactives from Polygonum viviparum. A total of 21 secondary metabolites were characterized according to their retention times, ultraviolet (UV) spectra, exact mass and fragmentation ions in MS/MS spectra, and 18 of them displayed antioxidant activity (response as negative peaks in antioxidant assay). This work describes a simple, green and efficient approach to minimize the sample consumption (only 0.4 mg was required) and eliminate complex sample treatment procedures. The developed OLE-HPLC-DAD-QTOF-MS/MS-ABTS system offers new perspectives for rapid chemical profiling of natural products and their antioxidants discovery.

Comparison and application of two microextractions based on syringe membrane filter.

Two proposed syringe membrane filter solid phase microextraction and syringe membrane filter liquid/solid phase microextraction, coupled separately with high performance liquid chromatography, were developed for simultaneous enrichment and determination of the trace level of flavonoids in traditional Chinese medicine. In syringe membrane filter solid phase microextraction, the membrane of syringe membrane filter was served as a solid adsorption film to adsorb target analytes. And in syringe membrane filter liquid/solid phase microextraction, the membrane of syringe membrane filter was used as not only an adsorption phase, but also as a holder of extraction solvent to realize liquid-solid synergistic extraction. The simple operation, rapid extraction, and little or no organic solvent consumption make the two approaches very interesting. To evaluate the two proposed approaches, the crucial parameters affecting the enrichment factors of target analytes were investigated and optimized, and the two microextractions were intercompared. Moreover, their microextraction mechanisms were analyzed and described. Under the optimized conditions, both the new approaches achieved good linearities, accuracies, precisions, and low limits of detection, and the two methods were successfully applied for concentration of the flavonoids in traditional Chinese medicines.

Trace analysis of rimantadine in human urine after dispersive liquid liquid microextraction followed by liquid chromatography-post column derivatization.

The first dispersive liquid liquid microextraction scheme followed by liquid chromatography-post column derivatization for the determination of the antiviral drug rimantadine in urine samples is demonstrated. The effect of the type and volume of organic extraction solvent, type and volume of disperser solvent, sample pH, ionic strength, extraction time, and centrifugation speed on the extraction efficiency were studied. Rimantadine and the internal standard (amantadine) were chromatographed using a reversed phase monolithic stationary phase with a mixture of equal volumes of methanol and phosphate buffer (pH = 3) as mobile phase. On-line post-column derivatization of the analyte was performed using a "two-stream" manifold with o-phthalaldehyde and N-acetyl-cysteine at alkaline medium. Under the optimized extraction conditions, the enrichment factor of rimantadine was 58. The linear range was 5-100 µg/L with correlation coefficient r of 0.9984 while the limit of detection achieved was 0.5 µg/L. The within-day and between-day precision for the tested concentration levels were less than 14.3% and the mean recoveries obtained from the spiked samples were ranged between 87.5 and 113.9%. The main advantages of the proposed method are the simplicity of operation, rapidity, low cost, and low limit of detection of the analyte.

Preparation of a new three-component deep eutectic solvent and its use as an extraction solvent in dispersive liquid-liquid microextraction of pesticides in green tea and herbal distillates.

BACKGROUND: A new solvent, deep eutectic solvent, in which there is growing interest, has been prepared and used as an extraction solvent in the dispersive liquid-liquid method of microextraction. To prepare the solvent, dichloroacetic acid, l-menthol, and n-butanol are mixed at a molar ratio of 4:1:1 and the deep eutectic solvent is formed after heating. Then a dispersive liquid-liquid microextraction method using the prepared solvent is used for the extraction and preconcentration of some pesticides from an aqueous sample. To carry out the procedure, the deep eutectic solvent is mixed with methanol and rapidly injected by a syringe into the aqueous sample containing the analytes. After centrifuging, an aliquot of the sedimented phase is injected into the gas chromatograph. The influence of several variables on the extraction efficiency was investigated and optimized. RESULTS: Extraction recoveries and enrichment factors were obtained in the ranges of 53-86% and 1760-2853, respectively. The intra- (n = 6) and inter-day (n = 5) precision of the method was satisfactory, with relative standard deviations ≤ 7% obtained at two concentrations of 10 and 50 µg L-1 of each analyte. Moreover, detection and quantification limits for the target analytes were obtained in the ranges of 0.11-0.23 and 0.38-0.74 µg L-1 , respectively. CONCLUSION: Different samples, including green tea, rose water, lemon balm, mint, and pussy willow distillates were analyzed successfully using the method that was developed, and chlorpyrifos was found in rose water at a concentration of 17 ± 1 µg L-1 (n = 3). © 2019 Society of Chemical Industry.

Homogenizer assisted dispersive liquid-phase microextraction for the extraction-enrichment of phenols from aqueous samples and determination by gas chromatography.

In this research, dispersive liquid-phase microextraction has been used for the extraction of some phenols including phenol, 3-methylphenol, 4-nitrophenol, 2-chlorophenol, tert-buthylphenol from aqueous samples, and then the analysis was done by the gas chromatography-flame ionization detector technique. For the first time, a laboratory homogenizer has been applied for dispersing of extracting organic solvent. To improve the chromatographic behavior, acetic anhydride was used as a derivatization reagent of the analytes. The effective parameters on the extraction and derivation process such as extraction solvent type and volume, amount and time of derivatization, sample pH and ionic strength, homogenization time and speed were investigated and optimized. The analytical performances of the method, such as linear dynamic range, repeatability, and detection limit were evaluated under the optimum condition. Under the optimal experimental conditions, the calibration plots were linear the range of 1-500 µg L-1 with the detection limits between 0.1-0.9 µg L-1, and the repeatability in the range of 2.6 to 10.0%. These values vary depend on the compounds. The proposed method was evaluated for the determination of the studied phenolic compounds in different real samples such as river water, tap water and industrial wastewater. The relative recoveries were between 90 and 111%.