Development of a new continuous homogenous liquid phase microextraction procedure based on in-situ preparation of deep eutectic solvent; application in the analysis of aliphatic amines in urine samples by GC-MS.

In the present work, a new microextraction procedure combined with gas chromatography-mass spectrometry has been developed for the analysis of several aliphatic amines from urine sample. The sample preparation method was a continuous homogenous liquid phase microextraction that was based on in-situ preparation of 4-chlorophenol: choline chloride deep eutectic solvent. The deep eutectic solvent was prepared by passing the mixture of related compounds through a syringe barrel filled with exothermic salts (calcium chloride and potassium bromide). The released heat by dissolving the salts and increasing the solution ionic strength assists the formation of the deep eutectic solvent. The influence of various factors on the efficiency of the proposed procedure including salts amount, flow rate, pH, salting-out effect, and extraction solvent volume was studied. The calibration curves were linear broadly over the concentration range of 1.2-250 ng mL-1 with coefficient of determinations ≥0.996. The enrichment factors were in the range of 188-246 and the limits of detection and quantification were 0.16-0.37 and 0.56-1.2 ng mL-1, respectively. Based on the results, the offered method was sensitive, rapid, eco-friendly, and efficient for extracting and determining aliphatic amines in urine samples.

Development of dispersive solid phase extraction based on magnetic metal organic framework for the extraction of sunitinib in biological samples and its determination by high performance liquid chromatography-tandem mass spectrometry.

Herein, a simple, sensitive, and reliable dispersive solid phase extraction was reported for the efficient extraction of sunitinib from biological samples. To facilitate the extraction of the desired analyte from urine and plasma samples, magnetic MIL-101Cr (NH2) @SiO2 @ NiFe2O4 was synthesized by a hydrothermal method and applied as an effective sorbent during the extraction process. After adsorption of the drug using 10 mg of MIL-101Cr (NH2) @ SiO2 @ NiFe2O4 nanoparticles through vortexing (1 min), the sorbent was separatedfrom the sample solution using a magnet. To eluate the drug, the sorbent containing the sunitinib was contacted with 100 µL dimethylformamide. The eluent was analyzed by high performance liquid chromatography-tandem mass spectrometry. Reasonable validation data consisting of low limits of detection (0.14, 0.35, and 0.70 ng mL-1 in deionized water, plasma, and urine) and quantification (0.48, 1.2, and 2.4 ng mL-1 in deionized water, plasma, and urine, respectively), a wide linear range of the calibration curve (0.48-200, 1.2-200, and 2.4-100 ng mL-1 in deionized water, plasma, and urine, respectively) good extraction recovery (76 %), and low relative standard deviations for inter- and intra-day precisions (6.9 %) were obtained by the method. Eventually, the proposed procedure was effectively implemented on both plasma and urine samples, yielding successful outcomes.

Development of a hollow fiber-liquid phase microextraction method using tissue culture oil for the extraction of free metoprolol from plasma samples.

In this research, a method known as a hollow fiber-liquid-phase microextraction was employed to extract and concentrate free metoprolol from plasma samples. The extracted analyte was subsequently determined using high-performance liquid chromatography coupled with a diode-array detector. Several parameters, including hollow fiber length, sonication time, extraction temperature, and salt addition, were investigated and optimized to enhance extraction efficiency. After extracting the analyte under optimum conditions from plasma samples, the enrichment factor and extraction recovery were 50 and 86 %, respectively. Moreover, the method exhibited detection and quantification limits of 0.41 and 1.30 ng mL-1, respectively. The analysis of real samples demonstrated satisfactory relative recoveries in the range of 91-99 %.

Deep eutectic solvent-based pressurized liquid extraction combined with dispersive liquid-liquid microextraction of organophosphorus pesticide residues in egg powder prior to high-performance liquid chromatography analysis.

Herein, a deep eutectic solvent (DES)-based miniaturized pressurized liquid extraction in combination with DES-based dispersive liquid-liquid microextraction (DLLME) was developed for the extraction of organophosphorus pesticides (parathion-methyl, triazophos, parathion, diazinon, and phoxim) from egg powder samples prior to their analysis by a high-performance liquid chromatography-diode array detector. In this work, first, the analytes' extraction was done by a pressurized liquid phase extraction for effective extraction of the analytes from the solid matrix, and then they were concentrated on a DLLME for more concentration of the analytes to reach low limits of detections. The use of DESs was done in both steps to omit the use of toxic organic solvents. Satisfactory results including high extraction recoveries (74-90%), great repeatability (relative standard deviations equal or less than 4.3% and 5.3% for intra- and inter-day precisions), and low limits of detection (0.11-0.29 ng/g) and quantification (0.38-0.98 ng/g) were attained under the optimum conditions. Lastly, the suggested approach was utilized for the determination of the studied pesticides in various egg powder samples marketed in Tabriz, Iran.

HPLC-FLD determination of aflatoxins M1 and M2 in raw cow milk samples using in-syringe gas-controlled density tunable solidification of a floating organic droplet-based dispersive liquid-liquid microextraction method.

Herein, an in-syringe gas-controlled density tunable solidification of a floating organic droplet-based dispersive liquid-liquid microextraction method was employed for the extraction of aflatoxin M1 and M2 from cow milk samples prior to their quantification with high-performance liquid chromatography equipped with a fluorescence detector. In this method, after precipitating the proteins of the sample using a zinc sulfate solution, the supernatant phase was transferred into a barrel of a glass syringe, with the end closed with a septum containing a mixture of menthol, phenylacetic acid DES (as the extraction solvent), and chloroform (as a density modifier). After that, an inert gas was bubbled into the syringe. In this manner, chloroform was evaporated and fine droplets of extractant were released, which extracted the analytes during their passing. Finally, the syringe was placed in an ice bath and the obtained solidified drop was injected into the separation system after diluting with a mobile phase. Under the best analysis conditions, low limits of detection (1.45 and 1.86 ng L-1 for AFM1 and AFM2, respectively) and quantification (4.83 and 6.21 ng L-1 for AFM1 and AFM2, respectively), high extraction recovery (75 and 70% for AFM1 and AFM2, respectively), and good precision (relative standard deviations ≤ 4.8%) were obtained by employing the approach reported in this study. In the end, this method was successfully employed to determine AFM1 and AFM2 in raw cow milk samples collected from Tabriz, Iran.

Dispersive solid phase extraction of tacrolimus from biological samples using curcumin and iron-based metal organic frameworks nanocomposite followed by LC-MS/MS determination.

Tacrolimus is a potent immunosuppressive drug used in the prevention of tissue rejection. It has a narrow therapeutic index. Therefore, the determination of its concentration in biological fluids like plasma and urine is a very crucial issue. In this research, tacrolimus concentrations in plasma and urine samples were determined with a dispersive solid phase extraction procedure coupled to high-performance liquid chromatography-tandem mass spectrometry. For this purpose, a curcumin modified metal-organic framework was synthesized and used in extraction procedure. Tacrolimus was adsorbed onto the sorbent surface with aid of vortexing. Then, the adsorbed tacrolimus was eluted by a suitable solvent. Important parameters in extraction procedure were optimized by "one-variable-at-a-time" approach and reported as below: sorbent amount, 10 mg; sample solution pH, 2; agitation mode, vortexing; adsorption and desorption times, 1 min, and eluent (volume), methanol (200 µL). Under the optimized conditions and according to the International Council for Harmonization guidelines, the validation of the method was performed, and the results showed acceptable accuracy and precision (relative standard deviations ≤14 %), good linearity in a wide range (4-200 ng mL-1), and low limits of detection (1.2 ng mL-1 in plasma and 0.34 ng mL-1 in urine) and quantification (4.7 ng mL-1 in plasma and 1.12 ng mL-1 in urine). Finally, the validated method was successfully applied for the determination of tacrolimus in the plasma samples of the patients.

Application of magnetic dispersive solid phase extraction combined with solidification of floating organic droplet-based dispersive liquid-liquid microextraction and GC-MS in the extraction and determination of polycyclic aromatic hydrocarbons in honey.

A magnetic dispersive solid phase extraction method combined with solidification of floating organic droplet-based dispersive liquid-liquid microextraction has been validated for the extraction of polycyclic aromatic hydrocarbons from honey samples. For this purpose, a carbonised cellulose-ferromagnetic nanocomposite was used as a sorbent through the magnetic dispersive solid phase extraction. For preparation of the sorbent, first, carbonised cellulose nanoparticles were created by treating cellulose filter paper with concentrated solution of sulfuric acid. Then, the prepared nanoparticles were loaded onto Fe3O4 nanoparticles through coprecipitation. In the extraction process, first, a few mg of the sorbent was added to the diluted honey solution and dispersed in it using vortex agitation. The particles were then separated and the adsorbed analytes were eluted with an organic solvent. The eluent was taken and after mixing with a water-immiscible extraction solvent was used in the following solidification of floating organic droplet-based dispersive liquid-liquid microextraction procedure. By performing the extraction process under the obtained optimum conditions, low limits of detection (0.08-0.17 ng g-1) and quantification (0.27-0.57 ng g-1), satisfactory precision (relative standard deviations ≤ 5.0%), and wide linear range (0.57-500 ng g-1) with great coefficients of determination (r2≥ 0.9986) were obtained.

In-situ formation of CO2-incorportaed solid sorbent for dispersive solid phase extraction of phenolic compounds from water and wastewater samples prior to gas chromatography-flame ionization detector.

BACKGROUND: Herein, a new extraction procedure based on in-situ formation of carbon dioxide-incorporated solid sorbent was introduced for dispersive solid phase extraction of phenolic compounds from aqueous samples. In this study, incorporation of carbon dioxide into the structure of a diamine led to the formation of a solid compound in the sample solution that adsorbed the analytes. RESULTS: The sample solution was mixed with isophorone diamine and placed under carbon dioxide stream. By doing so, isophorone diamine reacted with carbon dioxide and produced a carbamic acid analogue. It was dispersed into the sample solution as tiny particles that adsorbed the analytes. The adsorbed analytes were eluted by a volatile organic solvent and concentrated more by the vaporization of the eluate. The extraction procedure was done at low temperature to limit the releasing carbon dioxide from the produced compound. To obtain the reliable results, the method was validated and the obtained limits of detection and quantification were in the ranges of 0.29-41 and 0.96-1.3 ng/mL, respectively. Acceptable relative standard deviation (≤7.3%) and coefficient of determination (≥0.994) values confirmed the method repeatability and linearity. High enrichment factors (410-435) and extraction recoveries (82-87%) were attained with the introduced method. SIGNIFICANCE AND NOVELTY: In this work, a chemical reaction was done between isophorone diamine and carbon dioxide in solution. The produced product (sorbent) was insoluble in solution and dispersed in whole parts of the solution as tiny particles. A high contact area between the sorbent and analytes provided high extraction efficiency for the analytes. The method was successful utilized in determining target analytes in real samples and the matrix effect of the samples had no important effect on the obtained results.

Extraction of Covid-19 drug (Favipiravir) from plasma samples by yolk-shell mesoporous silica before HPLC-MS/MS determination.

In this work, a simple and inexpensive dispersive solid phase extraction method using SiO2 @MCM-41-Co3O4 yolk shell as a sorbent was developed for the extraction of favipiravir from plasma samples. The sorbent was synthesized with a simple and novel method. Optimization of the extraction procedure was performed using one parameter at a time strategy. For selective measurement of favipiravir in real samples, multiple reaction monitoring mode in high-performance liquid chromatography-tandem mass spectrometry was used. The synthesized sorbent presented a high adsorption capacity for favipiravir due to its mesoporous structure and different interactions. After optimization of effective parameters including the amount of sorbent, pH, and adsorption and desorption times, the analytical parameters of the method were evaluated. The developed method exhibited a wide linear range from 0.50 to 1000 µg/L. The detection limit and quantification limit of the method were 0.15 and 0.50 µg/L, respectively. The relative standard deviation of the method was obtained by using intra- and inter-day tests, and in both cases, it was less than 6.0%. Finally, the method was successfully used to measure favipiravir in plasma samples with relative recoveries in the range of 87-105%.

MIL-68 (Ga) for the extraction of derivatized and non-derivatized parabens from healthcare products.

This study was the first-ever attempt to apply MIL-68 (Ga) in developing an analytical method. The method extracts and preconcentrates some parabens from mouthwash and hydrating gel samples. The variable extraction parameters were optimized, and the figures of merit were documented. Avogadro software was used besides discussing intermolecular interactions to clarify the absorption process. ComplexGAPI software was also exploited to assess the greenness of the method. After the derivatization of the parabens using acetic anhydride in the presence of sodium carbonate, sodium chloride was added to the solution and vortexed to dissolve. A few milligrams of MIL-68 (Ga) were added into the solution and vortexed. Centrifugation separated the analyte-loaded absorbent, which was treated with mL volume of methanol through vortexing for desorption aim. A few microliters of 1,2-dibromoethane were merged with the methanolic phase and injected into a sodium chloride solution. One microliter of the extracted phase was injected into a gas chromatograph equipped with a flame ionization detector. High enrichment factors (200-330), reasonable extraction recoveries (40-66%), wide linear ranges (265-30,000 µg L-1), and appreciable coefficients of determination (0.996-0.999) were documented. The applicability of dispersive solid phase extraction for extracting polar analytes, imposing no additional step for performing derivatization, the capability of MIL-68 (Ga) for the absorption of both derivatized and non-derivatized parabens, the use of only 10 mg absorbent, and one-pot synthesis besides no high temperature or long reaction time in the sorbent provision are the highlights of the method.

Simultaneous derivatization and extraction of amphetamine and methamphetamine using dispersive liquid-liquid microextraction prior to their analysis using GC-FID in creatine supplements.

This study was focused on the development of a sensitive, reliable, and efficient extraction procedure for the determination of amphetamine and methamphetamine utilized in the adulteration of creatine sports supplements. The separation and detection of the analytes were conducted using the gas chromatography-flame ionization detection method. In this study, the analytes were extracted from a supplement powder into a proper solvent by sonication. Then, the extract was mixed with butyl chloroformate to obtain their butylated derivatives and then concentrated by a dispersive liquid-liquid microextraction procedure. The method was performed in a short time. Under optimized extraction conditions, a linear range of 2.01-500 ng g-1 was obtained by a coefficient of determination ≥0.996. Low detection (0.22 ng g-1 and 0.61 ng g-1 for amphetamine and methamphetamine, respectively) and quantification (0.73 ng g-1 and 2.01 ng g-1 for amphetamine and methamphetamine, respectively) limits, good precision (relative standard deviations ≤8.2%), and high extraction recoveries (79% and 86% for amphetamine and methamphetamine, respectively) were achieved. The usefulness of the method in the analysis of the target compounds was confirmed by studying the matrix effect and analysis of the analytes in different real samples.

Bimetallic metal-organic framework as an efficient sorbent for the extraction of tacrolimus and cyclosporine from plasma before HPLC-MS/MS analysis.

This study investigated the application of pores-size protocols into metal-organic frameworks that can lead to improved adsorption capacity of sorbents. A selective, fast, and sensitive analytical procedure based on dispersive solid phase extraction using a bimetallic metal organic framework named ZrZnMOF coupled with high-performance liquid chromatography-tandem mass spectrometry was established for the simultaneous quantification of tacrolimus and cyclosporine in plasma. The effects of several parameters, such as the dosage of sorbent, separation and elution times, volume and type of elution solvent, were investigated. Under optimal conditions, high extraction recovery (70 and 89 for tacrolimus and cyclosporine, respectively), low limits of detection (0.15 and 0.31 µg L-1 for tacrolimus and cyclosporine, respectively) and quantification (1.0 and 0.51 µg L-1 for tacrolimus and cyclosporine, respectively) wide linearity (1.0-1000 and 0.51-500 µg L-1 for tacrolimus and cyclosporine, respectively), and acceptable repeatability (n = 5, relative standard deviation less than 5.6 %) were attained. The validated method was successfully applied to quantify tacrolimus and cyclosporine A in plasma samples obtained from different volunteers.

Surfactant-enhanced air-agitation liquid-liquid microextraction of polycyclic aromatic hydrocarbons from edible oil using magnetic deep eutectic solvent prior to HPLC determination.

Herein, an air-agitation liquid-liquid microextraction procedure was developed for the extraction of several polycyclic aromatic hydrocarbons from edible oil samples. In this study, the extraction procedure was achieved using a new magnetic deep eutectic solvent as the extraction solvent, in which there was no need for centrifugation. To enhance the rate of extraction of the analytes from the samples, the method was promoted by the use of surfactant addition. The extracted analytes were determined by high-performance liquid chromatography with a diode array detector. The influence of various parameters on the extraction efficiency was studied by response surface methodology using a central composite design. Under optimal conditions, linear calibration curves for the target analytes were achieved in the range of 0.43-250 ng g-1. The limits of detection and quantification were in the ranges of 0.04-0.13 and 0.13-0.43 ng g-1, respectively. The repeatability of the method in terms of intra- and inter-day precision was ≤4.7% and ≤6.7%, respectively. The extraction recovery of the method ranged from 75 to 88%. The obtained results show that the proposed method is efficient for the analysis of the target analytes in various oil samples without obvious matrix effects. Pyrene was found in olive oil at a concentration of 42 ng g-1.

NiGA MOF-based dispersive micro solid phase extraction coupled to temperature-assisted evaporation using low boiling point solvents for the extraction and preconcentration of butylated hydroxytoluene and some phthalate and adipate esters.

The first-ever attempt to apply nickel gallic acid metal-organic framework (NiGA MOF) in analytical method development was done in this research by the extraction of some plasticizers from aqueous media. The greenness of the method is owing to the use of gallic acid and nickel as safe reagents and water as the safest solvent. Low boiling point solvents were applied as desorption solvents that underwent temperature-assisted evaporation in the preconcentration step. Performing the evaporation using a low-temperature water bath for a short period of time streamlines the preconcentration section. Into the solution of interest enriched with sodium sulfate, a mg amount of NiGA MOF was added alongside vortexing to extract the analytes. Following centrifugation and discarding the supernatant, a µL level of diethyl ether was added onto the analyte-loaded NiGA MOF particles and vortexed. The analyte-enriched diethyl ether phase was transferred into a conical bottom glass test tube and located in a water bath set at the temperature of 35 °C under a laboratory hood. After the evaporation, a µL level of 1,2-dibromoethane was added to the test tube and vortexed to dissolve the analytes from the inner perimeter of the tube. One microliter of the organic phase was injected into a gas chromatograph equipped with flame ionization detection. Appreciable extraction recoveries (61-98%), high enrichment factors (305-490), low limits of detection (0.80-1.74 µg L-1) and quantification (2.64-5.74 µg L-1), and wide linear ranges (5.74-1000 µg L-1) were obtained at the optimum conditions.

Deep eutectic solvent-based modified quick, easy, cheap, effective, rugged, and safe extraction combined with solidification of floating organic droplet-dispersive liquid-liquid microextraction of some pesticides from canola oil followed by gas chromatography analysis.

Herein, a modified quick, easy, cheap, effective, rugged, and safe extraction was developed based on deep eutectic solvent for the extraction of several pesticides from canola oil samples. In this work, first, different sorbents were selected to remove the sample interferences, and the composition of the sorbents was optimized by simplex centroid design. The extracted analytes were more concentrated by solidification of floating deep eutectic solvent droplet-dispersive liquid-liquid microextraction. Low limits of detection (0.15-0.23 ng/g) and quantification (0.49-0.76 ng/g), high extraction recoveries (74-87%) and enrichment factors (224-263), and good repeatability (relative standard deviation equal to or less than 5.1 and 4.7% for intra- and interday precisions, respectively) were achieved using the proposed method. The suggested approach was used for the quantification of the analytes in different canola oil samples. Additionally, the effects of microwave irradiations exposure and sonication in decontamination of the samples were evaluated. In this method, there was no need for centrifugation and toxic solvents. Also, effective extraction of the analytes and minimizing interferences were achieved through the use of various sorbents.

Correction: Extraction of diazinon, haloxyfop-R-methyl, hexaconazole, diniconazole, and triticonazole in cheese samples using a ferrofluid based liquid phase extraction method prior to gas chromatography.

Correction for 'Extraction of diazinon, haloxyfop-R-methyl, hexaconazole, diniconazole, and triticonazole in cheese samples using a ferrofluid based liquid phase extraction method prior to gas chromatography' by Mahdi Rouhi et al., Anal. Methods, 2023, 15, 3043-3050, https://doi.org/10.1039/D3AY00160A.

Development of homogeneous dispersive solid phase extraction using albumin as a green sorbent and its combination with dispersive liquid-liquid microextraction: application in extraction of pesticides from fruit juices.

In the current study, salt- and pH-induced homogeneous dispersive solid phase extraction was developed using albumin as a sorbent for the extraction of some pesticides (diazinon, diniconazole, haloxyfop-R-methyl, and hexaconazole) from fruit juice of orange, pomegranate, and barberry. The extracted analytes were more concentrated by dispersive liquid-liquid microextraction to obtain high enrichment factors and low detection limits prior to their determination by gas chromatography-mass spectrometry. In the extraction process, human serum albumin solution was added to the sample solution at the µL-level and a homogeneous solution was obtained. Then, albumin was precipitated into the solution by adding an inorganic salt and decreasing the solution pH. By doing so, the analytes were adsorbed by albumin effectively due to their high adsorption capacity and large surface area. Following this, the pesticides were eluted from the albumin sorbent using an elution solvent and used in a dispersive liquid-liquid microextraction step. Under the optimum extraction conditions, low limits of detection and quantification were achieved in the ranges of 0.02-0.04 and 0.07-0.13 ng mL-1, respectively. The calibration curves were linear in the range of 0.13-250 ng mL-1. Relative standard deviation as a criterion for precision and the method repeatability were in the ranges of 2.9-4.2% for intra- (n = 5, C = 5 or 50 ng mL-1) and 3.2-5.2% for inter-day (n = 5, 50 ng mL-1) precisions. The enrichment factors and extraction recoveries were in the ranges of 390-460 and 78-92%, respectively. Finally, the offered procedure was applied for the analysis of pesticide residues in some fruit juice samples.

Development of deep eutectic solvent-based microwave-assisted extraction combined with temperature controlled ionic liquid-based liquid phase microextraction for extraction of aflatoxins from cheese samples.

In this study, for the first time, a deep eutectic solvent-based microwave-assisted extraction was combined with ionic liquid-based temperature controlled liquid phase microextraction for the extraction of several aflatoxins from cheese samples. Briefly, the analytes are extracted from cheese sample (3 g) into a mixture of 1.5 mL choline chloride:ethylene glycol deep eutectic solvent and 3.5 mL deionized water by exposing to microwave irradiations for 60 s at 180 W. The liquid phase was taken and mixed with 55 µL 1-hexyl-3-methylimidazolium hexafluorophosphate. By cooling the solution in the refrigerator centrifuge, a turbid state was obtained and the analytes were extracted into the ionic liquid droplets. The analytes were determined by high-performance liquid chromatography equipped with fluorescence detector. Low limits of detection (9-23 ng kg-1 ) and quantification (30-77 ng kg-1 ), high extraction recovery (66%-83%), acceptable enrichment factor (40-50), and good precision (relative standard deviations ≤ 5.2%) were obtained using the offered approach. These results reveal the high extraction capability of the method for determination of aflatoxins in the cheese samples. In this method, there was no need for organic solvents and it can be considered as green extraction method.

Introduction of a new and safe synthesis procedure for Ni-MOF-I in aqueous solution and its application for the extraction of some pesticides from different beverages.

For the first time, this research introduces an analytical application of Ni-MOF-I, which was used as an adsorbent in a dispersive micro solid phase extraction procedure followed by dispersive liquid-liquid microextraction for the extraction and preconcentration of seven pesticides from different fruit juices. Also, Ni-MOF-I was synthesized by a new and green method with many advantages over the previously published synthesis procedures. For example, effortless and green synthesis, no need for autoclaves and ovens, and elimination of organic solvent usage are the main highlights. The synthesized Ni-MOF-I was characterized by applying nitrogen adsorption/desorption, energy-dispersive X-ray, scanning electron microscopy, Fourier transform infrared spectrophotometry, and X-ray diffraction analyses. The studied pesticides were extracted and preconcentrated by the proposed method. Then, the extracted analytes in the sedimented organic phase were injected into a gas chromatography-flame ionization detector. Acceptable analytical results such as low limits of detection (0.15-0.60 µg L-1) and quantification (0.50-2.0 µg L-1), reasonable extraction recoveries (51-80%), high enrichment factors (255-400), satisfactory relative standard deviation values of 4.8-7.2% (intra-day precision, n = 6) and 5.3-7.5% (inter-day precision, n = 4), and wide linear ranges were obtained. The proposed method can be introduced as an effective analytical technique based on Ni-MOF-I for the analysis of different pesticides in fruit beverages.