Deep Eutectic Solvent-based Liquid-liquid Microextraction Research Articles

Spectrophotometric determination for green hydrophobic deep eutectic solvent-based microextraction of Brilliant Blue FCF (E133) from beverages

In this study, a simple, sensitive, and rapid method called green hydrophobic deep eutectic solvent-based liquid-liquid microextraction was developed to extract Brilliant Blue FCF dye from beverages. This method utilizes hydrophobic DES obtained by forming tetrabutylammonium bromide and 1-octanol in a 1:5 ratio as green extraction solvent. The transition of Brilliant Blue FCF to the DES phase occurred on its own, without the need for any reagents such as added salt or tetrahydrofuran. Several crucial factors were tried to get the best extraction efficiency, including species, DES volume and molar ratio, solution pH, ultrasonication, and centrifugation time. Under optimum conditions, extraction recoveries were achieved in the range of 95.1–101.3 % with the method developed for Brilliant Blue FCF. The detection and determination limits were observed to be 4.1 μg l-1 and 12.1 μg l-1, respectively. In addition, the relative standard deviation values for the method's accuracy were found to be 2.23 % and 3.48 % within and between days, respectively. It has been established that the developed method is highly environmentally friendly thanks to the application of the Analytical GREENness (AGREE) and Green Analytical Procedure Index (GAPI) tools. This study shows that DES applications can be carried out without the use of emulsifiers and dispersants by prioritizing the use of hydrophobic DES compounds as environmentally friendly and green extraction solvents in food samples.

Natural deep eutectic solvent for the simultaneous derivatization and microextraction of isoniazid from human plasma

BackgroundPersonalized medicine is a rapidly revolving field that offers new opportunities for tailoring disease treatment to individual patients. The main idea behind this approach is to carefully select safe and effective medications and treatment plant based on each patient's unique pharmacokinetic profile. Isoniazid is a first-line anti-tuberculosis drug that has interindividual variability in its metabolic processing, leading to significant differences in plasma concentrations among patients receiving equivalent doses. This variability necessitates the creation of individualized treatment regimens as part of personalized medicine to achieve more effective therapy. ResultsIn this work, a deep eutectic solvent-based liquid-liquid microextraction approach for the separation and determination of isoniazid in human plasma by high-performance liquid chromatography with UV–Vis detection was developed for the first time. A new natural deep eutectic solvent based on thymol as a hydrogen bond donor and 4-methoxybenzaldehyde as a hydrogen bond acceptor was proposed as the extraction solvent. The developed microextraction procedure assumed two simultaneous processes during the mixing of the sample and extraction solvent: the derivatization of the polar analyte in the presence of 4-methoxybenzaldehyde (component of the natural deep eutectic solvent) with the formation of a hydrophobic Schiff base (1); mass transfer of the Schiff base from the sample phase to the extraction solvent phase (2). Under optimal conditions, the limits of detection and quantification were 20 and 60 μg L−1, respectively. The RSD value was <10 %, the extraction recovery was 95 %. SignificanceIn this work, the possibility of isoniazid derivatization in the natural deep eutectic solvent phase with the formation of the Schiff base was presented for the first time. The approach provided the separation and preconcentration of polar isoniazid without the use of expensive derivatization agents and solid-phase extraction cartridges. The formation of the Schiff base was confirmed by mass spectrometry.

Development of CO2-switchable deep eutectic solvent-based liquid-liquid microextraction approach: Application in urinary excretion and tissue distribution studies

BackgroundPharmacokinetic studies are pivotal in drug development, focusing on absorption, distribution, and excretion of active compounds. Effective sample preparation methods play a crucial role in these studies. Traditional techniques like protein precipitation and liquid-liquid extraction often involve toxic solvents and are time-consuming. Recently, deep eutectic solvent (DES) has emerged as an eco-friendly alternative due to its high efficiency, low cost, and low toxicity. This study introduces a novel sample pretreatment method using CO2-switchable DES in liquid-liquid microextraction (LLME) to enhance speed, accuracy, and sensitivity in complex biological samples analysis. ResultsA liquid-liquid microextraction sample pretreatment method based on switchable DES combined with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established for the analysis of urine and tissue samples. The method was optimized through systematic investigation of key parameters, including DES type, volume, molar ratio, pH, vortex time, gas purge time, and salt addition. The resulting procedure exhibited satisfying linearity (r2 ≥ 0.9958), good precision (RSD ≤6.01 %), desirable recovery (52.44%–98.12 %) and matrix effect (86.22%–119.30 %), and the accuracy and precision of stability were within the ±15 % limit. The proven methods were further applied to urinary excretion study and tissue distribution study of Nelumbinis plumula (NP) extract. The results indicated that the total cumulative excretion of liensinine, isoliensinine and neferine in urine within 240 h was 4.96 %, 0.66 % and 0.44 %, respectively. The tissue distribution study showed that alkaloids mainly distribute in liver, kidney, and spleen. SignificanceThis research introduces a groundbreaking technique distinguished by its simplicity, speed, cost-effectiveness, and environmental friendliness. This approach, utilizing CO2-switchable DES as an extraction solvent for LLME, integrates deproteinization and removal of interfering molecules into a single step. This integration showcases its efficiency and convenience, demonstrating significant promise for various applications in the analysis of biological samples. Additionally, this study provides the first report on urinary excretion and tissue distribution of alkaloids from NP using a DES-LLME method. These findings offer valuable insights into the in vivo behavior of herbal medicine, enhancing understanding of pharmacological actions and facilitating clinical rational administration.

Highly efficient natural deep eutectic solvent-based liquid-liquid microextraction and inductively coupled plasma mass spectrometry for selective determination of inorganic selenium species in nut samples

A novel method involving the use of a hydrophobic natural deep eutectic solvent (NADES) in the vortex-assisted liquid-liquid microextraction technique based on the solidification of floating NADES for inorganic Se speciation analysis was developed. In this work, Se(IV) species was selectively complexed with ammonium pyrrolidinedithiocarbamate (APDC) and extracted with 50 μL of the NADES thymol:decanoic acid (THY:DA) (1:2) followed by fast phase separation upon freezing. Se(VI) species remaining in the aqueous phase was directly determined by inductively coupled plasma mass spectrometry (ICP-MS) while total inorganic Se concentration was determined by direct analysis of the acidic extract originated from the samples. Therefore, Se(IV) was calculated by subtracting the concentration of Se(VI) from the total inorganic Se concentration. Extraction conditions such as pH, sample volume, and type and volume of NADES were optimized, yielding an extraction efficiency of 99.6% for Se(IV). Limits of detection of 0.31 μg L−1 for Se(IV) and 0.24 μg L−1 for Se(VI), relative standard deviations of 3.5% for Se(IV) and 3.0% for Se(VI) and a linear range of 0.78–1000 μg L−1 were obtained. This work reports the first application of the NADES THY:DA (1:2) for the separation and determination of Se species in complex matrix samples such as almond, hazel nut, peanut, walnut, cashew nut, pecan nut and Brazil nut.

Deep eutectic solvent-based liquid-liquid microextraction for the HPLC-DAD analysis of bisphenol A in edible oils

Abstract A sample preparation method for the extraction of bisphenol A (BPA) from edible oils was established via simple, green, and sensitive deep eutectic solvent-based liquid-liquid microextraction (DES-LLME) before high-performance liquid chromatography (HPLC) with diode array detector (DAD). The deep eutectic solvent (DES) formed by tetrabutylammonium bromide (TBAB) and methanol was acted as the extractant. All parameters in the DES-LLME step, including the type and volume of extractants, the extraction time, and centrifugation time, were investigated and optimized. The application of hydrophilic DES in oils expands the selection of LLME extractants. Under the optimized conditions, the calibration curves in the range of 10–500 ng g−1 with a correlation coefficient of r > 0.999, and the detection limit was 0.8 ng g−1. The relative standard deviations of intra-day and inter-day repeatability were 4.3% and 6.2%, respectively, and the recoveries varied between 88.7% and 97.3%. This developed method was successfully employed for measuring BPA in 6 edible oil samples.

Vortex-Assisted Deep Eutectic Solvent-Based Liquid-Liquid Microextraction for the Analysis of Alkyl Gallates in Vegetable Oils

This study investigates the feasibility of using hydrophilic deep eutectic solvent (DES) as green and effective extractant for the extraction and preconcentration of alkyl gallates from vegetable oils. In a typical experiment, 120 αL of choline chloride:ethylene glycol DES was added to 1.0 g of oil sample which was previously diluted with 1 mL of n-hexane. The extraction was accelerated by vortex stirring of the two phases. At this stage, hydrogen bonding interactions between the phenyl hydroxyls of alkyl gallates and chloride anion of choline salt were likely the main forces driving the extraction. After extraction, the analytes in the DES phase were separated and determined by high-performance liquid chromatography with ultraviolet detection. The method detection limits for propyl gallate and octyl gallate were 2.1 and 4.6 αg kg-1, respectively. The precision of the method varied between 4.6-6.4% (intra-day) and 5.4-7.5% (inter-day). The recoveries (accuracies) obtained from spiked vegetable oil samples were in the range of 78-106%.