A gadolinium-based magnetic ionic liquid for supramolecular dispersive liquid–liquid microextraction followed by HPLC/UV for the determination of favipiravir in human plasma

Favipiravir is a potential antiviral medication that has been recently licensed for Covid-19 treatment. In this work, a gadolinium-based magnetic ionic liquid was prepared and used as an extractant in dispersive liquid–liquid microextraction (DLLME) of favipiravir in human plasma. The high enriching ability of DLLME allowed the determination of favipiravir in real samples using HPLC/UV with sufficient sensitivity. The effects of several variables on extraction efficiency were investigated, including type of extractant, amount of extractant, type of disperser and disperser volume. The maximum enrichment was attained using 50 mg of the Gd-magnetic ionic liquid (MIL) and 150 μl of tetrahydrofuran. The Gd-based MIL could form a supramolecular assembly in the presence of tetrahydrofuran, which enhanced the extraction efficiency of favipiravir. The developed method was validated according to US Food and Drug Administration bioanalytical method validation guidelines. The coefficient of determination was 0.9999, for a linear concentration range of 25 to 1.0 × 10⁵ ng/ml. The percentage recovery (accuracy) varied from 99.83 to 104.2%, with RSD values (precision) ranging from 4.07 to 11.84%. The total extraction time was about 12 min and the HPLC analysis time was 5 min. The method was simple, selective and sensitive for the determination of favipiravir in real human plasma.     

Microextraction of metal ions based on solidification of a floating drop: Basics and recent updates

This review provides a comprehensive evaluation of solidified floating organic drop microextraction (SFODME) procedures for metal ions preconcentration and their contributions to green chemistry. In this article we focused on the modifications that have been performed in the recent years to improve this environmentally friendly procedure. Among the most important of these modifications are the inclusion of ultrasonic energy, vortex and air agitation to enhance the dispersion process. The article also discussed new challenges in the procedure by using more ecofriendly solvents as extractants such as ionic liquids, deep eutectic. and supramolecular solvents. The coupling of SFODME with solid phase extraction increases selectivity and efficiency of the preconcentration procedure.     

Preparation and application of molecularly imprinted polymer solid‐phase microextraction fiber for the selective analysis of auxins in tobacco

As signal molecules, auxins play an important role in mediating plant growth. Due to serious interfering substances in plants, it is difficult to accurately detect auxins with traditional solid‐phase extraction methods. To improve the selectivity of sample pretreatment, a novel molecularly imprinted polymer ‐coated solid‐phase microextraction fiber, which could be coupled directly to high‐performance liquid chromatography, was prepared with indole acetic acid as template molecule for the selective extraction of auxins. The factors influencing the polymer formation, such as polymerization solvent, cross‐linker, and polymerization time, were investigated in detail to enhance the performance of indole acetic acid‐molecularly imprinted polymer coating. The morphological and chemical stability of this molecularly imprinted polymer‐coated fiber was characterized by scanning electron microscopy, infrared spectrometry, and thermal analysis. The extraction capacity of the molecularly imprinted polymer‐coated solid‐phase microextraction fiber was evaluated for the selective extraction of indole acetic acid and indole‐3‐pyruvic acid followed by high‐performance liquid chromatography analysis. The linear range for indole acetic acid and indole‐3‐pyruvic acid was 1–100 µg/L and their detection limit was 0.5 µg/L. The method was applied to the simultaneous determination of two auxins in two kinds of tobacco (Nicotiana tabacum L and Nicotiana rustica L) samples, with recoveries range from 82.1 to 120.6%.     

Combination of a modified quick,easy, cheap,efficient, rugged,and safe extraction method with a deep eutectic solvent based microwave‐assisted dispersive liquid–liquid microextraction: Application in extraction and preconcentration of multiclass pesticide residues in tomato samples

In this study, a new two–step extraction procedure based on the combination of a modified quick, easy, cheap, effective, rugged, and safe extraction method with a deep eutectic solvent based microwave‐assisted dispersive liquid–liquid microextraction has been developed for the extraction of multiclass pesticides in tomato samples before their analysis by gas chromatography with flame ionization detection. In this method, initially, an aliquot of tomato is crushed and diluted with deionized water. The mixture is then passed through a filter paper and its residue and aqueous phase are separated. Afterwards, acetonitrile as an extraction/disperser solvent is passed through the filter paper containing the refuse. The analytes remained in the refuse are extracted into the acetonitrile and then the obtained extract is mixed with a deep eutectic solvent. The obtained mixture is injected into the tomato juice and placed in a microwave oven for 15 s. Consequently, a cloudy state is formed and the extractant containing the analytes are sedimented at the bottom of the tube after centrifugation. Finally, 1 μL of the sedimented phase is removed and injected into the separation system. Under the optimum conditions, limits of detection and quantification were in the ranges of 0.42–0.74 and 1.4–2.5 ng/g, respectively.     

Photo-recycling the Sacrificial Electron Donor: Towards Sustainable Hydrogen Evolution in a Biphasic System

H₂ may be evolved biphasically using a polarised liquid|liquid interface, acting as a “proton pump”, in combination with organic soluble metallocenes as electron donors. Sustainable H₂ production requires methodologies to recycle the oxidised donor. Herein, the photo-recycling of decamethylferrocenium cations (DcMFc⁺) using aqueous core-shell semiconductor CdSe@CdS nanoparticles is presented. Negative polarisation of the liquid|liquid interface is required to extract DcMFc⁺ to the aqueous phase. This facilitates the efficient capture of electrons by DcMFc⁺ on the surface of the photo-excited CdSe@CdS nanoparticles, with hydrophobic DcMFc subsequently partitioning back to the organic phase and resetting the system. TiO₂ (P25) and CdSe semiconductor nanoparticles failed to recycle DcMFc⁺ due to their lower conduction band energy levels. During photo-recycling, CdS (on CdSe) may be self-oxidised and photo-corrode, instead of water acting as the hole scavenger.     

Enhanced headspace single drop microextraction method using deep eutectic solvent based magnetic bucky gels: Application to the determination of volatile aromatic hydrocarbons in water and urine samples

A facile headspace single drop microextraction method was developed using deep eutectic solvent‐based magnetic bucky gel as the extraction solvent for the first time. The hydrophobic magnetic bucky gel was formed by combining choline chloride/chlorophenol deep eutectic solvent and magnetic multiwalled carbon nanotube nanocomposite. Magnetic susceptibility, high viscosity, high sorbing ability, and tunable extractability of organic analytes are the desirable advantages of the prepared gel. Using a rod magnet as a suspensor in combination with the magnetic susceptibility of the prepared gel resulted in a highly stable droplet. This stable droplet eliminated the possibility of drop dislodgement. The prepared droplet made it possible to complete the extraction process in high temperatures and elevated agitation rates. Furthermore, using larger micro‐droplet volumes without any operational problems became possible. These facts resulted in shorter sample preparation time, higher sensitivity of the method, and lower detection limits. Under the optimized conditions, an enrichment factor of 520–587, limit of detection of 0.05–0.90 ng/mL, and linearity range of 0.2–2000 ng/mL (coefficient of determination = 0.9982–0.9995) were obtained. Relative standard deviations were < 10%. This method was successfully coupled with gas chromatography and used for the determination of benzene, toluene, ethylbenzene, and xylene isomers as harmful volatile organic compounds in water and urine samples.     

Rapid analysis of ultraviolet filters using dispersive liquid–liquid microextraction coupled to headspace gas chromatography and mass spectrometry

An ionic‐liquid‐based in situ dispersive liquid–liquid microextraction method coupled to headspace gas chromatography and mass spectrometry was developed for the rapid analysis of ultraviolet filters. The chemical structures of five ionic liquids were specifically designed to incorporate various functional groups for the favorable extraction of the target analytes. Extraction parameters including ionic liquid mass, molar ratio of ionic liquid to metathesis reagent, vortex time, ionic strength, pH, and total sample volume were studied and optimized. The effect of the headspace temperature and volume during the headspace sampling step was also evaluated to increase the sensitivity of the method. The optimized procedure is fast as it only required ∼7–10 min per extraction and allowed for multiple extractions to be performed simultaneously. In addition, the method exhibited high precision, good linearity, and low limits of detection for six ultraviolet filters in aqueous samples. The developed method was applied to both pool and lake water samples attaining acceptable relative recovery values.     

The kinetics of solid-phase microextraction measured for freshly added and aged hydrophobic compounds in two different soils

The proper choice of exposure times is critical if the freely dissolved concentration of chemicals in soil porewater is to be measured via the equilibrium solid-phase microextraction (SPME) as the times to equilibrium may vary depending on compound and soil properties. To reveal the effects of compound hydrophobicity, ageing and soil organic matter content on times to equilibrium, the SPME uptake was measured for five freshly added and aged hydrophobic organic compounds (phenanthrene, pyrene, lindane, p,p′-DDT and polychlorinated biphenyl (PCB) 153) in two contrasted soils (arable and forest soil). The tested compound-soil systems behaved kinetically different. Longer equilibrium times were observed with increasing hydrophobicity of compounds for aged compared to freshly added chemicals and for the forest soil in comparison to the arable soil. The calculated soil–porewater partition coefficients (i.e. sorption coefficients, K_d) of chemicals differed between soil types mainly due to various organic carbon (OC) contents as evidenced by the comparable K_oc values (i.e. K_d values normalised to soil OC content). Similar K_oc values were also found with the various extent of ageing, indicating that both the freshly added and aged compounds linearly partitioned between the soil organic matter and porewater. Our results suggest that, for a respective compound, variations in equilibrium times may be expected depending upon the residence time and the organic matter content in soil where the longest equilibrium times seems to appear for a combination of aged compounds and high organic soils. With regard to this outcome, the effect of the level of sample depletion due to the SPME extraction (LD_SPME) on equilibrium times was assessed. At LDs_SPME of up to 10%, equilibrium times increases linearly with LDs_SPME for p,p′-DDT and PCB 153. For phenanthrene (LD_SPME<10%), and for lindane and pyrene (1.2% < LD_SPME > 40%), no clear relationships were observed.     

A hydrophobic deep eutectic solvent‐based vortex‐assisted dispersive liquid–liquid microextraction combined with HPLC for the determination of nitrite in water and biological samples

In recent years, hydrophobic deep eutectic solvents as new generation of green solvents have attracted wide attention in liquid microextraction technique. In this article, four hydrophobic deep eutectic solvents composed of trioctylmethylammonium chloride and oleic acid were designed and prepared firstly. Combined with high‐performance liquid chromatography, these deep eutectic solvents were used as an extraction solvent in vortex‐assisted dispersive liquid–liquid microextraction for the selective enrichment and indirect determination of trace nitrite from real water and biological samples. This method is based on the diazotization‐coupling reaction of nitrite with p‐nitroaniline and diphenylamine in acidic water, and then the nitrite is quantified indirectly by measuring the obtained azo compounds. Some factors influencing the extraction efficiency, including the reaction and extraction conditions, were investigated. Under the optimized conditions, the method has a linear range of 1–300 μg/L with a correlation coefficient of 0.9924, limit of detection of 0.2 μg/L, limit of quantitation of 1 μg/L, intraday and interday relative standard deviations of 4.0 and 6.0%. This method was successfully applied in determination of nitrite from three environmental water and two biological samples with the recovery in the range of 90.5–115.2%. In addition, these results were well agreement with those obtained by the conventional Griess method.     

Novel and Rapid Deep Eutectic Solvent (DES) Homogeneous Liquid–Liquid Microextraction (HLLME) with Flame Atomic Absorption Spectrometry (FAAS) Detection for the Determination of Copper in Vegetables

Novel and fast deep eutectic solvent (DES)-based homogeneous liquid–liquid microextraction (HLLME) was applied for the extraction of copper from vegetable samples followed by flame atomic absorption spectrometry (FAAS). 1,5-diphenyl carbazone (DPC) was used as the chelating agent, and a DES was used as the extraction media. The utilized DES was based on benzyl triphenyl phosphonium bromide and ethylene glycol in a 1:8?mole ratio. The phase separation phenomenon was occurred by changing of sample temperature. Several factors influencing the extraction efficiency were investigated and optimized. Under the optimized conditions, an enhancement factor of 64 was obtained. The limit of detection, based on three signal-to-noise ratio, and limit of quantification were found to be 0.13?µg L^?1 and 5.0?µg L^?1, respectively. The calibration curve was linear within the range of 5.0–250?µg L^?1 with r² > 0.9957. Intra- and inter-day relative standard deviations (%) of 2.1% and 2.6% were obtained at the concentration of 25?µg L^?1. The accuracy of the proposed method was evaluated by analyzing a tomato leaves certified reference material and the results were to be in agreement with the certified value. Finally, the feasibility of the method was successfully confirmed by determination of copper in spinach, lettuce, broccoli, potato, carrot and parsley samples.