Hydrophilic Deep Eutectic Solvents Research Articles

Simultaneous extraction and deglycosylation for flavonoid analysis in Ginkgo biloba products using a two-phase deep eutectic solvent system

Total flavonoid content is one of the most important quality indicators of Ginkgo biloba leaves and its products, but the complex pretreatment procedures and the excessive use of organic solvents complicate the detection process. In response, an innovative and efficient two-phase deep eutectic solvent (DES) system—composed of an acidic hydrophilic DES and a hydrophobic DES—was developed to quantify flavonoids for quality control of G. biloba products. High-performance liquid chromatography (HPLC) detection conditions were optimized, followed by systematic screening and design of the two-phase DES system through adjustments to polarity, hydrophilicity, and acidity. Optimal pretreatment conditions were established through operating condition optimization. This approach enabled simultaneous extraction, deglycosylation, and enrichment of all flavonoids from G. biloba samples into the hydrophobic phase in a single step. Method validation showed strong linearity with a correlation coefficient (R2 > 0.9995). The detection (LOD) and quantification (LOQ) limits were between 0.35 and 0.37 mg/kg, and 0.92 and 0.96 mg/kg, respectively. The method also exhibited high sensitivity and accuracy, with a recovery rate of 96.91–100.39%. A greenness assessment with the ComplexGAPI tool confirmed this method’s eco-friendly advantages over conventional techniques, aligning well with green chemistry and economic principles. Ultimately, this technique effectively measured flavonoid levels in different G. biloba products. The method developed in this work not only enhances the efficiency of simultaneous extraction and deglycosylation by modifying the polarity, hydrophilicity, and acidity of the two-phase DES system, but also offers valuable insights for the advancement of environmentally friendly analysis technology for flavonoids.

Lipase Substrate Anchoring Dynamics Guided the Rational Design of Novel Deep Eutectic Solvents for Glucose Ester Synthesis.

Glucose esters, heralded for their emulsifying and solubilizing properties, have found increasing application in food, pharmaceutical, and cosmetic sectors. However, the environmental impact of chemical synthesis and the problem of enzyme inactivation in enzymatic synthesis have hindered their application. To this end, deep eutectic solvents (DESs) with stabilized enzyme activity and better solubility properties are considered a promising solution. In the study, 12 kinds of hydrophilic DESs and 22 kinds of hydrophobic DESs were screened, and we examined their efficiency in the synthesis of glucose esters. The results indicated that d,l-menthol-based DESs have excellent performance, with the highest yield of 92.85%. The molecular dynamics simulations suggested that it can be attributed to DESs changing the size of substrate binding pocket, which in turn affects the substrate anchoring ability and the catalytic efficiency of lipase. To further evaluate the effects of the solvent on the substrate anchoring ability of enzymes, a novel strategy, namely, substrate anchoring index, which is based on the stability of the tetrahedral intermediate, was proposed and used for the designing of more efficient DESs. Fortunately, novel DESs based on cyclohexanone (menthol analogues) were successfully developed with a yield of 98.85%.

Exploring Deep Eutectic Solvents as Pharmaceutical Excipients: Enhancing the Solubility of Ibuprofen and Mefenamic Acid.

Objectives: The study explores the potential of various deep eutectic solvents (DESs) to serve as drug delivery systems and pharmaceutical excipients. The research focuses on two primary objectives: evaluating the ability of the selected DES systems to enhance the solubility of two poorly water-soluble model drugs (IBU and MFA), and evaluating their physicochemical properties, including density, viscosity, flow behavior, surface tension, thermal stability, and water dilution effects, to determine their suitability for pharmaceutical applications. Methods: A range of DES systems containing pharmaceutically acceptable constituents was explored, encompassing organic acid-based, sugar- and sugar alcohol-based, and hydrophobic systems, as well as menthol (MNT)-based DES systems with common pharmaceutical excipients. MNT-based DESs exhibited the most significant solubility enhancements. Results: IBU solubility reached 379.69 mg/g in MNT: PEG 400 (1:1) and 356.3 mg/g in MNT:oleic acid (1:1), while MFA solubility peaked at 17.07 mg/g in MNT:Miglyol 812®N (1:1). In contrast, solubility in hydrophilic DES systems was significantly lower, with choline chloride: glycerol (1:2) and arginine: glycolic acid (1:8) showing the best results. While demonstrating lower solubility compared to the MNT-based systems, sugar-based DESs exhibited increased tunability via water and glycerol addition both in terms of solubility and physicochemical properties, such as viscosity and surface tension. Conclusions: Our study introduces novel DES systems, expanding the repertoire of pharmaceutically acceptable DES formulations and opening new avenues for the rational design of tailored solvent systems to overcome solubility challenges and enhance drug delivery.

Formulation and Characterization of Deep Eutectic Solvents and Potential Application in Recycling Packaging Laminates.

Deep Eutectic Solvents (DESs) show promising abilities for the delamination of multilayer packaging films that are used in food packaging and in pharmaceutical blister packs. Due to the complexity of their structure, the recycling of such materials is a challenging task, leading to the easiest or cheapest disposal option of either landfill or incineration. Towards the development of 'green' solvents for efficient waste management and recycling, this research focuses on the preparation of a range of hydrophobic and hydrophilic DESs based on carboxylic acids in combination with various naturally derived aliphatic and aromatic organic compounds as well as amino acids. Chemical and physical characterization of the solvents was undertaken using differential scanning calorimetry, rheometry, and density measurements for the determination of their properties. Subsequently, batches of solvent were tested against different types of consumer packaging to evaluate the ability of the DES to delaminate these structures into their component materials. The laminate packaging waste products tested were Al/PE, PE/Al/PET, Al/PE/paper, and PVC/PE/Al. Separated films were collected and studied to further examine the effect of solvent delamination on the materials. Depending on the DES formulation, the results showed either partial or full delamination of one or more of the packaging materials, albeit there were challenges for certain solvent systems in the context of delivering a broad delamination efficiency. Variables including temperature, agitation rate, mixing time, and solvent ratios were investigated via a Design of Experiments process to assess the effects of these parameters on the delamination outcome. The results showed that the DESs presented in this research can offer an efficient, low-energy, affordable, and green option for the delamination of laminate packaging materials.

A novel temperature-responsive biphasic deep eutectic solvent-based solvent system: Integrated efficient extraction, enrichment and recovery of phytochemicals

The current large-scale use of organic and some toxic reagents hinders the development of plant secondary metabolite extraction and processing industry. Here, a biphasic temperature-responsive solvent system consisting of hydrophilic deep eutectic solvent (choline chloride: levulinic acid) and fatty acid-based hydrophobic deep eutectic solvent is developed. Some characteristics of this intelligent solvent system, including hundreds of synthesis ratios and corresponding switching temperatures, phase ratios, etc., have been comprehensively determined. Subsequently, it is applied to different plant matrices. The extraction efficiencies ranged from 1.006 to 6.807 times higher than those of conventional organic reagents, with separation efficiencies ranging from 60.7 % to 100 %, besides the fact that the hydrophilic components are almost entirely distributed in the lower phase. The recovery of targeted phytochemicals achieves satisfactory results during the simultaneous extraction and enrichment process. Mechanisms of switching, extraction, and enrichment have been elucidated to a certain extent from the point of view of chemical computational simulations. Overall, this new green solvent system is universal and can be applied to a wide range of phytochemicals extraction and separation from plants in a one-pot operating unit. Also, it is almost the greenest of the temperature-responsive solvents studied so far and has superior application prospects.

A recoverable hydrophilic deep eutectic solvent for efficient extraction of polyphenolic compounds from raspberry root.

Green deep eutectic solvents (DESs) are widely used to extract bioactive components from plant biomass; however, hydrophilic DES and bioactive component isolation methods have not been developed. In this study, we synthesized hydrophilic DES (CL-CA-DES) using citric acid and choline chloride. We combined this with environmentally friendly anion- and cation-exchange resin column chromatographic isolation methods. This approach extracted and isolated four polyphenolic compounds (catechins, epicatechins, procyanidin B1, and procyanidin B2) from raspberry root and efficiently recovered the hydrophilic DES. CL-CA-DES extracted significantly higher contents of catechin and procyanidin B2 from raspberry root compared to other solvents. It also extracted substantially higher contents of epicatechin compared to butyl alcohol, 70% ethanol, and water, but there was no significant difference when compared with acetone and ethyl acetate. Additionally, CL-CA-DES extracted significantly higher contents of procyanidin B1 compared to butyl alcohol, water, and ethyl acetate, with no significant difference when compared with 70% ethanol and acetone. The isolation efficiency of the bioactive components in the raspberry root extract by anion- and cation-exchange resin column chromatography was higher than that of the organic solvent extraction and precipitation generation methods, and the method was effective in recovering CL-CA-DES with a recovery rate higher than 60%. In conclusion, this study developed a new method for the efficient recovery of hydrophilic CL-CA-DES, which can be used for isolating polyphenolic compounds from raspberry root.

A Novel DLLME Method Involving a Solidifying Hydrophobic Deep Eutectic Solvent Using Hydrophilic Deep Eutectic Solvent as the Dispersant for the Determination of Polychlorinated Biphenyls in Water Samples.

This paper presents a novel dispersive liquid-liquid microextraction (DLLME) method that employs solidified hydrophobic deep eutectic solvent (DES) with hydrophilic DES acting as the dispersant. The aim is to enrich polychlorinated biphenyls (PCBs) from water samples for subsequent determination by gas chromatography-mass spectrometry. The effects of both the hydrophobic DES as the extractant and the hydrophilic DES as the dispersant were thoroughly investigated. Optimization of the key factors influencing extraction efficiency was performed, and the method was subsequently validated. Specifically, a hydrophobic DES called DES2, prepared by combining thymol and decanoic acid in a molar ratio of 3:2, was selected as the extraction solvent. Meanwhile, a hydrophilic DES named DES6, prepared from choline chloride and acetic acid in a molar ratio of 1:2, was chosen as a dispersant. Under the optimal extraction conditions, the developed method exhibited excellent linearity over the concentration range of 0.01-5.0 µg/L, low limits of detection ranging from 3.0 to 5.1 ng/L, relative standard deviations less than 4.1%, and enrichment factors between 182 and 204 for PCBs. Finally, the effectiveness of the developed method was successfully demonstrated through residue determination of PCBs in water samples.

Synthesis and Properties of Hydrophilic and Hydrophobic Deep Eutectic Solvents via Heating-Stirring and Ultrasound.

Deep eutectic solvents (DESs) have emerged as a greener alternative to other more polluting traditional solvents and have attracted a lot of interest in the last two decades. The DESs are less toxic dissolvents and have a lower environmental footprint. This paper presents an alternative synthesis method to the classical heating-stirring method. The ultrasound method is one of the most promising synthesis methods for DESs in terms of yield and energy efficiency. Therefore, the ultrasound synthesis method was studied to obtain hydrophobic (Aliquat 336:L-Menthol (3:7); Lidocaine:Decanoic acid (1:2)) and hydrophilic DESs based on choline chloride, urea, ethylene glycol and oxalic acid. The physical characterization of DESs via comparison of Fourier transform infrared (FTIR) spectra showed no difference between the DESs obtained by heating-stirring and ultrasound synthesis methods. The study and comparison of all the prepared DESs were carried out via nuclear magnetic resonance spectroscopy (NMR). The density and viscosity properties of DESs were evaluated. The density values were similar for both synthesis methods. However, differences in viscosity values were detected due to the presence of some water in hygroscopic DESs.

A new green approach to synthesizing MIP-202@porous silica microspheres for positional isomer/enantiomer/hydrophilic separation

Metal-organic frameworks (MOFs) with superior physicochemical properties have great potential for applications in chromatographic separation. However, currently popular methods for the synthesis of MOF-based silica composite materials usually require the use of harmful organic solvents and long-term high-temperature sealing reactions. In order to respond to the needs of green chromatography, it is urgent to develop a new green organic-solvent-free strategy for the synthesis of MOF@SiO2 composites. MIP-202 is a zirconium-MOF constructed from zirconium ion and L-aspartic acid, which features green synthesis as well as good hydrolytic stability and chemical stability. In this paper, SiO2-NH2 was first prepared in a hydrophilic deep eutectic solvent, and then an amino acid-based MOF material (MIP-202) was modified on the surface of the SiO2-NH2 in an aqueous solution to obtain a MIP-202@SiO2 composite material. The multi-mode separation performance of MIP-202@SiO2 as a promising liquid chromatographic stationary phase was particularly evaluated and the separation mechanisms were discussed. The MIP-202@SiO2 column exhibited excellent separation ability for aromatic positional isomers. In addition, chiral enantiomers and hydrophilic analytes were also satisfactorily detected and separated. This work provides a new approach for the facile synthesis of MOF-based liquid chromatographic separation material by using green deep eutectic solvent and water as the reaction media.

The usability of green deep eutectic solvents in hollow fiber Liquid-Phase microextraction for the simultaneous extraction of analytes of different Natures: A comprehensive study

In the current study, a wide range of deep eutectic solvents (DESs) with different properties (hydrophilic, hydrophobic, ionic, and nonionic) were prepared in the initial phase. Subsequently, an assessment was conducted to evaluate some characteristics of the produced DESs, including their stability at room temperature and their capacity to extract three distinct types of analytes (anionic, cationic, and non-ionic) simultaneously through hollow fiber-liquid phase microextraction (HF-LPME) technique. To carry out the extraction procedure, the prepared DESs were inserted into the pores (as supported liquid membrane (SLM)) and lumen of hollow fiber membrane (HF) to apply two-phase and three-phase HF-LPME techniques. After a thorough evaluation, the three-phase HF-LPME technique (HF(3)-LPME) was chosen by using a mixture of menthol/TBAB-based hydrophobic DES (DES-35) as SLM and the mixture of malic acid/citric acid/water-based hydrophilic DES (DES-2) as an extraction solvent in the lumen of HF. All factors affecting the extraction recovery (including pH, extraction time, extraction temperature, stirring speed, and salt effect) were optimized utilizing the one-variable-at-a-time (OVAT) methodology. After applying the extraction procedure, all extracted samples were analyzed using the UV–Vis spectrometer and results were recorded at different wavelengths including 655 nm for Methylene blue, 550 nm for Amaranth, and 375 nm for Quercetin. The calibration graphs showed linearity in the range of 20.0–1500 µg/L, with a limit of detection of 6.2–15.1 µg/L and correlation coefficients higher than 0.9913 for the studied analytes. Moreover, the intra-day RSD, inter-day RSD, preconcentration factor (PF), enrichment factors (EF), and extraction recoveries (ER%) were obtained in the range of 3.1–4.8, 3.8–6.7, 125, 102.9–111.4, and 82.3–89.1 %, respectively. The use of the selected DES in the HF-LPME methodology resulted in an ecologically friendly strategy, as evidenced by the use of green metrics from the SPMS tool. The proposed strategy is also considered environmentally friendly due to its use of minimal solvents, waste reduction, and low energy consumption. The proposed technique effectively and simultaneously extractedmethylene blue, amaranth, and quercetin analytes in different real samples.

Development of magnetic matrix solid phase dispersion method for the extraction of crystal violet and rhodamine B from sediments based on magnetic ZIF-8 and a deep eutectic solvent

A magnetic matrix solid phase dispersion (MSPD) method based on magnetic ZIF-8 (SDS@MZIF-8) and a deep eutectic solvent was developed and used to the extraction of crystal violet and rhodamine B in lake sediments. SDS@MZIF-8 was prepared and used as the extraction sorbent and dispersant in MSPD. The magnetic property of MZIF-8 facilitated the recovery of the extraction sorbent after the blending step. Hydrophilic deep eutectic solvents were prepared and used as efficient green dispersing solvents in MSPD. The use of magnetic sorbent in MSPD is simple and fast, eliminating some additional steps commonly used in the classical MSPD and shortening the extraction time. The parameters influencing the extraction efficiency were investigated and optimized. Under the optimized conditions, the intra- and inter-day relative standard deviations were less than 4.9 %. The linearity ranged from 2-400 µg g−1 with coefficients of determination higher than 0.9943. The detection and quantification limits of RB and CV varied between 0.3–0.5 μg g−1 and 1.0–1.8 μg g−1, respectively. Finally, the developed method was applied to the analysis of RB and CV in the sediment samples. The recoveries ranged from 93.2 to 107.3 % and the relative standard deviations ranged from 0.8 to 4.9 %. The results suggest a high potential use of the proposed method to determine the organic pollutants in solid samples. Compared with the conventional MSPD extraction technique, the developed method considerably reduced the sample and solvent consumption, offering important environmental benefits.

Simultaneous and selective extraction of different polarity bioactive substances from Ligustri Lucidi Fructus based on a designable biphasic deep eutectic solvent

Most plants contain hydrophilic and hydrophobic bioactive compounds, traditional organic solvent extraction processes can often only extract one of the components, resulting in a cumbersome process and a waste of resources. To make full use of the active resources in Ligustri Lucidi Fructus, a biphasic deep eutectic solvent (DES) system was established. By adjusting the polarity, oleanolic acid (OA) and ursolic acid (UA) were enriched in the hydrophobic phase, and flavonoids and procyanidine (PAC) in the hydrophilic phase, respectively. Established with a 1:1 vol ratio of hydrophobic DES MIA (DL-menthol: isopropyl alcohol, 1:1) and hydrophilic DES CBE (choline chloride: betaine: ethylene glycol, 1:1:2). The biphasic system had the highest extraction rate. The response surface method was used to further optimize the extraction conditions. After optimization, the extraction yields of OA and UA were 10.96 ± 0.35 mg/g and 11.67 ± 0.26 mg/g in the MIA phase, and the extracted yields of flavonoids and PAC in the CBE phase were 77.38 ± 0.62 mg/g and 5.20 ± 0.03 mg/g, respectively. Compared with the conventional single-phase extraction with organic solvents, the biphasic system provided higher extraction rate and selectivity and the extracts showed stronger antioxidant activity. Compared to the single-phase extraction utilizing conventional organic solvents, the results demonstrated significant improvement. Consequently, by adjusting the polarity of the biphasic DES system, this study supplies an argument for increasing the extraction efficiency of plant resources. This expands the application of the biphasic DES system and contributes to the high-value exploitation of natural commodities.

Switchable hydrophilicity solvents incorporating hydrophilic deep eutectic solvents: A sustainable alternative for oil-based drilling cuttings washing

Oil-based drilling cuttings (OBDC) contaminated by total petroleum hydrocarbons (TPH) causes detrimental environmental consequences. Solvents washing is capable of separating TPH from OBDC efficiently, but their high volatility and toxicity limit the large-scale application. Here a sustainable OBDC washing strategy is developed by using a heterogeneous mixture (SHSs&HDESs) which is consisted of switchable hydrophilicity solvents (SHSs) and hydrophilic deep eutectic solvents (HDESs). N, N-Dimethylcyclohexylamine (DMCHA) and CHEG (choline chloride/ethylene glycol) is respectively selected as the optimum SHSs and HDESs, considering the miscibility with TPH and recovery capacity. The advantage of the sustainable washing strategy originates from the synergistic effect for enhancing forward the TPH removal efficiency, where DMCHA plays the role on TPH extraction and dilution, and CHEG promotes the detachment of TPH from sands surfaces. Based on the Box-Behnken experimental design of response surface method, the TPH removal efficiency reaches a maximum value of 96.02 % at the derived optimal washing conditions, including 32 °C, 19.81 mL DMCHA, and 9.62 mL CHEG. TPH can be separated from DMCHA by CO2-induced hydrophobicity transformation, DMCHA is recovered upon N2/65 °C afterwards, and CHEG is recovered by liquid separation. The recovered SHSs&HDESs heterogeneous mixture shows good reusability in subsequent OBDC washing processes. Our findings offer a sustainable approach for efficiently OBDC washing, which is expected to overcome the inherent defects of solvents washing methods.

Critical overview on the use of hydrophobic (deep) eutectic solvents for the extraction of organic pollutants in complex matrices

During the last decades, many efforts have been devoted to the adaptation of sample preparation techniques and methods to the principles of Green Analytical Chemistry. Among them, this article review focusses on those aimed to green the solvents involved in sample treatment. Research in this field started in the late 1990s with the synthesis of room temperature ionic liquids, which were later replaced by the deep eutectic solvents (DESs). During the last years, a subclass of DESs, the so-called hydrophobic deep eutectic solvents (HDESs) have attracted attention. HDESs have contributed to circumventing some of the limitations of early-synthesised hydrophilic DESs regarding the cost of raw materials, the simplicity of synthesis, and the biocompatibility and, apparently, the biodegradability of the mixtures. In addition, these mixtures allowed the treatment of aqueous samples and the extraction of non-polar analytes.This article discusses fundamental aspects regarding the nomenclature used concerning HDESs, summarises the main physicochemical properties of these mixtures, and through discussion of key application studies, describes current progress in the use of these green solvents for the extraction of trace organic contaminants from a variety of matrices. Remaining gaps and possible lines of future development in this emerging, active and attractive research area are also identified and critically discussed.

Experimental density and volumetric properties of DESs based on tetrabutylammonium bromide and used for effective extraction of naphthol green B and malachite green

AbstractBACKGROUNDTo improve the quality of wastewater and thereby to meet the standards as per environmental production agency in US and UK. In the present work, Malachite green (MG) and Naphthol Green B (NGB) has been taken as model dyes in wastewater. Solvent extraction process was carried out using deep eutectic solvents (DESs) as an alternative solvent for organic and ionic liquids.RESULTSThe possible molecular interaction between DESs and selective dyes in water were analyzed and discussed in details using volumetric properties including excess molar volume , partial molar volume , excess partial molar volume , apparent molar volume , isobaric thermal expansion () and excess isobaric thermal expansion (αE). Further, the extraction of selective dyes was conducted and characterized in terms of extraction efficiency (η), effect of temperature on extraction efficiency, effect of shaking time on extraction efficiency, effect of concentration on extraction efficiency, effect of HBD on extraction efficiency, distribution coefficient (D). Finally, the thermodynamic extraction feasibility was analysed by means of Gibbs free energy , change in enthalpy , and change in entropy .CONCLUSIONThere is possible molecular interaction between hydrophilic DESs and NGB/MG in water at molecular level. 96% of extraction efficiency was obtained for NGB using hydrophobic DESs like {[TBAB][DA]} and {[TBAB][OA]} whereas {[TBAB][DA]} and {[TBAB][OA]} gave above 72% removal efficiency of MG. Finally the thermodynamic feasibility of extraction process was analyzed and discussed. © 2023 Society of Chemical Industry (SCI).

Synthesis of tunable hydrophilic deep eutectic solvent for the extraction of antioxidants from Salvia officinalis L.

The leaves of Salvia officinalis L., a plant known for its high antioxidant content, were selected as the focus of this research. This research aimed to evaluate the antioxidant activity of sage leaves extract by varying the hydrophilic deep eutectic solvents (DESs) compositions and molar ratios. The hydrophilic DESs were synthesized using the heating method with diverse combinations of DES, including lactic acid (LA), oxalic acid (OA), succinic acid (SA), and ethylene glycol (EG) as hydrogen bond donors (HBDs) and choline chloride (ChCl) as the sole hydrogen bond acceptor (HBA) with varied molar ratios of HBA to HBD (1:1, 1:2, and 2:1). The antioxidants were extracted using ultrasound-assisted extraction method at 70°C of extraction temperature, 30 mins of sonication time, and 1:30 g/mL of solid-solvent ratio. The DES extraction efficiency was evaluated based on the antioxidant scavenging abilities measured by α, α-diphenyl-β-picrylhydrazyl (DPPH) free radical scavenging assay. The results revealed that the ChCl-OA showed the highest antioxidant activity (67.660 μg/mL), followed by ChCl-EG (52.327 μg/mL) and ChCl-LA (33.116 μg/mL) with molar ratios of 1:1, 1:2 and 1:2, respectively. As conclusion, ChCl-OA with molar ratio of 1:1 exhibited the highest extraction efficiency (77.259%) as compared to the other DES combinations using 70% of methanol (v/v).

Hydrophilic deep eutectic solvent based microextraction procedure for the determination of four paraben preservatives in vitamin D for babies: A green approach

In this study, an easily available, sensitive, and fast hydrophilic deep eutectic solvent-liquid phase microextraction method developed using deep eutectic solvent (DES) as a green solvent for the determination and microextraction of paraben (methyl, ethyl, propyl, and butyl) preservatives in vitamin D for babies. The highest yield for extraction recovery was obtained using DES consisting of a 1:4 M ratio of choline chloride and acetic acid. Moreover, various optimization parameters such as DES volume, DES type, sample volume, and centrifugation time were investigated in order to develop a real sample specific microextraction method. Relative standard deviation values were 0.92%-2.87%, the detection limit was 0.194–0.254 µg/mL, and extraction recovery values were between 87.40% and 102.98%. The method developed in this study was successfully applied to 5 different babies in vitamin D for babies obtained from pharmacies for the determination of methyl, ethyl, propyl, and butylparaben. As far as we know, it is the first study conducted both in terms of the determination of paraben preservatives in vitamin D for babies and in terms of the fact that DES used in this study is used for the first time in vitamin D for babies.

Hydrophilic and hydrophobic deep eutectic solvent-based extraction to determine parathion in cereals by digital image colorimetry integrated with smartphones

To determine parathion in cereals, hydrophilic and hydrophobic deep eutectic solvents (DESs) were used by digital image colorimetry with smartphones. In the solid-liquid extraction part, hydrophilic DESs were used as extractants to extract parathion from cereals. In the liquid-liquid microextraction part, hydrophobic DESs dissociated into terpineol and tetrabutylammonium bromide in situ. The dissociated hydrophilic tetrabutylammonium ions reacted with parathion extracted in hydrophilic DESs under alkaline conditions to produce a yellow product, which was extracted and concentrated by dispersed organic phase terpinol. Digital image colorimetry integrated with the use of a smartphone was used for quantitative analysis. The limit of detection and quantification were 0.003 mg kg−1 and 0.01 mg kg−1, respectively. The recoveries for parathion were 94.8–106.2% with a relative standard deviation less than 3.6%. The proposed method was applied to analyze parathion in cereal samples: the method has the potential to be applied to pesticide residue analysis in food products.

Multielemental analysis of oils and animal fat by using deep eutectic solvents assisted by an aerosol phase extraction procedure

In the present study, thirteen elements (Ag, Al, Ba, Cd, Cr, Cu, Fe, K, Li, Mg, Mn, Ni, Pb) have been extracted from used cooking oils, olive oils and animal fat. Either inductively coupled plasma optical emission spectrometry (ICP-OES) or tandem mass spectrometry (ICP-MS/MS) have been chosen as detection techniques. Due to the difficulty of directly introducing highly viscous organic samples into the spectrometer, a fast dispersive liquid – liquid aerosol phase extraction (DLLAPE) method has been selected to isolate the analytes from the sample matrix. The DLLAPE is based on the generation of an aerosol from the extracting phase with the help of a pneumatic nebulizer. This high velocity aerosol impacts and penetrates in the liquid sample. Consequently, the liquid – liquid exchange surface area becomes high, thus leading to high extraction yields. A hydrophilic deep eutectic solvent (DES) consisting of choline chloride and ethylene glycol (1:2 mass ratio) has been selected as the extracting solvent. Prior to undertaking the experiments, the extraction method has been evaluated in terms of precision under suitable conditions. In comparison with conventional methods based on sample digestion, sample dilution and shot analysis or extraction assisted by vortex agitation, the DLLAPE shows several advantages, because it is faster, and it provides lower limits of detection than the reference methodologies. The procedural limits of quantification for the determined elements with the DLLAPE in ICP-OES were 0.046 (Ag), 0.396 (Al), 0.013 (Cd), 0.033 (Cr), 0.040 (Cu), 0.20 (Fe), 0.026 (K), 0.026 (Li), 0.33 (Mg), 0.013 (Mn), 2.64 (Ni) and 0.53 (Pb) mg kg−1. Meanwhile, pLOQ in ICP-MS/MS lowered by roughly one order of magnitude. The accuracy of the aerosol phase extraction method has been evaluated through the determination of the recoveries for four representative analytes (Ca, Cu, Mg and Ni) from spiked real samples. For these elements, recovery has taken values of (100 ± 20)%. Moreover, a comparison of the multielemental concentration obtained with conventional methods (c.a., sample dilution and shot ICP analysis and liquid-liquid extraction using a vortex agitator) against that measured with the DLLAPE has been carried out. Multiemelemental concentrations have been obtained for real samples and the found levels have been similar to those encountered in previously published works.

Evaluation of blood BTEX levels in fuel stations workers using vortex-assisted dispersive liquid-liquid microextraction based on deep eutectic solvent followed by gas chromatography flame-ionization detector

In this research, an eco-friendly method was established by vortex-assisted dispersive liquid-liquid microextraction based on the deep eutectic solvent (VA–DLLME–DES). The performance of the proposed method was demonstrated by the determination of benzene, toluene, ethylbenzene, and xylene (BTEX) in blood samples of fuel stations workers combined with GC–FID. The selected hydrophilic deep eutectic solvent is consisting of l-menthol and (1S)-(+)-camphor-10-sulfonic acid (CSA) at a 5:1 molar ratio as a green solvent instead of traditional toxic organic solvents. Under the optimal extraction conditions, the introduced method exhibited good linearity with a coefficient of determinations (r 2) higher than 0.9985 and an acceptable linear range of 0.03–80 µg l–1. Accordingly, the limits of detection (S/N = 3) and limits of quantification (S/N = 10) were in the ranges of 0.01–0.04 µg l−1 and 0.03–0.10 µg l−1, respectively. Blood BTEX levels of fuel stations workers were analyzed based on age, duration of working at the station, smokers or nonsmokers, and station type (CNG, gasoline, and dual-purpose). The results showed that there was no significant difference between blood BTEX levels in different age groups, while the concentration of BTEX compounds increases with the increase of working time in the station. Blood BTEX levels were much higher in smokers than in nonsmokers.