Deep Eutectic Research Articles

Formation of Self-Healing Granular Eutectogels through Jammed Carbopol Microgels in Supercooled Deep Eutectic Solvent.

Typically, gel-like materials consist of a polymer network structure in a solvent. In this work, a gel-like material is developed in a deep eutectic solvent (DES) without the presence of a polymer network, achieved simply by adding microgels. The DES is composed of choline chloride and citric acid and remains stably in a supercooled state at room temperature, exhibiting Newtonian fluid behavior with high viscosity. When the microgel (Carbopol) concentration exceeds 2 wt %, the DES undergoes a transition from a liquid to a soft gel state, characterized as a granular eutectogel. The soft gel characteristics of eutectogels exhibit a yield stress, and their storage moduli exceed the loss moduli. The yield stress and storage moduli are observed to increase with increasing microgel concentration. In contrast, the ion conductivity decreases with increasing microgel concentration but eventually levels off. Because the eutectogel can dissolve completely in excess water, it is a physical gel-like material, attributed to the densely packed structure of microgels in the supercooled DES. Due to the absence of networks, the granular eutectogel has the capability to self-heal simply by being pushed together after being cut into two pieces.

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.

Access to Substituted 1,1-Diarylalkanes by Friedel-Crafts Benzylations Mediated by FeCl3-based Deep Eutectic Solvents.

The development of new, more efficient Friedel-Crafts benzylation methodologies that provide access to 1,1-diarylalkanes is an important objective of interest for the production of pharmaceuticals and fine chemical products. In this regard, this study introduces a novel synthetic route to 1,1-diarylalkanes conducted in the Deep Eutectic Solvent (DES) 3 FeCl3 ⋅ 6 H2O/Gly, which serves as both a reaction medium and promoter. Under these conditions, Friedel-Crafts benzylations of various arenes bearing activating and deactivating ortho-/para-directing groups, can be performed using diverse benzylating reagents such as styrenes, alcohols, acetates, ethers, and chlorides. Importantly, highly electronically deactivated electrophiles, including those with CF3 and NO2 groups, are suitable substrates. This methodology provides a wide range of asymmetric 1,1-diarylalkanes (up to 132 examples) with generally good yields and high regioselectivities. The efficiency of this approach was demonstrated with the multigram-scale synthesis (10 mmol) of 1-phenyl-1-xylyl ethane (PXE), a liquid with great industrial applicability. Moreover, the Fe(III)-based DES could be reused for 20 consecutive cycles with no appreciable erosion of the yields.

An Innovative Vortex-Assisted Liquid-Liquid Microextraction Approach Using Deep Eutectic Solvent: Application for the Spectrofluorometric Determination of Rhodamine B in Water, Food and Cosmetic Samples.

A new green and highly sensitive method for the determination of rhodamine B (RhB) by deep eutectic solvent-based vortex-assisted liquid-liquid microextraction with fluorescence detection (DES-VALLME-FLD) was developed. The extraction efficiency of conventional solvents and different deep eutectic solvent (DES) systems composed of tetrabutylammonium bromide (TBAB) and an alcohol (hexanol, octanol, or decanol) in different ratios were compared. DFT calculations of intermolecular electrostatic and non-covalent interactions of the most stable RhB forms with DES and water explain the experimental DESs' extraction efficiency. Semiempirical PM7 computations were used to obtain Hansen solubility parameters, which supported the good solubility of the monocationic RhB form in selected DESs. The dependence of the linear calibration of microextraction into 100 µL DES was observed in the RhB calibration range from 0.2 to 10.0 µg L-1 with a correlation coefficient of R2 = 0.9991. The LOD value was calculated to be 0.023 µg L-1. The accuracy and precision of the proposed method were verified over two days with RSD values of 2.9 to 4.1% and recovery of 94.6 to 103.7%. The developed method was applied to the determination of RhB in real samples (tap water, energy drink, and lipstick).

Molecular Dynamic Simulation of the Interaction of a Deep Eutectic Solvent Based on Tetraethylammonium Bromide with La3+ in Acidic Media

In recent years, noticeable progress has been made in the development of alternative extraction systems characterized by greater sustainability. In this context, deep eutectic solvents (DESs) have emerged as a promising alternative to the conventional solvents commonly used in metal extraction. This work focuses on investigating the extraction of lanthanum in an aqueous solution of sulfuric acid using a deep eutectic solvent, employing molecular dynamics simulations (MD). The structural characteristics of the solvent and its interactions with the components of the aqueous solution are explored. In this study, tetraethylammonium bromide (TEABr) is combined with ethylene glycol (EG) to form a DES, in which sodium cyanide (NaCN) is subsequently solubilized. According to the results obtained from the MD simulation, the primary interactions in the DESs are established through hydrogen bonds between the bromine and the hydrogens of the methyl group of tetraethylammonium at 3.5 Å, as well as between the bromine and the hydrogens of the methylene group of ethylene glycol at 3.5 Å. Similarly, the main interactions between the binary DES and sodium cyanide occur through the hydrogens of the hydroxyl group of EG and the carbon of cyanide at 1.7 Å, and between the oxygen of the hydroxyl group of EG and the sodium at 2.5 Å. In the acidic solution, the primary interaction is highlighted between the lanthanum ion and the oxygen of the bisulfate at 2.8 Å. Additionally, it is observed that the interaction between the DES and the aqueous solution occurs between the lanthanum and the oxygen of the hydroxyl group of EG, as well as between the lanthanum and the carbon of cyanide at 4.4 Å. It is important to note that, when increasing the temperature from 25 to 80 °C, the interaction distance between the lanthanum and the carbon of cyanide decreases to 2.4 Å, suggesting a possible correlation with the increase in lanthanum extraction, as experimentally observed. Overall, this study underscores the importance of considering the fundamental structural interactions of the DES with the lanthanum acid solution, providing an essential theoretical basis for future experimental investigations.

Deep Eutectic Solvent as an Additive to Improve Enzymatic Hydrolysis of Polyethylene Terephthalate (PET)

Deep Eutectic Solvent as an Additive to Improve Enzymatic Hydrolysis of Polyethylene Terephthalate (PET)

Glycol-based Alkaline Deep Eutectic Solvents for “Lignin-First” Dissolution from Coconut Shells

Glycol-based Alkaline Deep Eutectic Solvents for “Lignin-First” Dissolution from Coconut Shells

Application of a Green Deep Eutectic Solvent for Preconcentration and Determination of Copper and Cadmium in Food, Cosmetic, and Water Samples

Background:: Determination of environmental pollutants is important due to their harmful effects on the health of living organisms. However, direct measurement of many of these pollutants is not possible due to their low concentrations, which necessitates the need for sample preparation methods. One of the rapid and simple sample preparation methods is the Air-Agitated Liquid-Liquid Microextraction (AALLME) method, which requires toxic organic solvents that can lead to environmental pollution. Therefore, finding green solvents like Deep Eutectic Solvents (DESs) to replace them can be investigated. Methods:: A novel Deep Eutectic Solvent (DES) was synthesized from a combination of choline chloride and 2-phenylethanol with a molar ratio of 1:4, and it was examined using FT-IR analysis. This solvent was used in an AALLME method for measuring copper and cadmium heavy metal ions in complex real samples with Flame Atomic Absorption Spectroscopy (FAAS). Results:: The influential parameters of this method, such as solution pH (5.4), extraction cycles (12), and extraction solvent volume (440 μL), were optimized utilizing central composite design (CCD). Underneath the optimized circumstances, the detection limits for Cu2+ and Cd2+ were 0.14 and 0.09 ng mL-1, and the linear dynamic range was 0.47-50.0 and 0.32-22.5 ng mL-1, respectively. The preconcentration factors for these cations were 139.7 and 133.4, respectively. Conclusion:: Combining this novel green solvent and rapid sample preparation method for the preconcentration and determination of the studied heavy metal ions has shown promising results in terms of enrichment factors and detection limit values.

Optimization of Ultrasound-Assisted Deep Eutectic Solvent Extraction, Characterization, and Bioactivities of Polysaccharide from Pericarpium Citri Reticulatae.

The ultrasonic-assisted deep eutectic solvent method was used to extract the polysaccharides of Pericarpium Citri Reticulatae (PCRP), and the ultrasound-assisted DES extraction process was optimized by Box-Behnken response surface test using the extraction rate of the PCRP as an index; the in vitro activities of purified the PCRP(PCRPs-1) were investigated by determining the scavenging rate of DPPH• and ABTS•+ as well as by enzyme inhibition assay. The monosaccharide composition was analyzed by HPLC. The best process conditions for response surface optimization were a material-liquid ratio of 1:37g/mL, water content of 44%, time of 89min, and power of 320 W. The polysaccharide extraction rate was measured to be 5.41%, which was well optimized when compared with that of the ordinary aqueous extraction method of 3.92%. By α-glucosidase and α-amylase inhibition activity test, it showed that the PCRPs-1 had hypoglycemic activity. The DPPH radical scavenging activity test and ABTS + scavenging activity test indicated that the PCRPs-1 had good biological activity. Analysis of the monosaccharide fractions showed that the PCRPs-1 consisted of mannose, rhamnose, glucuronic acid, galacturonic acid, glucose, galactose, xylose, and arabinose, with molar ratios of 1:39.24:4.41:8.91:7.83:86.00:1.02:9.17. The activity studies showed that PCRPs-1 possessed certain hypoglycaemic and antioxidant activities.

Metal Ion Microwave-Assisted Depolymerization of Poly(Ethylene Terephthalate): A Zinc Salts-Based Deep Eutectic Solvent as Case Study

In this study, a new and very quick method to depolymerize PET plastics is reported. The depolymerization experiments were conducted using a type-IV deep eutectic solvent containing ZnCl2 and urea, and a microwave oven as reactor. Different combinations of power and reaction times were employed while keeping the total energy constant. Successful conversions were obtained carrying out the process at 180 W for 2 min and 360 W for 1 min, whereas at higher powers and shorter times, an inclusion likely occurs of some solvent into the structure of the recovered PET flakes, as suggested by the porosity of the flakes, imaged by SEM microscopy. The flakes increase their crystalline character during the treatment, as indicated by the appearance of narrow diffraction peaks in the XRD patterns, at variance with the broad signals observed in the case of the pristine amorphous polymer. The NMR analysis of the supernatant liquid above the partially solubilized PET shows the presence of terephthalic acid peaks. The infrared spectra of the solid powder achieved upon the acidic treatment of the extract reveal the presence of C=O stretching peaks and the absence of typical CH2 wagging absorptions that satisfactorily comply with the presence of terephthalic acid.

Efficient Hydrochlorination of Acetylene by the Ag–Ru Bimetallic Catalyst in a Deep Eutectic Solvent

Efficient Hydrochlorination of Acetylene by the Ag–Ru Bimetallic Catalyst in a Deep Eutectic Solvent

Preparation of Cellulose Fiber from Cattail Using Two-Stage Pretreatment and Choline Chloride-Oxalic Acid Deep Eutectic Solvent Extraction for Oil Adsorption

Preparation of Cellulose Fiber from Cattail Using Two-Stage Pretreatment and Choline Chloride-Oxalic Acid Deep Eutectic Solvent Extraction for Oil Adsorption

Investigation of antifungal and antibacterial potential of green extracts of propolis

Propolis extracts have been used in traditional medicines since ages due to its advantageous complex chemical composition. However, the antibacterial and antifungal activity of poplar propolis extracts prepared in Natural Deep Eutectic Solvent (NADES) are seldom studied. This study investigates suitable alternate for ethanol as a solvent for extraction for Polish poplar propolis. It also attempts to identify suitable extraction condition for the efficient transfer of compounds from propolis to the solvents. The extraction efficiency of NADES extracts was assessed in terms of total phenolic content, antioxidant activity and antimicrobial activity. The chemical composition of the extracts was analysed using UHPLC-DAD-QqTOF-MS. Four extracts, prepared in Propylene Glycol, Choline Chloride:Propylene Glycol (1:3), Choline Chloride:Propylene Glycol (1:4) and Choline Chloride:Glycerol (1:2), demonstrated activity and properties similar to ethanolic extract and extraction at 50 °C was found the most suitable for propolis. HPLC analysis confirmed that the chemical cocktail extracted by these solvents from propolis were identical with minor variations in their concentration as compared to its ethanolic extract. Thus, extracts of propolis at 50 °C in Propylene Glycol, Choline Chloride:Propylene Glycol (1:3) and Choline Chloride:Propylene Glycol (1:4) can be alternates for ethanolic extracts.

Assessment of COSMO-RS for Predicting Liquid–Liquid Equilibrium in Systems Containing Deep Eutectic Solvents

Assessment of COSMO-RS for Predicting Liquid–Liquid Equilibrium in Systems Containing Deep Eutectic Solvents

A New Capillary-Channel Agarose Sponge Assembled with Deep Eutectic Solvent Based Magnetic Fluid for Rapid Hemostasis and Prevention of Bacterial Infection.

A new composite sponge assisted by magnetic field-mediated guidance was developed for effective hemostasis. It was based on polydopamine capillary-channel agarose (PDA-CAGA) sponge as matrix; meanwhile, the combination of deep eutectic solvent (DES, choline chloride:glycerol = 1:1, M/M)-dispersed Fe3O4 nanoparticles after fabrication by tannic acid (DES-Fe3O4@TA) was applied as hemostatic magnetic fluid. This sponge had oriented and aligned capillary channels realized by a 3D printed pattern, which endowed them with obvious shape memory and liquid absorption performance. Computational simulation was performed to describe the fluid status in channels; DES-Fe3O4@TA exhibited good magnetic properties, fluidity, and stability. In addition, the sponge driven to react rapidly with the bleeding site under the effect of a magnetic field presented a shorter hemostasis time (reduced by 85.02% in the tail and 81.07% in the liver of rats) and less blood loss (reduced by 97.08% in the tail and 91.50% in the liver) than those of medical gelatin sponge (GS). Meanwhile, the multifunctional material also exhibited better biocompatibility, procoagulant performance, and significant inhibition on S. aureus and E. coli than GS. As a whole, this work proposed a new strategy for rapid hemostasis by designing a magnetic field assisted composite bacteriostatic material, which also expanded the applications of green solvents in the clinical management field.

Chitosan/Polyvinyl Alcohol-Based Biofilms Using Ternary Deep Eutectic Solvents towards Innovative Color-Stabilizing Systems for Anthocyanins.

Anthocyanins are amazing plant-derived colorants with highly valuable properties; however, their chemical and color instability issues limit their wide application in different food industry-related products such as active and intelligent packaging. In a previous study, it was demonstrated that anthocyanins could be stabilized into green plasticizers namely deep eutectic solvents (DESs). In this work, the fabrication of edible films by integrating anthocyanins along with DESs into biocompatible chitosan (CHT)-based formulations enriched with polyvinyl alcohol (PVA) and PVA nanoparticles was investigated. CHT/PVA-DES films' physical properties were characterized by scanning electron microscopy, water vapor permeability, swelling index, moisture sorption isotherm, and thermogravimetry analysis. Innovative red-to-blue formulation films were achieved for CHT/PVA nanoparticles (for 5 min of sonication) at a molar ratio 1:1, and with 10% of ternary DES (TDES)-containing malvidin-3-glucoside (0.1%) where the physical properties of films were enhanced. After immersion in solutions at different pH values, films submitted to pHs 5-8 were revealed to be more color stable and resistant with time than at acidic pH values.

Study on electrodeposition of gallium-selenium binary alloy films from Deep Eutectic Solvent

Ga-Se alloy coatings were successfully electrodeposited at different deposition potentials from Deep Eutectic Solvent (choline chloride-ethylene glycol). The co-deposition mechanism of Ga and Se was investigated through cyclic voltammetry (CV) and chronoamperometry (CA). The results indicate that the co-deposition of Ga and Se occurs through an induced co-deposition mechanism, with Se deposition taking place initially, followed by the induced deposition of Ga. Furthermore, the Ga-Se co-deposition process was analyzed with the Scharifker-Hills model. The research results indicate that with the negative shift of the deposition potential, the Ga-Se co-deposition process gradually transitions from diffusion-controlled three-dimensional progressive nucleation and growth to three-dimensional instantaneous nucleation and growth.Characterization of the surface morphology and composition of the obtained coatings at different potentials was analyzed by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The results reveal that with the negative shift of the deposition potential, the morphology of the coating transforms from spherical to granular, and as the deposition potential continues to decrease, the granules further refine. Simultaneously, with the negative shift of the deposition potential, the relative content of Ga in the coating increases, while the relative content of Se decreases. The Ga-Se alloy coatings before and after annealing were characterized by X-ray diffraction spectroscopy (XRD). The results indicate that, after annealing, the coating exhibits the phase of GaSe. Besides, the optical and electrical properties of the annealed Ga-Se alloy coating were investigated by UV–visible spectroscopy and photoelectrochemical techniques. The results demonstrate that the coating exhibits excellent optical and electrical characteristics, with a photocurrent response of 0.014 mA/cm2, a bandgap of 1.98 eV, and p-type conductivity.

Exploring Phenolic Compounds Extraction from Saffron (C. sativus) Floral By-Products Using Ultrasound-Assisted Extraction, Deep Eutectic Solvent Extraction, and Subcritical Water Extraction.

Saffron (Crocus sativus) floral by-products are a source of phenolic compounds that can be recovered and used in the nutraceutical, pharmaceutical, or cosmetic industries. This study aimed to evaluate the phenolic compounds' extraction using green extraction techniques (GETs) in saffron floral by-products and to explore the influence of selected extraction techniques on the phytochemical composition of the extracts. Specifically, ultrasound-assisted extraction (UAE), subcritical water extraction (SWE), and deep eutectic solvents extraction (DESE) were used. Phenolic compounds were identified with (HR) LC-ESI-QTOF MS/MS analysis, and the quantitative analysis was performed with HPLC-PDA. Concerning the extraction techniques, UAE showed the highest amount for both anthocyanins and flavonoids with 50:50% v/v ethanol/water as solvent (93.43 ± 4.67 mg/g of dry plant, dp). Among SWE, extraction with 96% ethanol and t = 125 °C gave the best quantitative results. The 16 different solvent mixtures used for the DESE showed the highest amount of flavonoids (110.95 ± 5.55-73.25 ± 3.66 mg/g dp), while anthocyanins were better extracted with choline chloride:butane-1,4-diol (16.0 ± 0.80 mg/g dp). Consequently, GETs can be employed to extract the bioactive compounds from saffron floral by-products, implementing recycling and reduction of waste and fitting into the broader circular economy discussion.

Application of Choline Chloride - Ethylene Glycol Deep Eutectic Solvent for the Extraction of Monocylclic Aromatic Hydrocarbon Contaminants from Soil

Abstract Monocyclic aromatic hydrocarbons like Benzene, toluene, ethylbenzene and xylene (BTEX) are among environmental pollutants that are considered among chemicals of concern. They are often found in industrial effluents, which when discharged into farmlands end up contaminating the soils. Such happenings warrant the remediation of the soil for environmental sustainability. Solvent extraction, prominent among the techniques employed for this remediation, is limited by the type of solvent used, as volatile organic solvents end up producing secondary pollutants. Various kinds of green solvents like Ionic Liquids (ILs) and Deep Eutectic Solvents (DESs) have been used in this technique as replacements for the conventional ones. In this study, DES made from choline chloride and ethylene glycol in the ratio of 1:2 was synthesized, characterized and used for the remediation of soils contaminated with monocyclic aromatic hydrocarbons (BTEX). Response surface methodology was employed to model and optimize the extraction process. Extraction efficiencies of 76.25, 79.04, 81.93 and 78.66% were obtained for benzene, toluene, ethylbenzene and xylene in a single stage extraction at optimum condition of 45 minutes, 0.841 and 440 rpm for extraction time, solvent mass fraction and mixing rate respectively. Further studies on the solvent regeneration and reuse were conducted. The findings showed that the solvent has capacity to perform effectively in two (2) successive extraction cycles without regeneration, and can undergo up to five (5) cycles upon regeneration without significant loss in its extracting ability. These studies show the possibility of remediating soils contaminated with BTEX using DES under mild extraction conditions.

The Properties of Xylan Extracted from Corncob Using Deep Eutectic Solvent

Abstract Corncob is an abundant agricultural biomass that is generally underutilized and discarded. It has potential to be a resource for high-value products due to its cellulose and hemicellulose content. Xylan, which is the primary constituent of hemicellulose, can serve as a raw material or intermediary in both non-food and food industry. This research aims to study the extraction of xylan from corncob using deep eutectic solvent (DES) for clean processing and analyzes the characteristics of corncob xylan. DES comprises choline chloride and acetic acid with a molar ratio of 1:2. Xylan was extracted from corncobs by immersion in aqueous DES (70% and 90%) and heating using an autoclave at 105°C for 15 minutes. FT-IR and NMR characterized the chemical structures of xylan, while FE-SEM observed the surface. The FT-IR result showed that xylan had a peak range of 1041 cm−1, which is attributed to the glycosidic bond. A delignification process seems to have occurred as indicated by the absorption peak at 1475-1477 cm−1, indicating the presence of lignin in xylan and solid residue. Both types of extracted xylan had similar NMR spectra in the 3-4.3 ppm range, which indicates that they contained xylose. The solid residue structure obtained from extracting two DES concentrations shows the difference in the extraction process. However, the surface morphology of the two types of extracted xylan had a similar irregular shape and roughness. The use of the DES choline chloride-acetic acid could lead to the extraction and separation of xylan from lignocellulosic corncob.