Hydrophobic Deep Eutectic Solvents Research Articles

Development of a dispersive liquid–liquid microextraction procedure based on a natural deep eutectic solvent for ligand-less preconcentration and determination of heavy metals from water and food samples

In the current study, a ligand-less dispersive liquid–liquid microextraction technique assisted ultrasound and vortex equipment (DLLME-A-US-V) procedure was used for the simultaneous preconcentration and extraction of heavy metal ions. The proposed method was done by a natural hydrophobic deep eutectic solvent for the extraction of arsenic, cadmium, lead, and mercury ions without a complexing agent. The natural deep eutectic solvent was prepared from l-menthol (M) and salicylic acid (SA). The precursor of deep eutectic solvents strongly affects the extraction of metal ions. Among the studied solvents, hydrophobic deep eutectic solvents showed the highest extraction recovery. Under optimal experimental conditions, the method linearity, limits of detection (LOD), limits of quantification (LOQ), relative standard deviations (RSD %), enrichment factors (EF), and extraction recovery (% ER) were equal to 0.005–14 µg/L, 0.0043–0.0088 µg/L, 0.0143–0.0294 µg/L, 1.66–2.83 %, 112–120, and 90–96 %, respectively. The obtained coefficients of determination (r2) were also higher than 0.991. This method was successfully applied to determine some heavy metals in food samples in the ultra-trace range with the recovery values of real samples being 93–108 %.

Formation of Ethanolamine-Mediated Surfactant-Free Microemulsions Using Hydrophobic Deep Eutectic Solvents.

Hydrophobic deep eutectic solvents (HDESs) are emerging as versatile, relatively benign, and inexpensive alternatives to conventional organic solvents in a diverse set of applications. In this context, the formation of microemulsions with HDES replacing the oil phase has become an area of active exploration. Because of recent reports on the undesirable toxicity of many common surfactants, efforts are under way to investigate the formation of surfactant-free microemulsions (SFMEs) using HDES as an oil phase. We present SFME formation using HDESs constituted of n-decanoic acid and five (5) structurally different terpenoids [thymol, l(-)-menthol, linalool, β-citronellol, and geraniol] at a 1:1 molar ratio as the oil phase and water as the hydrophilic phase. Ethanolamine (ETA) exhibited the best potential as a hydrotrope among several other similar small molecules. Results showed a drastic increase in water solubility within the HDESs in the presence of ETA. ETA exerted its hydrotropic action at different extent for each DES system via chemical interaction with the H-bond donor (HBD) constituent of the HDES. The optimum hydrotropic concentration (minimum hydrotrope and maximum water retention, XETAOPT) assigned for each DES/ETA/water system and water loading are reported, and the trends are discussed in detail. Ternary phase diagrams are constructed using visual observation and the dye staining method. The area under the single- and multiple-phase regions (assigned in ternary phase diagrams) was estimated. "Pre-Ouzo" enforced by ETA was investigated using dynamic light scattering (DLS) of the DES/ETA/water systems at XETAOPT. A systematic growth in nanoaggregates was observed with the subsequent addition of water in DES/ETA systems while continuously changing the existing microstructure. The presence of a core (oil)-shell (water)-like structure as indicated by the fluorescence response of Nile red in the "pre-Ouzo" region is speculated. We were able to prepare a homogeneous solution of [K3Fe(CN)6] salt in "pre-Ouzo" mixtures with no apparent deviation in the Beer-Lambert law.

Acid induced dispersive liquid–liquid microextraction based on in situ formation of hydrophobic deep eutectic solvents for the extraction of bisphenol A and alkylphenols in water and beverage samples

This study describes the development of an acid induced dispersive liquid–liquid microextraction method based on the in situ formation of hydrophobic deep eutectic solvents for the extraction of bisphenol A and alkylphenols from environmental water and beverage samples. Hydrochloric acid altered the hydrophilic-hydrophobic state of fatty acid salts to obtain hydrophobic fatty acids, which formed hydrophobic deep eutectic solvents with analytes in situ to extract the analytes. Under optimized conditions, the limits of detection and limits of quantitation were 0.03–0.1 μg L-1 and 0.12–0.3 μg L-1, the intraday and interday relative standard deviations were less than 3.9 %, and the enrichment factor was 29–32. The recoveries of bisphenol A and alkylphenols were 95.9–104.9 % and 86.9–105.0 %, respectively. The extraction process used only hydrochloric acid and fatty acid salts, and the extraction process required less than 1 min. This method has the advantages of simplicity, speed, low cost and environmental friendliness.

Antibacterial performance enhancement using hydrophobic deep eutectic solvents: COSMO-RS prediction, experimental validation, and synergistic action with antibiotics

Microbial infection is a hazardous and challenging clinical problem that has attracted considerable attention recently, primarily owing to the noticeable rise in antimicrobial resistance. To address the medical requirements to encounter this dilemma, we present hydrophobic deep eutectic solvents (HDESs) that combine experimental research and computational prediction; conductor-like screening model for real solvents (COSMO-RS). Menthol-based HDESs were successfully obtainedwhen mixed with fatty acids, and their thermal profiles were analyzed. The HDES systems and their synergistic effects demonstrated potent antimicrobial activity against Gram-positive and Gram-negative bacteria, with DES 4 (menthol:decanoic acid) exhibiting the highest bactericidal activity at a molar ratio of 1:5. The interaction between the HDESs and bacterial cell wall structural compounds was confirmed by field-emission scanning electron microscopy and Fourier transform infrared spectroscopy. The results revealed a favorable concurrence between the projected and empirical outcomes, indicating that DES 4 exhibited bacteriostatic properties and could be a viable substitute for managing bacterial infections of diverse origins. In addition, the synergistic effect of DES 4 and tetracycline showed promising potential. The successful integration of experimental and computational approaches in this study also sets a precedent for the rational design of future antimicrobial agents and opens new avenues for tackling other clinical challenges.

Preconcentration of Heterocyclic Aromatic Amines in Edible Fried Insects Using Surfactant-Assisted Hydrophobic Deep Eutectic Solvent for Homogeneous Liquid-Liquid Microextraction prior to HPLC.

Thermal processing techniques are often accompanied by the production of many harmful compounds such as heterocyclic aromatic amines (HAAs). To protect human health, an efficient and environmentally friendly method, namely, homogeneous liquid-liquid microextraction (HLLME), was investigated. This method is based on a surfactant-assisted hydrophobic deep eutectic solvent for the determination of HAAs in edible fried insect samples prior to their analysis by high-performance liquid chromatography coupled with UV detection. A hydrophobic deep eutectic solvent (as extraction solvent) was synthesized using decanoic acid as a hydrogen bond donor and tetrabutylammonium bromide (TBABr) as a hydrogen bond acceptor and then characterized by Fourier transform infrared (FTIR) spectroscopy. The surfactant was used as the emulsifier and induces mass transfer, resulting in an increasing extraction efficiency of the proposed method. Various factors affecting the extraction performance were investigated and optimized. A matrix-match calibration method was used to analyze HAAs in high heat-treated edible fried insect samples. Under optimized conditions, the proposed method showed good linearity (R2 ≥ 0.99) with satisfactory limits of detection and satisfactory reproducibility with relative standard deviation of less than 10.0%. Furthermore, the procedure greenness was assessed using the Analytical Eco-Scale. This paper represents the first application of HLLME based on a surfactant-assisted hydrophobic deep eutectic solvent to analyze HAAs in edible fried insect samples.

3D printed personalized wound dressings using a hydrophobic deep eutectic solvent (HDES)-formulated emulgel.

Curcuminoids, known for their antibacterial, anti-inflammatory, and wound healing properties, face challenges in medical applications due to their limited water solubility, resulting in poor bioavailability and clinical efficacy. This study introduces a novel approach to formulating 3D printing ink for personalized wound dressings by utilizing hydrophobic deep eutectic solvents (HDES) to incorporate poorly water-soluble compounds from Curcuma longa (i.e., curcuminoids and ar-turmerone) into hydrogels. The use of HDES, comprising either acetic acid or octanoic acid combined with menthol in a 2 : 1 molar ratio, significantly improved the solubility of curcuminoid derivatives and ar-turmerone by approximately 10 to 600 times, depending on the intrinsic chemical polarities of each compound, compared to conventional extraction solvents (i.e., ethanol and water). By formulating an emulgel using HDES as the oil phase in a gelatin methacryloyl (GelMA) solution stabilized by a biocompatible surfactant, we achieved a 3D biocompatible printing ink with preserved rheological characteristics, enabling the production of personalized wound dressings using a custom-designed, syringe-based 3D printer. The emulgel constructs exhibited regulated swelling profiles, prolonged release of curcuminoids over 60 days as monitored by a Franz cell diffusion assay, and promoted human dermal fibroblast proliferation in vitro. Additionally, the emulgel components worked synergistically with curcuminoids to significantly enhance anti-biofilm activity against Staphylococcus aureus, offering an effective strategy to prevent wound infections. Our findings have demonstrated, for the first time, the formulation of biochemical ink for 3D printing harnessing HDES, providing a new pathway for developing advanced wound dressings with relatively high concentrations of poorly soluble plant bioactive compounds tailored for chronic wound management.

Assessing hydrophobic deep eutectic solvents for intramolecular excimer formation.

Intramolecular excimer formation by a dipyrenyl probe, 6-(1-pyrenyl)hexyl-11(1-pyrenyl)-undecanoate [1-Py(CH2)10COO(CH2)61-Py], is used to assess hydrophobic deep eutectic solvents (HDESs) for the purpose. n-Decanoic acid (DA), L(-)-menthol (Men) and thymol (Thy) have been utilized to form HDESs with different pairs of constituents in different molar ratios, namely Men : DA (2 : 1, 1 : 1, and 1 : 2), Thy : DA (2 : 1, 1 : 1, and 1 : 2), and Thy : Men (5 : 1, 2 : 1, 1 : 1, 1 : 2, and 1 : 5). The maximum of the excimer-to-monomer emission intensity ratio, (IE/IM)max, is observed at 343.15-353.15 K for all DESs irrespective of the constitution, and it varies in a narrow range exhibiting no correlation with the dynamic viscosity (η) of the DES which varies between 2.05 and 3.56 mPa s. Excited-state intensity decay data reveal excimer dissociation back to the excited monomer to be negligible in all DESs at lower temperatures (T ≤ 323.15 K); the simplistic Birks scheme is followed at higher temperatures (T > 323.15 K). The rate constant for excimer formation/association, ka, ranges from (3.00 ± 0.50) × 106 s-1 to (103 ± 10) × 106 s-1, which is similar to that reported in other media. The temperature-dependence of the equilibrium constant for excimer formation follows the van't Hoff equation with recovered standard enthalpy (ΔaH*⊖) and standard entropy (ΔaS*⊖) changes, indicating the reversible intramolecular excimer formation to be exothermic and energetically-favorable but entropically unfavorable. A plot of kavs. T/η for all the DES systems investigated exhibits a fairly good linear correlation, indicating the adherence to the Stokes-Einstein formulation within the HDESs further emphasizing the homogeneous nature of the solubilizing media. The work helps to highlight the potential of HDESs for intramolecular excimer formation involving non-polar reactants.

Hydrophobic deep eutectic solvents as emerging green reaction media for biocatalytic processes: impacts of solvent properties and compositions

Hydrophobic deep eutectic solvents (HDESs) are a new generation of water-immiscible solvents that have shown potential as green and sustainable reaction media for biocatalytic applications.

Hydrophobic deep eutectic solvents characterization and performance for efficient removal of heavy metals from aqueous media

In this study, we successfully extracted copper, cobalt, and nickel metals from aqueous media using hydrophobic deep eutectic solvents (DESs). The DESs designed for this research consisted of a combination of carboxylic acids, namely Octanoic acid, Nonanoic acid, Decanoic acid, and Dodecanoic acid. Before and after the extraction process, the prepared DESs underwent comprehensive characterization using various analytical techniques. Viscosity measurements demonstrated that the prepared solvents exhibited low viscosity at room temperature, making them well-suited for extraction processes. Moreover, Karl Fischer Titration was employed to accurately determine the water content, which is crucial for evaluating hydrophobicity. We investigated the influence of various parameters on the metal extraction yield, including the initial concentration, temperature, and time. Under optimized conditions, using Dodecanoic acid + Octanoic acid as the most efficient DES, extraction yields of 85.61 % for Cu, 96.19 % for Co, and 76.54 % for Ni were achieved. Furthermore, through approximately three extraction steps, complete removal of metal ions from the aqueous medium was achieved. Due to its superior performance, the DES composed of Dodecanoic acid + Octanoic acid was selected for further investigations. The DESs exhibited favorable characteristics such as low viscosity and hydrophobicity, positioning them as promising for extraction in aqueous environments.

Improved separation of rare earth elements using hydrophobic deep eutectic solvents: liquid–liquid extraction to selective dissolution

Tuning steric environment of hydrophobic deep eutectic solvents improves dissolution selectivity of rare earth elements.

New low transition temperature mixture menthol:salicylaldoxime – a designer solvent for extraction of metal species

A new hydrophobic deep eutectic solvent was designed by combining menthol and salicylaldoxime.

Detection of Surfactants using a Hydrophobic Natural Deep Eutectic Solvent and Smartphone

We report on the advantages of a green method to detect surfactants in environmental water samples. The approach is based on the use of a hydrophobic natural deep eutectic solvents...

Alternative Assisted Extraction Methods of Phenolic Compounds Using NaDESs.

A renewed understanding of eco-friendly principles is moving the industrial sector toward a shift in the utilization of less harmful solvents as a main strategy to improve manufacturing. Green analytical chemistry (GAC) has definitely paved the way for this transition by presenting green solvents to a larger audience. Among the most promising, surely DESs (deep eutectic solvents), NaDESs (natural deep eutectic solvents), HDESs (hydrophobic deep eutectic solvents), and HNaDESs (hydrophobic natural deep eutectic solvents), with their unique features, manifest a wide-range of applications, including their use as a means for the extraction of small bioactive compounds. In examining recent advancements, in this review, we want to focus our attention on some of the most interesting and novel 'solvent-free' extraction techniques, such as microwave-assisted extraction (MAE) and ultrasound-assisted extraction (UAE) in relation to the possibility of better exploiting DESs and NaDESs as plausible extracting solvents of the phenolic compounds (PCs) present in different matrices from olive oil components, such as virgin olive pomace, olive leaves and twigs, virgin and extra virgin olive oil (VOO and EVOO, respectively), and olive cake and olive mill wastewaters (OMWW). Therefore, the status of DESs and NaDESs is shown in terms of their nature, efficacy and selectivity in the extraction of bioactive phytochemicals such as secoiridoids, lignans, phenolic acids and alcohols. Related studies on experimental design and processes' optimization of the most promising DESs/NaDESs are also reviewed. In this framework, an extensive list of relevant works found in the literature is described to consider DESs/NaDESs as a suitable alternative to petrochemicals in cosmetics, pharmaceutical, or food applications.

An environmentally friendly hydrophobic deep eutectic solvent dispersive liquid liquid microextraction for spectrophotometric analysis of indigo carmine (E132)

An environmentally friendly hydrophobic deep eutectic solvent dispersive liquid liquid microextraction for spectrophotometric analysis of indigo carmine (E132)

PEBAX polymer inclusion hydrophobic deep eutectic solvent membranes for pervaporation of biobutanol: Mass transfer and COSMO-RS analysis

Deep Eutectic Solvent(DES) and specifically Hydrophobic Deep Eutectic Solvents (HDES) are considered a relatively novel class of solvents, which show good features to include them in pervaporation membranes. Polymer inclusion HDES membranes offer a separation media, which shows a faster molecular diffusion than polymeric membranes, combining the best properties of liquid and polymer membranes, such a high selectivity with high burst pressure and durability.The aim of this work focuses on the development of different PEBAX/ lidocaine-thymol [2:1] (Lidol HDES) membranes by the temperature-induced phase-inversion technique to be used in the pervaporation process to recover butanol from ABE model solution. The mass transfer modeling through the membrane using the resistances-in-series approach was implemented to find the mass transfer resistance distribution.The polymer inclusion membranes showed improved results for the butanol/water selectivity compared to the single PEBAX membrane used as a reference. The flux of butanol obtained with the 30 % w/w Lidol HDES membrane was 0.112 kg m−2 hr−1. The flux of water was 0.445 kg m−2 hr−1 showing a selectivity value for butanol/water of 20 % bigger than single PEBAX membrane. The improvement in the selectivity can be explained by the synergic effect of the HDES in the membrane.After use, the polymer inclusion membrane consistently demonstrated a stable performance in effectively separating butanol from the ABE solution. It was seen that the overall resistance decreases as the liquid flow rate increases; regarding the liquid side resistance, it becomes important at smaller flow rates and is almost negligible for turbulent regimen.

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.

Hydrophobic deep eutectic solvents as the green media for highly efficient extraction of Cr(VI) over a broad pH range and low oil-water ratio

The occurrence of Cr(VI) ions in aquatic ecosystems poses serious public health risks, making the development of effective removal technology for Cr(VI) ions urgent. This study presents a green and effective method for extracting Cr(VI) ions using hydrophobic deep eutectic solvents (HDESs) composed of tetran-octyl ammonium bromide and carboxylic acids. The results show that the extraction efficiency of [N8888][Br]-C6OOH(1:2) for Cr(VI) is as high as 98.2 % for high concentration of Cr(VI) (500 mg⋅g−1) with a low oil–water ratio of 1:66. Surprisingly, these HDESs demonstrate remarkable efficacy in extracting Cr(VI) ions over a broad pH range and at a low oil–water ratio, even in the presence of multiple competing ions. A serious of kinetic, thermodynamic, and spectroscopic experiments suggested that the extraction mechanism of Cr(VI) ions is a synergistic dissolution diffusion and ion exchange. As a proof of concept, we have successfully demonstrated the application of prepared HDESs for extracting trace amounts of Cr(VI) ions from H3PO4 solutions with varying mass fractions, and the extraction process resulted in a Cr(VI) removal rate that achieved 99.7 %. Furthermore, the extraction performance HDESs for Cr(VI) ions remained nearly unchanged after eight cycles of continuous extraction and regeneration. Impressively, a precipitation method was also employed to convert the isolated Cr(VI) ions into valuable BaCrO4. The research findings provide valuable insights for the development of highly efficient Cr(VI) extractants.

Plant-based meat substitute analysis using microextraction with deep eutectic solvent followed by LC-MS/MS to determine acrylamide, 5-hydroxymethylfurfural and furaneol

For the analysis of plant-based meat substitutes and the determination of Maillard reaction products such as acrylamide, 5-hydroxymethylfurfural and furaneol, a novel and effective procedure based on hydrophobic natural deep eutectic solvent and liquid chromatography coupled with tandem mass spectrometry was developed for the first time. The 49 compositions of the deep eutectic solvents were designed and screened to select the most suitable option. The terpenoids eugenol and thymol in a molar ratio of 2:1 were selected as precursors for solvent formation, allowing effective extraction of the target analytes. The developed procedure comprised two main steps: extraction — in which the analytes are isolated from the solid sample due to the salting-out effect and pre-concentrated in the deep eutectic solvent, and back-extraction — in which the analytes are re-extracted into the formic acid solution for subsequent mass spectrometric detection. As the density of the aqueous phases changed during the extraction and back-extraction steps, the phenomenon of inversion of the coalesced organic phase was observed, which simplified the withdrawing of the phases. The linear range was 1–50 ng/mL for acrylamide, 10–1000 ng/mL for 5-hydroxymethylfurfural and 200–1000 ng/mL for furaneol with coefficients of determination above 0.9952. The developed method was fully validated and found recoveries were in the range 83–120%, with CVs not exceeding 4.9%. The method was applied to real sample analysis of pea-based meat substitutes.Graphical abstract

Green, recyclable, mechanically robust, wet-adhesive and ionically conductive cellulose-based bioplastics enabled by supramolecular covalent hydrophobic eutectic networks

The development of novel cellulose-based bioplastics (CBPs) is highly desirable because CBPs are green, rationally use resources, and lead to a reduction in environmental pollution compared to alternative materials. However, incorporating high transparency, water resistance, mechanical robustness, wet-adhesion, ionic conductivity and recyclability into CBP remains a challenge. In this paper, novel CBPs with supramolecular covalent networks are fabricated by introducing polymerizable hydrophobic deep eutectic solvents (HDES) into ethylcellulose (EC) networks through in situ plasticization followed by a rapid photopolymerization process. The excellent molecular interfacial compatibility enables EC to be loaded with a high content of poly(HDES), while allowing high transparency (more than 90 %) of the prepared CBPs. Multiple intermolecular interactions provide CBPs with mechanical robustness, water resistance, and underwater adhesion, and CBPs can be readily recovered by the solvent in a closed loop. Moreover, CBPs possess inherent ionic conductivities, and using them as green substrates, personalized electroluminescent devices can be successfully constructed. The method proposed in this paper provides a new strategy for the preparation of multifunctional CBPs, which will greatly enrich their applications in self-adhesive materials, green flexible electronics and other package materials.

Extraction of Phenol as Pollutant from Aqueous Effluents Using Hydrophobic Deep Eutectic Solvents

Due to their toxicity and persistence in the environment, phenolic pollutants pose a serious threat to the ecosystem. In this work, the performance of hydrophobic deep eutectic solvents (HDESs) for phenol removal from aqueous effluents is thoroughly investigated using COSMO-RS screening followed by experimental validation. The screening results of 73 HDESs showed that the efficacy of phenol removal is significantly affected by chain length, functional groups, and aromaticity. Trioctylphosphine oxide (TOPO)-based HDESs were found to be the most effective HDESs for phenol elimination combined either with menthol (Men), 1-hexanol (Hex), Decanoic acid (DecA), or Thymol (Thy) all in 1:1 molar ratios. The better phenol elimination abilities of the selected HDESs were confirmed by experimental LLE data obtained at 298.15 K and 101 kPa. In fact, it has been found that there is a positive correlation between extraction efficiency and phenol content. For instance, at a phenol concentration of 7%, TOPO:Men had the highest extraction efficiency (96%). Moreover, the physicochemical properties of the selected HDESs, such as density, viscosity, FTIR, 1HNMR, and TGA, were also measured. The results showed their high thermal stability and low water solubility, which makes them suitable for phenol extraction applications. This study shows that HDESs are capable of removing phenolic contaminants from aqueous effluents in a sustainable and efficient manner and that the selected TOPO-based HDESs are of particular interest for further research and application in phenol removal.