Natural Deep Eutectic Solvents Research Articles

PH-Responsive Natural Deep Eutectic Solvent: An Environmental Alternative for the Sustainable Extraction of Petroleum Hydrocarbons from Oil Sands.

The reversible shift in polarity or hydrophilicity/hydrophobicity of switchable solvents greatly simplifies the recovery capacity in extraction applications. However, the environmental and economical advantages of switchable solvents are not significant. In this work, we designed three pH-responsive natural deep eutectic solvents (NADESs) by combining the pH-switchable solvent fatty acids with the nonswitchable solvent ethyl lactate (EL), followed by the exploration of the solubilization and separation performance of these NADESs for petroleum hydrocarbons. EL can be miscible in fatty acids and water; however, when in contact with both at the same time, EL binds to fatty acids through stronger intermolecular hydrogen bonds, whereas when fatty acids are deprotonated to fatty acid salts, EL can bind to water. The deprotonation/protonation of fatty acids could reversibly change the NADES hydrophilicity, and the recovery of NADES HA/EL could exceed 95% after three cycles. Furthermore, after extractive separation of simulated oils of differing complexity, NADES HA/EL was selected as the best extractant. Compared with the extraction of oil sands with a single solvent, NADES provides better wetting of the sand surface, better stripping efficiency of the heavy components that adhere to the surface of oil sands, and better dispersion of the stripped petroleum hydrocarbons. Petroleum hydrocarbons can be separated by NaOH-induced hydrophilic changes in NADES, which can be regenerated upon the addition of HCl. The recovered NADES showed good reusability in the cleaning of oil sands. The oil removal rates were 96.9%, 94.4%, and 91.9% after three cycles of cleaning with NADES at 25 °C. This method is expected to expand the application of nonswitchable solvents in sustainable extraction.

New emerging materials with potential antibacterial activities.

The increasing prevalence of multidrug-resistant pathogens is a critical public health issue, necessitating the development of alternative antibacterial agents. Examples of these pathogens are methicillin-resistant Staphylococcus aureus (MRSA) and the emergence of "pan-resistant" Gram-negative strains, such as Pseudomonas aeruginosa and Acinetobacter baumannii, which occurred more recently. This review examines various emerging materials with significant antibacterial activities. Among these are nanomaterials such as quantum dots, carbon quantum dots, metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and layered double hydroxides, all of which demonstrate excellent antibacterial properties. Interestingly, including antibacterial agents within the structure of these materials can help avoid bacterial resistance and improve the long-term efficacy of the materials. Additionally, the antibacterial potential of liquid solvents, including ionic liquids and both deep eutectic solvents and natural deep eutectic solvents, is explored. The review discusses the synthesis methods, advantages, and antibacterial efficacy of these new materials. By providing a comprehensive overview of these innovative materials, this review aims to contribute to the ongoing search for effective solutions to combat antibiotic resistance. Key studies demonstrating antibacterial effects against pathogens like Escherichia coli, Staphylococcus aureus, and multidrug-resistant strains are summarized. MOFs have exhibited antibacterial properties through controlled ion release and surface interactions. COFs have enhanced the efficacy of encapsulated antibiotics and displayed intrinsic antibacterial activity. Other nanomaterials, such as quantum dots, have generated reactive oxygen species, leading to microbial inactivation. This review aims to provide insights into these new classes of antibacterial materials and highlight them for addressing the global crisis of antibiotic resistance. KEY POINTS: • Nanomaterials show strong antibacterial effects against drug-resistant bacteria • Emerging solvents like ionic liquids offer novel solutions for bacterial resistance • MOFs and COFs enhance antibiotic efficacy, showing promise in combating resistance.

Structural characterization and physicochemical properties of different hydrophilic natural deep eutectic solvents.

To overcome the toxic nature of organic solvents, scientific interest in the use of green solvents, particularly natural deep eutectic solvents (NADES), has increased over the past decade, leading to new applications in the food, nutraceutical, pharmaceutical, and cosmetic industries. Understanding the physicochemical properties and molecular interactions of NADES is essential for uncovering new potential applications in these fields. In this study, several lactic and citric acid-based NADES, as well as chloride choline- and urea-based NADES, were evaluated for their physicochemical properties, including density, pH, viscosity, conductivity, and refractive index. Additionally, nuclear magnetic resonance (NMR), and in particular nuclear Overhauser enhancement spectroscopy (NOESY), was employed to investigate the intermolecular interactions between the NADES components to confirm the formation of the eutectic mixture. The extraction efficiency of the confirmed NADES was tested for extracting polyphenols as a proof of concept to highlight their relationship with the measured properties. Lactic and choline chloride-based NADES provided the highest extraction yields. These results were also compared with the predicted extraction capabilities of each NADES provided by the COSMO-RS software.

Physicochemical and Antimicrobial Properties of Lactic Acid-Based Natural Deep Eutectic Solvents as a Function of Water Content

The interest in natural deep eutectic solvents (NADESs) in green technology as an alternative to organic solvents has grown over the past decades. In this work, for the first time, the effect of dilution with water on the physicochemical and antimicrobial properties of lactic acid-based NADES with choline chloride (NADES1), sorbitol (NADES2), and glucose (NADES3) was systematically studied. According to FTIR data, after the dilution of NADESs with water, the strong hydrogen bonds weakened, however, were not destroyed after dilution of up to 40% water. The dilution of NADES with water resulted in a linear decrease in density and refractive index and in a linear increase in pH. The equations for the prediction of NADES density, pH, and refractive index as a function of water content were calculated. The viscosity decreased by half after adding approximately 10% water. The initial viscosity of NADES2 and NADES3 was significantly different. However, after adding 20% of the water, the viscosity was almost the same. The most pronounced decrease in surface tension (by 46.7%) was found for NADES1. The water activity was decreased in the following order: NADES3 > NADES1 > NADES2. The dilution of NADES with water caused a gradual increase in water activity. NADES1 showed the lowest minimal inhibitory concentrations (MIC) (7.8, 3.9, and 0.98 mg/mL) and minimum bactericidal concentrations (MBC) (15.6, 7.8, and 1.95 mg/mL) for Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus, respectively. The antimicrobial activity was decreased by 2–8 times after the addition of 40% water. The water activity for all tested NADES together with low pH could explain the antimicrobial effect. The revealed regularity can be useful for the prediction of NADES properties and for the selection of green solvents on a laboratory and industrial scale.

Development of Alginate Hydrogels Incorporating Essential Oils Loaded in Chitosan Nanoparticles for Biomedical Applications

A hybrid alginate hydrogel–chitosan nanoparticle system suitable for biomedical applications was prepared. Chitosan (CS) was used as a matrix for the encapsulation of lavender (Lavandula angustifolia) essential oil (LEO) and Mentha (Mentha arvensis) essential oil (MEO). An aqueous solution of an acidic Natural Deep Eutectic Solvent (NADES), namely choline chloride/ascorbic acid in a 2:1 molar ratio, was used to achieve the acidic environment for the dissolution of chitosan and also played the role of the ionic gelator for the preparation of the chitosan nanoparticles (CS-NPs). The hydrodynamic diameter of the CS-MEO NPs was 130.7 nm, and the size of the CS-LEO NPs was 143.4 nm (as determined using Nanoparticle Tracking Analysis). The CS-NPs were incorporated into alginate hydrogels crosslinked with CaCl2. The hydrogels showed significant water retention capacity (>80%) even after the swollen sample was kept in the aqueous HCl solution (pH 1.2) for 4 h, indicating a good stability of the network. The hydrogels were tested (a) for their ability to absorb dietary lipids and (b) for their antimicrobial activity against Gram-positive and Gram-negative foodborne pathogens. The antimicrobial activity of the hybrid hydrogels was comparable to that of the widely used food preservative sodium benzoate 5% w/v.

Hydrophobic deep eutectic solvent-ferrofluid microextraction followed by liquid chromatography-mass spectrometry for the enantioselective determination of chiral agrochemicals in natural waters.

The increasing use of chiral agrochemicals sold as racemic formulations raises concern for the negative impacts that inactive enantiomers can have on aquatic life and human health. The present work just focuses on the determination of ten chiral pesticides in river water samples by applying a ferrofluid-based microextraction followed by their stereoselective liquid chromatography analysis. To develop the ferrofluid, magnetite nanoparticles were prepared and coated with oleic acid and then dispersed in a hydrophobic natural deep eutectic solvent (NaDES), composed ofL-menthol and thymol (1:1). The stable colloidal dispersion was characterised by scanning electron microscopy, thermogravimetric analysis, energy-dispersive X-ray spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. The analyte microextraction from 5ml river samples was performed using 50µl of ferrofluid, while acidified acetonitrile (150µl) was used to break down the ferrofluid and solubilise the NaDES containing the analytes. All the extracts were analysed by high-performance liquid chromatography-tandem mass spectrometry. For each analyte, the baseline separation of isomers was achieved on a Lux i-Amylose-3 column (amylose tris(3-chloro-5-methylphenylcarbamate) working in reversed-phase mode; the combination with mass spectrometry detection allows the overall separation of 24 isomers (ten chiral analytes among which eight containing a single (one) chiral centre, one with two chiral centres and the last one existing in four stereoisomeric forms, due to the presence of two regioisomers with a chiral carbon) within 37min. The method showed very good figures of merit in terms of recoveries (77.7-97.5%), intra-day and inter-day precision (2.7-7.7% and 6.9-14.9%, respectively), limit of detection (0.01-0.35µg/L), limit of quantitation (0.03-1.20µg/L), linear dynamic range, and intra-day and inter-day accuracy (1.2-14.8% and 1.8-15.0%, respectively). The presented method was able to detect 14 out of 24 isomers at the preventive limit established by the Italian legislation for single pesticide (that for a chiral pesticide is the sum of all its isomers) in surface waters, set at 0.1µg/l. Finally, the method was evaluated using AGREEprep and ComplexGAPI metrics, compared with other ferrofluid-based methods, and applied to the analysis of water samples from two Italian rivers (the Nera River and the Tiber River), providing to be sustainable and reliable for the application to real river matrices.

Unravelling the Molecular Dialogue of Beneficial Microbe-Plant Interactions.

Plants are an intrinsic part of the soil community, which is comprised of a diverse range of organisms that interact in the rhizosphere through continuous molecular communications. The molecular dialogue within the plant microbiome involves a complex repertoire of primary and secondary metabolites that interact within different liquid matrices and biofilms. Communication functions are likely to involve membrane-less organelles formed by liquid-liquid phase separation of proteins and natural deep eutectic solvents that play a role as alternative media to water. We discuss the chemistry of inter-organism communication and signalling within the biosphere that allows plants to discriminate between harmful, benign and beneficial microorganisms. We summarize current information concerning the chemical repertoire that underpins plant-microbe communication and host-range specificity. We highlight how the regulated production, perception and processing of reactive oxygen species (ROS) is used in the communication between plants and microbes and within the communities that shape the soil microbiome.

Efficient membrane separation of SO2 by choline chloride-based natural deep eutectic solvents: The role of hydrogen bonding sites

Natural deep eutectic solvents (NDESs) are recognized as promising membrane materials for sustainable SO2 separation. Evaluating their separation performances is necessary, as well as understanding of the role that each hydrogen bonding site (including anion and functional groups in NDESs) plays in SO2 separation. Herein, three choline chloride (ChCl)-based NDESs bearing different number and type of functional groups were firstly incorporated into Pebax matrix to fabricate blended membranes for removing SO2 from CO2 and N2. The Pebax/NDES membranes show SO2 permeability up to 10502 Barrer (0.20 bar and 40 °C), with excellent SO2/N2 and SO2/CO2 selectivity of 1808 and 62.5 obtained, respectively, which are enhanced by 156 %, 61.5 % and 56.1 % compared with those in neat Pebax membrane. By means of gas solubility and diffusivity measurements, quantum chemical calculations and spectral characterizations, the highly-reversible multi-site interactions between SO2 and hydrogen bonding sites in NDESs (Cl−···SO2, carbonyl O···SO2 and hydroxyl O···SO2) were revealed. Meanwhile, the strength of hydrogen bonding network inside the NDESs, which is governed by the hydrogen bonding sites, is found to significantly influence the gas diffusion. More importantly, SO2/CO2/N2 (2.5/15/82.5 mol%) mixed gas separation experiment also displays the superior separation performance and long-term stability of Pebax/NDES membrane.

Stable and environmentally benign nanofluids for direct absorption solar collectors based on natural deep eutectic solvents

Stable and environmentally benign nanofluids for direct absorption solar collectors based on natural deep eutectic solvents

Green extraction using natural deep eutectic solvents for determination of As, Cd, and Pb in plant and food matrices by ICP-MS

Green extraction using natural deep eutectic solvents for determination of As, Cd, and Pb in plant and food matrices by ICP-MS

A Novel Approach for the Synthesis of 3,3′-((4-Methoxyphenyl)methylene)bis(4-hydroxyfuran-2(5H)-one) Employing Natural Deep Eutectic Solvents and Microwave Irradiation

Tetronic acid, a five-membered heterocyclic moiety present in various natural products, has emerged as a significant building block for many pharmaceutically active compounds. In this study, a novel protocol for the synthesis of the bis-tetronic acid 3,3′-((4-methoxyphenyl)methylene)bis(4-hydroxyfuran-2(5H)-one) (3) via a domino Knoevenagel–Michael reaction is presented. The natural deep eutectic solvent L-proline/glycerol 1:2 molar ratio was utilized as a solvent and catalyst, while the reaction was further promoted via microwave irradiation, providing the desired product in high yield (83%). The solvent was successfully recycled and reused up to three times.

Novel application of citric acid based natural deep eutectic solvent in drilling fluids for shale swelling prevention

Swelling of shale in clastic reservoirs poses a significant challenge, causing instability in wellbores. Utilizing water-based drilling mud with shale inhibitors is preferable for environmental reasons over oil-based mud. Ionic liquids (ILs) have garnered interest as shale inhibitors due to their customizable properties and strong electrostatic features. However, widely used imidazolium-based ILs in drilling fluids are found to be toxic, non-biodegradable, and expensive. Deep Eutectic Solvents (DES), considered a more economical and less toxic alternative to ILs, still fall short in terms of environmental sustainability. The latest advancement in this field introduces Natural Deep Eutectic Solvents (NADES), renowned for their genuine eco-friendliness. This study explores NADES formulated with citric acid (as a Hydrogen Bond Acceptor) and glycerine (as a Hydrogen Bond Donor) as additives in drilling fluids. The NADES based drilling mud was prepared according to API 13B-1 standards and their efficacy was compared with KCl, imidazolium based ionic liquid, and Choline Chloride: Urea-DES based mud. A thorough physicochemical characterization of the in-house prepared NADES is detailed. The research evaluates rheological, filtration and shale inhibition properties of the mud, demonstrating that NADES enhanced the yield point to plastic viscosity ratio (YP/PV), reduced mudcake thickness by 26%, and decreased filtrate volume by 30.1% at a 3% concentration. Notably, NADES achieved an impressive 49.14% inhibition of swelling and improved shale recovery by 86.36%. These outcomes are attributed to NADES’ ability to modify surface activity, zeta potential, and clay layer spacing which are discussed to understand the underlying mechanism. This sustainable drilling fluid promises to reshape the drilling industry by offering a non-toxic, cost-effective, and highly efficient alternative to conventional shale inhibitors, paving the way for environmentally conscious drilling practices.

In-Syringe Vortex-Assisted Liquid-Liquid Microextraction Based on Natural Deep Eutectic Solvent for Simultaneous Determination of the Two Anticancer Polyphenols Chrysin and Resveratrol.

The simultaneous determination of multiple anticancer drugs in combination therapy poses a significant analytical challenge due to their complex nature and low concentrations. In this study, we propose an in-syringe vortex-assisted liquid-liquid microextraction (IS-VA-LLME), based on a green natural deep eutectic solvent (NaDES) for the simultaneous determination of two coadministered anticancer drugs (resveratrol and chrysin) prior to the HPLC-UV analysis, for the first time. The key parameters affecting the extraction efficiency, such as extraction solvent, vortex time, pH, and ionic strength were optimized. Under optimal conditions, the method demonstrates good linearity over the range of 0.05-15.0 μg/mL for RVT and 0.50-15.0 μg/mL for CHR with low limits of detection (LODs) of 16.78 and 161.60 ng/mL for RVT and CHR, respectively, confirming the high sensitivity of the method. The interday and intraday precision values, expressed as %RSDs, are below 2.0%, indicating good repeatability and reproducibility. Furthermore, the proposed method could be efficiently applied for the determination of the two drugs in human plasma and river water. The obtained results show satisfactory % recoveries (97.80%-102.04%), highlighting the accuracy and reliability of the developed method. The sustainability of the method was comprehensively evaluated using seven different tools. In conclusion, the developed IS-VA-LLME-NaDES allows for enhanced extraction efficiency, reduced extraction time, and improved recovery of the target analytes. This method holds great promise for applications in clinical and environmental research, enabling the precise quantification of these anticancer drugs in complex matrices.

A new Fe3O4-MWCNTs-reinforced hollow fiber solid/liquid phase microextraction-based natural deep eutectic solvent for determination of trace phthalate esters in aqueous samples using HPLC–DAD

A new Fe3O4-MWCNTs-reinforced hollow fiber solid/liquid phase microextraction-based natural deep eutectic solvent for determination of trace phthalate esters in aqueous samples using HPLC–DAD

An eco-friendly kapok fiber-supported liquid microextraction using natural deep eutectic solvent as extractant for convenient biological samples preparations: A proof-of-concept study

The use of natural materials and reagents is crucial for developing environmentally friendly methods. This study proposed an excellent green, convenient, cost-effective and rapid sample preparation method called kapok fiber-supported liquid-phase microextraction using natural deep eutectic solvent (KF-SLME-NADES). Natural kapok fiber and NADES were used as greener alternatives to conventional support medium and extractants. Low-toxic ethanol was employed as the desorption solvent. The extraction process was streamlined in a syringe form, allowing for simple pull-push operations. As a proof of concept, the developed methodology was utilized for extracting antidepressants from 3 mL of diluted biological fluids. The optimized KF-SLME-NADES conditions were obtained by single-factor experiments and Box-Behnken design as follows: 2 mg of kapok fiber, 13 μL of NADES composed of menthol and thymol in an equal molar ratio as the extractant, a sampling solution with a pH of 8.0, a desorption solution of 100 μL of ethanol, and four pull-push cycles for both extraction and elution. The validated method provided good linearity (0.05–5.00 μg/mL, R2 > 0.999) and possessed limits of quantification spanning from 0.025 to 0.048 μg/mL. Satisfied accuracies and precisions were obtained with relative recoveries ranging in 93.3–107.2% and intra- and inter-day RSD(%) being below 7.7%. The method greenness was found to be excellent by assessing five greenness evaluation metrics. The devised KF-SLME-NADES strategy provides a sustainable and effective method for bioanalysis.

Life Cycle Assessment of Extraction of Cellulose from Date Palm Biomass Using Natural Deep Eutectic Solvent (NaDES) via Microwave-Assisted Process

This study investigates the extraction of cellulose from Saudi Arabia-based date palm biomass utilizing a natural deep eutectic solvent (NaDES) integrated with a microwave-assisted process. A comprehensive life cycle assessment (LCA) was conducted in accordance with the ISO 14040 standard, encompassing four key stages: goal and scope definition, life cycle inventory analysis (LCI), life cycle impact assessment (LCIA) and interpretation. The analysis was confined to a gate-to-gate boundary in which two impact assessment methods, namely, ReCiPe Midpoint (H) 2016 and ILCD 2011 Midpoint, were used to assess the environmental impacts. The OpenLCA software (version 2.1.1) with the European Life Cycle Database 3.2 (ELCD 3.2) was used in the study. The ReCiPe method identified impact categories such as fossil resource scarcity, terrestrial ecotoxicity, freshwater ecotoxicity, water consumption, human carcinogenic toxicity and marine ecotoxicity. Conversely, the ILCD method identified freshwater ecotoxicity, water resource depletion, mineral, fossil and resource depletion, human toxicity and cancer effects. The results indicate that freshwater ecotoxicity presents the most substantial environmental impact across both assessment methods, surpassing other categories. Fossil resource scarcity, even though originally appearing impactful, demonstrated a relatively lower normalized score compared to freshwater ecotoxicity. Terrestrial ecotoxicity and water consumption were found to be negligible in their impact. Our findings provide important insights into sustainable material science and waste management, affording potential applications for biomass utilization in the Gulf region.

Green and sustainable technologies for extraction of carotenoids from natural sources: a comprehensive review.

In recent years, driven by increasing consumer demand for natural and healthy convenient foods, the food industry has been shifting from synthetic to natural products. This shift is also reflected in the growing popularity of non-conventional extraction methods for pigments, which are favored for sustainability and environment-friendliness compared to conventional processes. This review aims to investigate the extraction of carotenoids from a variety of natural sources, including marine sources like fungus, microalgae, and crustaceans, as well as widely studied plants like tomatoes and carrots. Additionally, it delves into the recovery of valuable carotenoids from waste products like pomace and peels, highlighting the nutritional and environmental benefits. The review also emphasizes the role of green solvents such limonene, vegetable oils, ionic liquids, supercritical fluids, and natural deep eutectic solvents in effective and ecologically friendly carotenoid extraction. These technologies support the ideas of a circular and sustainable economy in addition to having a smaller negative impact on the environment. Overall, the present study highlights the crucial importance of green extraction technologies in achieving the dual goals of sustainability and public safety.

Fast and green methodology based on miniaturised liquid–liquid extraction with a hydrophobic natural deep eutectic solvent of opium alkaloids from poppy seed beverages

Currently, the development of environmentally friendly analytical methodologies is a challenge for analytical chemistry. Therefore, the search for solvents to extract analytes of interest from complex matrices has progressed considerably in recent years. In the present work, 15 hydrophobic natural deep eutectic solvents (HNADES) consisting of a mixture of different donors and acceptors in different ratios have been prepared and compared to evaluate the most efficient extraction of opium alkaloids (OA) from fortified water samples. After selecting the most effective one consisting in a mixture of thymol and camphor in the ratio 1:1 ([Thy]:[Cam] 1:1), a rapid analytical methodology to determine OA in poppy seed beverages was optimised and validated for the first time. It was based on a miniaturised liquid–liquid extraction (m-LLE) with 0.5 mL of sample and 0.5 mL of HNADES by vortexing for 1 min, followed by 1 min centrifugation and subsequent analysis by high-performance liquid chromatography with diode array detector (HPLC-DAD). The validation was successful, showing extraction efficiencies between 91 and 107 % for all analytes, low limits of quantification (0.1 µg/mL for all analytes, except for morphine, 0.4 µg/mL) and precision values below 15 %. In addition, the greenness of the method was evaluated, obtaining a 0.79 on the AGREEprep metric scale. Therefore, it was demonstrated that the methodology developed to analyse OAs in poppy seed beverage was efficient, fast, simple and environmentally friendly.

Synthesis and Properties of Physically Cross-Linked Silica-Mediated Novel Eutectogels Developed from Carboxylic Acid-Based Natural Deep Eutectic Solvents

Synthesis and Properties of Physically Cross-Linked Silica-Mediated Novel Eutectogels Developed from Carboxylic Acid-Based Natural Deep Eutectic Solvents

Optimization of ultrasonic and microwave-assisted extraction with natural deep eutectic solvents for enhanced recovery of phenolics and terpenoids from celery leaves

Optimization of ultrasonic and microwave-assisted extraction with natural deep eutectic solvents for enhanced recovery of phenolics and terpenoids from celery leaves