Aqueous Solutions Of Ionic Liquids Research Articles

Binary imidazolium based aqueous ionic liquid droplet on a rough surface: a molecular dynamics study

Ionic liquids (ILs) have garnered immense attention due to their tunable physicochemical properties. In this study, we delve into the wetting behaviour and interfacial properties of aqueous binary IL mixtures containing [EMIM] [BF4] and [HMIM] [BF4] on both smooth and rough graphite surfaces. Employing classical molecular dynamics simulations, we systematically explored the effects of IL concentration and surface morphology on wetting phenomena. To ensure the equilibrium of the systems, we began by calculating the interaction energies between the components. Subsequently, contact angles were computed, shedding light on the wetting characteristics of the aqueous binary IL mixtures. We meticulously examined the density profiles of the IL systems from the substrate to unravel the dominance of one IL over the other, exploiting the hydrophilic nature of [EMIM] [BF4] and the hydrophobic nature of [HMIM] [BF4]. A comprehensive analysis of hydrogen bond distribution allowed us to discern the intricate nature of these aqueous binary IL droplets. We probed the changes in intermolecular forces within the aqueous IL solution by investigating surface tensions. The tunability of these ILs emerges as a significant aspect of our study, paving the way for their tailored application in engineering and scientific domains. Schematic diagram showing the density distribution of hydrophilic and hydrophobic ILs ([EMIM] [BF4] and [HMIM] [BF4]) in water and also the hydrogen bond (HB) distribution of anion ([BF4]−) water inside the droplet on a pillared surface with a surface fraction ( f ) of 0.4 and pillar height of H = 4 .

Investigation of the double layer structure of 1-butyl-3-methylimidazolium thiocyanate at the air-water interface using sum-frequency generation vibrational spectroscopy.

The interfacial structure and adsorption behavior of 1-butyl-3-methylimidazolium thiocyanate ionic liquids (ILs) aqueous solutions were investigated using sum-frequency generation vibrational spectroscopy (SFG-VS) and surface tension measurements. Polarization-dependent measurements revealed a dramatic increase in the SFG signal for both CH and CN stretching modes with increasing ILs concentration, reaching a maximum at a mole fraction of 0.01. This concentration dependence was accompanied by a dramatic drop in surface tension. Upon further increasing the concentration, surface tension varied slightly and reached a constant value, while the SFG signal decreased significantly. Quantitative polarization analysis showed that as the bulk concentration increased, the apparent molecular orientation of the SCN- transition dipole at the interface changed from 51° to 46°, and the tilt angle of CH3 group of the butyl chain attached to the imidazole cationic ring changed from 18° to 32°. The decrease in the SFG signal can be explained by the formation of a double layer adsorption structure at the air/water interface. It was also demonstrated that the anions were adsorbed at the interface simultaneously with the cationic group, rather than by successive adsorption as proposed in a previous study. Using the Shereshefsky model, the thermodynamic Gibbs free energy of adsorption deduced from surface tension data was compared with SFG results.

Choline Oxidase and Choline Ionic Liquids in Biocatalytic Heme Peroxidase Cascades

Choline oxidase from Alcaligenes sp. (ChOx) is used to generate hydrogen peroxide in situ from choline‐based ionic liquids (ILs) to fuel peroxidase‐mediated biocatalysis, while mitigating oxidative degradation of the heme‐dependent enzymes. Horseradish peroxidase (HRP) and chloroperoxidase from Caldariomyces fumago (CPO), in combination with the ChOx, are evaluated in enzymatic cascades for the ability of the biocatalytic systems to withstand elevated concentrations of different choline additives in oxidative and halogenative enzymatic assays. The findings are applied in various synthetic scenarios to produce important oxygen‐ and nitrogen‐containing heterocycles, using choline ILs in a dual‐purpose fashion, as a substrate‐solubilizing component in the reaction medium as well as the source for hydrogen peroxide. The ChOx/HRP couple is used to induce intramolecular cyclizations of hydroxamic acids and hydroxycarbamates in a nitroso‐ene‐type pathway with choline dihydrogen phosphate as IL additive. The ChOx/CPO cascade successfully mediates brominative cyclizations of α‐allenic alcohols, while amphiphilic surfactants are employed to turn the aqueous choline propionate IL media into a colloidal suspension. ChOx/CPO partnering is also evaluated in an oxygenative rearrangement of 1‐furylethanol with choline acetate IL. The results show the wide potential of choline oxidase for hydrogen peroxide‐driven biocatalysis with both aqueous and micellar choline ionic liquid solutions.

Temperature-dependent physicochemical studies of sodium salicylate in aqueous solutions of ionic liquids {[BMIm]Br and [EMIm]Cl}

The current study explores the impact of two different imidazolium based ionic liquids, having diverse side chains and anions: 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) and 1‑butyl‑3-methylimidazolium bromide ([BMIm]Br) on the thermodynamic and transport properties of sodium salicylate. This inquiry examines the sodium salicylate's density, sound velocity, and viscosity within aqueous solutions of these ionic liquids across a temperature range of 283.15 K to 313.15 K at atmospheric pressure. Various parameters, including apparent molar volume (Vϕ), limiting apparent molar volume (Voϕ), transfer volume (ΔtrV∘ϕ), limiting apparent molar expansibility (E∘∅), Hepler's constant, apparent molar isentropic compression (Kϕ,s), limiting apparent molar isentropic compression (K∘ϕ,s), transfer parameter of isentropic compression (ΔtrK∘ϕ,S), and viscosity B-coefficient, were computed from experimental values. Additionally, we have analyzed the trends in computed parameters, considering the interactions between `solute and solvent along with solute-solute interactions in the systems under investigation. Our results suggest a predominance of hydrophilic-hydrophilic and ion-hydrophilic interactions within studied systems. The observed magnitudes of these parameters affirm a stronger interaction between sodium salicylate and [BMIm]Br in comparison to those with [EMIm]Cl.

Competitive Effects of Anions on Protein Solvation by Aqueous Ionic Liquids.

The present study utilizes molecular dynamics simulations to examine how different anions compete for protein solvation in aqueous solutions of ionic liquids (ILs). Ubiquitin is used as model protein and studied in IL mixtures sharing the same cation, 1-ethyl-3-methylimidazolium (EMIM), and two different anions in the same solution, from combinations of dicyanamide (DCA), chloride (Cl), nitrate (NO3), and tetrafluoroborate (BF4). Our findings reveal that specific interactions between anions and the protein are paramount in IL solvation, but that combinations of anions are not additive. For example, DCA exhibits a remarkable ability to form hydrogen bonds with the protein, resulting in a significantly stronger preferential binding to the protein than other anions. However, the combination of DCA with NO3, which also forms hydrogen bonds with the protein, results in a smaller preferential solvation of the protein than the combination of DCA with chloride ions, which are weaker binders. Thus, combining anions with varying affinities for the protein surface modulates the overall ion accumulation through nonadditive mechanisms, highlighting the importance of the understanding of competition for specific interaction sites, cooperative binding, bulk-solution affinity, and overall charge compensations, on the overall solvation capacity of the solution. Such knowledge may allow for the design of novel IL-based processes in biotechnology and material science, where fine-tuning protein solvation is crucial for optimizing performance and functionality.

Exploration of diverse interactions of nonionic poly(vinylpyrrolidone) (PVP) and anionic sodium carboxymethylcellulose (NaCMC) polymers in aqueous imidazolium-based surface active ionic liquid solutions

The binding interactions in complex formation between surface active ionic liquids (SAILs) and polymers (nonionic or anionic) are gaining attention because of their potential applications in novel materials. Therefore, the use of a variety of measurements is required for a better understanding of the interactions involved in polymer/SAIL formation. Here, we have investigated the interactions of nonionic poly(vinylpyrrolidone) (PVP) and anionic sodium carboxymethylcellulose (NaCMC) polymers with SAIL 1-tetradecyl-3-methylimidazolium chloride [C14mim][Cl] in aqueous solution using different measurements such as conductivity, surface tension, fluorescence spectroscopy, dynamic light scattering (DLS) and rheometric measurements. The surface tension, conductivity and fluorescence profiles for SAIL-NaCMC systems provide distinct breakpoints that correspond to four different aggregation states: the concentration at which SAIL monomers begin to attach to the polymer chain (C1), the critical aggregation concentration C2 (cac), the saturation concentration (CS) and the critical micelle concentration (cmc). In the case of SAIL-PVP systems, the surface tension and fluorescence profiles confer three transition states: C2 (cac), CS and cmc and only two transition states have been observed in conductivity curves. The cooperative binding of SAIL to the NaCMC/PVP chain at the solution interface was analyzed by calculating various thermodynamic and interfacial parameters. Strong complexation was observed between NaCMC-SAIL molecules compared to PVP-SAIL systems at the air-solution surface. This is due to the non-ionic character of the PVP chain, which shows weak interactions with SAIL in comparison to NaCMC. Furthermore, DLS and fluorescence measurements were used to investigate the interactions between SAIL and polymers.

Studies on wetting behaviour of pure and aqueous protic ionic liquids (PIL) solutions on different surfaces: ILphobicity to ILphilicity

In this study, the wetting behaviour of pure protic ionic liquids (PILs) and their mixture with water was studied at ambient conditions. Ethanolammonium acetate [EAAc], ethanolammonium butyrate [EABu], and ethanolammonium hexanoate [EAHx] were used as PILs for the wetting studies on various surfaces. The contact angle and wetting area of pure and mixed PIL solutions were determined on superhydrophobic, hydrophilic, and total wetting surfaces. Smaller alkyl chain PIL, ethanolammonium acetate (EAAc) displayed the highest contact angle (CA) of 141° on superhydrophobic surfaces. On hydrophilic polycarbonate (PC), shorter anionic chain PILs demonstrated CA < 90°, showing the ILphilic behaviour, and the variation of CA was PIL anionic chain length dependent. Total wetting glass exhibited the lowest CA for [EAAc], which increased with the PIL anionic chain. A binary mixture of PIL with water demonstrated unique wetting behaviour on the total wetting surface. The aqueous drops of EAHx exhibited a dynamic contact line on the glass surface, showing the greatest expansion in wetting area compared to drops of aqueous EAAc or aqueous EABu. This occurrence could be ascribed to the substantial decrease in water surface tension induced by the hydrophobic hexanoate anion, potentially leading to improved spreading characteristics.

On the Moisture Absorption Capability of Ionic Liquids.

Due to their many attractive physicochemical properties, ionic liquids (ILs) have received extensive attention with numerous applications proposed in various fields of science and technology. Despite this, the molecular origins of many of their properties, such as the moisture absorption capability, are still not well understood. For insight into this, we systematically synthesized 24 types of ILs by the combination of the dimethyl phosphate anion with various types of alkyl group-substituted cyclic cations─imidazolium, pyrazolium, 1,2,3-triazolium, and 1,2,4-triazolium cations─and performed a detailed analysis of the dehumidification properties of these ILs and their aqueous solutions. It was found that these IL systems have a high dehumidification capability (DC). Among the monocationic ILs, the best performance was obtained with 1-cyclohexylmethyl-4-methyl-1,2,4-triazolium dimethyl phosphate, whose DC (per mol) value is 14 times higher than that of popular solid desiccants like CaCl2 and silica gel. Dicationic ILs, such as 1,1'-(propane-1,3-diyl)bis(4-methyl-1,2,4-triazolium) bis(dimethyl phosphate), showed an even better moisture absorption, with a DC (per mol) value about 20 times higher than that of CaCl2. Small- and wide-angle X-ray scattering measurements of eight types of 1,2,4-triazolium dimethyl phosphate ILs were performed and revealed that the majority of these ILs form nanostructures. Such nanostructures, which vary with the identity of the IL and the water content, fall into three main categories: bicontinuous microemulsions, hexagonal cylinders, and micelle-like structures. Water in the solutions exists primarily in polar regions in the nanostructures; these spaces function as water pockets at relatively low water concentrations. Since the structure and stability of the aggregated forms of the ILs are mainly governed by the interactions of nonpolar groups, the alkyl side chains of the cations play an important role in the DC and temperature-dependent equilibrium water vapor pressure of the IL solutions. Our experimental findings and molecular dynamics simulation results shed light on the moisture absorption mechanism of the IL aqueous solutions from a molecular perspective.

Insight into the Inflection Point of Surface Tension in Aqueous Solution of Imidazolium-Based Ionic Liquids

Insight into the Inflection Point of Surface Tension in Aqueous Solution of Imidazolium-Based Ionic Liquids

Exploration of Solvation Consequences of Nicotinic Acid (Vitamin B3) Prevailing in Two Significant Aqueous Ionic Liquid Solutions by Physicochemical and Computational Studies

Exploration of Solvation Consequences of Nicotinic Acid (Vitamin B3) Prevailing in Two Significant Aqueous Ionic Liquid Solutions by Physicochemical and Computational Studies

Pretreatment of wastepaper with an aqueous solution of amino acid-derived ionic liquid for biochar production as adsorbent

The carbonization of lignocellulosic biomass with ionic liquids (ILs) are considered as an advantageous approach for the preparation of carbonaceous materials. The commonly used imidazolium and pyridinium based ILs have drawbacks such as toxicity, resistance to biodegradation, high cost and viscosity. These issues can be mitigated by diluting ILs with water, although excessive water content above 1 wt% can reduce the solubility of biomass. This research aims to investigate the potential of pretreating wastepaper with a “fully green” ILs, amino acid-based IL with high water content, followed by pyrolysis without IL, in enhancing the properties of biochar. For this purpose, the paper was treated with an aqueous solution of IL cysteine nitrate ([Cys][NO3]), and the IL was not involved in the pyrolysis process to prevent the formation of secondary gaseous pollutants. The findings revealed that the hemicellulose and mineral filler in the paper were eliminated during pretreatment, leading to higher carbon content but lower oxygen content. As a result, the biochar exhibited micropores of 0.42 cm3g-1 and a specific surface area of 1011.21 m2 g−1. The biochar demonstrated high adsorption capacities for Cd2+, enrofloxacin, bisphenol A, ciprofloxacin, and tetracycline, with values of 45.20 mg g−1, 49.82 mg g−1, 49.90 mg g−1, 49.88 mg g−1, and 49.65 mg g−1, respectively. The proposed mechanism for the adsorption of enrofloxacin by the biochar primarily involves physical adsorption such as pore filling and electrostatic interactions, along with chemical adsorption facilitated by graphitic nitrogen.

Performance and mechanism of DL‐alanine ionic liquid shale inhibitor

AbstractShale hydration and expansion during drilling can lead to wellbore instability, sticking, and frequent leakage accidents. To prevent these issues, an ionic liquid (IL) inhibitor solution was synthesized using DL‐alanine and 98% concentrated sulphuric acid as raw materials. The optimum composition and effect of the synthesized inhibitor in oilfield water‐based drilling fluids were evaluated through anti‐expansion, linear expansion rate, water washing resistance, and clay hydration dispersion experiments. The inhibition mechanism was investigated by thermogravimetric analysis, infrared spectroscopy, zeta potential, contact angle, and X‐ray diffraction analysis. The results show that the optimum IL consists of a 1:1 molar ratio of DL‐alanine to concentrated sulphuric acid synthesized under a reaction temperature and time of 70°C and 18 h, respectively. The resulting DL‐alanine IL exhibited the best inhibitory effect on the hydration, dispersion, and expansion of clay at a concentration of 0.5% in aqueous solution, and its linear expansion rate was only 18.49%. After adding a quantitative amount of clay to different concentrations of DL‐alanine IL aqueous solution, the expansion volume of the clay decreased and the water washing resistance significantly improved. These results provide a theoretical basis for improving the safety and efficiency of shale horizontal well drilling operations.

Toward Greater DNA Stability by Leveraging the Proton-Donating Ability of Protic Ionic Liquids.

Deoxyribonucleic acid (DNA) stability is a prerequisite in many applications, ranging from DNA-based vaccines and data storage to gene therapy. However, the strategies to enhance DNA stability are limited, and the underlying mechanisms are poorly understood. Ionic liquids (ILs), molten salts of organic cations and organic/inorganic anions, are showing tremendous prospects in myriads of applications. With a judicious choice of constituent ions, the protic nature of ILs can be tuned. In this work, we investigate the relative stability of full-length genomic DNA in aqueous IL solutions of increasing protic nature. Our experimental measurements show that the protic ionic liquids (PILs) enhance the DNA melting temperature significantly while unaltering its native B-conformation. Molecular dynamics simulations and quantum mechanical calculation results suggest that the intramolecular Watson-Crick H-bonding in DNA remains unaffected and, in addition, the PILs induce stronger H-bonding networks in solution through their ability to make multiple intermolecular H-bonds with the nucleobases and among its constituent ions, thus aiding greater DNA stability. The detailed understanding obtained from this study could bring about the much-awaited breakthrough in improved DNA stability for its sustained use in the aforesaid applications!

Advanced Uranium Removal with Pure, Nonfluorinated Ionic Liquids: Fine-Tuning Hydrophilic and Hydrophobic Properties for Enhanced Selectivity.

Ionic liquids (ILs) have significant potential for eco-friendly extraction of uranium from aqueous solutions, which is critical for nuclear technology, fuel cycle management, and environmental protection. This study examines the impact of the adjustable hydrophobic/hydrophilic properties of ILs on the removal of uranium(VI) (UO22+) from aqueous solutions utilizing both a novel hydrophilic IL (1-butoxyethyl-1-methylmorpholinium butoxyethylphosphite - Mor1-2O4-BOEP) and 1-heptyl-1-methylmorpholinium heptylphosphite (Mor1-7-HP) as an example of a hydrophobic IL with a similar structure. The transfer mechanism of uranyl ions from water to organic or solid phases closely depends on the physicochemical properties of ILs, especially their hydrophobicity. The hydrophobic Mor1-7-HP extracts uranyl via neutral complex formation as UO2(NO3)2-(Mor1-7-HP)2. Conversely, hydrophilic Mor1-2O4-BOEP induced selective precipitation as UO2(NO3)-(BOEP), transferring uranyl to the solid phase. Optimization of the working parameters, in terms of acidity of the aqueous solution and amount of ILs used, allowed the extraction of over 98% of U(VI). The stoichiometry of the organic complex and the precipitate was determined using physicochemical techniques. These tunable H-phosphonate-based ILs have advantages over traditional solvent extraction and conventional ILs, allowing easier handling, improved selectivity, and lower environmental impact. This work advances uranium separation techniques with applications in hydrometallurgy, particularly in the treatment of wastewater and radioactive waste for sustainable uranium recovery.

Unraveling the emulsifying activity of bio-based ionic liquids in the formation and stabilization of oil-in-water emulsions

Bio-based ionic liquids (ILs), especially those derived from fatty acids (FAs) have been considered promising compounds for the agri-food and bioproduct industries, due to their sustainable appeal, possibly low or non-toxic effect and the nutritional value of FAs. However, studies have been mainly focused on the use of ILs as greener solvents. This work investigated the application of ILs derived from FAs and diethanolamine as emulsifiers to form and stabilize oil-in-water emulsions using ultraturrax (PM) and high-pressure homogenization (H). The influence of the IL type obtained from different FAs (stearic or oleic acids), and vegetable oil type (sunflower or olive oil) and concentration (30:70 or 70:30, oil:water phase ratio) on the formation and stabilization of emulsions was evaluated. This study was focused on the zeta potential of IL aqueous solutions in different pH conditions, interfacial tension between vegetable oils and IL aqueous solutions at different concentrations, kinetic stability, droplet size and size distribution, optical microscopy, viscosity profile and rheological behavior of the emulsions. ILs presented highly negative ZP charge (−12.97–−74.81), high emulsifying ability at low concentrations (1 %) and led to emulsions with high kinetic stability (>30 days). The electrostatic stabilization mechanism may predominate over the steric in IL-based emulsions. The stabilization of emulsions with ILs was associated to lower oil droplet size (D3,2 = 0.60–4.09 µm, D4,3 = 0.95–9.91 μm) and emulsion viscosity (4.8 mPa·s-1.13 Pa·s), which were related to the IL molecular structure, oil type and concentration, and process. Emulsions prepared with stearic-based IL and sunflower oil by PM+H presented higher kinetic stability. The proposed ILs are presented as highly effective emulsifiers with potential application in the agri-food, pharmaceutical and cosmetic industries.

Dissolution and regeneration of starch in hydroxyl-functionalized ionic liquid aqueous solution

There have been continuous quests for suitable solvents for starch, given the importance of effective starch dissolution in its modification and subsequent materials production. In light of this, the potential of hydroxyl-functionalized ionic liquid (IL) as a promising solvent for starch was investigated. Within this study, a hydroxyl-functionalized IL 1-(2,3-dihydroxypropyl)-3-methylimidazole chloride ([Dhpmim][Cl]) was synthesized, and the dissolution of starch in this IL and its aqueous solutions was examined. Starch (5.35 wt%) was completely dissolved in [Dhpmim][Cl] within 2 h at 100 °C. The solubility of starch in [Dhpmim][Cl]-water mixtures initially increased and then decreased with rising water content. The optimal ratio was found to be 1:9 (wt/wt) water:[Dhpmim][Cl], achieving the highest solubility at 9.28 wt%. Density functional theory (DFT) simulations elucidated the possible interactions between starch and solvents. After dissolution and regeneration in the 1:9 water:[Dhpmim][Cl] mixture, starch showed no discernible change in the molecular structure, with no derivatization reaction observed. Regenerated starch exhibited a transformation in crystalline structure from A-type to V-type, and its relative crystallinity (12.4 %) was lower than that of native starch (25.2 %), resulting in decreased thermal stability. This study suggests that the hydroxyl-functionalized IL, [Dhpmim][Cl], and its aqueous solutions serve as effective solvents for starch dissolution.

Efficient Extraction of Sericin Protein from Mulberry and Non‐Mulberry Silk Fibers: Utilizing Aqueous Ionic Liquid Solutions as Green Solvents

AbstractProtein extraction from silk is a unique area of research and the foremost need is the efficient extraction of the silk proteins namely fibroin and sericin from the silk fibres, which is conventionally done using chemicals. In this work, we show that Ionic liquids (ILs) can be employed as a green and alternative method for degumming sericin from both mulberry (B. mori) and non‐mulberry (A. assamensis and P. ricini) silk. Six different ILs with varying tail lengths were studied for their degumming efficiencies. The interaction between silk proteins and IL ions involves a complex ionic disruption of hydrogen bonds, non‐polar interactions, and electrostatic effects. We have found that 1‐Butyl‐3‐methylimidazolium chloride (BMIM.Cl), 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIM.BF4) and Tetraethylammonium bromide (TEAB) bring in higher weight loss % in silk fibres compared to other ILs, indicating that it can be used in better sericin removal without significant damage to the silk fibre. TEAB emerged as a potential candidate for sericin extraction due to its promotion of protein destabilization. Additionally, no drastic changes in the structure of the extracted silk protein sericin were observed, as evident from the FTIR spectra and SEM images. This work highlights for the first time, the use of ILs for extraction of non‐mulberry silk sericin and also proves that ILs can be a potential green solvent for sericin extraction.

A novel synergistic intensification method for CO2 absorption by metal salt and task-specific ionic liquids hybrid solvent in microchannel reactor

A novel metal salt-promoting mass transfer intensification method for CO2 absorption into task-specific ionic liquids aqueous solution was proposed. The mass transfer intensification and intrinsic mechanisms of different concentrations of metal salts (NaBF4, KBF4, KCl, and CuCl2) with task-specific ionic liquids (1-aminopropyl-3-methylimidazolium tetrafluoroborate [Apmim] [BF4]) aqueous solutions for CO2 capture process were visually investigated using a microchannel reactor. The results showed that adding metal salts could remarkably enhance the interaction between metal cations and ionic liquid anions, thereby decreasing the interaction between anions and cations within the ionic liquid molecules and promoting the chemical reaction between ionic liquid cations and CO2. Under the condition of the same salt concentration, the addition of KBF4 has more obvious enhancement for mass transfer in CO2 absorption process. The mass transfer coefficient increases as the gas-liquid phase flow rate rise under slug flow condition. In addition, based on the effects of metal salt concentration, absorbent density, and gas-liquid phase flow rate on the CO2 volumetric mass transfer coefficient kLa, a new correlation for predicting the volumetric mass transfer coefficient of CO2 absorption into the hybrid solvent in microchannel reactor was proposed and validated.

Capacity of Aqueous Solutions of the Ionic Liquid 1-Ethyl-3-methylimidazolium Acetate to Partially Depolymerize Lignin at Ambient Temperature and Pressure.

Lignin is a very attractive and abundant biopolymer with the potential to be a biorenewable source of a large number of value-added organic chemicals. The current state-of-the-art methods fail to provide efficient valorization of lignin in this regard without the involvement of harsh conditions and auxiliary substances that compromise the overall sustainability of the proposed processes. Making an original approach from the set of mildest temperature and pressure conditions, this work identifies and explores the capacity of an aqueous solution of the nonvolatile ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) to partially depolymerize technical lignin (Indulin AT) by means of a treatment consisting in the simple contact at ambient temperature and pressure. Among a considerable number of valuable phenolic molecules that were identified in the resulting fluid, vanillin (yield of about 3 g/kg) and guaiacol (yield of about 1 g/kg) were the monophenolic compounds obtained in a higher concentration. The properties of the post-treatment solids recovered remain similar to those of the original lignin, although with a relatively lower abundance of guaiacyl units (in agreement with the generation of guaiacyl-derived phenolic molecules, such as vanillin and guaiacol). The assistance of the treatment with UV irradiation in the presence of nanoparticle catalysts does not lead to an improvement in the yields of phenolic compounds.

Enhanced Antimalarial Activity of Extracts of Artemisia annua L. Achieved with Aqueous Solutions of Salicylate Salts and Ionic Liquids.

Artemisinin, a drug used to treat malaria, can be chemically synthesized or extracted from Artemisia annua L. However, the extraction method for artemisinin from biomass needs to be more sustainable while maintaining or enhancing its bioactivity. This work investigates the use of aqueous solutions of salts and ionic liquids with hydrotropic properties as alternative solvents for artemisinin extraction from Artemisia annua L. Among the investigated solvents, aqueous solutions of cholinium salicylate and sodium salicylate were found to be the most promising. To optimize the extraction process, a response surface method was further applied, in which the extraction time, hydrotrope concentration, and temperature were optimized. The optimized conditions resulted in extraction yields of up to 6.50 and 6.44 mg·g-1, obtained with aqueous solutions of sodium salicylate and cholinium salicylate, respectively. The extracts obtained were tested for their antimalarial activity, showing a higher efficacy against the Plasmodium falciparum strain compared with pure (synthetic) artemisinin or extracts obtained with conventional organic solvents. Characterization of the extracts revealed the presence of artemisinin together with other compounds, such as artemitin, chrysosplenol D, arteannuin B, and arteannuin J. These compounds act synergistically with artemisinin and enhance the antimalarial activity of the obtained extracts. Given the growing concern about artemisinin resistance, the results here obtained pave the way for the development of sustainable and biobased antimalarial drugs.