Search

Deep eutectic solvents have recently gained significant attention as versatile and inexpensive materials with many desirable properties and a wide range of applications. In particular, their characteristics, similar to those of ionic liquids, make them a promising class of liquid electrolytes for electrochemical applications. In this study, we utilized a local equivariant neural network interatomic potential model to study a series of deep eutectic electrolytes based on lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) using molecular dynamics (MD) simulations. The use of equivariant features combined with strict locality results in highly accurate, data-efficient, and scalable interatomic potentials, enabling large-scale MD simulations of these liquids with first-principles accuracy. Comparing the structure of the liquids to the reported results from classical force field (FF) simulations indicates that ion–ion interactions are not accurately characterized by FFs. Furthermore, close contacts between lithium ions, bridged by oxygen atoms of two amide molecules, are observed. The computed cationic transport numbers (t+) and the estimated ratios of Li+–amide lifetime (τLi–amide) to the amide's rotational relaxation time (τR), combined with the ionic conductivity trend, suggest a more structural Li+ transport mechanism in the LiTFSI:urea mixture through the exchange of amide molecules. However, a vehicular mechanism could have a larger contribution to Li+ ion transport in the LiTFSI:N-methylacetamide electrolyte. Moreover, comparable diffusivities of Li+ cation and TFSI− anion and a τLi–amide/τR close to unity indicate that vehicular and solvent-exchange mechanisms have rather equal contributions to Li+ ion transport in the LiTFSI:acetamide system. [ABSTRACT FROM AUTHOR]

The glass formation and the dipolar reorientational motions in deep eutectic solvents (DESs) are frequently overlooked, despite their crucial role in defining the room-temperature physiochemical properties. To understand the effects of these dynamics on the ionic conductivity and their relation to the mechanical properties of the DES, we conducted broadband dielectric and rheological spectroscopy over a wide temperature range on three well-established carboxylic acid-based natural DESs. These are the eutectic mixtures of choline chloride with oxalic acid (oxaline), malonic acid (maline), and phenylacetic acid (phenylaceline). In all three DESs, we observe signs of a glass transition in the temperature dependence of their dipolar reorientational and structural dynamics, as well as varying degrees of motional decoupling between the different observed dynamics. Maline and oxaline display a breaking of the Walden rule near the glass-transition temperature, while the relation between the dc conductivity and dipolar relaxation time in both maline and phenylaceline is best described by a power law. The glass-forming properties of the investigated systems not only govern the orientational dipolar motions and rheological properties, which are of interest from a fundamental point of view, but they also affect the dc conductivity, even at room temperature, which is of high technical relevance. [ABSTRACT FROM AUTHOR]

Glass formation and reorientational motions are widespread but often-neglected features of deep eutectic solvents although both can be relevant for the technically important ionic conductivity at room temperature. Here, we investigate these properties for two mixtures of ethylene glycol and ZnCl2, which were recently considered superior electrolyte materials for application in zinc-ion batteries. For this purpose, we employed dielectric spectroscopy performed in a broad temperature range, extending from the supercooled state at low temperatures up to the liquid phase around room temperature and beyond. We find evidence for a relaxation process arising from dipolar reorientation dynamics, which reveals the clear signatures of glassy freezing. This freezing also governs the temperature dependence of the ionic dc conductivity. We compare the obtained results with those for deep eutectic solvents that are formed by the same hydrogen-bond donor, ethylene glycol, but by two different salts, choline chloride and lithium triflate. The four materials reveal significantly different ionic and reorientational dynamics. Moreover, we find varying degrees of decoupling of rotational dipolar and translational ionic motions, which can partly be described by a fractional Debye–Stokes–Einstein relation. The typical glass-forming properties of these solvents strongly affect their room-temperature conductivity. [ABSTRACT FROM AUTHOR]

Using deuteron spin-lattice and spin-spin relaxometry, the reorientational dynamics of ethaline (choline chloride/ethylene glycol) and reline (choline chloride/urea) are studied in a component-selective, isotope-edited manner over a wide temperature range, thereby complementing previous work on glyceline (choline chloride/glycerol). Differences in the hydrogen bond propensities effectuate that in reline and glyceline, the choline ions move faster than the hydrogen bond donors, glycerol and urea; in ethaline, the ethylene glycol molecules are reorienting faster. For glyceline and reline, the increase in the corresponding time scale ratio indicates a pronounced strengthening of the glycerol and urea networks upon cooling, while in ethaline, the time scale ratio remains essentially constant. For the three deep eutectic solvents, a comparison of the present component-selective results with the dielectric time constants shows that the latter are primarily sensitive to the dynamics of the respective hydrogen bond donors. In a Walden-type plot, the reorientation rates, selectively determined for the hydrogen bond donors and acceptors, are compared with their conductivity and fluidity, revealing that the dynamics of the choline ions relate most directly to the charge transport. [ABSTRACT FROM AUTHOR]

Brewers' spent grain is known as the main by-product obtained during the initial stage of brewing, accounting for 85% of the overall solid by-product from the process. This material contains valuable components, including lignocellulose, proteins, lipids, minerals, vitamins, and phenolic compounds. To recover these constituents, various extraction techniques have been used. Deep Eutectic Solvents (DES) are an emerging group of green solvents utilized for the extraction of organic compounds from biomasses. DES is composed of two or more compounds that act as hydrogen bond acceptors and hydrogen bond donors. Choline chloride is mostly used as a hydrogen bond acceptor in combination with several hydrogen bond donors. While many methods can be used to prepare the solvents, heating with continuous stirring at approximately 50–80°C is the most common technique. To improve extraction efficiency, the physicochemical properties of solvent mixtures need to be considered, such as the composition of those solvents, viscosity, polarity, and molar ratio of solvents. Extraction time and temperature, solid-to-liquid ratio, and water content, are also important. This review intends to present information on deep eutectic solvents and their current application in extracting brewers' spent grain. [ABSTRACT FROM AUTHOR]

Sequential ultrasound‐ and microwave‐assisted natural deep eutectic solvents (NADES) were used for the extraction of pectin from mango peels in this study. The two different NADES composed of proline: malonic acid (Pro: MA) and choline chloride: tartaric acid (ChCl: TA) which resulted in higher pectin yield were selected for further optimization studies. The processing conditions such as sonication duration, microwave intensity, microwave processing duration, and liquid–solid ratio were optimized using Box–Behnken design. The optimized conditions are sonication duration (7.5 min), microwave intensity (40 W/g), microwave processing duration (5 min), and liquid–solid ratio (65%). The physicochemical and technofunctional properties of pectin extracted using NADES were compared with conventional acid–extracted pectin. The moisture and ash content of NADES‐extracted pectin were within the specified limit provided by the International Pectin Producers Association. The NADES‐based extracted pectin contains galacturonic acid content higher than 65%, as mentioned by the Joint FAO/WHO Expert Committee on Food Additives and the European Commission. The higher anhydrouronic acid content of pectin (88.8 ± 0.21%–90.82 ± 0.11%) represents the superior purity of pectin. The higher degree of esterification (> 50%) indicates the extracted pectin is a high ester pectin. The similarity of FT‐IR spectra at 800–1300 cm−1 with the "fingerprint zone" of carbohydrates indicates that extracted pectin is functional pectin. The results showed that ultrasound‐ and microwave‐assisted NADES are efficient systems for extracting pectin with a high degree of esterification from mango peels. [ABSTRACT FROM AUTHOR]

Introduction: Deep eutectic solvents (DESs) have emerged as green solvents with versatile applications, demonstrating significant potential in biocatalysis. They often increase the solubility of poorly water-soluble substrates, serve as smart co-substrates, modulate enzyme stereoselectivity, and potentially improve enzyme activity and stability. Despite these advantages, screening for an optimal DES and determining the appropriate water content for a given biocatalytic reaction remains a complex and time-consuming process, posing a significant challenge. Methods: This paper discusses the rational design of DES tailored to a given biocatalytic system through a combination of experimental screening and computational tools, guided by performance targets defined by solvent properties and process constraints. The efficacy of this approach is demonstrated by the reduction of CO2 to formate catalyzed by NADH-dependent formate dehydrogenase (FDH). By systematically analyzing FDH activity and stability, NADH stability (both long-term and short-term stability after solvent saturation with CO2), and CO2 solubility in initially selected glycerol-based DESs, we were able to skillfully guide the DES screening process. Results and discussion: Considering trade-offs between experimentally determined performance metrics of DESs, 20% solution of choline chloride:glycerol in phosphate buffer (ChCl:Gly80%B) was identified as the most promising solvent system for a given reaction. Using ChCl:Gly as a co-solvent resulted in an almost 15-fold increase in FDH half-life compared to the reference buffer and stabilized the coenzyme after the addition of CO2. Moreover, the 20% addition of ChCl:Gly to the buffer improved the volumetric productivity of FDH-catalyzed CO2 reduction in a batch system compared to the reference buffer. The exceptional stability of the enzyme in this co-solvent system shows great potential for application in continuous operation, which can significantly improve process productivity. Additionally, based on easily measurable physicochemical solvent properties and molecular descriptors derived from COSMO-RS, QSAR models were developed, which successfully predicted enzyme activity and stability, as well as coenzyme stability in selected solvent systems with DESs. [ABSTRACT FROM AUTHOR]

The "New Journal of Chemistry" published by the Royal Society of Chemistry features a variety of research articles in the field of chemistry. The latest issue includes papers on topics such as the synthesis of acyclic analogues of adenosine sulfonamides, construction of covalent organic frameworks, and studies on various chemical compounds and reactions. The journal aims to connect the global chemistry community and invest profits back into the field of chemistry. [Extracted from the article]

With the continuing development in the electric industry, highly efficient heat dissipation is of great significance due to the shrinkage of electric elements and increase in energy input. Working fluid, acting as a heat transfer medium, plays a core role in the thermal management. While, traditionally used working fluids suffer from either low thermal conductivity or relatively narrow liquid range that are unable to meet the growing demands for highly efficient thermal management. In this work, a silica decorated graphene (SDG) was fabricated using a sol-gel method and dispersed in a deep eutectic solvent (DES) system with the aim at addressing the poor thermal conductivity, stability and narrow working temperature range simultaneously. It is verified that the stability of nanofluids can be significantly improved since it could be kept for one week without obvious precipitation and aggregation due to the presence of silica coating on the layer of graphene. On the other hand, an 11.26% thermal conductivity enhancement was obtained by filling only 3.0 wt.% of the SDG. Moreover, viscosity study reveals that the presence of SDG has a slight influence on the rheological property of the nanofluids. [ABSTRACT FROM AUTHOR]

Dynamic mechanical spectroscopy is a common analysis for polymers. Rectangular specimens are usually used for measurement in the solid state due to their easy designing. However, in reason of the non‐symmetric shape of sample, rectangular specimens do not experience linear stress on their all body, leading to overestimation of shear modulus. Corrections are required to determine the right shear modulus. In this present work, straight shear modulus determination is carried out using specimens with a cylindrical shape. The reliability of the technique is described on a biosourced polymer materials made of thermoplastic starch, plasticized by glycerol, choline chloride/urea mixture (ChCl/U), 1‐ethyl‐3‐methylimidazolium chloride ([EMIM]Cl) and 1‐ethyl‐3‐imidazolium acetate ([EMIM]Ac). The technique is shown to be particularly interesting to avoid any additional shaping of the specimens prior to measurements, that can be detrimental to their properties (evaporation, degradation). A comparison between cylinder and rectangular specimen has also been made to illustrate the interest of cylinder clamping on biosourced polymer material. [ABSTRACT FROM AUTHOR]

The development of new materials for the controlled release of molecules represents a topic of primary importance in medicine, as well as in food science. In recent years, eutectic solvents have been applied as releasing media due to their improved capacity to interact with specific molecules, offering a broad range of tunability. Nevertheless, their application in essential oil dissolution are rare and more data are needed to develop new generations of effective systems. Herein, three eutectic systems, respectively, composed of choline chloride and ethylene glycol (1:2 molar ratio), methyltriphenylphosphonium bromide and ethylene glycol (molar ratio 1:5), and choline chloride and glycerol (molar ratio 1:1.5) were tested as materials for the controlled release of an essential oil derived from Citrus lemon leaves. Through static headspace fractionation, followed by gas chromatographic analysis, the performances of the three systems were assessed. The specific composition of DESs was pivotal in determining the releasing polar molecules as aldehydes and alcohols. A sustainability ranking based on the EcoScale tool highlighted the superior characteristics of the choline chloride–glycerol DES. [ABSTRACT FROM AUTHOR]

Deep eutectic solvent (DES) has been considered as a useful catalyst and reaction medium for various organic transformations. Herein, we report the catalytic application of novel deep eutectic solvent- based surfactant (DES surfactant) for the selective and fast oxidation of alcohols to aldehydes. The readily accessible DES surfactants (FeCl3/BHDC) was prepared using inexpensive ferric chloride (FeCl3) and benzyl hexadecyl dimethyl ammonium chloride in a simple manner. The synthesized FeCl3/BHDC was characterized using various techniques, including, FTIR spectroscopy, thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), and energy- dispersive X-ray spectroscopy (EDS) to determine its structure. The catalytic activity of FeCl3/BHDC in the selective oxidation of various alcohols to corresponding aldehyde derivative was investigated. The results showed the reaction could be completed within very short reaction times ranging from 2 to 15 min, while achieving good to excellent yields. This protocol offers a facile strategy and excellent efficiency in selectively oxidizing various alcohol derivatives to their respective aldehydes and ketones, utilizing hydrogen peroxide in the presence of catalytic DES surfactant. [ABSTRACT FROM AUTHOR]

Piper betle L. (Piperaceae) is a herbal plant used in Thai traditional medicine for its antifungal and antiallergic properties, particularly through topical application. This study aimed to optimize the extraction of Piper betle leaves using natural deep eutectic solvents to enhance the extraction efficiency of eugenol, the active compound in Piper betle leaves. Various types of hydrogen bond donors—including glycolic acid, lactic acid, malic acid, tartaric acid, ascorbic acid, and citric acid—were combined with a hydrogen bond acceptor, choline chloride, to prepare natural deep eutectic solvents. The results indicated that lactic acid was the most effective hydrogen bond donor for eugenol extraction. Subsequently, the choline chloride:lactic acid molar ratios, the natural deep eutectic solvent:water mass ratios, and ultrasonication times were varied. Results showed that the optimal conditions based on one‐factor‐at‐a‐time approach were a choline chloride:lactic acid molar ratio of 1:5, a natural deep eutectic solvent:water mass ratio of 2:1, and an ultrasonication time of 30 min. Under these conditions, the eugenol concentration reached 457.22 ± 21.68 µg/mL, compared to 224.76 ± 6.99 µg/mL when ethanol was used. In conclusion, this study successfully optimized the extraction of eugenol from Piper betle leaves using natural deep eutectic solvents. These findings suggest that natural deep eutectic solvents could be a more effective solvent for the extraction of eugenol. [ABSTRACT FROM AUTHOR]

The paper production industry annually produces approximately 50 million tons of lignin, an intermediate product. While lignin has the potential for producing valuable chemicals and energy materials, an effective method for its conversion is yet to be developed. This study aims to establish a sustainable and environmentally friendly approach for electrochemically synthesizing valuable compounds from lignin with using natural deep eutectic solvents as electrolytes. The study used cyclic voltammetry (CV) for the electrochemical depolymerization of Kraft lignin, examining the effects of different scan numbers on depolymerization and the resulting lignin derivatives. Observed changes in the depolymerization peak current of lignin were reported as the number of scans increased. Choline chloride: Lactic acid (CC:LA), Choline chloride: Ethylene glycol (CC:EG), and Lactic acid:1,2-propanediol (LA:PR) were used as green electrolytes. Syringaldehyde was found to be the major compound obtained by this method. As a result of statistical analysis performed using The Grey Relations Analysis method, it was determined that the conditions that utilized Kraft lignin with the highest added value involved performing five cycles of CV scans with the CC:LA electrolyte. CV scans in DES environments increased the yield of lignin-derived phenolic compounds. [ABSTRACT FROM AUTHOR]

Phenolic compounds in jackfruit (Artocarpus heterophyllus Lam.) peel were extracted using novel sequential microwave-ultrasonic-assisted extraction (SMUAE) and a natural deep eutectic solvent (NADES). Choline chloride-lactic acid (ChCl-LA) was an optimal NADES. Optimal conditions of SMUprobeAE (SMUpAE) were 415 W microwave power, 124 s irradiation time, and 7 min ultrasonic time. Total phenolic content (TPC) of a crude extract (CJPE) under the optimum conditions was 53.16 ± 1.23 mg GAE/g DW. SMUbathAE (SMUbAE) could be used instead of SMUpAE to prevent the corrosion of the probe. The different sequences of applying ultrasonic wave and microwave did not differently influence TPC, antioxidant activity of CJPE, and microstructure of peel residues. LC-QTOF-MS/MS profiling of natural products in purified extracts (PJPE) was differently affected by ChCl-LA and 60% EtOH. Chlorogenic acid was the main phenolic compound in PJPE. Glycyrrhetinic acid was found for the first time in ChCl-LA-PJPE. Therefore, SMUbAE integrated with ChCl-LA was an alternative green technique for extraction of phenolic compounds. [ABSTRACT FROM AUTHOR]

This work studies gold nanoparticle (AuNP) nucleation and growth mechanism from deep eutectic solvent (DES)-based choline chloride and glycerol (glyceline) onto glassy carbon electrode (GCE) and its application for DNA biosensor. Investigation of the current density transients indicated that the AuNPs were formed by the simultaneous presence of Au diffusion-controlled 3D nucleation and growth and residual water reaction over the Au nuclei growing surfaces. The AuNP structure was characterized by the field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. AuNPs were used to fabricate electrochemical DNA sensor. The hybridization was monitored by cyclic voltammetry and electrochemical impedance spectroscopy measurement using potassium ferri/ferrocyanide redox probes F e (C N) 6 3 - / 4 - as the indicator probe. Results show that the biosensor exhibited a linear correlation to the logarithm of the target DNA concentration ranged from 1.10−14 M to 1.10−9 M, and the limit of detection was 1.10−14 M. Furthermore, the findings indicate that the prepared electrode exhibited excellent reproducibility and long-term stability when applied for determining M. tuberculosis samples. [ABSTRACT FROM AUTHOR]

Gas dehydration plays a critical role in gas refining processes due to the potential problems caused by the presence of water vapor. The inclusion of water vapor can lead to issues such as hydrate formation, pressure drop, and pipeline corrosion. In this research, a deep eutectic solvent (DES) absorbent was employed to absorb water vapor and subsequently, its absorption performance was compared with the absorption of tri-ethylene glycol (TEG) and lithium chloride, the most commonly used absorbents in water vapor separation processes. To do so, the influence of several effective parameters, including the inlet air flow rate, different ratios of choline chloride to urea (ChCl:Urea), the weight percentage of liquid water in the absorbent, and the viscosity of DES were investigated. The results demonstrated that DES is highly efficient for water vapor separation, outperforming both TEG and aqueous lithium chloride solutions. Moreover, increasing the inlet air flow rate was found to decrease absorption recovery due to reduced residence time. Additionally, a ChCl ratio of 1:2 yielded the highest absorption efficiency. [ABSTRACT FROM AUTHOR]

Environmental hazards, especially particulates, and microbiological pollutants, have resulted in significant negative impacts on human health. In this study, 3D biodegradable cellulose filters were made from nanocellulose and tested for the removal efficiency of airborne particulates. Cellulose was first extracted from palm empty fruit bunches (EFBs) using green Deep Eutectic Solvents (DESs) under moderate temperature and then homogenized at high pressure to produce cellulose at the nanoscale size. Three types of renewable choline chloride (ChCl)‐based DESs were used: lactic acid, 1,3‐butanediol, and oxalic acid. The maximum cellulose yield from DES pretreatment was 38.78 % based on raw EFB (100 % cellulose yield based on cellulose in EFB) with ChBu60 C and the maximum nanocellulose yield was 68.49 % based on cellulose in EFB with ChLa80 C after 12‐pass high pressure homogenization. The cellulose air filter was fabricated using tert‐butyl alcohol (tBuOH) solvent exchanged under freeze‐drying conditions and characterized by different state‐of‐the‐art techniques. It was shown that the ChBu80 C filter had the lowest pressure drop (10.16 mmH2O or 2.07 mmH2O cm−2) and the maximum particle filtration efficiency (32.51 % for 0.1 μm and 93.63 % for 1.0 μm particles). The process simulation and techno‐economic analysis were performed for nanocellulose production and air filter fabrication to select the most feasible technology. [ABSTRACT FROM AUTHOR]

Enzymatic hydrolysis of polyethylene terephthalate (PET) for surface modification of polyester fibers has attracted considerable research attention in recent years. However, the high crystallinity of polyester fibers, combined with limited enzyme activity and stability, challenges the surface modification study of enzymes. Deep eutectic solvents (DES) can create a favorable environment for proteins and are a new generation of biodegradable solvents. Few studies have been conducted on the use of DES to enhance enzymatic degradation. Therefore, we attempted to hydrolyze PET with DES-activated enzymes to increase the hydrolysis yield and thus improve PET modification. Using betaine and choline chloride as hydrogen bond acceptors and polyols as hydrogen bond donors, we investigated the effects of DES type, molar ratio, and concentration on enzymatic hydrolysis. Humicola insolens cutinase (HiC) was used as the biocatalyst for PET fabric hydrolysis, the role of DES as an additive in improving the yield of enzymatically hydrolyzed PET fabric was investigated. The results showed that under the conditions of an enzyme concentration of 6.5% v/v (volume of enzyme on the total volume), a temperature of 60 °C, and a reaction time of 72 h, the low concentration (20% v/v) of DES (betaine: sorbitol; 1:2 molar ratio) increased the hydrolysis yield by more than 1.5 times. Enzymatic hydrolysis in DES aqueous solution (betaine: sorbitol; 1:2 molar ratio) and DES single-component aqueous solution (betaine, sorbitol without synthesis of DES) indicated that the increase in hydrolysis yield was mainly due to the formation of hydrogen bonds between betaine and sorbitol, rather than the superposition of individual components. Further analysis revealed that HiC exhibited high relative enzyme activity and stability at low DES concentrations. Additionally, CD spectroscopy and fluorescence spectroscopy analyses demonstrated the effective preservation of HiC structure by DES. Our work provides insights into the development of efficient and sustainable methods to enhance HiC hydrolysis of PET fabric, unlocking new opportunities and potential for the comprehensive utilization of DES in the bio-modification of PET fabric. [ABSTRACT FROM AUTHOR]

A new polyol derived from gamma-valerolactone with 10 carbon chain and four hydroxyl groups was used in combination with choline chloride for the production of a deep eutectic solvent (DES) employed as plasticizer for chitosan. The polyol estimated boiling point was 340 °C and the glass transition temperature (Tg) was − 6 °C. No crystallization temperature was observed due to the non-symmetric structure of polyol and because it is a mixture of stereoisomers. A eutectic condition was detected in an interval of choline chloride(ChCl)/polyol composition from 2:1 to 1:10. It was observed that only the mixtures with higher ChCl content showed melting points, so the eutectic composition was chosen by the lowest Tg that was obtained by the 1:1 molar ratio mixture, circa − 40 °C. This ChCl/Polyol composition was used to prepare plasticized chitosan film, by hot pressing. The glycerol/choline chloride mixture was also used as DES for comparison purposes. Both DES acted as plasticizer to obtain chitosan thermoplastic films, verified by the significant Tg drop from 165 °C, for unplasticized film, to -2 °C and − 30 °C, for films plasticized with DES based on ChCl-polyol and ChCl-glycerol, respectively. The materials plasticized with ChCl-polyol, showed a decrease in modulus of about 54% and an increase of 455% in elongation compared to ChCl/Glycerol, indicating better plasticization efficiency of the polyol based DES. The use of ChCl/Polyol have opened up a new opportunity for the use of chitosan as a plastic material and the high boiling point of polyol has made it a real and highly stable plasticizer. [ABSTRACT FROM AUTHOR]

AbstractThe present study reports the green synthesis of cellulose nanocrystals from the shells of Sterculia foetida (SFS) cellulose. Three different methods, alkali, acid and organic acid, were screened for the maximum cellulose extraction. A maximum cellulose yield, 30.6 ± 0.84 w/w, was obtained using 90% formic acid at 110 °C in 120 min. The extracted cellulose was characterized and identified by instrumental analyses. SEM analysis showed skeletal rod-like microfibril structures and similar intra-fibrillar widths. CP/MAS 13C NMR and FTIR spectrum revealed the purity of cellulose and the absence of other components like hemicellulose and lignin. XRD study revealed a cellulose crystallinity index of 88.07%. BET analysis showed a good surface area (3.3213 m2/g) and a micro-pore area of 1.871 m2/g. The cellulose nanocrystals were synthesized from the extracted cellulose using deep eutectic solvents (DES), choline chloride and lactic acid (1:2 ratio). The cellulose nanocrystals (CNC) synthesized from DES-based exhibited zeta potential and particle size of −16.7 mV and 576.3 d.nm. DES-synthesized cellulose nanocrystals were spherical-like shapes, as observed from TEM images. The present results exposed that formic acid is an effective and green catalyst for the extraction of cellulose and DES for the sustainable synthesis of CNC. [ABSTRACT FROM AUTHOR]

This research introduces a new method to synthesize poly(vinyl) alcohol (PVA)-based deep eutectic solvent (DES)-supported anion-exchange membranes (AEMs) for alkaline fuel cell (AFC) applications. The fabrication method involved the modification of a PVA-based crosslinked nanofiber mat with DES prepared by mixing choline chloride (ChCl) and ethylene glycol (EG) in a 1:3 molar ratio. Various concentrations of glutaraldehyde (GA) solution were used to cross-link of the PVA fibers. The composite AEM developed using DES was designated as DES3@PVA4 and showed improved performance with a high hydroxide conductivity of 1.05 mS/cm at 60 °C, which is higher than that of the unmodified AEM (0.77 ± 0.01 mS/cm at 60 °C). The absence of swelling, enhanced elongation at break, and improved alkaline stability were further confirmed for the DES-modified AEM; the ionic conductivity remained stable after one month of soaking in 1 M potassium hydroxide solution. These results demonstrate that DES-enhanced PVA-based AEMs can be used for AFCs with improved conductivity, flexibility, mechanical strength, and alkaline stability compared to conventional AEMs. [ABSTRACT FROM AUTHOR]

Choline chloride (ChCl) based binary and ternary deep eutectic solvents (DES) were evaluated for methylene green electropolymerization with oxalic acid (OA) and ethylene glycol (EG) as hydrogen bond donors. Binary DES ChCl : OA in molar ratios 1 : 1 and 2 : 1 and ChCl : EG 1 : 2 and ternary DES (tDES) in different molar ratios and percentages of water were evaluated. The highest polymer growth was in ChCl : OA : EG‐tDES with 13% added water, that had a lower viscosity and higher ionic conductivity when associated with HCl as dopant. This enhanced the formation of more cation radicals and, consequently, more polymer formation. The PMG/MWCNT/GCE‐tDES sensor was successfully applied to the simultaneous determination of 5‐aminosalicylic acid (5‐ASA) and acetaminophen (APAP) by differential pulse voltammetry in the concentration range 1 μM–200 μM, with detection limits of 0.37 μM and 0.49 μM for 5‐ASA and APAP, respectively. The sensor demonstrated good repeatability, reproducibility and stability, and was successfully applied in pharmaceutical formulations. [ABSTRACT FROM AUTHOR]

ABSTRACT We develop a nonsolvatochromic comparison method for the determination of the α1 scale of solvent hydrogen‐bond acidity by means of 19F NMR spectrometry. We compare the 19F chemical shifts of 4‐fluoro‐2‐methylpyridine (as a sensitive hydrogen‐bond acceptor probe) and of 4‐fluoronitrobenzene (as a chemically similar but less basic reference probe). This so‐called 19F solvatomagnetic comparison method yields the hydrogen‐bonding contribution to δ (19F)(4‐fluoro‐2‐methylpyridine) that is well correlated to α1 values obtained from the solvatochromism of Reichardt's betaine dye. Therefore, this solvatomagnetic comparison method is applied to determine the α1 values of 13 choline chloride–based deep eutectic solvents. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) are popular green media used for various industrial, pharmaceutical, and biomedical applications. However, the possible compositions of eutectic systems are so numerous that it is impossible to study all of them experimentally. To remedy this limitation, the solubility landscape of selected active pharmaceutical ingredients (APIs) in choline chloride- and betaine-based deep eutectic solvents was explored using theoretical models based on machine learning. The available solubility data for the selected APIs, comprising a total of 8014 data points, were collected for the available neat solvents, binary solvent mixtures, and DESs. This set was augmented with new measurements for the popular sulfa drugs in dry DESs. The descriptors used in the machine learning protocol were obtained from the σ-profiles of the considered molecules computed within the COSMO-RS framework. A combination of six sets of descriptors and 36 regressors were tested. Taking into account both accuracy and generalization, it was concluded that the best regressor is nuSVR regressor-based predictive models trained using the relative intermolecular interactions and a twelve-step averaged simplification of the relative σ-profiles. [ABSTRACT FROM AUTHOR]

The chemical stability of tetramethylammonium (TMA) head groups, both with and without the presence of a choline chloride and ethylene glycol-based deep eutectic solvent (DES), was studied using Density Functional Theory (DFT) calculations and ab initio Molecular Dynamics (MD) simulations. DFT calculations of transition state energetics ( Δ E reaction , Δ G reaction , Δ E activation , and Δ G activation ) for key degradation mechanisms, ylide formation (YF) and nucleophilic substitution ( S N 2 ), suggested that the presence of DES enhances the stability of the TMA head groups compared to systems without DES. Ab initio MD simulations across hydration levels (HLs) 1 to 5 indicated that without DES, YF dominates at lower HLs, while S N 2 does not occur. In contrast, both mechanisms are suppressed in the presence of DES. Temperature also plays a role: without DES, YF dominates at 298 K, while S N 2 becomes prominent at 320 K and 350 K. With DES, both degradation mechanisms are inhibited. These findings suggest DES could improve the chemical stability of TMA head groups in anion exchange membranes. [ABSTRACT FROM AUTHOR]

This study aimed to determine the effectiveness of different green extraction techniques (GETs) on targeted bioactive compounds from artichoke leaf by-products using deep eutectic solvent extraction (DESE), supercritical CO2 extraction (SCO2E), subcritical water extraction (SWE), and ultrasound-assisted extraction (UAE). Moreover, (HR) LC-ESI-QTOF MS/MS and HPLC-PDA analyses were used to perform qualitative–quantitative analysis on the extracts, enabling the detection of several bioactive compounds, including luteolin, luteolin 7-O-glucoside, luteolin 7-O-rutinoside, apigenin rutinoside, chlorogenic acid, and cynaropicrin as the most representative ones. SWE showed better results than the other GETs (TPC: 23.39 ± 1.87 mg/g of dry plant, dp) and appeared to be the best choice. Regarding UAE, the highest total phenols content (TPC) was obtained with 50:50% v/v ethanol: water (7.22 ± 0.58 mg/g dp). The DES obtained with choline chloride:levulinic acid showed the highest TPC (9.69 ± 0.87 mg/g dp). Meanwhile, SCO2E was a selective technique for the recovery of cynaropicrin (48.33 ± 2.42 mg/g dp). Furthermore, the study examined the antioxidant activity (1.10–8.82 mmol Fe2+/g dp and 3.37–31.12 mmol TEAC/g dp for DPPH• and FRAP, respectively) and total phenols content via Folin–Ciocalteu's assay (198.32–1433.32 mg GAE/g dp), of which the highest values were detected in the SWE extracts. The relationship among the GETs, antioxidant assays, and compounds detected was evaluated using Principal Component Analysis (PCA). PCA confirmed the strong antioxidant activity of SWE and showed comparable extraction yields for the antioxidant compounds between UAE and DESE. Consequently, GETs selection and extraction parameters optimization can be employed to enrich artichoke leaf by-products' extracts with targeted bioactive compounds. [ABSTRACT FROM AUTHOR]

The growing demand for more sustainable routes and processes in the mixture separation and purification industry has generated a need to search for innovations, with new solvent alternatives being a possible solution. In this context, a new class of green solvents, known as deep eutectic solvents (DESs), has been gaining prominence in recent years in both academic and industrial spheres. These solvents, when compared to ionic liquids (ILs), are more environmentally friendly, less toxic, low-cost, and easier to synthesize. In addition, they have significantly lower melting points than their precursors, offering a promising option for various applications in this industrial sector. Understanding and studying the thermodynamic behavior of systems composed of these substances in purification and separation processes, such as liquid–liquid extraction and azeotropic distillation, is extremely important. This work aimed to study the phase behavior of liquid–liquid equilibrium (LLE) and vapor–liquid equilibrium (VLE) of water + 1-butanol + DES (choline chloride + glycerol) systems with a molar ratio of 1:2. Experimental LLE data, obtained at 298.15 K and 101.3 kPa, and VLE data, obtained at 101.3 kPa and in the temperature range of 364.05 K–373.85 K, were submitted to the thermodynamic quality/consistency test, proposed by Marcilla et al. and Wisniak, and subsequently modeled using the gamma–gamma approach for the LLE and gamma–phi for the VLE. The non-random two-liquid (NRTL) model was used to calculate the activity coefficient. The results are presented for the VLE in a temperature–composition phase diagram (triangular prism) and triangular phase diagrams showing the binodal curve and tie lines (LLE). The separation and distribution coefficients of LLE were determined to evaluate the extractive potential of the DES. For the VLE, the values of the relative volatility of the system were calculated, considering the entrainer free-basis, to evaluate the presence or absence of azeotropes in the range of collected points. From these data, it was possible to compare DES with ILs as extracting agents, using data from previous studies carried out by the research group. Therefore, the results indicate that the NRTL model is efficient at correlating the fluid behavior of both equilibria. Thus, this study serves as a basis for future studies related to the understanding and design of separation processes. [ABSTRACT FROM AUTHOR]

Aiming at sustainable solutions suitable for industrial‐scale catalysis catalytic phase containing lipase and deep eutectic solvent (DES) was designed. To achieve this, both physical and chemical immobilizations of lipases were performed on the surface of silica and carbon materials. The catalytic activity of developed biosystem was tested in biotransformation of α‐angelica lactone into butyl levulinate at 60 °C. The best results were achieved for Candida antarctica lipase B adsorbed on fumed silica suspended in choline chloride: glycerol (1:2) with the addition of 20 wt% of water. Under these conditions 99.9% conversion of α‐angelica lactone and 100% selectivity to butyl levulinate were obtained after 45 min. The biocatalytic system maintained its activity for up to five consecutive reaction cycles with full conversion of lactone to ester. The heterogenization of the enzyme allowed the biocatalyst to be integrated into the bulk of the DES, which includes essential water. This combination resulted in the formation of a stable and easy‐to‐operate catalytic phase where reagents formed a second organic phase. The integration of cost‐effective biocatalyst with process efficiency provides a greener alternative with significant potential for industrial use. [ABSTRACT FROM AUTHOR]

ABSTRACT Twenty new substituted erlotinib analogs with anticancer activity were produced with good to excellent yields through the one‐step reaction of erlotinib, aromatic aldehydes, and cyclic secondary amines such as piperidine, morpholine, pyrrolidine, N‐methylpiperazine, or imidazole using nano‐CuO in choline chloride: urea (ChCl:urea) solvent under ultrasound irradiation at 80°C. MTT protocol was applied to investigate the cytotoxicity of all produced substituted erlotinib analogs in A431 (human epidermoid carcinoma cell) and HU02 (foreskin fibroblast) cell lines. The results illustrated that at a concentration of less than 10 μM, the growth of A431 cells could be inhibited by the produced compounds. Compared to erlotinib as positive control, the highest cytotoxic activity with IC50 equal to 2.58 ± 0.57 μM belonged to compound 4c carrying 4‐fluorobenzene with piperidine substitution. All of the synthesized compounds showed significant cytotoxic activity on A431, while showing no apparent cytotoxicity to HU02. The reasons for the stronger cytotoxic activity 4c can be most probably attributed to the two phenomena of greater solubility of the fluoro derivative and the flexibility of piperidine. Based on this study, compound 4c is the most promising compound with anticancer properties. [ABSTRACT FROM AUTHOR]

Extracting and purifying lignin from wood without compromising cellulose quality is a challenging process. Lactic acid: choline chloride is a deep eutectic solvent (DES) that has been identified as acceptable delignification solvent, producing lignin and hemicellulose as byproducts to the cellulose. Hemicellulose is partly transformed into furanic compounds (such as furfural and 5-HMF). While the larger lignin can be obtained by water precipitation from DES, smaller lignin molecules and furanics can be recovered by liquid–liquid extraction (LLX), either directly or after precipitation of the larger lignin molecules. The presence of water in the DES after water precipitation reduced the mutual miscibility with the solvents, allowing the use of a wider range of solvents in the LLX process. In the precipitation step, all the larger molecular weight lignin (Mw > 5000 Da) can be recovered when adding at least 3.5:1 [g/g] water to DES-black liquor. For the LLX step, guaiacol was found as suitable alternative to the previously published 2-methyltetrahedrofuran (2-MTHF). In addition, here we report the use of 2,2,5,5-Tetramethyl oxolane (TMO), a recent addition to the palette of (potentially) bio-based solvents. The distribution coefficients of smaller lignin molecules and furanics in LLX with guaiacol, TMO and 2-MTHF were compared, revealing that smaller lignin molecules (500–5000 Da) can be recovered with a reasonable distribution coefficient by 2-MTHF and guaiacol. Furfural showed distribution coefficients of at least 1.27 in all three solvents. Guaiacol and TMO both showed a significantly lower lactic acid leaching than 2-MTHF. This makes them potential alternatives for 2-MTHF in this technique. [ABSTRACT FROM AUTHOR]

5‐Hydroxymethylfurfural (5‐HMF) is an important biomass‐based platform compound that links biomass feedstocks with petrochemical refinery products. In this work, we developed a novel approach using triethylbenzylammonium chloride (TEBAC)‐based acidic deep eutectic solvents (ADESs) to synthesize 5‐HMF through the dehydration of fructose. Our approach demonstrates significant improvements in both 5‐HMF yield and process efficiency compared to conventional solvent systems. Under optimal experimental conditions (90 °C, 4.5 h), a maximum 5‐HMF yield of 97.77±3.20 % was achieved at a TEBAC:acetic acid ratio of 2 : 3 with 1 wt % fructose loading, which represents a notable advancement over other methods. Notably, our system inhibits the formation of by‐products such as levulinic acid (LA) and formic acid (FA), which are commonly detected in other dehydration processes. Additionally, higher 5‐HMF yields of 76.67±0.33 % and 73.51±1.14 % were achieved with 10 wt % and 20 wt % fructose loadings, respectively, further highlighting the scalability of the process. The acidity of ADESs was found to significantly affect the dehydration rate and yield, as demonstrated through Hammett's acidity function analysis. The key innovation of our study lies in the strategic selection of hydrogen bond donors and acceptors in the DES, enabling both high efficiency and selectivity in 5‐HMF production. These findings provide a promising pathway for large‐scale biomass conversion with reduced by‐product formation. [ABSTRACT FROM AUTHOR]

In the presented work, a new original procedure for the interfacial synthesis of the magnetic nanoparticles (MNPs) modified with a polymer shell and functionalized by an ionic liquid or a deep eutectic solvent in aqueous biphasic systems (ABSs) is proposed. The synthesis is carried out at the interface of immiscible liquids based on aqueous solutions of polyethylene glycol and inorganic salts. The advantages of the ABSs are biocompatibility, availability, and the high solvating properties of the components, which leads to control the composition and size of the prepared MNPs. The synthesis of the Fe3O4@PEG, Fe3O4@PEG@Cyphos IL 101, and Fe3O4@PEG@TOPO/butanol MNPs has been provided for biomedical and analytical applications. The morphology and structure of MNPs have been characterized by scanning and transmission electron microscopy, thermogravimetry, X-ray diffraction, and FT-IR spectroscopy. The average diameter of the MNPs is 12–14 nm with a narrow size distribution. Their superparamagnetic nature has been described using magnetometry. The synthesis parameters have been optimized and statistically analyzed using response surface methodology. The developed approach of interfacial synthesis can be potentially scaled up and/or be used to obtain nanoparticles of various composition and application. [ABSTRACT FROM AUTHOR]

The valorization potential of industrial walnut pruning wastes was investigated as a value-added product. Nanofibrillated cellulose (NFC) was prepared from walnut pruning wastes via hydrated choline chloridelactic acid deep eutectic solvent (ChCl-LA DES) pretreatment followed by grinding, and these were used as paper strength additives. The effect of reaction time on NFC properties were investigated and compared. The structure of nanocellulose was determined by Fourier transform infrared, scanning electron microscopy (SEM), and rheological analysis. The results show that carboxylated NFC having high aspect ratio could be successfully isolated after DES-pretreatment with the average diameter of 39 to 77 nm. Prepared NFC was added to the bulk suspensions of papermaking slurries at various percentages (up to 8%) together with poly(diallyldimethylammonium chloride). The drainage and electrokinetic properties of the pulp and mechanical properties of fabricated handsheets were analyzed and compared. The addition of 1% NFC to the bulk suspensions increased tensile index by 14.2% and burst index by 6.3%. There were further increases observed up to 71.8% in tensile index and up to 72.3% in burst index at 8% NFC addition. Results indicate that DES pretreated cellulose nanofibrils have great potential as reinforcing agent in papermaking. [ABSTRACT FROM AUTHOR]

In this work, deep eutectic polymer blend Choline chloride with polyvinyl alcohol (PVA) and eutectogel based on PVA and deep eutectic solvent (DES) (Choline Chloride-Xylitol) were synthesized. Quantum chemistry calculations (QCC) and Fourier transforms middle infrared (FTIR), Cl3 and H1 NMR spectroscopy were used to study the interactions between Choline Chloride and Xylitol at the formation of DES. The H–H interaction in the DES was detected in the 4.0 to 6.5 ppm range in H1 NMR, corresponding to hydrogen bonding between hydroxyl groups and chloride ions. QCC show that DES is a stable solvent with an energy gap between the donor and the acceptor of 0.39 eV. The thermal stability, viscosity and electrical resistance of the DES have been studied. The perspective of using a DES to obtain a hydrophilic polymer was shown. The FTIR results reveal that intermolecular hydrogen bonds are formed between PVA and Choline Chloride and DES Choline Chloride-Xylitol in the composites. The physical properties (thermal stability) of hydrophilic polymers were investigated. The Tonset, of the DES is 160 ºC, Tdecomp, ºC amounts to 280 ºC. For the polymers the Tdecom up to 300 and 410 ºC were increases by the Choline Chloride or DES addition, respectively. The DES has fairly high electrical (0.129 Sm/m). The eutectogel also exhibited good functional properties such as stability in various pH and absorptivity capacity. Every sample showed maximal swelling at acidic pH and reduced swelling at neutral pH; hydrogels began to swell once again at pH = 9.18. The addition of Choline Chloride and DES did not affect the microstructure of PVA. While the microstructures of PVA and the blend of PVA and Choline Chloride exhibited comparable morphologies, there was little variation when compared to pure PVA at a Choline Chloride level of 10:3. Additionally, a series of experiments was carried out to assess the eutectic polymer blend and DES-Based eutectogel antibacterial efficacy against C. albicans. [ABSTRACT FROM AUTHOR]

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

Recently, eutectogels have emerged as ideal candidates for flexible wearable strain sensors. However, the development of eutectogels with robust mechanical strength, high stretchability, excellent transparency, and desirable conductivity remains a challenge. Herein, a covalently cross-linked eutectogel was prepared by exploiting the high solubility of oligoethylene glycol in a polymerizable deep eutectic solvent (DES) form of acrylic acid (AA) and choline chloride (ChCl). The resulting eutectogel exhibited high transparency (90%), robust mechanical strength (up to 1.5 MPa), high stretchability (up to 962%), and desirable ionic conductivity (up to 1.22 mS cm−1). The resistive strain sensor fabricated from the eutectogel exhibits desirable linear sensitivity (GF: 1.66), wide response range (1–200%), and reliable stability (over 1000 cycles), enabling accurate monitoring of human motions (fingers, wrists, and footsteps). We believe that our DES-based eutectogel has great potential for applications in wearable strain sensors with high sensitivity and reliability. [ABSTRACT FROM AUTHOR]

A sustainable and scalable protocol for synthesizing variously functionalized sulfonamides, from amines and sulfonyl chlorides, has been developed using environmentally responsible and reusable choline chloride (ChCl)‐based deep eutectic solvents (DESs). In ChCl/glycerol (1 : 2 mol mol−1) and ChCl/urea (1 : 2 mol mol−1), these reactions yield up to 97 % under aerobic conditions at ambient temperature within 2–12 h. The practicality of the method is exemplified by the sustainable synthesis of an FFA4 agonist and a key building block en route to anti‐Alzheimer drug BMS‐299897. A subtle interplay of electronic effects and the solubility characteristics of the starting materials in the aforementioned DESs seem to be responsible for driving the reaction successfully over the hydrolysis of sulfonyl chlorides. The procedure's eco‐friendliness is validated by quantitative metrics like the E‐factor and the EcoScale, with products isolated by extraction or filtration after decantation. [ABSTRACT FROM AUTHOR]

Citrus fruits are widely consumed worldwide; however, one of their primary uses is juice production, resulting in over 40 million tons of agro-industrial waste. Citrus peel is the main agro-industrial by-product in citrus production. In recent years, secondary metabolites of interest, mainly polyphenols such as hesperidin, have been identified in citrus peels. Currently, green alternatives like natural deep eutectic solvents (NADES) based on choline chloride and glucose (Glu), combined with ultrasound-assisted extraction, are studied to obtain polyphenol-rich extracts with potential health applications. This study aims to evaluate the effect of: (1) molar ratios (MR) of 1:0.5, 1:1 or 1:2 mol/mol of choline chloride (ChCl):glucose (Glu); (2) the percentage of added water (WA: 50, 60 or 70%) to NADES; and (3) different citrus peels of Citrus aurantium (bitter orange), Citrus sinensis (sweet orange), and Citrus limon (lemon) used for extraction, on polyphenol profiles, total polyphenol content (TPC), and antioxidant capacity (Ax) of the extracts. The extracts were analyzed using ultra-performance liquid chromatography (UPLC) and evaluated using the Folin–Ciocalteu method for TPC and DPPH assay for quantifying AC. A factorial experimental design 33 was implemented. The extract obtained with an MR of 1:1 (ChCl:Glu) from Citrus aurantium peel exhibited the highest concentration of hesperidin (2003.37 ± 10.91 mg/100 g dry mass), whereas an MR of 1:2 (ChCl:Glu) exhibited the highest concentration of neohesperidin (1045.94 ± 1.27 mg/100 g dry mass), both using 60% WA. This extract also showed the highest antioxidant capacity, achieving 100% inhibition. On the other hand, the highest concentration of total phenolic content (TPC) (96.23 ± 0.83 mg GAE/100 g dry mass) was obtained using C. aurantium peel with an MR of 1:0.5 (ChCl:Glu) and 60% WA. The extracts also presented high concentrations of rutin and catechin. These findings highlight the potential of revalorizing citrus peels, particularly Citrus aurantium, and their extracts obtained with NADES for possible health applications. [ABSTRACT FROM AUTHOR]

Three cheap DESs comprising of N-methyldiethanolamine (MDEA) and imidazole (Im), 1,2,4-triazole, and tetrazole were investigated for capturing SO2 at low concentrations. Surprisingly, with the addition of Im, the SO2 absorption capacity and desorption efficiency were improved. Spectroscopic analysis and quantum chemical calculations confirmed that MDEA–Im effectively and reversibly captured SO2 through the hydrogen bond network and synergistic action between MDEA and Im. [ABSTRACT FROM AUTHOR]

This work focuses on the use of the deep eutectic solvent composed of choline chloride and acetic acid (1 : 2) in the pretreatment of the perennial energy crop Miscanthus, commonly called silvergrass. The pretreatment time and temperature were optimized to achieve a maximum of the glucan and minimum of the lignin contents in the pretreated biomass. In the optimization approach, the maximal glucan recovery in the pretreated solid was also considered. The performed optimization resulted in conditions (2 h 52 min and 150 °C), at which a pretreated biomass contained 74.1 wt% and 9.5 wt% of glucan and lignin respectively, and a glucan recovery was as high as 87.0 wt%. Furthermore, the biocompatibility of deep eutectic solvent was evaluated by using enzymatic hydrolysis washed and unwashed pretreated biomass produced at optimal conditions. The enzymatic hydrolysis of washed biomass resulted in higher glucan and xylan conversion than those achieved from unwashed biomass, deeming the step of biomass washing necessary. This was confirmed by the fractal kinetics modelling that confirmed higher accessibility of glucan for washed biomass than for unwashed Miscanthus sample. [ABSTRACT FROM AUTHOR]

Copyright of Food & Fermentation Industries is the property of Food & Fermentation Industries and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Pd nanoparticles (PdNPs) are deposited electrochemically on the glassy carbon electrode surface using PdCl 2 dissolved in a deep eutectic solvent composed of choline chloride and urea (reline). The morphology and particle size of the PdNPs are determined from SEM exhibiting a homogeneous distribution with potential deposition depending on particle size. The particles display a core-shell morphology, consisting of Pd(0) as the core and Pd(OH) 2 as the shell. The ethanol oxidation reaction, EOR, is evaluated at different KOH concentrations. The electrocatalyst with the highest mass activity is achieved at −750 mV potential deposition and 1 M KOH, exhibiting 3126 ± 606 mAmg Pd −1. However, when 0.1 M KOH is used the mass activity decreases to one-third the value obtained at 1 M KOH. Notwithstanding, the mass activity displayed by these PdNPs is superior to that reported for other Pd-based nanoparticles synthesized using more complex, time-consuming and costly methods reported in the literature. [Display omitted] • PdNPs were prepared by electrodeposition method using reline as DES. • The morphology of the electrodeposited PdNPs is core-shell Pd@Pd(OH) 2. • PdNPs electrodeposited at −750 mV was the best MA for EOR using 1 M KOH. • Different KOH concentrations were employed to evaluate the EOR. • The optimal concentration of KOH in the EOR was 1 M followed by 0.5 and 0.1 M. [ABSTRACT FROM AUTHOR]

α-Cyanophosphonates, which are useful reagents for the Horner–Wittig reaction, were synthesized under solvent-free conditions by using a choline chloride–zinc chloride deep-eutectic solvent (DES) as a catalyst. This is only the second report on the synthesis of these compounds. In the previous report, diethyl trimethylsilyl phosphite was used as a reagent and TiCl4 as a catalyst, whereas in this study, both the reagent (triphenylphosphine) and the catalyst (choline chloride–zinc chloride DES) are cheaper, more readily available, and less harmful than those used in the previous work. Moreover, the process involves an interesting cascade reaction between a β-nitrostyrene and two equivalents of triphenyl phosphite, leading to the desired product by a new synthetic route. The products can be used in the pharmaceutical and agricultural industries, in addition to their synthetic applications in the preparation of α,β-unsaturated nitriles. The reactions were completed on using 20 mol% of DES at 80 °C in six hours. Ten different β-nitrostyrenes were synthesized in yields of 55–87% after purification. β-Nitrostyrenes containing electron-donating groups showed higher yields. The reaction failed when aliphatic or heteroaromatic nitroalkenes or β-nitrostyrenes with electron-withdrawing substituents were employed. Finally, three plausible mechanistic routes are proposed for the reaction, starting with the nucleophilic addition of triphenyl phosphite to the carbon, nitrogen, or oxygen atom in the α-position. [ABSTRACT FROM AUTHOR]

Using natural deep eutectic solvents (NADESs) as a green reagent is a step toward producing environmentally friendly and sustainable technology. This study screened three natural DESs developed using quaternary ammonium salt and organic acid to analyse their capability to extract nickel ions from contaminated mangrove soil, which are ChCl: Acetic Acid (ChCl-AceA), ChCl: Levulinic Acid (ChCl-LevA), and ChCl: Ethylene Glycol(ChCl-Eg) at molar ratio 1:2. The impact of various operating parameters such as washing agent concentration, pH solution, and contact time on the NADES performance in the dissolution of Ni ions batch experiments were performed. The optimal soil washing conditions for metal removal were 30% and 15% concentration, a 1:5 soil-liquid ratio, and pH 2 of ChCl-LevA and ChCl-AceA, respectively. A single removal washing may remove 70.8% and 70.0% Ni ions from the contaminated soil. The dissolution kinetic of Ni ions extraction onto NADES was explained using the linear kinetic pseudo and intraparticle mass transfer diffusion models. The kinetic validation demonstrates a good fit between the experimental and pseudo-second-order Lagergren data. The model's maximum Ni dissolution capacity, Qe are 51.56 mg g−1 and 52.00 mg g−1 of ChCl-LevA and ChCl-AceA, respectively. The synthesised natural-based DES has the potential to be a cost-effective, efficient, green alternative extractant to conventional solvent extraction of heavy metals. [ABSTRACT FROM AUTHOR]

Antibacterial materials with high hydrophobicity have drawbacks such as protein adsorption, bacterial contamination, and biofilm formation, which are responsible for some serious adverse health events. Therefore, antibacterial materials with high hydrophilicity are highly desired. In this paper, UV‐curable antibacterial materials are prepared from silicone−containing Choline chloride (ChCl) functionalized hyperbranched quaternary ammonium salts (QAS) and tri−hydroxylethyl acrylate phosphate (TAEP). The materials show high hydrophilic performance because their water contact angle is as low as 19.3°. The materials also exhibit quite high antibacterial efficiency against S. aureus over 95.6%, fairly high transmittance over 90%, and good mechanical performance with tensile strength as high as 6.5 MPa. It reveals that it is a feasible strategy to develop antibacterial materials with low hydrophobicity from silicone‐modified ChCl‐functionalized hyperbranched QAS. [ABSTRACT FROM AUTHOR]

A ligand-free approach for the Suzuki-Miyaura cross coupling reaction using Natural Deep Eutectic Solvents (NaDES) towards coumarin analogs is described. A model reaction between the synthetically prepared 3-(4-acetyloxy-phenyl)-6-bromo-4-methyl-coumarin (3b) and phenylboronic acid was performed in five different NaDES as well as in pure glycerol, using two inorganic bases and palladium catalysts. The reaction proceeded smoothly in Choline Chloride/Glycerol (ChCl/Gly) and Betaine/Glycerol (Bet/Gly) NaDES at 90 °C in 24 h, affording the desired product in high yields up to 95%. The combination of K2CO3, Pd(OAc)2 and ChCl/Gly NaDES provided optimum yields and high purity of the desired compounds, while the solvent was successfully recycled and reused up to two times. The developed methodology is applicable to boronic acids bearing various substituents. The formation of palladium nanoparticles in the reaction mixture was observed, and the size of the nanoparticles was associated with the reaction yield. In addition, in all the glycerol-based NaDES, an effective removal of the acetyl group of the acetyloxy–coumarin analogs was observed; thus, it is noteworthy that the Suzuki–Miyaura coupling and the deacetylation reaction were achieved in one pot. The ten novel coumarin derivatives synthesized were structurally characterized using 1D and 2D NMR spectroscopy and were tested for their cytotoxicity against the A431 squamous cancer cell line, presenting significant activity. [ABSTRACT FROM AUTHOR]

This work studies the partition of phenolic compounds, namely caffeic acid, syringic acid, vanillic acid, ferulic acid, and vanillin, in aqueous two-phase systems (ATPSs) formed by acetonitrile and deep eutectic solvents (DESs) based on choline chloride ([Ch]Cl) and carbohydrates (sucrose, d-glucose, d-mannose, arabinose, and d-xylose). The binodal curves built at 25 °C and 0.1 MPa using DES were compared with ATPS composed of [Ch]Cl and the same carbohydrates. The ability to form ATPS depends on the number and kind of hydroxyl groups in DES's hydrogen-bond donor compound (carbohydrates). ATPS based on DES showed biphasic regions larger than the systems based on [Ch]Cl and carbohydrates alone due to the larger hydrophilicity of DES. The ATPS were used to study the partition of the phenolic compounds. For all the systems, the biomolecules preferentially partitioned to the acetonitrile-rich phase (K > 1), and the best recovery in the top phase ranged between 53.36% (caffeic acid) and 90.09% (vanillin). According to the remarkable results, DES-based ATPS can selectively separate ferulic acid and vanillin for the top phase and syringic, caffeic, and vanillic acids for the bottom phase, achieving a selectivity higher than two. [ABSTRACT FROM AUTHOR]

Pomegranate (Punica granatum L.) peel is a potential source of bioactive phenolic compounds such as ellagic acid and α- and β-punicalagin. This work explores the efficiency of natural deep eutectic solvents combined with ultrasound-assisted extraction (UAE) and pressurized liquid extraction (PLE) for their extraction. Five NaDESs were evaluated by employing UAE (25 °C, for 50 min) to determine their total phenolic content (Folin–Ciocalteu assay) and ellagic acid and α- and β-punicalagin contents (high-performance liquid chromatography (HPLC-DAD)). The NaDES composed of choline chloride (ChCl) and glycerol (Gly) (1:2, molar ratio) was the most efficient in the UAE when compared with the rest of the NaDESs and water extracts. Therefore, ChCl:Gly was further evaluated using PLE at different temperatures (40, 80, 120 and 160 °C). The PLE-NaDES extract obtained at 80 °C for 20 min at 1500 psi exhibited the highest contents of ellagic acid and α- and β-punicalagin compared to the rest of the temperatures and PLE-water extracts obtained under the same extraction conditions. Combining UAE or PLE with a NaDES emerges as a sustainable alternative for extracting ellagic acid and α- and β-punicalagin from pomegranate peel. [ABSTRACT FROM AUTHOR]