Choline Chloride-based Deep Eutectic Solvents Research Articles

Enhancing CO2/N2 and CO2/CH4 Separation Properties of PES/SAPO-34 Membranes Using Choline Chloride-Based Deep Eutectic Solvents as Additives

CO2 separation is an important environmental method mainly used in reducing CO2 emissions to mitigate anthropogenic climate change. The use of mixed-matrix membranes (MMMs) arrives as a possible answer, combining the high selectivity of inorganic membranes with high permeability of organic membranes. However, the combination of these materials is challenging due to their opposing nature, leading to poor interactions between polymeric matrix and inorganic fillers. Many additives have been tested to reduce interfacial voids, some of which showed potential in dealing with compatibility problems, but most of them lack further studies and optimization. Deep eutectic solvents (DESs) have emerged as IL substitutes since they are cheaper and environmentally friendly. Choline chloride-based deep eutectic solvents were studied as additives in polyethersulfone (PES)/SAPO-34 membranes to improve CO2 permeability and CO2/N2 and CO2/CH4 selectivity. SAPO-34 crystals of 150 nm with a high surface area and microporosity were synthesized using dry-gel methodology. The PES/SAPO-34 membranes were optimized following previous work and used in a defined composition, using 5 or 10 w/w% of DES during membrane preparation. All MMMs were characterized by their ideal gas permeability using N2 and CO2 pure gasses. Selected membranes were also tested using CH4 pure gas. The results presented that 5 w/w%, in polymer mass, of ChCl–glycerol presented the best result over the synthesized membranes. An increase of 200% in CO2 permeability maintains the CO2/N2 selectivity for the non-modified PES/SAPO-34 membrane. A CO2/CH4 selectivity of 89.7 was obtained in PES/SAPO-34/ChCl-glycerol membranes containing 5 w/w% of this DES, which is an outstanding ideal separation performance for MMMs when compared to other results in the literature. FTIR analysis reiterates the presence of glycerol in the membranes prepared. Dynamic Mechanical Thermal Analysis (DMTA) shows that the addition of 5 w/w% of DES does not impact the membrane flexibility or polymer structure. However, in concentrations higher than 10 w/w%, the inclusion of DES could lead to high membrane rigidification without impacting the overall thermal resistance. SEM analysis of DES-enhanced membranes presented asymmetric final membranes and reaffirmed the results obtained in DMTA about rigidified structures and lower zeolite–polymer interaction with higher concentrations of DES.

DES/O microemulsion for solubilizing and delivering curcumin via the nasal administration to treat acute asthma

As a natural small molecule drug derived from turmeric, curcumin is known for its good biosafety and a range of beneficial effects, including anti-inflammatory, anti-spasmodic, antioxidant, antibacterial, anti-tumor, and neuroprotective effects. Even though, its insolubility in water and instability severely limit its bioavailability and clinical applications. The present study developed a deep eutectic solvent (DES) in oil microemulsion (DES/O-ME) system loaded with Cur for intranasal administration, aiming to enhance both the solubility and permeability of Cur to significantly increase its bioavailability. The project first constructed and screened the optimal choline chloride-based DES. Subsequently, the DES/O-ME system was prepared and optimized to achieve uniform particle size and stability using a pseudo-ternary phase diagram and electrical conductivity measurements. The resulting DES/O-ME system was thoroughly evaluated for its solubilization efficacy, permeability, mucosal cytotoxicity, and stability. Additionally, the therapeutic efficacy of the Cur-DES/O-ME was assessed in vivo using a murine model of allergic asthma. This comprehensive evaluation highlights the potential of the DES/O-ME system as a promising intranasal drug delivery platform to overcome the limitations of curcumin’s bioavailability and clinical application.

Enhancing the anodic dissolution uniformity of dendritic-structured refractory high entropy alloys using a split electrolytic cell with a deep eutectic solvent

The attainment of uniform anodic dissolution in dendritic-structured refractory high entropy alloys (RHEAs) during the electropolishing process is essential for their utilization in high-precision components. Nevertheless, the intricate microstructures of these materials impede uniform dissolution, resulting in suboptimal surface quality. In this work, based on a choline chloride-based deep eutectic solvent and suitable polarization parameters selected by linear scanning voltammetry, a split electrolytic cell (SEC) was proposed to alter the traditional integrated electrolytic cell (IEC) to enhance the anodic dissolution uniformity of dendritic-structured RHEAs. A much smoother surface with Ra of 0.233 μm and a smaller height discrepancy of 0.8 μm was obtained, compared to those processed in IEC at the same condition. The non-uniform anodic dissolution was mainly attributed to the cathode-forming (hydroxide ion (OH−), dissolution of tungsten (W) in the dendrite region under the attack by OH−, and the formation of by-product, i.e., the water molecule. The positive impact of SEC on dissolution uniformity could be ascribed to its role in inhibiting OH− from interacting with the anode, as well as to the enhancement of solution acidity on the anode side, which facilitated the dissolution of metal oxides. The suggested reaction pathway was subsequently validated through experiments with controlled water concentration and assessing of electrochemical kinetics. Finally, the effects of SEC under different parameters were demonstrated. This work provides valuable insight into the precise, micro/nanoscale manufacturing and green electrochemical surface finishing of RHEAs in the future.

Probing the role of hydrogen bond donors on the speciation and electrochemical behavior of Eu(III) in choline chloride-based DESs

This study explores the electrochemical properties and speciation of Eu(III) ions in choline chloride (ChCl)-based deep eutectic solvents (DESs), focusing on how different hydrogen bond donors—urea (U), ethylene glycol (EG), and malonic acid (MA)—influence the stability of europium complexes. Employing electrochemical methods, spectroscopic analysis, and theoretical approaches, the research examines how changes in hydrogen bonding during complexation affect Eu(III) coordination. Cyclic voltammetry highlights the role of complex formation and DES viscosity in controlling mass transport and electron transfer rates. Theoretical and experimental data show that the ChCl:1MA DES forms the most stable europium complex, driven by strong hydrogen bonding and robust Eu-DES interactions, as supported by optimized geometries and favorable electrochemical stability. This stability is further confirmed by the high negative binding and formation free energies of Eu(NO3)3·5H2O in all three DES systems. Photoluminescence spectroscopy reveals fluorophore formation due to interactions between hydrogen bonds and functional groups such as –NH2, –COOH, and –OH, enhancing the understanding of Eu3+-DES complexes for potential applications in materials science. By clarifying how hydrogen bond donors affect Eu(III) speciation and reactivity, this research advances lanthanide chemistry in DESs and opens avenues for designing Eu(III)-based materials with specialized properties for various technological uses.

Gold and Gold Alloys Electropolishing in Choline Chloride-Glycerol Deep Eutectic Solvents

Electropolishing (EP) is a finishing technique used to reduce the roughness of metallic surfaces while enhancing their brightness. This process enables the treatment of complex shaped parts and reduces processing time compared to conventional mechanical polishing methods. Electropolishing of precious metals typically requires the use of electrolytes containing cyanides and other toxic compounds, which reduces its attractiveness from an industrial perspective. Deep Eutectic Solvents (DES) are emerging as a good alternative for the chemical and electrochemical dissolution of valuable metals, like gold, silver and copper. However, their use in the specific context of electrochemical polishing of precious alloys has not been considered so far. This work aims to evaluate the effectiveness of choline chloride-based DES in electropolishing 18K gold alloys. Their performance will be assessed in terms of roughness reduction, brightness enhancement and color preservation, all characteristics associated with the presence of a uniform dissolution.

Pretreatment of Vine Shoot Biomass by Choline Chloride-Based Deep Eutectic Solvents to Promote Biomass Fractionation and Enhance Sugar Production.

Vine shoots hold promise as a biomass source for fermentable sugars with efficient fractionation and conversion processes. The study explores vine shoots as a biomass source for fermentable sugars through pretreatment with two deep eutectic solvents mixtures: choline chloride:lactic acid 1:5 (ChCl:LA) and choline chloride:ethylene glycol 1:2 (ChCl:EG). Pretreatment conditions, such as temperature/time, solid/liquid ratio, and biomass particle size, were studied. Chemical composition, recovery yields, delignification extent, and carbohydrate conversion were evaluated, including the influence of washing solvents. Temperature and particle size notably affected hemicellulose and lignin dissolution, especially with ChCl:LA. Pretreatment yielded enriched cellulose substrates, with high carbohydrate conversion rates up to 75.2% for cellulose and 99.9% for xylan with ChCl:LA, and 54.6% for cellulose and 60.2% for xylan with ChCl:EG. A 50% acetone/water mixture increased the delignification ratios to 31.5%. The results underscore the potential of this pretreatment for vine shoot fractionation, particularly at 30% solid load, while acknowledging the need for further process enhancement.

EFFICACY OF DEEP EUTECTIC SOLVENTS (DESs) FOR MITIGATING BIODETERIORATION IN CULTURAL HERITAGE: IN SITU EVALUATION

The preservation of stone materials faces significant challenges due to biological deterioration, compromising the visual appearance and structural integrity of artifacts. Current cleaning treatments use toxic chemical biocides, with a high impact on the environment and human health. Research is turning to eco-friendly alternatives, such as Deep Eutectic Solvents (DESs), which offer a promising combination of biocidal properties and eco-friendly, as well as features such as biodegradability, non-flammability and non-volatility. This study defines the efficacy of Choline Chloride-based DESs reported in the literature as biocides in a real case study on an outdoor exposed magmatic effusive rock at the University of Calabria. Several analytical techniques were used to define DESs biocidal efficacy, monitoring their action for 6 months. This study contributes to the evidence of DESs' ability to keep treated surfaces clean, thus promoting the long-term preservation of materials. Macroscopic and microscopic observations, spectrocolorimetry, bioluminometry and FTIR spectroscopy have highlighted the significant potential of DESs as sustainable biocidal solvents for the preservation of stone materials exposed outdoors.

Production of 5-hydroxymethylfurfural from chitosan using choline chloride-based deep eutectic solvents as catalyst

This study explores an efficient catalytic system for the conversion of chitosan into 5-hydroxymethylfurfural (5-HMF) under hydrothermal conditions. The catalysts used are deep eutectic solvents (DESs) comprising choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and various organic acids as the hydrogen bond donor (HBD). Among the DESs tested, the ChCl: oxalic acid (OA) combination exhibits the highest catalytic activity, resulting in a yield of 27.5% 5-HMF employed the optimized conditions. To elucidate the interaction between ChCl and OA, various analytical techniques were employed, including quantum chemical calculations, nuclear magnetic resonance (NMR), and Fourier transform infrared spectroscopy (FTIR). These investigations confirmed the formation of strong hydrogen-bonds between ChCl and OA. Furthermore, the solid residues obtained during the conversion process were characterized using FTIR, X-ray diffraction (XRD), and scanning electron microscopy (SEM). These analyses provide insights into the chemical structures and morphologies of the residues, revealing the gradual conversion of chitosan, along with the formation of humin by-products.

Life cycle assessment of tomato biomass residue anaerobic digestion preceded by ethanol-based organosolv and choline chloride-based deep eutectic solvent

Anaerobic digestion (AD) of lignocellulosic wastes (LW) has garnered substantial interest because of its notable energy and nutrient recovery, along with its potential for reducing greenhouse gas emissions. However, the LW is resistant to degradation, and its hydrolysis typically requires harsh conditions, hence the need for a pretreatment. Conducting a life cycle assessment (LCA) to evaluate the pretreatment of LW is an effective way to assess the environmental impacts associated with various pretreatment methods. This work evaluates and compares three scenarios for handling lignified tomato green waste (TGW), generated in the Greater of Agadir in Morocco, in terms of their environmental impacts and energy demand, using the LCA approach, performed with OpenLCA software. To achieve this aim, the impact of these scenarios on 11 indicators is studied. The analyzed management options include a base case scenario S0 where TGW undergoes a direct anaerobic digestion (AD), organosolv pretreatment of TGW followed by AD of the free-lignin fraction (S1), and choline chloride-based deep eutectic solvent (DES) delignification followed by AD of the free-lignin fraction (S2). The data used for the analysis comes from the Tamelast landfill, laboratory tests, literature, CML-IA baseline and Monte Carlo simulation calculations. The results obtained showed that the introduction of pretreatments in S1 and S2 mitigates significantly the environmental impact in different categories compared to S0. Scenario S2, with its enhanced recovery processes, shows the highest positive environmental contributions, despite its reliance on additional external electricity. S1 and S0 both respect energy circularity. Through this study, it has been demonstrated that chemical pretreatment of LW is energy, water and solvent-intensive and requires a large investment. It opens up perspectives for further works on pretreatment using natural DES technology, its development and its applications in the delignification of ligneous biomass on an industrial scale.

Enhanced water absorption in pectin-chitosan hydrogel via modification with deep eutectic solvent: Optimisation and characterisation

Natural polymers are widely available, nontoxic, and biodegradable but have lower absorption when used to create hydrogels. Thus, a new modification of hydrogel combining pectin and chitosan was developed using choline chloride-based deep eutectic solvents (DESs) with ethylene glycol (DES1), glycerol (DES2), and acetic acid (DES3) called eutectogel. DES was added due to the hydrophilic site, which can increase water absorption. The eutectogel with each DES, including control (without DES), were optimized in their ratio of pectin to chitosan (0.5:1, 1:1, 1.5:1, and 2:1) and DES concentration (10 %, 20 %, and 30 %) to obtain the highest water absorption capacity (WAC). All developed gels showed the highest WAC at a ratio 0.5:1 of pectin to chitosan, with 20 % each of DES1, DES2, and DES3 labeled as E20, G20, and A20 having WAC values of 16.02, 13.50, and 12.50 g/g, respectively, owing to the existence of additional hydrophilic sites from DES within the gel for water binding. While the WAC value for the control was 6.2 g/g, this study proves the ability of DES to increase the WAC of E20, G20, and A20 more than two times compared to the control. E20 showed the highest water sorption because of the shorter and smaller size of ethylene glycol in DES1, with two less hindered hydroxyl groups efficiently binding with water molecules compared to glycerol and acetic acid. The interactions were observed through FTIR analysis, specifically in the amino groups of chitosan and carboxyl groups of pectin at the peak of 1636 to 1642 cm−1, which served as indicators of the electrostatic interaction with the modified DES and peak 3335 to 3350 cm−1 indicated of hydrogen bonding. The hydrogen bonding was also confirmed via DSC thermal analysis at 164.06°C to 188.44 °C. Characterization with FTIR, UV–Vis, and DSC confirmed the successful integration of DES, and it revealed that the new hydrogels had better transparency and thermal stability, with E20 showing the best overall performance in enhanced water absorption.

Efficient binary diol-based deep eutectic solvent pretreatment for enhancing enzymatic saccharification and lignin fractionation from eucalyptus

An innovative binary biol-based deep eutectic solvent (DES), specifically ethylamine hydrochloride-ethylene glycol (EaCl-EG), was developed for efficient pretreatment of eucalyptus biomass. This DES exhibited superior performance in achieving high delignification (85.0%) and xylan removal (80.0%), while preserving a significant amount of cellulose (94.5%) compared to choline chloride-based DES. Notably, the pretreated eucalyptus residues showed a remarkable glucose yield of over 92.5%, representing a substantial enhancement of up to 15 times compared to untreated eucalyptus. Furthermore, the pretreated liquor yielded high-purity lignin with a yield of 97.8%, characterized by well-preserved β-O-4 structure and nanoscale dimensions. These lignin nanoparticles (LNPs) were subsequently self-assembled into lignin nanobottles (LNBs), adding further value to the pretreatment process. The proposed novel binary EaCl-EG DES presented great potential as an efficient pretreatment solvent for future biomass fractionation processes.

Viscosity of deep eutectic solvents: Predictive modeling with experimental validation

Viscosity, the measure of a fluid's resistance to deformation, is a critical parameter in many industries. Being able to accurately predict viscosity is essential for the successful design and optimization of technological processes. In this research, regression models were created to predict the viscosity of deep eutectic solvents (DESs). Machine learning models were trained using a data set of 3440 data points for two component DESs. Different algorithms, such as Multiple Linear Regression, Random Forest, CatBoost, and Transformer CNF, were employed alongside a variety of structural representations like fingerprints, σ-profiles, and molecular descriptors. The effectiveness of the models was assessed for interpolation tasks within the training data and extrapolation outside of it. The results indicate that a rigorous splitting of the dataset into subsets is necessary to accurately evaluate the performance of the models. Two new choline chloride-based DESs were prepared and their viscosities were measured to evaluate the predictive capabilities of the models. The CatBoost algorithm with CDK molecular descriptors was chosen as the recommended model. The average absolute relative deviations (AARD) of this model exhibited fluctuations during 5-fold cross-validation, ranging from 10.8 % when interpolating within the dataset to 88 % when extrapolating to new mixture components. The open access model was presented in this study (http://chem-predictor.isc-ras.ru/ionic/des/).

One-Pot Sequential Synthesis of Alkenylated Dihydroquinolinones and Hexahydroacridinones in Deep Eutectic Solvent Medium.

The sequential synthesis of N-heterocycles from saturated ketones poses significant challenges and has rarely been reported. Herein, an efficient synthesis of alkenylated dihydroquinolinones 7 and hexahydroacridinones 8 is achieved from saturated ketones 1 or 2 via dehydrogenation, cyclization, oxidation, and α-alkenylation in choline chloride-based deep eutectic solvent (DES) medium. This strategy provides alkenylated dihydroquinolinones 7 and hexahydroacridinones 8 in excellent yield from low-cost, readily available starting materials under environmentally benign conditions. Furthermore, the synthesized compounds (4, 5, 7, and 8) were investigated for their photophysical properties through absorption and emission spectral studies.

Green leaching and predictive model for copper recovery from waste smelting slag with choline chloride-based deep eutectic solvent

This research was performed to investigate the optimization of copper recovery from copper smelting slag (CSS) with a deep eutectic solvent as green reagent. The effect of important parameters on leaching efficiency of copper and zinc (as well as dissolution of iron), such as leaching time, leaching temperature, liquid/solid ratio, and particle size was studied. In order to model the copper recovery, an optimization method was used. According to the chemical analysis of CSS, the slag contains 0.9% copper, 3.3% zinc, and 36.7% iron. Also, it was found that the CSS is mainly composed of Fe2SiO4, Fe3O4, and SiO2. Copper-containing structures were determined as CuO and CuS. As a result of leaching experiments, 80% copper and 61% zinc recoveries were obtained at 48 h, 95 °C, 1/25 g·ml–1, and -33 μm. It is noted that the iron and silicon dissolution remained negligible under the selected conditions. According to the mathematical model, the highest copper leaching efficiency (up to 100%) could get under optimum working conditions as 48.5 °C leaching temperature, 40.1 hours leaching duration, and 62.3 ml·g–1 liquid/solid ratio. Also, the proposed model revealed that wide range of experimental levels can be used as leaching parameter to get desired metal leaching efficiency.

Green Approaches for the Extraction of Banana Peel Phenolics Using Deep Eutectic Solvents.

Banana peels, comprising about 35% of the fruit's weight, are often discarded, posing environmental and economic issues. This research focuses on recycling banana peel waste by optimizing advanced extraction techniques, specifically microwave-assisted (MAE) and ultrasound-assisted extraction (UAE), for the isolation of phenolic compounds. A choline chloride-based deep eutectic solvent (DES) with glycerol in a 1:3 ratio with a water content of 30% (w/w) was compared to 30% ethanol. Parameters, including sample-to-solvent ratio (SSR), extraction time, and temperature for MAE or amplitude for UAE, were varied. Extracts were analyzed for hydroxycinnamic acid (HCA) and flavonoid content, and antioxidant activity using FRAP and ABTS assays. DES outperformed ethanol, with HCA content ranging from 180.80 to 765.92 mg/100 g and flavonoid content from 96.70 to 531.08 mg/100 g, accompanied by higher antioxidant activity. Optimal MAE conditions with DES were an SSR of 1:50, a temperature of 60 °C, and a time of 10 min, whereas an SSR of 1:60, time of 5 min, and 75% amplitude were optimal for UAE. The polyphenolic profile of optimized extracts comprised 19 individual compounds belonging to the class of flavonols, flavan-3-ols, and phenolic acids. This study concluded that DESs, with their superior extraction efficiency and environmental benefits, are promising solvents for the extraction of high-value bioactive compounds from banana peels and offer significant potential for the food and pharmaceutical industries.

Recovery of Metals from the "Black Mass" of Waste Portable Li-Ion Batteries with Choline Chloride-Based Deep Eutectic Solvents and Bi-Functional Ionic Liquids by Solvent Extraction.

Lithium-ion portable batteries (LiPBs) contain valuable elements such as cobalt (Co), nickel (Ni), copper (Cu), lithium (Li) and manganese (Mn), which can be recovered through solid-liquid extraction using choline chloride-based Deep Eutectic Solvents (DESs) and bi-functional ionic liquids (ILs). This study was carried out to investigate the extraction of metals from solid powder, black mass (BM), obtained from LiPBs, with various solvents used: six choline chloride-based DESs in combination with organic acids: lactic acid (1:2, DES 1), malonic acid (1:1, DES 2), succinic acid (1:1, DES 3), glutaric acid (1:1, DES 4) and citric acid (1:1, DES 5 and 2:1, DES 6). Various additives, such as didecyldimethylammonium chloride (DDACl) surfactant, hydrogen peroxide (H2O2), trichloroisocyanuric acid (TCCA), sodium dichloroisocyanurate (NaDCC), pentapotassium bis(peroxymonosulphate) bis(sulphate) (PHM), (glycine + H2O2) or (glutaric acid + H2O2) were used. The best efficiency of metal extraction was obtained with the mixture of {DES 2 + 15 g of glycine + H2O2} in two-stage extraction at pH = 3, T = 333 K, 2 h. In order to obtain better extraction efficiency towards Co, Ni, Li and Mn (100%) and for Cu (75%), the addition of glycine was used. The obtained extraction results using choline chloride-based DESs were compared with those obtained with three bi-functional ILs: didecyldimethylammonium bis(2,4,4-trimethylpentyl) phosphinate, [N10,10,1,1][Cyanex272], didecyldimethylammonium bis(2-ethylhexyl) phosphate, [N10,10,1,1][D2EHPA], and trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate, [P6,6,6,14][Cyanex272]/toluene. The results of the extraction of all metal ions with these bi-functional ILs were only at the level of 35-50 wt%. The content of metal ions in aqueous and stripped organic solutions was determined by ICP-OES. In this work, we propose an alternative and highly efficient concept for the extraction of valuable metals from BM of LiPBs using DESs and ILs at low temperatures instead of acid leaching at high temperatures.

Probing the interaction mechanism of choline chloride-based deep eutectic solvents with flavonoid and polyphenol systems

Choline chloride-based deep eutectic solvents (DES) have been demonstrated as promising green solvents for the extraction of flavonoids and polyphenols. This study investigates the interaction between six different hydrogen bond donors (HBD) choline chloride-based DES and three types of polyphenolic flavonoid substrates. Density functional theory (DFT) and molecular dynamics (MD) simulations suggest that Cl− dominates the interaction primarily through electrostatic forces. The extraction effect of alcohol DES on rutin was optimized obviously, and the maximum interaction could reach 737.6 kJ/mol. Acid DES has a better extraction effect on anthocyanins, with a maximum interaction of 376.4 kJ/mol. With the increase of the carbon chain of HBA and the increase of the number of functional groups, the interaction between DES and the active substance decreases. As HBD, ethanolamine with both hydroxyl and amino groups showed the best effect in the extraction process of DES, forming the maximum interaction energy of 1575.8 kJ/mol. Additionally, multivariate analysis is employed to establish the relationship between different variables and interaction energy. This study provides micro-theoretical support for the extraction of flavonoids and polyphenols.

Measurement and thermodynamic modelling of the solubilities of caffeic acid, p-coumaric acid and ferulic acid in three choline chloride-based deep eutectic solvents

This work presents experimental solubility measurements for three cinnamic acid derivatives (CADs) namely caffeic acid (CA), p-coumaric acid (p-CA) and ferulic acid (FA) in three Deep Eutectic Solvents (DESs), choline chloride-1,2 butanediol (ChCl:1,2 butanediol (1:4)), choline chloride-1,4 butanediol (ChCl:1,4 butanediol (1:4)) and choline chloride-acetic acid (ChCl:Acetic Acid (1:2)). All measurements were performed in the temperature range of 293.15 to 323.15 K and at atmospheric pressure. Density and viscosity measurements of pure DESs ChCl:1,2 butanediol (1:4) and ChCl:1,4 butanediol (1:4) are also reported. ChCl:1,4 butanediol (1:4) and ChCl:1,2 butanediol (1:4) reveals the highest solvation capacity for CADs among the examined solvents, while p-CA was found to be less soluble than CA and FA in all solvents. Thermodynamic functions of dissolution were also determined using the Van’t Hoff equation and the results imply that the process is endothermic for all systems studied. Finally, UNIQUAC and NRTL activity coefficient models were satisfactorily implemented to correlate the experimental solubilities.

Effects of hydrogen bond donors on PVDF membrane modification using choline chloride-based deep eutectic solvents

Deep eutectic solvents (DESs) were investigated as promising candidates in modifications towards hydrophobic polyvinylidene fluoride (PVDF) membranes based on its hydrophilic and hygroscopic properties. Five choline chloride-based DESs with various hydrogen bond donor (HBD) components were investigated as PVDF membrane modifiers by blending it with the membrane dope solution at 2 wt%. The incorporation of DESs appeared to influence the structure and morphology of the membranes, where macrovoid formations were suppressed and the formation of thin, densely porous skin layers were promoted as observed through SEM imaging. DES incorporation showed effects in contact angle reduction of the PVDF membranes from 90.22° to 60.07°, indicating hydrophilic modifications. Additionally, modifications with DESs yielded improvements in membrane flux (62.49 L/m2·h using glycerol-HBD) and protein solute rejection (74.62 % using glucose-HBD), though the overall tensile strength of the membranes were decreased from 4.24 MPa to the lowest value of 2.92 MPa. Ultimately, DESs were shown to be significant pore-forming agents in altering the morphology of PVDF membranes, and improving the thermal stability. Among the five tested DESs, PVDF modified with glycerol-HBD DES yielded the best membrane parameters and performances. DESs were demonstrated as prospective membrane modifiers in inducing hydrophilicity and influencing membrane morphology.

Experimental and Theoretical Insights into the Intermolecular Interactions in Saturated Systems of Dapsone in Conventional and Deep Eutectic Solvents.

Solubility is not only a crucial physicochemical property for laboratory practice but also provides valuable insight into the mechanism of saturated system organization, as a measure of the interplay between various intermolecular interactions. The importance of these data cannot be overstated, particularly when dealing with active pharmaceutical ingredients (APIs), such as dapsone. It is a commonly used anti-inflammatory and antimicrobial agent. However, its low solubility hampers its efficient applications. In this project, deep eutectic solvents (DESs) were used as solubilizing agents for dapsone as an alternative to traditional solvents. DESs were composed of choline chloride and one of six polyols. Additionally, water-DES mixtures were studied as a type of ternary solvents. The solubility of dapsone in these systems was determined spectrophotometrically. This study also analyzed the intermolecular interactions, not only in the studied eutectic systems, but also in a wide range of systems found in the literature, determined using the COSMO-RS framework. The intermolecular interactions were quantified as affinity values, which correspond to the Gibbs free energy of pair formation of dapsone molecules with constituents of regular solvents and choline chloride-based deep eutectic solvents. The patterns of solute-solute, solute-solvent, and solvent-solvent interactions that affect solubility were recognized using Orange data mining software (version 3.36.2). Finally, the computed affinity values were used to provide useful descriptors for machine learning purposes. The impact of intermolecular interactions on dapsone solubility in neat solvents, binary organic solvent mixtures, and deep eutectic solvents was analyzed and highlighted, underscoring the crucial role of dapsone self-association and providing valuable insights into complex solubility phenomena. Also the importance of solvent-solvent diversity was highlighted as a factor determining dapsone solubility. The Non-Linear Support Vector Regression (NuSVR) model, in conjunction with unique molecular descriptors, revealed exceptional predictive accuracy. Overall, this study underscores the potency of computed molecular characteristics and machine learning models in unraveling complex molecular interactions, thereby advancing our understanding of solubility phenomena within the scientific community.