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Theophylline, a typical representative of active pharmaceutical ingredients, was selected to study the characteristics of experimental and theoretical solubility measured at 25 °C in a broad range of solvents, including neat, binary mixtures and ternary natural deep eutectics (NADES) prepared with choline chloride, polyols and water. There was a strong synergistic effect of organic solvents mixed with water, and among the experimentally studied binary systems, the one containing DMSO with water in unimolar proportions was found to be the most effective in theophylline dissolution. Likewise, for NADES, the addition of water (0.2 molar fraction) resulted in increased solubility compared to pure eutectics, with the highest solubilisation potential offered by the composition of choline chloride with glycerol. The ensemble of Statistica Automated Neural Networks (SANNs) developed using intermolecular interactions in pure systems has been found to be a very accurate model for solubility computations. This machine learning protocol was also applied as an extensive screening for potential solvents with higher solubility of theophylline. Such solvents were identified in all three subgroups, including neat solvents, binary mixtures and ternary NADES systems. Some methodological considerations of SANNs applications for future modelling were also provided. Although the developed protocol is focused exclusively on theophylline solubility, it also has general importance and can be used for the development of predictive models adequate for solvent screening of other compounds in a variety of systems. Formulation of such a model offers rational guidance for the selection of proper candidates as solubilisers in the designed solvents screening.

In this study, the temperature-dependent solubility of nicotinamide (niacin) was measured in six neat solvents and five aqueous-organic binary mixtures (methanol, 1,4-dioxane, acetonitrile, DMSO and DMF). It was discovered that the selected set of organic solvents offer all sorts of solvent effects, including co-solvent, synergistic, and anti-solvent features, enabling flexible tuning of niacin solubility. In addition, differential scanning calorimetry was used to characterize the fusion thermodynamics of nicotinamide. In particular, the heat capacity change upon melting was measured. The experimental data were interpreted by means of COSMO-RS-DARE (conductor-like screening model for realistic solvation–dimerization, aggregation, and reaction extension) for concentration dependent reactions. The solute–solute and solute–solvent intermolecular interactions were found to be significant in all of the studied systems, which was proven by the computed mutual affinity of the components at the saturated conditions. The values of the Gibbs free energies of pair formation were derived at an advanced level of theory (MP2), including corrections for electron correlation and zero point vibrational energy (ZPE). In all of the studied systems the self-association of nicotinamide was found to be a predominant intermolecular complex, irrespective of the temperature and composition of the binary system. The application of the COSMO-RS-DARE approach led to a perfect match between the computed and measured solubility data, by optimizing the parameter of intermolecular interactions.

The solubility of theobromine was studied both experimentally and theoretically. The solubility was determined spectrophotometrically at 25 °C in neat organic solvents, aqueous binary mixtures, Natural Deep Eutectic Solvents (NADES) and ternary NADES mixtures with water. It was found that addition of water in unimolar proportions with some organic solvents increases theobromine solubility compared to neat solvents. Additionally, using NADES results in a solubility increase of the studied compound not only in relation to water but also DMSO. The addition of water (0.2 molar fraction) to NADES is responsible for an even larger increase of solubility. The measured solubilities were interpreted in terms of three theoretical frameworks. The first one—belonging to the set of data reduction techniques—proved to be very efficient in quantitative back-computations of excess solubility of theobromine in all studied systems. The default approach utilizing the well-recognized COSMO-RS (Conductor-like Screening Model for Real Solvents) framework offered at most a qualitative solubility description. The extended search for possible contacts provided evidence for the existence of many intermolecular complexes that alter the electron density of the solute molecule, thus influencing solubility computations. Taking into account such intermolecular contacts by using the COSMO-RS-DARE (Conductor-like Screening Model for Realistic Solvation-Dimerization, Aggregation, and Reaction Extension) framework seriously increased the accuracy of solubility computations.

Structurally modified hydroxyl functionalized pyridinium ionic liquids (ILs), liquid at room temperature, were synthesized and characterized. Alkylated N-(2-hydroxyethyl)-pyridinium ILs were prepared from alkylpyridines via corresponding bromide salts by N-alkylation (65–93%) and final anion exchange (75–96%). Pyridinium-alkylation strongly influenced the IL physicochemical and electrochemical properties. Experimental values for the ILs physicochemical properties (density, viscosity, conductivity, and thermal decomposition temperature), were in good agreement with corresponding predicted values obtained by theoretical calculations. The pyridinium ILs have electrochemical window of 3.0–5.4 V and were thermally stable up to 405°C. The IL viscosity and density were measured over a wide temperature range (25–80°C). Pyridine alkyl-substitution strongly affected the partial positive charge on the nitrogen atom of the pyridinium cations, as shown by charge distribution calculations. On-going studies on Mg complexes of the new ILs demonstrate promising properties for high current density electrodeposition of magnesium.

The use of ionic liquids (ILs) in applications ranging from catalysis to reaction media in organic synthesis has been successfully demonstrated in several cases. For any given IL application, fundamental properties, such as viscosity, thermal stability, and toxicity have to be considered. Another property of interest is the polarity, which is a crucial indicator of solvent effects on chemical processes. Given the near-infinite combinations of cations and anions, experimental determination of solvatochromic parameters, such as the hydrogen-bond acidity and basicity, and dipolarity-polarizability is prohibitive. To address this, we evaluate the utility of alternative schemes based on parameters derived from COSMO-RS (COnductor-like Screening MOdel for Real Solvents) computations. The scheme is applied to a large library of yet-to-be-synthesized ionic liquids, to identify promising candidates for applications in biomass dissolution.

Background: Solubility is a fundamental physicochemical property of active pharmaceutical ingredients. The optimization of a dissolution medium aims not only to increase solubility and other aspects are to be included such as environmental impact, toxicity degree, availability, and costs. Obtaining comprehensive solubility characteristics of chemical compounds is a non-trivial and demanding process. Therefore, support from theoretical approaches is of practical importance., Objectives: This study aims to examine the accuracy of the reference solubility approach in the case of sulfanilamide dissolution in a variety of binary solvents. This pharmaceutically active substance has been extensively studied, and a substantial amount of solubility data is available. Unfortunately, using this set of data directly for theoretical modeling is impeded by noticeable inconsistencies in the published solubility data. Hence, this aspect is addressed by data curation using theoretical and experimental confirmations., Material and Methods: In the experimental part of our study, the popular shake-flask method combined with ultraviolet (UV) spectrophotometric measurements was applied for solubility determination. The computational phase utilized the conductor-like screening model for real solvents (COSMO-RS) approach., Results: The analysis of the results of solubility calculations for sulfonamide in binary solvents revealed abnormally high error values for acetone-ethyl acetate mixtures, which were further confirmed with experimental measurements. Additional confirmation was obtained by extending the solubility measurements to a series of homologous acetate esters., Conclusions: Our study addresses the crucial issue of coherence of solubility data used for many theoretical inquiries, including parameter fitting of semi-empirical models, in-depth thermodynamic interpretations and application of machine learning protocols. The effectiveness of the proposed methodology for dataset curation was demonstrated for sulfanilamide solubility in binary mixtures. This approach enabled not only the formulation of a consistent dataset of sulfanilamide solubility binary solvent mixtures, but also its implementation as a qualitative tool guiding rationale solvent selection for experimental solubility screening.

We have predicted acid dissociation constants (p K a ), octanol-water partition coefficients ( K ) of 150 different eight-carbon-containing poly-/perfluoroalkyl carboxylic acids (C8-PFCAs) utilizing the COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) theory. Different trends associated with functionalization, degree of fluorination, degree of saturation, degree of chlorination, and branching are discussed on the basis of the predicted values for the partition coefficients. In general, functionalization closest to the carboxylic headgroup had the greatest impact on the value of the predicted physicochemical properties.OW ), and DMPC lipid membrane-water partition coefficients ( K lipid-w ) of 150 different eight-carbon-containing poly-/perfluoroalkyl carboxylic acids (C8-PFCAs) utilizing the COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) theory. Different trends associated with functionalization, degree of fluorination, degree of saturation, degree of chlorination, and branching are discussed on the basis of the predicted values for the partition coefficients. In general, functionalization closest to the carboxylic headgroup had the greatest impact on the value of the predicted physicochemical properties., Competing Interests: The authors declare no competing financial interest.

Deep eutectic solvents (DES) present interesting properties, mostly connected to their solvation ability, and have been subject to much research in the recent past. Currently, the discovery of new eutectic solvents is accomplished by experimentally measuring the eutectic point of random systems, often using choline chloride as a hydrogen bond acceptor. In this work, the eutectic temperatures of new choline chloride-based eutectic systems were experimentally assessed. These data, along with other previously reported in the literature, were used to evaluate a method based on COSMO-RS to predict the eutectic temperature of choline-chloride based mixtures. The predictive methodology herein developed allows for the quick scanning of a large matrix of systems in order to identify those more promising to be in the liquid state at a given temperature. To validate this method, the eutectic temperature of pharmaceutical drug mixtures was predicted and, then, assessed experimentally, showing that COSMO-RS is useful in the design of liquid drug-based formulations. [ABSTRACT FROM AUTHOR]

Nowadays, green extraction processes are focused on the development of new strategies to achieve sustainable separation processes, promoting the use of alternative solvents from renewable sources. Green solvents have risen as an option that can replace petroleum based solvents, however, they should retain the same extraction properties and technological features. The choice of the solvent is a crucial step in the solvent-substitution process, so Hansen solubility parameters (HSP) have been successfully used as a real decision-making tool. For the first time, this work aims to give an overview of HSP as solvent selection tool for extraction of bioactive compounds from natural products. It includes a brief description about the emerging green solvents extraction, the HSP theory and an updated discussion of the most recent publications (from 2009 till January 2019). Finally, some concluding remarks about the importance of using this solvent selection approach in the near future are included. • Hansen solubility parameters is used as solvent selection tool for green extraction. • In the last 10 years, there has been a notably increase on HSP research publications. • Emerging extraction technologies have been employed Hansen approach with success. • Solubility of terpenes, phenolic compounds and fatty acids have been predicted by HSP. • COSMO-RS is another powerful approach employed to understand solubility mechanism. [ABSTRACT FROM AUTHOR]

In many applications, such as substitution of nonrenewable molecules by renewable ones in formulations or screening of pharmaceutical compounds, knowing whether molecules have associating properties in the liquid phase (i.e., if they are surfactants, hydrotropes, cosolvents, solvosurfactants, or cosurfactants) prior to any experiment may be useful. In this work, two new molecular properties derived from local surface polarity of molecules, denoted as polarity moment and heteropolarity, are proposed. It is shown that when predicted from Density Functional Theory (DFT)‐conductor‐like screening model (COSMO) polarization charge densities, polarity moment, heteropolarity, and polarity can help determine whether molecules are surfactants or solubilizers (hydrotropes, cosolvents, and solvosurfactants) prior to any experimental measurements. Results also indicate that these molecular properties predict cosurfactant behavior, as fatty esters and long‐chain fatty alcohols appear to cluster in a distinct region of the two‐dimensional map built by the two molecular properties. In particular, for complex molecular structures, modeling interfacially relevant conformations appeared as an important step to avoid misclassification in the process of calculating the polarity moment. [ABSTRACT FROM AUTHOR]

• 3 ammonium-based DESs were used to separate styrene from ethylbenzene by LLE. • NRTL model was successfully applied to describe the LLE behavior of all ternary systems. • The ternary tie lines for all systems were predicted using COSMO-RS approach. • 1H NMR spectroscopy confirmed the absence of DESs in the raffinate phases. Separation of styrene from ethylbenzene is challenging because of their close boiling points and similar chemical characteristics. In this study, we utilized three ammonium-based deep eutectic solvents (DESs) with glycols as hydrogen bond donors to separate styrene from ethylbenzene via liquid-liquid extraction at room temperature and atmospheric pressure, with styrene concentration in the feed mixture ranging from (10 to 80) wt%. Consistency of the experimental data was ascertained by Othmer-Tobias and Hand correlations, and the NRTL binary interaction parameters were also validated for thermodynamic consistency. Distribution ratios of styrene were found to be comparable to that obtained using ionic liquids, although the selectivity values were much lower. The ternary liquid-liquid equilibria for the systems {ethylbenzene (1) + styrene (2) + DES (3)} were correlated with the NRTL model and predicted using the COSMO-RS approach. The average RMSD from the experimental data for NRTL correlation is 1.41% and for COSMO-RS prediction is 4.74%. [ABSTRACT FROM AUTHOR]

• Solubility data of chlorinated phenols in ionic liquids is reported for the first time. • The effect of temperature on the solubility data was investigated. • The solubility of the chlorophenols depended on the structure of ionic liquids. • COSMO-RS and NRTL model were used to predict and correlate the experimental data. Chlorophenols (CPs) are synthetic chemicals that are generated and used widely by different industries such as textile, pharmaceutical, metallurgic, oil, and pulp and paper manufacturing. Except water, most of the solvents used in these industries are volatile and toxic. Therefore, there is an imminent need for replacing these solvents by solvents that have less negative impact on the environment. In addition, CPs are considered as hazardous pollutants due to their resistance to biodegradation and persistence in the environment. Their toxic effects are severe including DNA damage, endocrine disruption, cytotoxicity, mutagenicity, and carcinogenicity. Hence, the water contaminated by CPs must be treated before being released to the environment. Ionic liquids (ILs) are molten salts that are liquid below 100 °C, which have been used as solvents for many processes including liquid-liquid extraction and as electrolytes in electrochemical devices. ILs are characterized by negligible vapor pressure and non-flammability. These compounds are liquid over a wide range of temperatures; possess high thermal and chemical stability. ILs are being used as media for many reactions to reduce the negative impact of traditional solvents on the environment. In addition, using ILs as green solvents in water treatment has become a research hotspot. Solubility data of CPs in ILs is important for assessing the potential use of ILs as reaction media and in water treatment, but relevant data for ILs are scarce. To our best knowledge, no solubility data of chlorophenols in ILs were reported in the literature. Thus, in this study, the solubility of 3-chlorophenol (3-CP), 2,5-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP), and pentachlorophenol (PCP) in six hydrophobic bis(trifluoromethylsulfonyl)imide based ILs at 25 °C, 35 °C and 45 °C was investigated. It was found that the solubility of 3-CP in all studied ILs at 25 °C was greater than 70 wt%, thus the solubility measurements of 3-chlorophenol in the studied IL were stopped at 70 wt% and further measurement was not conducted. The solubility of other CPs in all studied ILs decreased with increasing the number of chlorine atoms in the CP and increased with the increase in temperature, but the degree of increase depended on the structure of both the IL and chlorinated phenol. In general, it was found that the tested chlorophenols have substantial solubility in pyridinium and imidazolium-based ILs. In addition, the non-random two-liquid model (NRTL) and Conductor-like Screening Model for Real Solvents (COSMO-RS) models were applied to predict the solubility of chlorophenols in all ILs used in this study. There was a good quantitative and qualitative agreement between experimental and calculated solubility data in most of the cases. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The kinetics of an IL synthesis is auto-catalytic. • The reaction rate coefficient is clearly dependent on the solvent environment. • Two bends in the rate coefficient are based on sudden changes in the environment. • Theoretical rate coefficients show a good accordance with the experiment. Abstract This work focuses on the ionic liquid (IL) synthesis starting from dimethyl carbonate and 1-ethylimidazole in methanol. In-situ IR-spectroscopy is used to gain time-dependent concentrations for kinetic analysis. The reaction is found to be self-accelerating, since the solvent polarity increases with the formation of the ionic product. This corresponds to a salting-out effect. Since the reaction rate is increasing in the beginning, pre-dosing of the product is proposed to enhance the overall productivity. Therefore, the space-time-yield is calculated as the arithmetic mean of the reaction rate with a varying starting point. It turns out that pre-dosing does not enhance the productivity here, since the space-time-yield of the complete reaction progress is below the initial reaction rate. Beyond that, two sharp bends can be observed in the progress of the reaction rate coefficient that point towards sudden changes in the reaction environment. The first bend can be assigned to a phase separation of the ionic liquid on a microscopical scale. The second bend takes place when the IL concentration surpasses roughly one sixth of the methanol concentration. Above that threshold, the whole amount of methanol is captured in the solvation shell of the anion monomethyl carbonate, as quantum chemical calculations suggest. Finally, the reaction rate coefficients were calculated using quantum chemical methods with respect to the solvent environment. The theoretical results show a good accordance with experimental values for the starting compositions. Thus, theoretical calculations help to estimate productive reaction mixtures. [ABSTRACT FROM AUTHOR]

A switch from batch to continuous manufacturing of gallium-68 (68Ga) and 68Ga-labeled pharmaceuticals can be advantageous, as it recycles isotopically-enriched zinc-68 (68Zn), removes pre- and post-irradiation target manipulations, and provides scalability via dose-on-demand production. Herein we report efficient extraction of radiogallium (66,67,68Ga = *Ga) from ZnCl2/HCl solutions in batch and in flow using a membrane-based liquid-liquid separator. From 5.6 M ZnCl2/3 M HCl, a 1/2 (v/v) diisopropyl ether (iPr2O)/trifluorotoluene (TFT) solvent extracts 76.3 ± 1.9% of *Ga and 1.9 ± 1.6% of Zn in flow using a single pass through. From 1 M ZnCl2/6 M HCl, a 1/2 (v/v) n-butyl methyl ether (n-BuOMe)/TFT solvent extracts 95.7 ± 2.0% of *Ga and 0.005 ± 0.003% of Zn in flow. TFT plays a key role in controlling the interfacial tension between the aqueous and the organic phases, ensuring clean membrane-based separation. The process did not extract Cu, Mn, and Co but did extract Fe. Using HGaCl4 and ZnCl2 as the extractable species, the COSMO-RS theory predicts the solvation-driven extraction of Ga and Zn with a mean unsigned error of prediction of 4.0% and 3.4% respectively. [ABSTRACT FROM AUTHOR]

Objective: The aim of this study was to explore the possibility of using natural deep eutectic solvents (NADES) as solvation media for enhancement of solubility of sulfonamides, as well as gaining some thermodynamic characteristics of the analyzed systems. Significance: Low solubility of many active pharmaceutical ingredients is a well-recognized difficulty in pharmaceutical industry, hence the need for different strategies addressing this problem. Among such strategies, those that are environmentally and economically beneficial are of particular interest. Methods: The solubility of sulfanilamide and sulfacetamide in 21 different NADES compositions comprising choline chloride with sugars or sugar alcohols was measured spectrophotometrically. Thermodynamic parameters describing the studied systems were determined using the COSMO-RS computational protocol. Results: All of the considered NADES compositions gave an increase in solubility of the studied sulfonamides, with the highest solubilities obtained for the system comprising choline chloride and glycerol in unimolar proportions, which gave a solubility advantage of 83.7 and 73.8 for sulfanilamide and sulfacetamide, respectively. Theoretical studies indicated that the dissolution of both considered sulfonamides has a low endothermic character, with the lowest enthalpy values obtained for the most optimal, i.e. unimolar, proportions. The non-monotonous trend of enthalpy of dissolution was also discussed in terms of intermolecular interactions. Conclusions: The obtained results show the feasibility of using NADES as solubility enhancers for sulfonamides and encourage for further exploration in this field. [ABSTRACT FROM AUTHOR]

Solubilities of C 4 -hydrocarbons, 1,3-butadiene (13BD), trans/cis -2-butene (T2B and C2B), 1-butene (1B), isobutene (i -But), isobutane (i -B), and butane (B), in 3267 different imidazolium-type ionic liquids (ILs) in a temperature range from 273.15 to 373.15 K were estimated by means of the COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) calculations. Simple temperature-dependent mathematical expressions were developed to predict the solubility of 13BD, C2B, T2B, 1B, i -But, i -B, and B at any temperature in a range from 273 to 373 K. The COSMO-RS results for each hydrocarbon considered were then analyzed using machine learning tools, including association rule mining and decision tree classification, using semi-empirically derived molecular descriptors of ILs. It was found that the polarizabilities of both cation and anion, together with the anion's CPK (space filling model) area, are the most important descriptors for determining the affinity of ILs towards C 4 -hydrocarbons. Results also present the selection rules for imidazolium ILs, offering opportunities for the rational design of new ILs by using these simply-determined structural descriptors to meet the desired solubility (or selectivity) requirements for each C 4 -hydrocarbon considered. • Solubility of C 4 -hydrocarbons in 3267 different imidazolium-type ionic liquids were estimated by COSMO-RS calculations. • Temperature-dependent mathematical expressions were developed to predict solubility at any temperature from 273 to 373 K. • COSMO-RS results for each hydrocarbon were analyzed using association rule mining and decision tree classification. • Ion polarizability and anion's CPK (space filling model) area are the most important structural descriptors. • Selection rules determined for imidazolium ILs offer opportunities for rational design of new ILs. [ABSTRACT FROM AUTHOR]

Abstract In this work a new method for inclusion of pressure effects in COSMO-type activity coefficient models is proposed. The extension consists in the direct combination of COSMO-SAC and lattice-fluid ideas by the inclusion of free volume in form of holes. The effort when computing pressure (given temperature, volume, and mole numbers) with the proposed model is similar to the cost for computing activity coefficients with any COSMO-type implementation. For given pressure, computational cost increases since an iterative method is needed. This concept was tested for representative substances and mixtures, ranging from light gases to molecules with up to 10 carbons. The proposed model was able to correlate experimental data of saturation pressure and saturated liquid volume of pure substances with deviations of 1.16% and 1.59%, respectively. In mixture vapor-liquid equilibria predictions, the resulting model was superior to Soave-Redlich-Kwong with Mathias-Copeman α -function and the classic van der Waals mixing rule in almost all cases tested and similar to PSRK method, from low pressures to over 100 bar. Good predictions of liquid-liquid equilibrium were also observed, performing similarly to UNIFAC-LLE, with improved responses at high temperatures and pressures. Graphical abstract Image 1 [ABSTRACT FROM AUTHOR]

Abstract Quercetin is known as a bioflavonoid compound that has been successfully optimized to be a chemosensor probe for Fe3+ recognition. The sensitivity of quercetin towards Fe3+ increased in DMSO:deionized water with a 9:1 ratio at pH 4. There was also no significant interference from other metal ions, such as K+, Cr3+, Ag+, Cd2+, Mg2+, Pb2+, Co2+, Ni2+, Zn2+ and Cu2+ in the selectivity optimization. The detection limit of the probe was 20.5 μM. The stoichiometry of 1:1 quercetin:Fe3+ was calculated using the Job plot method. The sigma profile was calculated using COSMO-RS, which showed that quercetin formed stronger hydrogen bonds with the DMSO solvent. Density functional theory (DFT) calculations, such as molecular electrostatic potential (MEP) and the Fukui function, were performed to visualize and clarify the region of interaction between quercetin and Fe3+. The TD-DFT method was successfully used to investigate the electronic properties of quercetin and quercetin–Fe3+ and it showed good agreement between experimental and theoretical results. Graphical abstract Image 1 Highlights • A colorimetric chemosensor from the bioflavonoid quercetin for Fe3+ recognition was successfully developed. • Quercetin chemosensor selectively detected Fe3+ even in the presence of other metal ions. • An investigation of quercetin strips toward Fe3+ in different environmental water samples was also conducted. • The experimental results were supported by COSMO-RS and DFT calculations. [ABSTRACT FROM AUTHOR]

Abstract In recent years, the preparation of deep eutectic solvents (DESs) using amines as hydrogen bond donors (HBD) has been reported by several research groups. One of the potential use of this type of DESs is in the field of CO 2 capture, where the viscosity of the solvent before and after the absorption is of paramount importance. Since the number of possible combinations of DESs is huge, a mathematical model for the predicting of the viscosity of DESs at different temperatures is very important. In this work, a new mathematical model for the prediction of amine-based DESs viscosities using the quantitative structure property relationships (QSPR) approach is presented. A combination of multilinear regression (MLR) and artificial neural networks (ANN) methods is used for the development of the model. A data set of 108 experimental measurements of viscosity of five amines-based DESs, taken from the literature, is used for the development and subsequent verification of the model. The more appropriate model is determined by a dedicated statistical analysis, in which the most significant descriptors are preliminary determined. The results show that the proposed models are able to predict the DESs viscosities with very high accuracy, i.e. with a R2 value of 0.9975 in training and 0.9863 for validation using the ANN model and R2 value of 0.9305 for the MLR model. The retrieved model can be considered as a very reliable tool for the prediction of DESs viscosity when experimental data are absent. In turn, this can provide useful guidelines for the synthesis of low-viscosity DESs able to minimize energy requirements associated to their processing (e.g. power required for pumps), thus fostering their industrial-scale implementation. Highlights • A new mathematical model for the prediction of amines-based DESs viscosities using QSPR approach. • 108 experimental measurements reported for five amines-based DESs viscosities was used. • The modelling results showed that the proposed models were able to predict the DESs viscosities. • The two models can be considered as reliable and can be used in the absence of experimental measurements. [ABSTRACT FROM AUTHOR]

Abstract A theoretical study using density functional theory (DFT) is carried out to compare and explain the observed solubility of four antiemetic molecules, namely chlorpromazine, haloperidol, ondansetron and metoclopramide. The COSMO-RS (conductor-like screening model for real solvents) method is used to study the interaction between hydrogen bond acceptors (HBAs) and hydrogen bond donors (HBDs) of the antiemetic drugs, and their molecular interactions with water (dipole moments, interaction and solvation energies). In addition, the AIM (Atoms in Molecules) method is used to deeply study the hydrogen bonding interaction of the antiemetic drug which was found the most soluble in water, namely the metoclopramide. In fact, results show that atom O42 makes two H-bonds with two different water-oxygen atoms (BCP59 and BCP60). One of them, have another H-bond (BCP62) with the hydrogen H27. This study confirms that two of the three H-bonds with water are more stable than the intramolecular interaction between O9 and H27 (BCP1). These H-bonds are likely responsible of the highest solubility of metoclopramide. Graphical abstract Unlabelled Image Highlights • Theoretical study of the antiemetic solubility • Determination of the bonding type using σ-profile and σ-potential • The interaction mechanism between Metoclopramide and water molecules • The reactivity study of the antiemetic molecules [ABSTRACT FROM AUTHOR]

Abstract The conductor-like screening model for realistic solvation (COSMO-RS) and molecular dynamics simulation were used to evaluate the salting-out capacity of piperazine-containing Good's buffers (GBs) on the removal of 1,4-dioxane, 1,3-dioxolane, and acetonitrile from water. The general formula of piperazine-based GBs is 2-[4-(2-hydroxyethyl)piperazin-1-yl]alkanesulfonic acid, HO − (CH 2) 2 − N< CH 2 CH 2 CH 2 CH 2 > NH+ − (CH 2) n − SO 3 −, (n = 1–10). The buffers with n = 1 to 4 are commercially available, while the buffers with n = 5 to 10 are molecular designed in order to predict their salting-out effects on the organic solvent + water systems. The isobaric vapor-liquid equilibria of the ternary piperazine-based GB + organic solvent + water systems were predicted. The studied organic solvents are miscible with water at any composition under ambient condition and form a minimum boiling azeotropes. It was observed that the piperazine-based GBs are able to shift the azeotropic composition. The activity coefficients of water and organic solvents in presence of piperazine-based GBs were predicted using the COSMO-RS model. The influence of alkyl chain length between the zwitterion end groups on the phase behavior of the ternary systems was evaluated. Piperazine-based GBs have displayed potent mass-separating agents in the recovery of 1,4-dioxane, 1,3-dioxolane, or acetonitrile from water. The hydrogen bonds formation in MSA + organic solvent + water mixture was analyzed using molecular dynamics simulation. Highlights • Binary mixtures contain 1,4-dioxane, 1,3-dioxlane, or acetonitrile + water. • Piperazine–based compounds were tested to separate organic solvent-water. • The hydrogen bonds formed in the mixtures were analyzed. [ABSTRACT FROM AUTHOR]

The main objective of the study was to investigate the phase transition properties (melting temperature and heat of fusion) and chemical purity of coniferyl alcohol and D‐mannose by differential scanning calorimetry (DSC). The measurements have been performed at different heating rates from 1–20 °C/min under atmospheric inert gas. From the DSC analysis, the onset temperature, peak temperature, and the heat of fusion of both the compounds were measured. They were found to increase with an increase in the heating rate. The chemical purity of coniferyl alcohol and D‐mannose were determined based on the van't Hoff equation. The chemical purity of coniferyl alcohol was observed to be 99.54 mol% with a correction factor of 1.44 % at a 15 °C/min heating rate. The corresponding purity values for D‐mannose were 98.98 mol% at a correction factor of 6.76 % and 20 °C/min. The obtained results showed that the chemical purity of both the compounds was found to decrease with an increase in the correction factor. Furthermore, this study also focuses on the solubility of both substances in ionic liquids by applying the continuum solvation model (COSMO‐RS) using DSC measured melting properties as input. The GTOC provides the effect of different heating rates on the phase transition properties of coniferyl alcohol. [ABSTRACT FROM AUTHOR]

Highlights • 50 ILs were evaluated as CO 2 physical absorbents by simulations and experiments. • CO 2 absorption in commercial column is a strongly kinetically controlled process. • Key parameters to select ILs for CO 2 physical absorption is the low viscosity. • ILs with TCM, B(CN) 4 and DCN anions present favorable CO 2 absorbent properties. • ILs do not exhibit better performance in CO 2 capture stage than industrial physical absorbents. Abstract A comprehensive study of over 50 ionic liquids (ILs) -integrating molecular simulation, gravimetric experiments and process analysis- has been conducted to evaluate the role of thermodynamics and kinetics on the physical absorption of CO 2 by these widely researched solvents. Despite the common view, CO 2 molar gas solubility is found as a misleading criterion to select the adequate IL for being used as CO 2 absorbent in commercial separation columns, due to the strong kinetic control of the operation. In contrast, low viscosity and molar weight are demonstrated to be key parameters to minimize solvent consumption, energy duty and equipment size. Short-chain imidazolium-based ILs with tetracyanoborate, tricyanomethanide, and dicyanamide anions are proposed as adequate CO 2 absorbents with favorable transport and thermodynamic properties. Current results indicate that ILs do not exhibit better absorbent performance in the CO 2 capture unit than conventional organic solvents (such as glymes, components of Selexol) already used in the industry. IL regeneration stage need to be considered in future studies in order to state the promising advantages of IL absorbents in terms of thermal stability, energy consume and economy. [ABSTRACT FROM AUTHOR]

Highlights • The impacts of aromatic fluids on flash point of biofuels were investigated. • COSMO-RS was employed to calculated the flash point of fuel components. • COSMO-RS prediction results are in reasonable agreement with measured values. • COSMO-RS can be used for selection of aromatics for blending with biofuels. Abstract The flash point of biofuels and petroleum fuels is an essential safety-related property for fuel processing, transportation and storage. Hydroprocessed renewable diesel (HRD-76) and synthesized isoparaffin (SIP), two biofuel blend stocks, were blended with commercial petroleum aromatic fluids (aromatic 100, 150 and 200) to investigate the impacts of aromatics on biofuel flash point and to formulate blends with identical flash point characteristics as NATO F-76 marine diesel and JP-5 jet fuel. To overcome the complexity of the fuel blends, COSMO-RS ("conductor like screening model for realistic solvation") was employed to predict the flash point of these biofuel + aromatic systems. COSMO-RS calculated the flash point of alkanes and aromatics present in biofuel and petroleum fuels and the flash point of SIP + aromatics binary mixture systems. Based on the pure compound and binary mixture predictions, COSMO-RS calculations were expanded to develop surrogate mixtures for biofuels and aromatic fluids. The surrogates were in turn utilized to predict the flash point of biofuel blends with aromatics and to formulate blends with the same flash point as petroleum fuels. The COSMO-RS calculation also assisted the selection of aromatics suitable for blending with different biofuels. [ABSTRACT FROM AUTHOR]

Abstract New experimental infinite dilution activity coefficients (IDACs) of 45 different molecular solutes (alkanes, cycloalkanes, alkenes, alkynes, aromatics, alcohols, ethers, ketones, thiophene, acetonitrile, pyridine and 1-nitropropane) in the novel ionic liquid 1-(3-cyanopropyl)-1-methyl pyrrolidinium thiocyanate are presented. The considered IL has been in silico designed in our previous work by using empirical group contribution method for IDAC calculation. The experimental results shown in this paper are discussed in terms of the strength and the chemical nature of mutual interactions between the IL and the molecular solutes. An effect of nitrile group is elucidated by means of comparison of the measured data with those reported in the literature for non-functionalized counterpart of the studied IL. Furthermore, an impact of the studied "task-specific" cation on the infinite dilution selectivity in thiophene/ n -octane separation problem is highlighted. The entire data set presented herein is analyzed using linear solvation-energy relationship (LSER), regular solution theory and conductor-like screening model for real solvents (COSMO-RS). Graphical Abstract Highlights • Infinite dilution activity coefficients for a new task-specific IL are presented. • An impact of CN groups on the analyzed properties is discussed. • LSER correlation for the studied IL is developed. • Solubility parameters of the pure IL are calculated. • COSMO-RS method is tested on the measured data. [ABSTRACT FROM AUTHOR]

Abstract The new predictive electrolyte model COSMO-RS-ES is evaluated and refined for the calculation of solubilities of salts in mixed solvent systems. It is demonstrated that the model is capable of predicting solid-liquid equilibria at 25 °C for ammonium and alkali metal salts quite accurately in a wide variety of solvent mixtures. Furthermore, through the introduction of Gibbs free energies of transfer of single ions it is shown that the model performance can be improved even further. This new data type also allows for an ion-specific way of evaluating the model for the first time. For some systems when calculating the solubility, larger deviations are observed, but for the vast majority of systems the model delivers good predictions. This shows that COSMO-RS-ES is a valuable tool for calculation of phase equilibria in electrolyte systems especially when the scarcity of data impede the application of models that require a higher number of parameters. Highlights • Predictive calculation of solubilities of salts in mixed solvents possible. • Inclusion of Gibbs free energies of transfer of ions into training set. • New thermodynamic data leads to improved model. [ABSTRACT FROM AUTHOR]

Abstract Active pharmaceutical ingredients (APIs) in the form of crystalline solid are commonly produced in drug manufacturing industries. However, crystalline solid APIs have a low solubility and the ability to cause polymorphism transformation. In order to overcome these problems, a modification of APIs in the form of protic ionic liquids (PILs) has been proposed. In the present study, a series of five ferulate-based PILs were successfully synthesised and characterised by appropriate spectral analysis. The antioxidant activity of synthesised PILs was determined through the 2,2‑diphenyl‑1‑picrylhydrazyl (DPPH) free radical scavenging assays. The spectroscopy analysis confirmed the formation of PILs supported by the Density Function Theory (DFT) calculation. The synthesised ferulate-based PILs exhibited low EC 50 ranging from 12.93 ± 0.05 to 17.40 ± 0.04 μM indicating a strong antioxidant activity compared to parent acid (EC 50 of 21.40 ± 0.05 μM). Prediction of antioxidant activity of the PILs and their ionic interactions at the molecular level were studied by applying DFT calculation at B3-LYP/6-311G*** level and COSMO-RS. Based on the optimised geometry, the ion-pair of PILs formed a strong directional intermolecular hydrogen bond between the –NH group of the cation with the –COOH group of the anion with interaction energy of −111 to −120 kcal mol−1. Predicted antioxidant activity indicated that the PILs's cation has a weak interaction with an anion as observed from the σ-potential analysis. Graphical abstract Unlabelled Image Highlights • Five new ferulate-based protic ionic liquids (PILs) was successfully synthesised and characterised. • The optimization structure and interaction energy calculation was done by Density Function Theory (DFT). • COSMO-RS used to predict the antioxidant activity of the ferulate-based PILs. • The synthesised PILs was show remarkable higher antioxidant activity than parent acid. [ABSTRACT FROM AUTHOR]

Abstract In this work, aqueous 2‑amino‑1, 3‑propanediol solution (serinol) was investigated as a potential solvent for CO 2 capture from different gas streams. Prior to CO 2 solubility experiments, a qualitative prediction technique was performed on serinol to ensure its potentiality as a CO 2 capture solvent. This was done using COSMO-RS approach based on quantum chemistry calculations. Based on this approach, serinol showed good affinity towards hydrogen–bond donors which proved to be beneficial in developing intermolecular interaction between serinol and CO 2. The solubility of CO 2 in serinol was then investigated at serinol concentrations ranging from 1 M to 3 M, temperatures ranging from 313.15 K to 353.15 K and CO 2 partial pressures ranging from 1034.31 kPa to 2068.43 kPa. The solubility of CO 2 in serinol reached a highest value of 1.64 mol of CO 2 /mol of serinol when the serinol concentration was 1 M, at 313.15 K and 2068.43 kPa. Meanwhile, Henry's law constant of CO 2 in serinol was calculated using N 2 O analogy at 313.15 K and 333.15 K for molar concentrations of 1 M and 3 M of serinol. Results showed that the physical solubility of CO 2 in serinol increased as the temperature and the concentration of the solution decreased. The lowest value of Henry's law constant of CO 2 was 599.4 kPa·m3·kmol−1, for 1 M of serinol at 313.15 K. Furthermore, the recyclability of 3 M of serinol was investigated at 313.15 K and partial pressures ranging from 1034.31 kPa to 2068.43 kPa. At 1034.31 kPa, the solubility of CO 2 in 3 M of aqueous serinol after the 3rd regeneration cycles were reduced to 72.73%. Highlights • Qualitative hydrogen bonding interaction between solvents and CO 2 was predicted by COSMO-RS model. • The solubility of CO 2 in aqueous serinol was experimentally conducted. • Henry's law constants of CO 2 in aqueous serinol were obtained by N 2 O analogy. • The recyclability of aqueous serinol was investigated. [ABSTRACT FROM AUTHOR]

Abstract A novel simple method is presented for the characterization of ionic liquids as regards their thermodynamic behavior in bulk phases and interfaces. For this purpose, a simple consistent thermodynamic framework has been developed which may exploit a variety of experimental information, such as activity coefficients at infinite dilution, volumetric data over a temperature/pressure range, or wetting/contact angle data over a variety of solid surfaces. This experimental information is used in order to determine LSER (Linear Solvation Energy Relationships) type molecular descriptors and surface energies that uniquely characterize each ionic liquid. The interconnection of these descriptors with the more familiar equation-of-state scaling constants is established and explored. The emerging trends in the determined molecular descriptors and the consequences and perspectives are critically discussed. As shown by a variety of examples, the efficiency and versatility of the proposed characterization method are rather promising. Graphical abstract The interconnection of molecular descriptors for ionic liquids. Unlabelled Image Highlights • A novel approach for the efficient characterization of interactions in ionic liquids • New framework interconnecting equation-of-state, LSER, and surface energy descriptors • LSER descriptors of ionic liquids for calculations in bulk phases and interfaces [ABSTRACT FROM AUTHOR]

Abstract Solubility of active pharmaceutical ingredient (API) in solvents is very important for drug development and manufacturing. Solubility data may provide further information such as thermochemical properties and intermolecular interactions that may lead to a better understanding of the formation of API crystals. In this study, solubility of ascorbic acid was determined by gravimetric method in four different commonly used polar protic solvents: water, methanol, ethanol and 2-propanol. The solubility of ascorbic acid crystal was also predicted using Conductor-like Screening Model – Realistic Solvent (COSMO-RS) approach. In this computational analysis, the generated Δ G values are based on the solubilities that were experimentally obtained to simulate the intermolecular forces. The intermolecular interaction data from COSMO-RS provide an insight into the relationship between the intermolecular interactions and its crystal habit across four different polar protic solvents. The habit of the crystals was then determined using light microscopy and scanning electron microscopy techniques, while the polymorphic form of the crystals was identified by X-ray powder diffraction and single X-ray diffraction techniques. The solubility and characterization data showed that the solvents with high polarity increased the solubility of ascorbic acid. The data also showed that different solvent polarity influenced the crystal habit, but did not change the crystal structure to form a new polymorph. [ABSTRACT FROM AUTHOR]

The traditional production of long‐chain organic esters like isobutyl isobutyrate (BIBE) suffers from severe problems due to the homogenous catalyst in process and complex system thermodynamics. In this work, an innovative bifunctional deep eutectic solvent (DES) is introduced, playing as both reaction catalyst and extraction solvent, to intensify the esterification process. The DES was formed by imidazole (Im) and p‐toluenesulfonic acid (PTSA), which was for the first time found acid–base tunable, represented by weak basic DES [3Im:PTSA] and strong acidic DES [Im:2PTSA]. The formation mechanisms of [3Im:PTSA] and [Im:2PTSA] were illustrated by Fourier‐transform infrared spectroscopy (FTIR) and COnductor‐like Screening MOdel for Real Solvent (COSMO‐RS) combined with the Im‐PTSA phase diagram. The dual functions of the acidic [Im:2PTSA] in reactive extraction were evaluated by σ‐potential analysis and esterification experiments. The high conversion, easy product separation, and good solvent reusability confirm the excellent catalytic and solvent effect of [Im:2PTSA]. © 2018 American Institute of Chemical Engineers AIChE J, 65: 675–683, 2019 [ABSTRACT FROM AUTHOR]

Process concepts have been conceived and evaluated for the amine‐free homogeneous catalyzed hydrogenation of CO2 to formic acid (FA). Base‐free DMSO‐mediated production of FA has been shown to avoid the formation of stable intermediates and presumably the energy‐intensive FA recovery strategies. Here, we address the challenges in the development of an overall process: from catalyst immobilization to the FA isolation. The immobilization of the homogeneous catalyst was achieved using a multiphasic approach (n‐heptane/DMSO) ensuring high retention of the catalyst (>99%) and allowing facile separation of the catalyst‐free product phase. We show that the strong molecular interactions between DMSO and FA on the one hand shift the equilibrium towards the product side, on the other hand, lead to the formation of an azeotrope preventing a simple isolation step by distillation. Thus, we devised an isolation strategy based on the use of co‐solvents and computed the energy demands. Acetic acid was identified as best co‐solvent and its compatibility with the catalyst system was experimentally verified. Overall, the outlined process involving DMSO and acetic acid as co‐solvent has a computed energy demand on a par with state‐of‐the art amine‐based processes. However, the insufficient chemical stability of DMSO poses major limitations on processes based on this solvent. [ABSTRACT FROM AUTHOR]

Abstract In this study, the bamboo dissolution capability of six amino acid-based ionic liquids (AAILs) with two different cations, i.e. 1-ethyl-3-methylimidazolium (Emim) and Tetrabutylphosphonium (P 4444) and three anions derived from amino acids were investigated by Conductor-like screening model for real solvents (COSMO-RS) prediction and hydrogen bond basicity (β) of Kamlet–Taft parameters. COSMO-RS was used for calculating sigma profile, activity coefficients (γ i) and aqueous base dissociation constant of corresponding acids of the anions (pKa) of AAILs. The trends in sigma profile, γi and pKa for AAILs were compared with β values and the effect of structure moiety of ionic liquids was also discussed. The trend of COSMO-RS prediction for anions was noted similar to the β values of AAILs with the exception of serinate anion. Similarly, the trend predicted by COSMO-RS and β values was also found same while changing the cations of AAILs. To investigate, the correlation of the above-mentioned properties with experimental dissolution ability, tetrabutylphosphonium aminoethanic acid ([P 4444 ]Gly) and 1-ethyl-3-methylimidazolium aminoethanic acid ([Emim]Gly) ionic liquids were synthesized and evaluated. The trend predicted by COSMO-RS and the β values were not correlating with efficiency of AAILs for bamboo dissolution. Both AAILs were able to dissolve the bamboo. However, material of [P 4444 ]Gly treated sample was evaluated through XRD analysis where change in crystallinity of cellulose was identified after dissolution and regeneration of bamboo. Scanning Electron microscopy also showed homogenous structure for regenerated materials. Highlights • Amino acid based ionic liquids were evaluated for lignocellulosic dissolution. • COSMO-RS prediction and hydrogen bond basicity were correlated with dissolution ability. • Structural changes for lignocellulosic were analyzed using SEM and XRD. [ABSTRACT FROM AUTHOR]

This study assesses, qualitatively and quantitatively, the performance of ten bio-based solvents to replace hexane for the extraction of oil from Pistacia lentiscus edible fruits. Solvent screening was achieved through theoretical approach using the COnductor-like Screening MOdel for Realistic Solvation (COSMO-RS) predictions and an experimental protocol based on GC-FID and HPTLC analysis. Unsupervised multivariate analyses were performed on GC-FID and HPTLC data. Experiments corroborated theoretical predictions indicating that MeTHF was the best alternative solvent to replace hexane. Moreover, the obtained extract exhibited a good anti-inflammatory activity, inhibiting by 91.9% NO release in RAW 264.7 macrophages. These findings highlighted the potential of green solvents especially MeTHF in lipid extraction and exhibited that P. lentiscus oil presents a potential anti-inflammatory property and great nutritional value, notably high amount of oleic and linoleic acid, thus encouraging its valorization in food, cosmetic or pharmaceutical industry [ABSTRACT FROM AUTHOR]

Highlights • An IL-database is established for gas-IL systems, containing both experimental solubility data and Henry’s law constants of various gases in different ILs. • A corrected COSMO-RS based model is developed and can be used to generate additional pseudo-experimental activity coefficient of some light hydrocarbons (C 2 H 4 , C 2 H 6) in ILs. • UNIFAC-IL model is developed for the prediction of four-component shale gas solubility in ILs, indicating a very useful tool for task-specific design of ILs for gas separation. Abstract In recent years, due to their advantages on good stability, non-volatility, tunable viscosity and tailor-made properties, ionic liquids (ILs) have been regarded as novel potential solvents and alternative media for gas separation. However, the various cations and anions representing the ILs, together with limited experimental data, make it challenging to predict gas solubility in ILs and identify the optimal IL for a specific gas separation. In this work, a comprehensive Henry’s law constants database is first established for gas-IL which supplements an already established extensive gas solubility database. Because of the insufficient experimental data for both IL-C 2 H 4 and IL-C 2 H 6 systems, the COSMO-RS model is used after validation to generate additional pseudo-experimental data. Then, together with the sufficient experimental data of CO 2 -IL and CH 4 -IL systems, UNIFAC-IL is developed for the prediction of four-component shale gas (CH 4 , C 2 H 4 , C 2 H 6 , CO 2) solubility in ILs. A relatively good agreement between the model predicted and the experimental solubility data is observed. Moreover, the developed UNIFAC-IL model can be used to predict the solubility of gases in new ILs that are not included in parameter fitting due to its group contribution basis. For this reason, the model represents a very useful tool for task-specific design of ionic liquids for gas separations. [ABSTRACT FROM AUTHOR]

Abstract Conductor-like screening model for real solvents (COSMO-RS) is presented as thermodynamic predictive tool for calculating liquid-liquid equilibrium (LLE) phase diagrams in ternary mixtures {ionic liquid (IL) + 2-phenylethanol (PEA) + water} — a model system of extractive recovery of PEA bioproduced using yeast. Overview of the performance of the model is demonstrated by using the experimental LLE data available in the literature. An effect of quantum chemical theory level (BP-TZVP-COSMO vs. BP-TZVPD-FINE) on accuracy of thermodynamic data prediction is discussed. Capacity of the COSMO-RS approach in capturing effect of chemical structure of IL on LLE as well as LLE-derived properties (distribution ratio of PEA and PEA/water selectivity) is presented. Infinite dilution PEA/water selectivity is adopted to carry out the COSMO-RS-based screening of approximately 9000 ILs to find possibly the most effective extracting agent. On the basis on presented methodology, some general guidelines on a proper selection of IL for extraction of PEA form aqueous solutions are proposed and discussed. Graphical Abstract Highlights • Review of available LLE data for {IL + 2-phenylethanol + water} is presented. • Performance of the COSMO-RS method in predicting LLE is tested. • COSMO-RS-based screening for the best cation-anion combination is carried out. • Suggestion for a selection of promising ILs for PEA/water separation is given. [ABSTRACT FROM AUTHOR]

Abstract In this work the synthesis of five new Brönsted acidic ionic liquids (BAILs) bearing same anion (camphorsulfonate) but different cations; 3-(3-sulfopropyl)-imidazolium, 1-methyl-3-(3-sulfopropyl)-imidazolium, 1-methyl-3-(4-sulfobutyl)-imidazolium, 1-ethyl-3-(3-sulfopropyl)-imidazolium, 1-butyl-3-(3-sulfopropyl)-imidazolium) were synthesized and characterized. The characterization of BAILs was carried out using NMR, FTIR and elemental analysis (CHNS). The thermophysical properties of these ILs such as density, refractive index, viscosity and thermal stability were analyzed in wide temperature window. Furthermore, the effect of alkyl chain length of cations on thermophysical properties was well studied. The experimental values of density were further used to calculate other significant properties such as molar volume, standard molar entropy, lattice energy and thermal expansion coefficients. The Brönsted acidities of investigated ILs were determined using Hammett method. Furthermore, COSMO-RS study was performed to determine δ-surface, and δ-profile of the studied ILs. Graphical abstract Unlabelled Image Highlights • Five camphorsulfonate-based ILs with imidazolium and substituted imidazolium-based cations were synthesized and characterized. • Effect of cation and temperature on physicochemical properties was determined. • The Brönsted acidities of investigated ILs were evaluated using Hammett equation. • COSMO-RS model was used to determine δ-surface, δ-potential and δ-profile of the studied ILs. [ABSTRACT FROM AUTHOR]

A computational approach is presented for prediction of cellulose solubilities in ionic liquids (ILs) based on COSMO-RS (Conductor-like Screening Model for Real Solvents). Thermodynamically stable molecular structures were optimized from 2D structures of cellulose and ILs following specific force-field based search of conformation lowest in energy and quantum chemical optimizations of molecular geometry. The thermodynamic property of logarithmic activity coefficient (lnγ) and excess enthalpy (H E ) were calculated by COSMO-RS based on the COSMO molecular surfaces of cellulose and ILs to qualitatively predict the ability of ILs for cellulose dissolution. To evaluate the method, four sets of ILs were used to calculate lnγ and H E based on four different cellulose models. The goodness-of-fit of linear regressions between the experimental cellulose solubilities and the calculated lnγ and H E shows that lnγ is more reliable than H E for prediction of the dissolving power of ILs to dissolve cellulose. However, H E is more suitable for prediction of the dissolution ability of halogen-based ILs. Moreover, all the cellulose models gave comparably good prediction results regarding of the dissolving power of ILs based on the calculated lnγ, but the cellobiose model was identified as the optimal model due to the relatively higher prediction ability (R 2 ) across different IL datasets. The approach is time efficient and robust, which provides a novel method for large-scale screening of ILs for cellulose dissolution. [ABSTRACT FROM AUTHOR]

The search for economic and sustainable sources of polyunsaturated fatty acids (PUFAs) within the framework of the circular economy is encouraged by their proven beneficial effects on health. The extraction of monkfish liver oil (MLO) for the synthesis of omega-3 ethyl esters was performed to evaluate two blending systems and four green solvents in this work. Moreover, the potential solubility of the MLO in green solvents was studied using the predictive simulation software COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS). The production of ethyl esters was performed by one or two-step reactions. Novozym 435, two resting cells (Aspergillus flavus and Rhizopus oryzae) obtained in our laboratory and a mix of them were used as biocatalysts in a solvent-free system. The yields for Novozym 435, R. oryzae and A. flavus in the one-step esterification were 63, 61 and 46%, respectively. The hydrolysis step in the two-step reaction led to 83, 88 and 93% of free fatty acids (FFA) for Novozym 435, R. oryzae and A. flavus, respectively. However, Novozym 435 showed the highest yield in the esterification step (85%), followed by R. oryzae (65%) and A. flavus (41%). Moreover, selectivity of polyunsaturated fatty acids of R. oryzae lipase was evidenced as it slightly esterified docosahexaenoic acid (DHA) in all the esterification reactions tested.

Transforming carbon dioxide (CO2) into value-added products through electrochemical reduction reaction (CO2ERR) is a promising technique due to its potential advantages using renewable energy. The main challenge is to find a stable catalytic system that could minimize the reaction overpotential with high faradaic efficiency and high current density. Ionic liquids (ILs) as electrolyte in CO2ERR have attracted attention due to the advantages of their unique properties in enhancing catalytic efficiency. For better performance, a systematic understanding of the role of ILs as electrocatalyst is needed. Therefore, this paper aims to correlate the performance of ILs as co-catalyst in (CO2ERR) with the lowest unoccupied molecular orbital (LUMO) energy level and the interaction energy as predicted by quantum chemical calculation using Conductor like Screening Model for Real Solvents (COSMO-RS) and Turbomole. The results show strong linearity (R2=0.98) between hydrogen bond energy (HB) and LUMO values. It is demonstrated that as HB increases, the LUMO value decreases, and the catalytic activity for CO2ERR also increases. This result allows further understanding on the correlation between the molecular structure and the catalytic activity for CO2ERR. It can serve as a priori prediction to aid in the design of new effective catalysts.

This study compares the solubility predictions of the Flory-Huggins based on the Hansen Solubility Parameters (FH-HSP) model with those of openCOSMO-RS and PC-SAFT for evaluating the screening capabilities of the Hansen solubility parameters (HSP) using the relative energy difference (RED). Two deep eutectic solvents, thymol + L-menthol (TM) and thymol + cyclohexanone (TC), and their precursors were investigated. The three models performed reasonably well in predicting the solubility of thymol and L-menthol in organic solvents but showed significant deviations in predicting the solubility of solid solutes in cyclohexanone. For solubility predictions in DES compared to available experimental data, the root-mean-square logarithmic deviation (RMSLD) values obtained with FH-HSP, openCOSMO-RS, and PC-SAFT were 0.86, 0.27, and 0.93, respectively. Using FH-HSP with HSP obtained from an ideal mixing rule of the parameters of pure compounds resulted in a deviation of 1.13. The screening assessment of the studied DES revealed a 70.4% match rate between the RED parameter and ln ⁡ γ i ∞ , with 6.9% false negatives. Using HSP obtained from the ideal mixing rule resulted in similar scores, with a 68.5% match rate and 10.4% false negatives. The results suggest that the HSP theory can aid DES screening processes by identifying promising DES-solute pairs, thus allowing the targeting of more robust methods of computational resources in smaller sets of compounds. • Experimentally calculated Hansen solubility parameters are able to capture solute-DES interactions tendency. • Hansen solubility parameters allow screening solute-DES interactions using the relative energy difference parameter. • Solubility calculations using Flory-Huggins and Hansen solubility parameters are not recommended if high accuracy is needed. [ABSTRACT FROM AUTHOR]

[Display omitted] • COSMO-RS predictions analysis performed over a wide set of reported APIs solubility values. • Eutectic solvent screening calculations carried out to identify enhanced APIs solubility systems. • Identified new eutectic solvents-APIs combinations showing higher experimental lidocaine and caffeine solubilities. • New eutectic solvents characterized in terms of density and viscosity. The reduced solubility of some active pharmaceutical ingredients (APIs) in water is a limiting factor for the development of new formulations. Therefore, the search of new compatible solvents would be convenient to overcome such limitation. Among this group, eutectic solvents stand out as good candidates. In this work, the systematic application of COSMO-RS as a predictive method to anticipate APIs solubility in systems involving natural eutectic solvents (NAESs) is presented. The methodology has been validated by using a collection of 50 APIs – NAESs systems from the literature. This predictive tool allowed the selection of four NAESs (reported in literature as natural eutectic mixtures) as good candidates to improve lidocaine and caffeine solubility in water and PEG 300 (benchmark solvents). The four NAESs candidates were prepared and experimentally characterized by means of density and viscosity measurements. Density values ranging from 1.0 to 1.3 g/mL and viscosities from 200 to 2,200 cP were found, with glycerol based NAESs as the most viscous systems. Solubility experiments were also carried out to analyze COSMO-RS predictions validity. Betaine: lactic acid and betaine: 1,2-propanediol are good candidates for lidocaine solutions, achieving 2,300 and 572 mg/mL values respectively, much higher than polyethylene glycol, PEG 300, (173 mg/mL), typically used as benchmark solvent. In the case of caffeine, proline:lactic acid was found as the best candidate with 30 mg/mL solubility (higher than water: 23 mg/mL and PEG 300: 18 mg/L). This work permits a systematic analysis of APIs solubility in NAESs (more than 80 systems reported) by using a total predictive tool (COSMO-RS predictions) to anticipate that promising solvents, with high solubilities for lidocaine and caffeine. [ABSTRACT FROM AUTHOR]

The presence of azole fungicides in aquatic environments is a significant issue due to their toxicity and persistence related to a low removal of these compounds by conventional processes in wastewater treatment plants. A growing environmental public concern is reflected in the inclusion of these compounds in the 2020 and 2022 European Surface Water Watch Lists. Therefore, it is necessary to develop efficient processes that allow their removal sustainably. This work applies liquid-liquid extraction using terpenes as green solvents and terpene-based eutectic solvents to remove azole fungicides from aqueous streams imazalil, metconozale, penconazole, prochloraz, and tebuconazole. First, an initial screening was performed by molecular simulation using the COSMO-RS method. The selected solvents were applied in the individual extraction of azole fungicides, and selecting the solvents thymol+octanoic acid and carvacrol. These solvents have been tested in studies with surface water matrix on the effect of temperature, initial concentration, and pH on extraction performance. From these results, it has been shown that carvacrol is the solvent that is least affected by these variables and obtains extraction yields higher than 97.88%, with a Solvent/Feed ratio up to 0.050, outperforming the conventional solvent methyl isobutyl ketone. This solvent has been used in solvent reuse cycles obtaining a reduction of less than 1% in three extraction cycles. Therefore, carvacrol is presented as a sustainable solvent for the extraction of azole fungicides from aqueous environments. [Display omitted] • COSMO-RS simulation identifies thymol+octanoic acid and carvacrol solvents. • Carvacrol outperforms conventional solvent MIBK. • Carvacrol offers >97.88% yield and solvent reusability. • Liquid-liquid extraction with green terpene solvents offers sustainable removal. [ABSTRACT FROM AUTHOR]

A new fibrous adsorbent, a composite of polyethylenimine, alginate, and activated carbon was developed for the removal of ionic and non-ionic pharmaceutical and personal care products (PPCPs) from aqueous phases. The adsorbent was conceptually designed to strongly adsorb charged and neutral PPCPs and to have a fibrous form for easy recovery after use. Instrumental analysis, isotherms, and modeling studies were used to characterize the adsorbent. The instrumental analysis provided the morphological properties, functional groups, and surface charges, and the isotherm study assisted in determining the adsorption affinity (K d) of the adsorbent for various PPCPs. The measured ranges of log K d were 1.22–1.82 for cations, 0.32–1.03 for anions, and 0.85–1.31 for non-ions. In addition, the effects of salts and wastewater on adsorption were examined. The results reveal that overall, the adsorbent has higher adsorption in salt-containing solutions and wastewater than pure water. In the modeling study, the quantitative structure-adsorption relationship was modeled to help rapidly estimate the K d of any PPCPs. The developed model was highly predictable, i.e., R2 of 0.892–0.894 and a standard error in log units of 0.150–0.151. Notably, the modeling study revealed that ionic and hydrogen-bond interactions were the primary adsorption interactions for the adsorbent. • Polyethylenimine, alginate, and activated carbon were composited and formed into fiber. • PEI-Alg-AC composite has high removability for ionic and non-ionic micropollutants. • The developed adsorbent has a higher uptake in the presence of salt than pure water. • The modeling result reveals that adsorption properties can be predicted with high accuracy. • Hydrogen-bond interaction-related parameters are highly correlated with adsorption properties. [ABSTRACT FROM AUTHOR]

[Display omitted] • The structure-solubility relationship of flavonoids in various solvents is investigated. • Dissolution difference of flavonoids depends on the synergistic influence of multiple factors. • Planarity of flavonoid molecules is the most important factor affecting dissolution. • Dissolution and nonplanarity of flavonoids: flavanone > isoflavone > flavone > flavonol. • Introducing ILs into molecular solvents or water has an enhanced solubilization effect for flavonoids. The dissolution behavior and structure-solubility relationships of diverse flavonoids in various solvent systems, including the pure molecular solvents, pure ionic liquids (ILs), and molecular solvent/IL mixtures, are investigated in conjunction with experiments as well as quantum chemical and COSMO-RS calculations. The dissolution of flavonoids is a complex process. The dissolution difference of various flavonoids is ascribed to the synergistic influence of multiple factors, including the structure and planarity of the diverse flavonoid molecules, the extent of delocalization, the type, number, and position of functional groups, properties of the various solvents, and inter/intramolecular interactions. The planarity of flavonoid molecules is usually the most critical of these factors. The degree of nonplanarity of flavonoids follows the order flavanone > isoflavone > flavone > flavonol, which basically coincides with the solubility ranking of diverse flavonoids. Additionally, the type, number, and position of functional groups capable of forming hydrogen bonds also significantly affect flavonoid dissolution in solvents. The dissolution sequence of different flavonoids in various solvents varies with the structure and configuration of flavonoids. Of all the investigated solvents, flavonoid compounds are the least soluble in water because of their hydrophobicity, and they are most easily soluble in ILs with higher HBA basicity due to solute–solvent hydrogen-bond interactions, such as [Bmim]Ac and [Bmim]NO 3. Adding ILs into molecular solvents or water has a significantly enhanced solubilization effect for the poorly soluble flavonoid compounds. In addition, water can act as an effective antisolvent, allowing for efficient recovery of flavonoids and ILs. [ABSTRACT FROM AUTHOR]