Conductor-like Screening Model For Real Solvents Research Articles

Solubility parameters and solvent affinities for polycaprolactone: A comparison of methods

ABSTRACTIntrinsic viscosity measurements were used in combination with the functional solubility parameter (FSP) and Hansen solubility parameter (HSP) fitting methods to determine the solubility parameters (SPs) of polycaprolactone (PCL). Despite using only eight solvents, a simple similarity criteria approach showed that the HSPs and FSPs were good predictors of the relative solvent‐PCL affinity compared to HSPs available in the literature and SPs calculated using additive group contribution methods. Three complementary computational methodologies—Conductor‐like Screening MOdel for Real Solvents (COSMO‐RS), partial solvation parameters (PSPs), and a thermodynamic quantitative structure–property relationship (QSPR) approach—were used to substantiate the relative solvent–PCL affinities revealed by the intrinsic viscosity measurements. The solvent affinities predicted by all three techniques were in good agreement with the trend observed in the experimental intrinsic viscosity data, but the COSMO‐RS activity coefficients, ln(γPCL), were slightly superior to the PSP and thermodynamic QSPR methods, particularly when incorporating the Elbro free‐volume combinatorial correction in the COSMO‐RS calculations. As part of this study, the FSP fitting algorithm was modified to obtain the PSPs for PCL in terms of the intrinsic viscosity data, thereby, presenting a promising new way to calculate the PSPs of polymers from empirical solubility and solvent affinity data. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48908.

Fluorescence and Molecular Simulation Studies on the Interaction between Imidazolium-Based Ionic Liquids and Calf Thymus DNA

This work presents a molecular level investigation on the nature and mode of binding between imidazolium-based ionic liquids (ILs) ([Cnbim]Br where n = 2, 4, 6) with calf thymus DNA. This investigation offers valuable insight into the mechanisms of interactions that can affect the structural features of DNA and possibly cause the alteration or inhibition of DNA function. To expedite analysis, the study resorted to using molecular docking and COnductor like Screening MOdel for Real Solvents (COSMO-RS) in conjunction with fluorescence spectroscopic data for confirmation and validation of computational results. Both the fluorescence and docking studies consistently revealed a weak interaction between the two molecules, which corresponded to the binding energy of a stable docking conformation in the range of −5.19 to −7.75 kcal mol−1. As predicted, the rod-like structure of imidazolium-based ILs prefers to bind to the double-helix DNA through a minor groove. Interestingly, the occurrence of T-shape π-π stacking was observed between the amine group in adenine that faces the aromatic ring of imidazole. In addition, data of COSMO-RS for the interaction of individual nucleic acid bases to imidazolium-based ILs affirmed that ILs showed a propensity to bind to different bases, the highest being guanine followed by cytosine, thymine, uracil, and adenine.

Synergistic kinetic inhibition of amino acids and ionic liquids on CH4 hydrate for flow assurance

In this study, the kinetic inhibition effects of amino acids and ionic liquids and the potential synergism of their mixtures on CH4 hydrates were investigated by adopting three different approaches. The sigma (σ) profiles of inhibitor molecules obtained from the Conductor-Like Screening Model for Real Solvents (COSMO-RS) software were used to estimate inhibitor–water interactions for the pre-screening of potential inhibitors, and thus glycine (an amino acid) and [BMIM][BF4] (an ionic liquid) were selected as candidates for kinetic hydrate inhibitors (KHIs). A non-stirred high-pressure micro-differential scanning calorimeter (HP μ-DSC) revealed that the glycine (0.5 wt%) and [BMIM][BF4] (0.5 wt%) mixture showed a synergism for CH4 hydrate as a KHI. The kinetic inhibition synergism of the glycine (0.5 wt%) and [BMIM][BF4] (0.5 wt%) mixture on CH4 hydrate was double-checked using a stirred high-pressure autoclave. The onset temperature of the glycine (0.5 wt%) and [BMIM][BF4] (0.5 wt%) mixture was found to be lower than that of poly(N-vinylcaprolactam) (PVCap; 1.0 wt%). Time-dependent Raman spectra demonstrated that the cage-specific inhibition of glycine and [BMIM][BF4] caused kinetic inhibition synergism and the consequent slow growth rate of CH4 hydrate. The synergistic kinetic inhibition of amino acids and ionic liquids will be helpful in understanding the accurate roles of inhibitors in inhibitor–water interactions and will contribute to opening up a new field related to the synergism of eco-friendly inhibitors for flow assurance in oil and gas pipelines.

Screening of ionic liquids for gas separation using COSMO-RS and comparison between performances of ionic liquids and aqueous alkanolamine solutions

Ionic liquids (IL) are considered viable alternative solvents for CO2 capture. Because of this and the unlimited number of possible combinations between cations and anions, it is important to develop a systematic approach based on a reliable model for defining the best combinations to promote natural gas sweetening by enabling the most efficient CO2 capture accompanied by minimal hydrocarbons losses. Hence, in this study, the conductor-like screening model for real solvents (COSMO-RS) model was employed to predict the solubility of CO2, CH4, C2H6, and C3H8 in eight selected ILs with varying combinations of cations and anions. All predictions have been compared against experimental data from the literature which was obtained at the same conditions. The model and experimental data show similar trends and moderate agreement for each of the selected ILs. The observed deviations were 8–62%, 8–40%, 1–37%, and 29–35%, for CO2, CH4, C2H6, and C3H8, respectively. Both the experimental data and predictions confirm that [hmim][TCB] IL is more suitable for natural gas sweetening because of its higher CO2 solubility and selectivity than that of other ILs. Finally, the experimentally determined solubilities of these gases in ILs and conventional amine solvents are compared with highlight the greater efficiency of ILs.

Tailor-made solvents for pharmaceutical use? Experimental and computational approach for determining solubility in deep eutectic solvents (DES)

A deep eutectic solvent (DES) is a mixture of two or more chemicals that interact via hydrogen bonding and has a melting point far below that of the individual components. DESs have been proposed as alternative solvents for poorly soluble active pharmaceutical ingredients (API). In this study, the solvation capacities of six deep eutectic solvents were compared to water and three conventional pharmaceutical solvents (PEG 300, ethanol and glycerol) for 11 APIs. The experimentally determined solubilities were compared to computational solubilities predicted by the Conductor-like Screening Model for Real Solvents (COSMO-RS). While the conventional pharmaceutical solvents PEG 300 and ethanol were the best solvents for the majority of the studied APIs, API-DES combinations were identified, which exceeded the API solubility found in the conventional pharmaceutical solvents. Furthermore, it was also possible to obtain high solubilities in the DESs relative to water, suggesting DESs to be potential solvents for poorly water soluble APIs. In addition, the relative increase in solubility found in the experimental data could be well predicted ab initio using COSMO-RS. Hence, COSMO-RS may in the future be used to reduce the experimental screening of potential DESs for a given API.

Understanding the effect of pH on the solubility of Gamavuton-0 in the aqueous solution: Experimental and COSMO-RS modelling

Solubility of pharmaceutical compound in aqueous solution is one of the most important parameters in the drug delivery and development. Especially, for the pharmaceutical compound that have varied solubility values in the aqueous solution with diverse pH condition. In this work, the solubility of newly synthesized pharmaceutical compound, namely Gamavuton-0 (GVT-0) in aqueous solution at four different pH = (2, 4, 6, and 8), within temperatures T = (300.15, 305.15, 310.15, and 315.15) K and atmospheric pressure (p = 0.1 MPa) were determined through experiment and computational modelling approaches. The experimental measurement showed that (i) the solubility increased with increasing the temperature and (ii) the solubility decreased from pH 2 to 4 and increased from pH to 4–8. The same trend of GVT-0 solubility in the studied pH of the aqueous solution was also observed from the computational modelling using Conductor-like Screening Model for Real Solvent (COSMO-RS). According to this model, there are three different GVT-0 species exist in aqueous solution at different pH: (1) The protonated form that exist as major species at pH 2, (2) neutral GVT-0 exist as main component at pH 4 and 6, and (3) the deprotonated form presents as primary species at pH 8. The equilibrium between the protonated – neutral – deprotonated of GVT-0 species responsible for their solubility in the aqueous solution in different studied pH condition. The solubility results of this study could be useful the formulation and development of GVT-0.

From Quantum Chemistry to Prediction of Drug Solubility in Glycerides.

Lipid-based delivery is a key technology for dealing with the challenges of poorly soluble drugs. Therefore, prediction of drug solubility in lipid-based excipients and their mixtures is an important research goal in computational pharmaceutics. This study is based on the conductor-like screening model for real solvents (COSMO-RS), which combines quantum chemical surface calculations with fluid phase thermodynamics. An experimental dataset of 51 drugs was collected with measured thermochemical data and solubility results in medium and long-chain tri- and monoglycerides. For the theoretical model, the excipients were represented by a single structure in a simplified glyceride approach. COSMO-RS was able to capture the solubility trends in the different excipients. Only a few compounds showed rather poor predictions and these outliers were often comparatively larger molecules. The present study also evaluated the effects of individual fatty acid hydrolysis on glycerides' solubilization capability. In conclusion, the application of COSMO-RS modeling for drug solubility prediction in lipid-based formulations is highly promising, in particular for rank-ordering excipients in an early development phase. In future, this in silico approach may also address solubilization effects of minor components in excipients or in excipient mixtures, which is interesting from a product quality perspective so that it can further advance this field of molecular pharmaceutics.

Establishing Predictive Models for Solvatochromic Parameters of Ionic Liquids.

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.

Alternative solvents for lipid extraction and their effect on protein quality in black soldier fly (Hermetia illucens) larvae

Abstract Scrutiny of alternative solvents for the extraction of lipid constituents from black soldier fly (BSF) was the main theme of this research. The present investigation compared a wide array of solvents for the extraction of desired components theoretically using tools like Hansen solubility parameters (HSP), conductor-like screening model for real solvents (COSMO-RS) and technical data (ACD labs) with the application of hurdle technology for solvent screening. The ideal solvent selected was 2-methyloxolane (2-MeO) which was employed for conventional and multistage cross-current lipid extraction and the experimental data obtained was compared with that of n-hexane extract. Fatty acid profile, lipid class, bioactivity of the oils were analysed and were in good correlation with the theoretical prediction. The kinetics and diffusion modelling for the extraction system was proposed. The effect of solvent on protein quality parameters like protein dispersibility index, solubility in alkaline solution, urease index in the defatted flour was elucidated. The defatting step had no deleterious effect on the molecular weight distribution of soluble proteins. Overall the study manifested that 2-MeO had better lipid recovery, enhanced bioactivity in the BSF oil, and relatively better protein quality in the defatted flour.

Orange peel waste valorisation through limonene extraction using bio-based solvents

Orange peel waste (OPW) can be an effective feedstock for extraction of natural bioactive components such as limonene, a high value-added chemical broadly exploited for food, pharmaceutical, and cosmetic industrial applications. Extraction of limonene from OPW has been conventionally performed via solvent extraction using hexane, a hazardous petrochemical solvent currently restricted under international regulations. In this work, we have conducted a comparative assessment of the performance of a variety of green solvents for sustainable valorisation of OPW through limonene extraction. In particular, cyclopentyl methyl ether (CPME), ethyl lactate (EL), isopropyl alcohol (IPA), polyethylene glycol 300 (PEG 300), isopropyl acetate (IAc), dimethyl carbonate (DMC), methyl ethyl ketone (MEK), 2-methyl-tetrahydrofuran (2-MeTHF) and ethyl acetate (EAc) have been evaluated as hexane replacement for the recovery of limonene from OPW. Initially, a preliminary solvent screening was carried out using the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) to estimate the solubility of limonene in the proposed solvents and rank their theoretical extraction performance. Afterwards, experimental studies were performed to determine the limonene extraction yields and optimize the operating conditions (temperature, time and solvent load) for limonene recovery from OPW using the various solvents, as confirmed by gas chromatography mass spectrometry (GC–MS) analysis. Overall, results support that CPME and 2-MeTHF bio-based solvents significantly outperform the benchmark petrochemical solvent hexane by increasing limonene extraction yields up to 80% and 40% respectively at optimum operating conditions. Moreover, recovery and reuse of these solvents in consecutive extraction cycles was successfully accomplished, while scanning electron microscopy analysis (SEM) suggests that solvent effects on biomass structure disruption could be beneficial for further bioprocessing.

Investigating the solubility of petroleum asphaltene in ionic liquids and their interaction using COSMO-RS

Dispersion of asphaltene in crude oil using ionic liquids (ILs) is being considered as a viable solution, in extraction and transportation processes. In this work, the interplay between asphaltene and ILs has been studied systematically to understand the effect of structural variation of ILs on asphaltene solubility. The activity coefficient of the total of 1517 ILs with different combinations of cation and anion of ILs for representative asphaltene molecule (asphaltene) was estimated via COSMO-RS (Conductor-like Screening Model for Real Solvents). COSMO_RS predictions were validated using experimental data on asphaltene solubility. Among the studied ILs, asphaltene showed high solubility in imidazolium-based ILs with hydrophobic anions. The present approach paved a way forward to rationally understand the impact of structural variation of ILs on their interaction with asphaltene molecule and to design new ILs for the dispersion and stabilization of asphaltene.

Application of the Consonance Solvent Concept for Accurate Prediction of Buckminster Solubility in 180 Net Solvents using COSMO-RS Approach

The default COSMO-RS (Conductor like Screening Model for Real Solvents) approach is incapable of accurate computation of C60 solubility in net solvents. Additionally, there is no adequate selection of single or multiple reference solvent, which can be applied to the whole population of 180 solvents for improving prediction of mole fraction at saturated conditions. This failure cannot be addressed to inaccurate data of the Buckminster fusion, although they pose a challenge for experimental measurement due to intense sublimation of C60 at elevated temperatures and the possibility of solvates precipitation. However, taking advantage of the richness of experimental data of fullerene solubility, it is possible to identify the source of errors expressed in terms of fluidization affinity. Classification of solvents according to the value of this fluidization term allowed for formulation of a consonance solvents approach, which enables accurate prediction of C60 solubility using the single reference solvent method.

H2 Solubility in Hydrocarbons Calculated by the COSMO-RS Method

The solubility of H2 in alkylic and aromatic hydrocarbons was quantum-chemical theoretically calculated through the conductor-like screening model for real solvents (COSMO-RS). The results show tha...

Characterization of bis(fluorosulfonyl)imide based ionic liquids by gas chromatography

Infinite dilution thermodynamic properties of organic solutes dissolved in four bis(sulfonyl)imide ionic liquids namely 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide, N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide, 1-ethyl-1-methylimidazolium bis(fluorosulfonyl)imide and 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide were measured in a large range of temperature using inverse gas chromatography. The characterization of ILs using the Abraham solvation model indicates that the cation has an impact on the polarizability and on the acidity of the solvent. The derived Abraham model correlations rigorously describe the experimental partition coefficient data to within 0.09 (or fewer) log units. In addition, the activity coefficient at infinite dilution of organic solutes in these ILs was predicted using the conductor-like screening model for real solvents (COSMO-RS). It was found that COSMO-RS give a reasonable representation of experimental data. Then, selectivity and capacity at infinity dilution have been determined for the separation problems (thiophene/water), (benzene/water), (acetone/water), (1-butanol/water), (acetonitrile/water) and (pyridine/water) at 323.15 K.

Tuning the aqueous solubility, chemical reactivity and absorption wavelength of azo dye through systematic adjustment of molecular charge density: a DFT study

ABSTRACT Effects of substituent groups on aqueous solubility, chemical reactivity and absorption wavelength of Disperse red 73 (DR73) were theoretically investigated using density functional theory (DFT) method. This study is in view of introducing new monoazo disperse dyes with improved aqueous solubility, absorption behaviour, and degradation tendency. Aqueous solubility was calculated using Cramer et al. solubility equation and the parameters used were obtained using conductor-like screening model for realistic solvation (COSMO-RS). Chemical reactivity and catalytic affinity were evaluated using some molecular orbital dependent reactivity descriptors. Susceptibility of the molecules to radical attacks was predicted using Fukui functions. Absorption wavelength was calculated using the B3LYP functional with the 6-31G* basis set. The results showed that electron withdrawing −CN substituent promoted aqueous solubility of DR73 more than the −NO2 counterpart, while the solubility is mostly enhanced by −NH2 substituent compared to the other electron donating groups studied. Most of the derivatives yielded longer absorption wavelength in the visible region and are chemically less stable (i.e. more degradable) compared to the parent molecule. Among the photocatalysts considered, ZnO is predicted as the most efficient candidate for degradation of the dyes. Predicted properties showed remarkable sensitivity to substitution positions in the parent molecule.

COSMO-based solvent selection and Aspen Plus process simulation for tar absorptive removal

Tar accumulation is a major problem that has critically hindered further development of biomass gasification. Current studies on oil washing technologies have made progress, but experimental screening of core absorbents and process performance lack theoretical insight. Therefore, based on the design of Quench Coupled with ABsorption Technology (QCABT), the benzene, toluene, phenol, and naphthalene mixture representing real tar components was used as a tar simulant. The method of screening absorbents by Conductor-like Screening Model for Real Solvents (COSMO-RS) combined with thermodynamic relationships was established, and the tar removal process was investigated by Aspen Plus simulation. The results revealed that the developed semi-quantitative absorbent screening method is more efficient than that using only infinite dilution activity coefficients. A mixture of screened soybean oil, and N-formylmorpholine (NFM) is the optimal tar absorbent. The maximum relative error between Aspen Plus simulation and the experiment is 9.5‰ indicating good reliability. The addition of 30 v/v% of NFM could effectively promote the absorption of benzene and toluene. Higher liquid–gas ratio of absorption, lower absorption temperature, and better regeneration could ensure the satisfactory gas purification degree. The loss tendency and rate of oleic and linoleic acids (soybean oil simulant) are basically the same, but the loss rate of NFM is 4–6 orders of magnitude higher—this has the biggest contribution to solvent loss. The 90 °C condenser at the outlet of the desorber can control the solvent loss rate effectively. Under optimal conditions, the content of tar, energy loss, as well as loss ratio can be reduced to below 30 mg/Nm3, 1600 kJ/kg, and 0.5‰, respectively. As a result, this fascinating method provides quantitative guidance for tar absorption and removal.

Towards a Zero-Waste Biorefinery Using Edible Oils as Solvents for the Green Extraction of Volatile and Non-Volatile Bioactive Compounds from Rosemary.

The zero-waste biorefinery concept inspired a green oleo-extraction of both natural volatile (e.g., borneol, camphor, o-cymene, eucalyptol, limonene, α-pinene, and terpinen-4-ol) and non-volatile (e.g., carnosol, carnosic, and rosmarinic acid) bioactive compounds from rosemary leaves with vegetable oils and their amphiphilic derivatives as simple food-grade solvents. It is noteworthy that soybean oil could obtain the highest total phenolic compounds (TPCs) among 12 refined oils including grapeseed, rapeseed, peanut, sunflower, olive, avocado, almond, apricot, corn, wheat germ, and hazelnut oils. Furthermore, the addition of oil derivatives to soybean oils, such as glyceryl monooleate (GMO), glyceryl monostearate (GMS), diglycerides, and soy lecithin in particular, could not only significantly enhance the oleo-extraction of non-volatile antioxidants by 66.7% approximately, but also help to remarkably improve the solvation of volatile aroma compounds (VACs) by 16% in refined soybean oils. These experimental results were in good consistency with their relative solubilities predicted by the more sophisticated COSMO-RS (COnductor like Screening MOdel for Real Solvents) simulation. This simple procedure of using vegetable oils and their derivatives as bio-based solvents for simultaneously improving the extraction yield of natural antioxidants and flavors from rosemary showed its great potential in up-scaling with the integration of green techniques (ultrasound, microwave, etc.) for zero-waste biorefinery from biomass waste to high value-added extracts in future functional food and cosmetic applications.

Holistic valorization of rapeseed meal utilizing green solvents extraction and biopolymer production with Pseudomonas putida

A rapeseed meal (RSM) valorization scheme was developed to utilize valuable fractions including phenolics (mainly sinapic acid), proteins and polysaccharides. This involved solvent extraction of phenolics, alkali extraction of proteins and fermentation of residual polysaccharide using Pseudomonas putida. For the first time, sustainable Deep eutectic solvents (DESs) were used in the extraction of rapeseed meal phenolics. With yields up to 85.69 % wt. DESs were able to outperform methanol (59.54 % wt.) at sinapic acid extraction. As shown by Conductor like Screening Model for Real Solvents (COSMO-RS), this is because DESs have greater capacity for H-bonding.Post-extraction RSM hydrolysate was shown to be a viable media for cultivation of P. putida with maximum cell dry weight of 4.89 g l−1 for DES-extracted RSM. 8-carbon and 10-carbon chain length polyhydroxyalkanoate biopolymers were synthesized. Biopolymer accumulation was reduced in RSM derived media due to high nitrogen concentration. These findings are beneficial for the development of a sustainable biorefining scheme based on rapeseed meal.

Experimental Data of Fluid Phase Equilibria- Correlation and Prediction Models: A Review

The examples of phase equilibria in binary systems, solid/liquid (SLE), liquid/liquid (LLE), vapor/liquid (VLE), as well as liquid/liquid equilibria in ternary systems mainly containing ionic liquids (ILs), or the infragrance materials, or pharmaceuticals with molecular organic solvents, such as an alcohol, or water, or hydrocarbons, are presented. The most popular correlation methods of the experimental phase equilibrium data are presented, related to the excess Gibbs free energy models such as Wilson, universal-quasichemical, UNIQUAC and non-random two-liquid model, NRTL as well as several popular theories for the modeling of the phase equilibria and excess molar enthalpy, HE in binary or ternary mixtures are presented: the group contribution method (Mod. UNIFAC) and modified UNIFAC model for pharmaceuticals and lattice theory based on non-random hydrogen bonding (NRHB). The SLE, LLE, or VLE and HE of these systems may be described by the Perturbed-Chain Polar Statistical Associating Fluid Theory (PC-SAFT), or a Conductor-like Screening Model for Real Solvents (COSMO-RS). The examples of the application of ILs as extractants for the separation of aromatic hydrocarbons from alkanes, sulfur compounds from alkanes, alkenes from alkanes, ethylbenzene from styrene, butan-1-ol from water phase, or 2-phenylethanol (PEA) from water are discussed on the basis of previously published data. The first information about the selectivity of extrahent for separation can be obtained from the measurements of the limiting activity coefficient measurements by the gas–liquid chromatography technique. This review outlines the main research work carried out over the last few years on direct measurements of phase equilibria, or HE and limiting activity coefficients, the possibility of thermodynamic modeling with emphasis on recent research achievements and potential for future research.

New phase equilibrium data at ambient and high pressure for strongly asymmetric mixtures containing menthol

New data on phase equilibria in binary and ternary mixtures containing (−)-menthol, n-decane, 1-decanol and water are presented and discussed. In particular, experimental liquid-liquid equilibrium phase diagrams in ternary systems {(−)-menthol + (n-decane, or 1-decanol) + water} are reported along with the predictions by means of leading thermodynamic models, namely, perturbed-chain statistical associating fluid theory (PC-SAFT) and conductor-like screening model for real solvents (COSMO-RS). Freezing pressure data for binary systems {(−)-menthol + (n-decane, or 1-decanol)} are reported and the corresponding high-pressure solid-liquid equilibrium phase diagrams are discussed and analyzed by using the Yang equation. The measured data are referred to ambient-pressure phase diagrams published previously.