Using COSMO-RS to design choline chloride pharmaceutical eutectic solvents

Abranches, Dinis O.; Larriba, Marcos; Silva, Liliana P.; Melle‐Franco, Manuel; Palomar, José; Pinho, Simão P.; Coutinho, João A. P.

doi:10.1016/j.fluid.2019.06.005

Cited by 79 publications

(70 citation statements)

References 56 publications

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“…Specifically, the COSMO-BP-TZVP template was employed, which includes a def-TZVP basis set, a DFT with the B-P86 functional and the COSMO solvation model (continuum solvent with infinite permittivity). In line with previous studies [69,70], and due to a shortcoming in the model regarding electrolyte species [71], all salts were optimized as neutral ionic pairs instead of separate cation and anion species. Finally, the COSMO-RS model was applied through the software COSMOtherm [72,73] using the BP_TZVP_C30_1701 parametrization.…”

Section: Cosmo-rsmentioning

confidence: 95%

Experimental solubility and density studies on aqueous solutions of quaternary ammonium halides, and thermodynamic modelling for melting enthalpy estimations

Vilas-Boas

Abranches

Crespo

et al. 2020

Journal of Molecular Liquids

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Aiming to extend the yet limited knowledge on phase equilibria and physical-chemical properties of quaternary alkylammonium halides and their aqueous binary systems, the solubilities of ten salts in water were measured in this work in the temperature range between 293.2 K and 348.2 K along with their densities. The PC-SAFT equation of state was then applied in the description of density as well as water activity coefficients data. The modelling results describe very satisfactorily the experimental data, and the non-associating parameters follow welldefined trends with the molecular weight of the alkylammonium halides. These parameters were applied in the prediction of the solubility data with unsatisfactory results, with mole fraction average absolute deviation (AAD = 0.018), deteriorating with increasing alkyl chain length. However, refitting the binary interaction parameter a much better description is obtained (AAD = 0.0045). COSMO-RS was also applied for the solubility prediction (AAD = 0.025), with poorer results for the chloride salts. After, the melting enthalpies of the quaternary alkylammonium halides were estimated using the PC-SAFT equation, which in spite of their uncertainty, are possibly the best option to perform solid-liquid equilibrium analysis of utmost importance when designing and screening new deep eutectic mixtures based on these compounds.

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Section: Cosmo-rsmentioning

confidence: 95%

Experimental solubility and density studies on aqueous solutions of quaternary ammonium halides, and thermodynamic modelling for melting enthalpy estimations

Vilas-Boas

Abranches

Crespo

et al. 2020

Journal of Molecular Liquids

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“…Owing to the previously mentioned difficulties, predictive methods are required. Abranches et al [34] proposed Conductor like Screening Model for Real Solvents (COSMO-RS) to predict the SLE of eutectic mixtures. Wolbert et al [35] used UNIFAC (Do) to model the activity coefficient of constituents in binary eutectic mixtures.…”

Section: Introductionmentioning

confidence: 99%

Design of Deep Eutectic Systems: A Simple Approach for Preselecting Eutectic Mixture Constituents

2020

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Eutectic systems offer a wide range of new (green) designer solvents for diverse applications. However, due to the large pool of possible compounds, selecting compounds that form eutectic systems is not straightforward. In this study, a simple approach for preselecting possible candidates from a pool of substances sharing the same chemical functionality was presented. First, the melting entropy of single compounds was correlated with their molecular structure to calculate their melting enthalpy. Subsequently, the eutectic temperature of the screened binary systems was qualitatively predicted, and the systems were ordered according to the depth of the eutectic temperature. The approach was demonstrated for six hydrophobic eutectic systems composed of L-menthol and monocarboxylic acids with linear and cyclic structures. It was found that the melting entropy of compounds sharing the same functionality could be well correlated with their molecular structures. As a result, when the two acids had a similar melting temperature, the melting enthalpy of a rigid acid was found to be lower than that of a flexible acid. It was demonstrated that compounds with more rigid molecular structures could form deeper eutectics. The proposed approach could decrease the experimental efforts required to design deep eutectic solvents, particularly when the melting enthalpy of pure components is not available.

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“…20 Interestingly, cholinium chloride-based DES are by far the most studied in the literature, 1−3,6−21 even though cholinium chloride typically displays a thermodynamically ideal behavior in these systems. 6,22 Its attractiveness as a DES component stems from its low toxicity, 23 high biodegradability, 24 and low melting enthalpy (4.3 kJ/mol), 25 causing it to present a steep solid−liquid equilibrium line and, thus, a sharp melting temperature depression effect.…”

Section: Introductionmentioning

confidence: 99%

Liquefying Compounds by Forming Deep Eutectic Solvents: A Case Study for Organic Acids and Alcohols

et al. 2020

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The criterion to distinguish a simple eutectic mixture from a deep eutectic solvent (DES) lies in the deviations to thermodynamic ideality presented by the components in the system. In this work, the current knowledge of the molecular interactions in types III and V DES is explored to liquefy a set of three fatty acids and three fatty alcohols, here used as model compounds for carboxyl and hydroxyl containing solid compounds. This work shows that thymol, a stronger than usual hydrogen bond donor, is able to form deep eutectic solvents of type V with the fatty alcohols studied. This is particularly interesting, since these DES formed are hydrophobic. Regarding type III DES, the results suggest that the prototypical DES hydrogen bond acceptor, cholinium chloride, is unable to induce negative deviations to ideality in the model molecules studied. By substituting choline with tetramethylammonium chloride, it is shown that the choline hydroxyl group is responsible for the difficulty in forming choline-based deep eutectic solvents and that its absence induces strong negative deviations to ideality in the alkylammonium side. Finally, it is demonstrated that tetrabutylammonium chloride acts as a chloride donning agent, causing significant negative deviations to ideality in both fatty acids and alcohols and leading to the formation of deep eutectic solvents of type III.

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Using COSMO-RS to design choline chloride pharmaceutical eutectic solvents

Cited by 79 publications

References 56 publications

Experimental solubility and density studies on aqueous solutions of quaternary ammonium halides, and thermodynamic modelling for melting enthalpy estimations

Experimental solubility and density studies on aqueous solutions of quaternary ammonium halides, and thermodynamic modelling for melting enthalpy estimations

Design of Deep Eutectic Systems: A Simple Approach for Preselecting Eutectic Mixture Constituents

Liquefying Compounds by Forming Deep Eutectic Solvents: A Case Study for Organic Acids and Alcohols

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