Insights into the orientation and hydrogen bond influence on thermophysical and transport properties in choline-based deep eutectic solvents and methanol

Cea-Klapp, Esteban; Garrido, José Matías; Quinteros-Lama, Héctor

doi:10.1016/j.molliq.2021.117019

Cited by 17 publications

(17 citation statements)

References 86 publications

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“…The most prevalent HBD used in DES synthesis is glycerol. However, synthesis of each type of DES predominantly requires a suitable choice of donors and acceptors. , If the target is the formation of low-viscosity eutectic mixtures, then a combination of diols and ammonium salts would be preferable. Similarly, the formation of NADES with higher viscosity results from combining carbohydrates with quaternary ammonium salts or urea.…”

Section: Synthesis and Characterization Of Desmentioning

confidence: 99%

“…These investigations cumulatively explains the relationship between various types of DES formed with diverse choice of HBAs and HBDs . However, each type of DES exhibits a signature physical property (Figure ) that influences its orientation to selectively extract a single type of nutraceutical . On general observation, it is concluded that density, conductivity and pH are the important essential proprties and molar solubility, excess molar volume, and spectral properties such as NMR and FTIR are the important empirical physical properties that must be determined to evaluate the suitability of the respective type of DES for nutraceutical extraction …”

Section: Synthesis and Characterization Of Desmentioning

confidence: 99%

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Sustainable and Green Engineering Insights on Deep Eutectic Solvents toward the Extraction of Nutraceuticals

Balaraman

Rangabhashiyam

Rangarajan

et al. 2021

ACS Sustainable Chem. Eng.

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Deep eutectic solvents (DES) hold promising potential in the selective purification of bioactive molecules from various complex sources. Although they are increasingly considered as a biocompatible extraction medium, adding the task-specific functionality, which makes DES distinctive for the selective extraction of compounds, requires appropriate tailoring of their physical properties. This critical review investigates the influential physical properties of deep eutectic solvents and their effect on various sustainable extraction methodsincluding both solid–liquid and liquid–liquidfor the separation of nutraceuticals. Various methods by which DES are employed as solvents, cosolvents, or as adjuvants in different extraction systems are compared in terms of their efficiency and selectivity. Furthermore, the correspondence between the type of DES and the nature of target nutraceuticals to be extracted is also discussed. The Review highlights the key achievements and future prospects of employing DES along with the lacunae in the current investigations and proposed various approaches for sustainable applications.

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Section: Synthesis and Characterization Of Desmentioning

confidence: 99%

Section: Synthesis and Characterization Of Desmentioning

confidence: 99%

Sustainable and Green Engineering Insights on Deep Eutectic Solvents toward the Extraction of Nutraceuticals

Balaraman

Rangabhashiyam

Rangarajan

et al. 2021

ACS Sustainable Chem. Eng.

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“…In turn, for ChCl-glycerol, Ferreira et al have recently shown that water is arranged interacting simultaneously with ChCl and glycerol through hydrogen bonds up to a mass concentration of 11%. After 11 wt %, water molecules start solvating the ChCl and glycerol, weakening the H-bonds network between ChCl and glycerol, forming smaller aggregates, − hence the almost constant value of surface tension. Surprisingly, although organic solvents have small tension than both DES, we can note that only a monotonic behavior is depicted.…”

Section: Resultsmentioning

confidence: 99%

Interfacial Properties of Deep Eutectic Solvents by Density Gradient Theory

Cea-Klapp

Gajardo‐Parra

Aravena

et al. 2022

Ind. Eng. Chem. Res.

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Deep eutectic solvents (DES) are room-temperature liquid mixtures constituted of a hydrogen-bonding acceptor (HBA) and a hydrogen-bonding donor (HBD). They have high practical potential due to their versatility, quick preparation, and wide applications. Therefore, it is appropriate to have robust models to predict their properties. In this work, the density gradient theory has been combined with the perturbed-chain statistical associating fluid theory to model and understand the interfacial behavior in systems of deep eutectic solvents. DESs were modeled as mixtures of their constituents, and a methodology is proposed for estimating the chemical potential of DESs to extend their study to the interfacial properties. Available experimental data of hydrophilic and hydrophobic DESs were used to calculate the influence parameters, providing a way to linearize them in terms of the molecular parameters of HBDs and their molar ratio between HBD and HBA. This treatment has made it feasible to predict the thermal dependence of surface tension in most of the DESs analyzed with an average absolute relative deviation of 1.26%. Furthermore, density gradient theory and perturbed-chain statistical associating fluid theory were applied to predict the vapor−liquid surface tension in mixtures of organic compounds with DES. In particular, we have calculated the surface tension in mixtures of ChCl-glycerol and ChCl-lactic acid with water, ethanol, propanol, phenol, acetone, and ethyl acetate without fitting binary interaction parameters. The behavior of density profiles suggests that the surface is enriched with DES components for the DES + water mixtures. In contrast, it is enriched with diluent for the other ternary systems (ethanol, isopropanol, phenol, acetone, and ethyl acetate).

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“…The Cl − -Cl − RDFs of selected simulated DES/water and methanol mixtures are reported in Figures 5A,B, respectively. These functions are frequently reported for the (simulated) pure DES and its aqueous mixtures (Perkins et al, 2014;Ferreira et al, 2016;Celebi et al, 2019;Kaur et al, 2019), though not for the DES/methanol mixtures (Cea-Klapp et al, 2022). In the pure ethaline DES, the function is characterized by a broad, apparently convoluted, first maximum at r ClCl ≈ 7-8 Å (we note that the corresponding RDF reported by Kaur et al (Kaur et al, 2019) is somewhat different, displaying a clear shoulder at short distances at 303 K); this convoluted first-maximum structure likely arises from Cl − pairs located in the different characteristic "bridging" configurations in the DES (Kaur et al, 2020), i.e., either separated by an EG molecule or Ch + , both of which are conformationally flexible.…”

Section: Radial Distribution Functionsmentioning

confidence: 96%

MD simulations explain the excess molar enthalpies in pseudo-binary mixtures of a choline chloride-based deep eutectic solvent with water or methanol

Engelbrecht

Carbonaro

et al. 2022

Front. Chem.

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The addition of molecular liquid cosolvents to choline chloride (ChCl)-based deep eutectic solvents (DESs) is increasingly investigated for reducing the inherently high bulk viscosities of the latter, which represent a major obstacle for potential industrial applications. The molar enthalpy of mixing, often referred to as excess molar enthalpy HE—a property reflecting changes in intermolecular interactions upon mixing—of the well-known ChCl/ethylene glycol (1:2 molar ratio) DES mixed with either water or methanol was recently found to be of opposite sign at 308.15 K: Mixing of the DES with water is strongly exothermic, while methanol mixtures are endothermic over the entire mixture composition range. Knowledge of molecular-level liquid structural changes in the DES following cosolvent addition is expected to be important when selecting such “pseudo-binary” mixtures for specific applications, e.g., solvents. With the aim of understanding the reason for the different behavior of selected DES/water or methanol mixtures, we performed classical MD computer simulations to study the changes in intermolecular interactions thought to be responsible for the observed HE sign difference. Excess molar enthalpies computed from our simulations reproduce, for the first time, the experimental sign difference and composition dependence of the property. We performed a structural analysis of simulation configurations, revealing an intriguing difference in the interaction modes of the two cosolvents with the DES chloride anion: water molecules insert between neighboring chloride anions, forming ionic hydrogen-bonded bridges that draw the anions closer, whereas dilution of the DES with methanol results in increased interionic separation. Moreover, the simulated DES/water mixtures were found to contain extended hydrogen-bonded structures containing water-bridged chloride pair arrangements, the presence of which may have important implications for solvent applications.

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Insights into the orientation and hydrogen bond influence on thermophysical and transport properties in choline-based deep eutectic solvents and methanol

Cited by 17 publications

References 86 publications

Sustainable and Green Engineering Insights on Deep Eutectic Solvents toward the Extraction of Nutraceuticals

Sustainable and Green Engineering Insights on Deep Eutectic Solvents toward the Extraction of Nutraceuticals

Interfacial Properties of Deep Eutectic Solvents by Density Gradient Theory

MD simulations explain the excess molar enthalpies in pseudo-binary mixtures of a choline chloride-based deep eutectic solvent with water or methanol

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