A comprehensive computational and principal component analysis on various choline chloride-based deep eutectic solvents to reveal their structural and spectroscopic properties

Rain, Mahmudul Islam; Iqbal, Humayun; Saha, Mousumi; Ali, A.; Chohan, Harmeet Kaur; Rahman, Sajjadur; Halim, Mohammad A.

doi:10.1063/5.0052569

Cited by 9 publications

(10 citation statements)

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“…While the wide design space offers opportunities for designing solvents for particular applications, it has also created obstacles in developing fundamental structure–property understanding. Many efforts pursuing such understanding have been carried out using a variety of techniques in recent years. ,,− However, few underlying principles are available to guide the design of a DES and broad fundamental understanding of the link between composition, structure, and properties of DESs is still missing. For example, ethaline is one of the most studied DESs over the past decade, which is a 1:2 molar ratio mixture of choline chloride (ChCl) and ethylene glycol (EG).…”

Section: Introductionmentioning

confidence: 99%

Refined Classical Force Field for Choline Chloride and Ethylene Glycol Mixtures over Wide Composition Range

et al. 2022

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A classical force field based on the General Amber Force Field (GAFF) was refined for the simulation of choline chloride (ChCl) and ethylene glycol (EG) mixtures over a wide composition range by scaling the partial charges and van der Waals parameters. The scaling factors were derived by fitting the simulation results to only eight experimental density and viscosity data points of pure EG, and ChCl/EG mixtures at 1:2, 1:4, and 1:6 molar ratios. Using the refined force field, properties essential for electrochemical applications such as density, viscosity, self-diffusion coefficient, and ionic conductivity were calculated, and excellent agreement to experimental results was found even for compositions and temperatures not used in the fitting procedure. In addition, new experimental data for density, viscosity, and ionic conductivity are reported as a function of temperature and composition for this mixture. To the best of our knowledge, this is the first classical force field developed for the study of ChCl/EG mixtures over a composition range that includes the eutectic point. Using the new model, the liquid dynamics was studied in terms of ionic conductivity. It was found that the dynamics in ChCl/EG mixtures with ChCl mole fraction higher than 20% is similar to that of ionic liquids, high temperature molten salts, and highly concentrated water-in-salt electrolytes.

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Section: Introductionmentioning

confidence: 99%

Refined Classical Force Field for Choline Chloride and Ethylene Glycol Mixtures over Wide Composition Range

et al. 2022

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“…94 They found maximum shifts for the OH functional group of Ch + after cluster formation, suggesting active participation in DES formation through hydrogen bonding with the acceptor groups of HBDs. 94 As the DES field continues to grow, the development of protic DESs may be envisioned as analogous to the protic ionic liquids (PIL) field. 95 As such, future computational studies in protic DES applications, for example, anhydrous proton-conducting electrolytes in fuel-cell technology, would require a method that could reproduce both hydrogen bonding and proton diffusion.…”

Section: Hydrogen Bondingmentioning

confidence: 97%

“… 93 Interestingly, Araujo et al also found urea's geometry to be more pyramidal (sp 3 ) in CCU compared to sp 2 planar in the crystal, which allows for a more flexible hydrogen bond network that encourages eutectic behavior 93 . Finally, Rain et al computed the IR spectra of nine different ChCl‐based DESs using ωB97XD and analyzed the results with principal component analysis (PCA) 94 . They found maximum shifts for the OH functional group of Ch + after cluster formation, suggesting active participation in DES formation through hydrogen bonding with the acceptor groups of HBDs 94 …”

Section: Quantum Mechanicsmentioning

confidence: 99%

“…Finally, Rain et al computed the IR spectra of nine different ChCl‐based DESs using ωB97XD and analyzed the results with principal component analysis (PCA) 94 . They found maximum shifts for the OH functional group of Ch + after cluster formation, suggesting active participation in DES formation through hydrogen bonding with the acceptor groups of HBDs 94 …”

Section: Quantum Mechanicsmentioning

confidence: 99%

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Simulation of deep eutectic solvents: Progress to promises

Velez

Acevedo

2022

WIREs Comput Mol Sci

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Deep eutectic solvents (DESs) are binary or ternary mixtures of compounds that possess significant melting point depressions relative to the pure isolated components. The discovery of DESs has been a major breakthrough with multiple fields benefitting from their low cost and tunable physiochemical properties. However, tailoring DESs for specific applications through their practically unlimited synthetic combinations can be as much a hindrance as a benefit given the expense and time-required to perform large-scale experimental measurements. This emphasizes the need for fast computational tools capable of making accurate predictions of DES physiochemical properties exclusively from molecular structure. Yet, these systems are not trivial to model or simulate at the atomic level given their exceedingly nonideal behaviors, asymmetry of components, and the complexity of their molecular electrostatic interactions. Despite the challenge, computational reports featuring quantum mechanical (QM) methods have provided significant understanding into the relationship between the melting point depression and the unique and complex hydrogen bond network present in DESs. Classical molecular dynamics (MD) methods have examined bulk-phase solvent organization in conjunction with thermodynamic and transport properties. Machine learning (ML) algorithms have shown great potential as structure-property prediction tools. Overall, this review highlights computational accomplishments that have meaningfully advanced our understanding of DESs and strives to give the reader a sense of the overall strengths and drawbacks of the methodologies employed while hinting at promises of advances to come.

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“…The interaction properties of 1:1 ChCl/MA and other ChCl-based deep eutectic solvents are similar to the 1:1 ChCl/CA eutectic system that we studied in our previous study. 33 Experimental ATR-FTIR and Raman. The study employed ATR-FTIR to examine the intermolecular interactions among the constituents of eutectic solvent systems (all five ratios) and their corresponding structural characteristics (Figure S4).…”

Section: ■ Experimental Detailsmentioning

confidence: 99%

Elucidating the Structure, Dynamics, and Interaction of a Choline Chloride and Citric Acid Based Eutectic System by Spectroscopic and Molecular Modeling Investigations

Ali,

Kaium,

Uddin

et al. 2023

ACS Omega

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Eutectic solvent systems are versatile solvents that have found widespread use in numerous applications. Traditional solvents are homogeneous, having only one component, and their chemistry is relatively simple, with some exceptions. On the other hand, deep eutectic solvents (DESs) comprise binary components, generally a donor and an acceptor in hydrogen bonding with varying ratios. The interaction chemistry among the donor and acceptor involved in hydrogen bonding in DESs is complicated. Although numerous research is focused on the synthesis and application of DESs, few studies are reported to elucidate the complex structure and dynamic and interaction behavior of DESs. In this study, we employed calorimetry, vibrational spectroscopy techniques including FTIR and Raman, and nuclear magnetic resonance to derive insight into the structural feature and noncovalent contact of choline chloride (ChCl) and citric acid (CA) while they formed DESs. The 1:1 ChCl/CA eutectic system showed phase transitions and melting peaks with the most pronounced peak at 156.22 °C, suggesting the DESs melting at a lower temperature than the melting temperatures of ChCl and CA. In addition to IR and Raman findings, 1 H NMR investigations demonstrate hydrogen bonding intermolecular interactions between ChCl and CA, supporting the formation of 1:1 ChCl/CA DESs based on the deshielded chemical shifts of the proton for Ch. The interaction of the chloride anion with the methyl protons (H4) and methylene protons (H3) of ChCl as well as the strong hydrogen bonding interactions between the hydroxyl hydrogen (H1) of ChCl with one of CA's carbonyl oxygens both supported the formation of conformer E. In addition, molecular dynamics followed by the density functional theory (DFT) was employed to visualize the structure and interaction of DESs using the ωB97XD theory and 6-311++G (d,p) basis set. Both experimental and theoretical IR, Raman, and structural analyses provided evidence of the formation of DESs by possessing hydrogen bonds. These multifaceted experimental and computational investigations provide details of structural and intermolecular interactions of ChCl/CA DESs.

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A comprehensive computational and principal component analysis on various choline chloride-based deep eutectic solvents to reveal their structural and spectroscopic properties

Cited by 9 publications

References 59 publications

Refined Classical Force Field for Choline Chloride and Ethylene Glycol Mixtures over Wide Composition Range

Refined Classical Force Field for Choline Chloride and Ethylene Glycol Mixtures over Wide Composition Range

Simulation of deep eutectic solvents: Progress to promises

Elucidating the Structure, Dynamics, and Interaction of a Choline Chloride and Citric Acid Based Eutectic System by Spectroscopic and Molecular Modeling Investigations

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