Force field parameters for N,N-Dimethylformamide (DMF) revisited: Improved prediction of bulk properties and complete miscibility in water

Vasudevan, Vallabh; Mushrif, Samir H.

doi:10.1016/j.molliq.2015.03.004

Cited by 24 publications

(25 citation statements)

References 26 publications

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“…37 Aqueous DMF mixtures are controversially discussed: while earlier studies favour micro heterogeneities, 16,38 an improved force field leads to a better prediction of bulk parameters, improves the miscibility, and leads to less heterogeneities on a molecular level. 39 In order to gain a better understanding of the underlying mechanisms in the considered mixtures, we want to look into two aspects: first the structural changes of the mixture by considering the thermal expansion coefficient and second the governing interactions especially the hydrogen bonding, which we try to quantify by its hydrophilicity.…”

Section: Discussionmentioning

confidence: 99%

Peptide model systems: Correlation between thermophilicity and hydrophilicity

Niether

Kriegs

Dhont

et al. 2018

The Journal of Chemical Physics

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In recent years, the response of biomolecules to a temperature gradient has been utilized to monitor reactions of biomolecules, but the underlying mechanism is not well understood due to the complexity of the multicomponent system. To identify some underlying principles, we investigate the thermal diffusion of small amide molecules in water systematically. We re-analyze previous measurements of urea and formamide and compare the results with acetamide, N-methylformamide, and N,N-dimethylformamide, amides with a lower hydrophilicity. It turns out that less hydrophilic substances do not show the typical temperature dependence of water soluble macromolecules. Analyzing temperature and concentration dependent measurements using an empirical expression originally derived for nonpolar mixtures, we find that the so-called isotope contribution depends strongly on the hydrophilicity of the solute. This can be qualitatively understood by comparing with molecular dynamic simulations of Lennard-Jones fluids. The hydrophobic/hydrophilic balance also influences the structure in the fluid and with that the thermal expansion coefficient, which correlates with the thermal diffusion coefficient. Furthermore, we observe a clear correlation of the temperature and concentration dependence of the Soret coefficient with the hydrophilicity, which can be quantitatively described by the partition coefficient log P.

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Section: Discussionmentioning

confidence: 99%

Peptide model systems: Correlation between thermophilicity and hydrophilicity

Niether

Kriegs

Dhont

et al. 2018

The Journal of Chemical Physics

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“…The system was equilibrated for the first 10 ns with an interval of 0.5 fs, and the data collected at 5 ps intervals during the last 5 ns were analyzed to obtain the X-ray weighted structure factors and radial distribution functions [ S MD ( q ) and G MD ( r ), respectively]. CLaP and OPLS-AA force fields, including intermolecular Lennard–Jones and Coulombic interactions and intramolecular interactions with (1) bond stretching, (2) angle bending, and (3) torsion of dihedral angles, were used for LiTFSA and DMF, respectively. − …”

Section: Methodsmentioning

confidence: 99%

Long-Range Ion-Ordering in Salt-Concentrated Lithium-Ion Battery Electrolytes: A Combined High-Energy X-ray Total Scattering and Molecular Dynamics Simulation Study

et al. 2017

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Herein, we report on a structural study for characterizing unique solution structures in the salt-concentrated electrolytes, which are promising new lithium (Li)-ion battery electrolytes. A combination of high-energy X-ray total scattering (HEXTS) experiments with all-atom molecular dynamics (MD) simulations was performed on the salt-concentrated electrolytes that were based on Li bis(trifluoromethanesulfonyl)amide (LiTFSA) and N,N-dimethylformamide (DMF). The radial distribution functions obtained from the HEXTS and MD approaches were in good agreement in the current LiTFSA/DMF solutions. We found that in the local structure: (1) the Li-ions were coordinated with both the DMF molecules and the TFSA anions in the concentrated solutions and (2) specific Li+···Li+ correlations were present in the radial distribution function over the r range of 3 Å–15 Å. The Li+···Li+ correlations originated from the extended multiple Li-ion complexes, that is, polymerized [Li+···TFSA–···Li+] n complexes so that they were highly structurally ordered. We concluded that this type of an ion-ordered structure plays a crucial role in the electrochemical stability and the ion-conducting mechanism, resulting in a unique LIB performance employing these salt-concentrated electrolytes.

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“…It has extensive miscibility with water, esters, ketones, alcohols, carbon disulfide, ethers, and chlorinated hydrocarbons . Due to its relatively high dielectric constant and large dipole moment, DMF is regarded as a “versatile solvent” and is widely used in a variety of industrial applications, including the production of synthetic leather, fiber, film and surface coatings, dyes, adhesives, pesticides, and pharmaceuticals. − DMF could enter the organs of the human and animal body via the respiratory tract, digestive tract, and skin touch, which can induce hepatotoxicity, carcinogenicity, alcohol intolerance, possible embryotoxicity, and teratogenicity. − On account of its various applications and severe toxic effects, DMF has been selected as one of the four priority compounds for human field studies by the National Toxicology Program (NTP) of the US National Institute of Environmental Health Sciences (NIEHS) . Until now, a series of approaches have been developed to recover DMF from industrial waste as much as possible.…”

Section: Introductionmentioning

confidence: 99%

Salt Effect on the Liquid–Liquid Equilibria for the Ternary System Water + N,N-Dimethylformamide (DMF) + Chloroform

Wang

et al. 2021

J. Chem. Eng. Data

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Wastewater containing DMF (N,N-dimethylformamide) and salt is generated in production of many chemicals and medicines. The composition of phase equilibrium should be known primarily for the recovery of DMF from salt-containing wastewater by solvent extraction. In this study, liquid–liquid equilibrium (LLE) and solubility data of water + DMF + chloroform in the presence of NaCl with various concentrations of 0, 2.5, 5.0, 7.5, 10.0, and 13.3 wt % and Na2SO4 with concentrations of 1.5 and 2.5 wt % were determined at T = 298.2 K and atmospheric pressure. Besides, the salt effect on the LLE data was investigated. Compared with the salt-free system, the salt led to an enhancement in the maximum DMF distribution coefficient by 13.4–102.6% for 2.5–13.3 wt % NaCl and 16.2–31.7% for 1.5–2.5 wt % Na2SO4, respectively. Since the distribution coefficient of water increased concurrently, the separation factor barely changed and the two-phase region expanded outward slightly. At the same salt mass fraction, the order of salting-out effect strength on extraction was Na2SO4 > NaCl, which was in good agreement with the Hofmeister series. The reliability of the experimental values was verified through the Eisen–Joffe equation. The NRTL thermodynamic model was applied to correlate the experimental data with a root-mean-square deviation less than 0.0062. The coherent consistency of the model parameters for the salt-free system was checked by topological analysis based on the Gibbs tangent plane test.

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Force field parameters for N,N-Dimethylformamide (DMF) revisited: Improved prediction of bulk properties and complete miscibility in water

Cited by 24 publications

References 26 publications

Peptide model systems: Correlation between thermophilicity and hydrophilicity

Peptide model systems: Correlation between thermophilicity and hydrophilicity

Long-Range Ion-Ordering in Salt-Concentrated Lithium-Ion Battery Electrolytes: A Combined High-Energy X-ray Total Scattering and Molecular Dynamics Simulation Study

Salt Effect on the Liquid–Liquid Equilibria for the Ternary System Water + N,N-Dimethylformamide (DMF) + Chloroform

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