INS, DFT and temperature dependent IR investigations of dynamical properties of low temperature phase of choline chloride

Pawlukojć, A.; Hetmańczyk, Łukasz

doi:10.1016/j.chemphys.2014.10.013

Cited by 11 publications

(10 citation statements)

References 40 publications

(43 reference statements)

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“…Intense modes in the 200-300 cm -1 region of the INS spectra are usually associated with torsions of methyl groups attached to a carbon atom 51 . In pure choline chloride 48 , methyl torsions appear as sharp peaks at 286 cm -1 , 341 cm -1 and 349 cm -1 , as highlighted in The experimental frequency shifts, relative to the choline chloride crystal, are in good agreement with those estimated in silico, as attested in Table 1. Table 1 -Wavenumbers at maximum intensity of ChCl and Reline's methyl torsional modes, as observed experimentally (TOSCA) and estimated in a periodic ab initio calculation (CASTEP)…”

Section: Chloride Anions Move Away From Choline's Headroupsupporting

confidence: 79%

“…Discrete and periodic calculations, complemented by the wellestablished vibrational analysis of choline chloride 48 and urea 39, 49 , have guided the spectral assignment of Reline's INS spectrum, presented in Fig. 4 and Table S2 (ESI).…”

Section: Estimating Reline's Spectra With Discrete and Periodic Calcumentioning

confidence: 99%

“…interval result from choline's CH 3 torsions and N(CH 3 ) 3 deformations 48 . Both periodic and discrete calculations suggest these to be complex, with a small contribution of NH 2 wagging vibrations which may accentuate the broadening of Reline's bands, relative to those of choline chloride.…”

Section: Vibrational Analysis Of Low Frequency Modes: <500 CM -1mentioning

confidence: 99%

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Inelastic neutron scattering study of reline: shedding light on the hydrogen bonding network of deep eutectic solvents

Araújo

Coutinho

Nolasco

et al. 2017

Phys. Chem. Chem. Phys.

146

155

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The solids choline chloride and urea, mixed in a 1 : 2 molar proportion, form the iconic deep eutectic solvent "Reline". A combination of computational and vibrational spectroscopy tools, including inelastic neutron scattering (INS), have been used to probe intermolecular interactions in the eutectic mixture. Reline's experimental spectra were estimated using discrete and periodic ab initio calculations of a molecular aggregate with two choline chloride and four urea units. This is the minimum size required to achieve satisfactory agreement with experiment, as smaller clusters cannot represent all of reline's significant intermolecular interactions. The INS spectrum of reline, compared with that of pure choline chloride, reveals a displacement of chloride anions away from their preferred positions on top of choline's methyl groups, whose torsional movement becomes less hindered in the mixture. Urea, which adopts a planar (sp) shape in the crystal, becomes non-planar (sp) in reline, a feature herein discussed for the first time. In reline, urea molecules form a wide range of hydrogen bonds, from soft contacts to stronger associations, the latter being responsible for the deviation from ideality. The chloride's interactions with choline are largely conserved at the hydroxyl end while becoming weaker at the cationic headgroup. The interplay of soft and strong interactions confers flexibility to the newly formed hydrogen-bond network and allows the ensemble to remain liquid at room temperature.

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Section: Chloride Anions Move Away From Choline's Headroupsupporting

confidence: 79%

Section: Estimating Reline's Spectra With Discrete and Periodic Calcumentioning

confidence: 99%

See 1 more Smart Citation

Inelastic neutron scattering study of reline: shedding light on the hydrogen bonding network of deep eutectic solvents

Araújo

Coutinho

Nolasco

et al. 2017

Phys. Chem. Chem. Phys.

146

155

View full text Add to dashboard Cite

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“…Calculated through DFPT, the phonon density of states not only enables to obtain a precise description of a thermodynamic state [161] by calculating the Gibbs free energy, enthalpy, entropy, or zero-point energy but also the generation of vibrational spectra such as IR, Raman, and INS. All these calculations are usually characterized by a very good agreement with the experimental results [170,171] and in many cases they reveal the reason (e.g., molecular structure in itself, crystal packing) for spectral differences between two polymorphs [172].…”

Section: Vibrational Propertiesmentioning

confidence: 66%

Periodic DFT Calculations—Review of Applications in the Pharmaceutical Sciences

2020

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In the introduction to this review the complex chemistry of solid-state pharmaceutical compounds is summarized. It is also explained why the density functional theory (DFT) periodic calculations became recently so popular in studying the solid APIs (active pharmaceutical ingredients). Further, the most popular programs enabling DFT periodic calculations are presented and compared. Subsequently, on the large number of examples, the applications of such calculations in pharmaceutical sciences are discussed. The mentioned topics include, among others, validation of the experimentally obtained crystal structures and crystal structure prediction, insight into crystallization and solvation processes, development of new polymorph synthesis ways, and formulation techniques as well as application of the periodic DFT calculations in the drug analysis.

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“…Both choline and the Chol-Mt complex showed strong bands at 1480-1475 cm −1 due to -CH 3 bending vibrations. Additional scissoring and bending vibration were observed at 1418 cm −1 and 1377 cm −1 , respectively [14].…”

Section: Intercalation Of Nutrients Into Montmorillonite To Redefine mentioning

confidence: 96%

Reducing Competition of Pepsin in Aflatoxin Adsorption by Modifying a Smectite with Organic Nutrients

Velázquez

Deng

2020

Toxins

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Carcinogenic aflatoxins can be inactivated by smectites (e.g., montmorillonite) through adsorption and degradation. Proteins in gastric fluids can reduce smectite’s adsorption capacity for aflatoxins. The objective of this study was to evaluate the efficiency of smectites modified with organic nutrients in restricting the influence of proteins on aflatoxin adsorption. Arginine, histidine, choline, lysine, and vitamin B1 were selected to occupy part of the interlayer space of montmorillonite to achieve a smectite structure more selective for aflatoxin adsorption, but not for the large protein molecules. The unmodified montmorillonite had a maximum adsorption capacity of 0.2 mol/kg in the presence of pepsin. The vitamin B1-montmorillonite showed significant improvements in the aflatoxin affinity constant from 0.065 to 0.201 μ M − 1 and the aflatoxin adsorption to 0.56 mol/kg. Choline-montmorillonite and histidine-montmorillonite showed a moderate increase in AfB1 adsorption. Arginine-montmorillonite and lysine-montmorillonite showed a slight increase in the adsorption capacity, but did not improve the affinity constant. The XRD results indicated that pepsin could still access the interlayer of nutrient-montmorillonite complexes. The intercalation of organic nutrients into the interlayer space of montmorillonite improved the AfB1 adsorption by restricting the adsorption of pepsin.

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INS, DFT and temperature dependent IR investigations of dynamical properties of low temperature phase of choline chloride

Cited by 11 publications

References 40 publications

Inelastic neutron scattering study of reline: shedding light on the hydrogen bonding network of deep eutectic solvents

Inelastic neutron scattering study of reline: shedding light on the hydrogen bonding network of deep eutectic solvents

Periodic DFT Calculations—Review of Applications in the Pharmaceutical Sciences

Reducing Competition of Pepsin in Aflatoxin Adsorption by Modifying a Smectite with Organic Nutrients

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