Insights into Hydration Dynamics and Cooperative Interactions in Glycerol–Water Mixtures by Terahertz Dielectric Spectroscopy

Charkhesht, Ali; Lou, Djamila; Sindle, Ben; Wen, Chengyuan; Cheng, Shengfeng; Vinh, N. Q.

doi:10.1021/acs.jpcb.9b07021

Cited by 37 publications

(38 citation statements)

References 51 publications

(139 reference statements)

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“…These features could be due to changes in hydrogen bonding network as we change the glycerol-water composition. A parallel trend was observed in the dielectric and THz study performed by Vinh and coworkers, 21 in aqueous solutions of glycerol. In that work, four hydrogen bonding networks were proposed, bulk water, solvated water, confined water and bulk glycerol.…”

supporting

confidence: 70%

A Direct Probe of the Hydrogen Bond Network in Aqueous Glycerol Aerosols

Weeraratna

Amarasinghe

et al. 2021

J. Phys. Chem. Lett.

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The properties of aerosols are of paramount importance in atmospheric chemistry and human health.The hydrogen bond network of glycerol-water aerosols generated from an aqueous solution with different mixing ratios, is probed directly with X-ray photoelectron spectroscopy. The carbon and oxygen X-ray spectra reveal contributions from gas and condensed phase components of the aerosol.It is shown that water suppresses glycerol evaporation up to a critical mixing ratio. A dielectric analysis using terahertz spectroscopy coupled with Infrared spectroscopy of the bulk solutions provides a picture of the microscopic heterogeneity prevalent in the hydrogen bond network when combined with the photoelectron spectroscopy analysis. The hydrogen bond network is comprised of three intertwined regions. At low concentrations, glycerol molecules are surrounded by water forming a solvated water network. Adding more glycerol leads to a confined water network, maximizing at 22 mol%, beyond which the aerosol resembles bulk glycerol. This microscopic view of hydrogen bonding networks holds promise in probing evaporation, diffusion dynamics and reactivity in aqueous aerosols.

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supporting

confidence: 70%

A Direct Probe of the Hydrogen Bond Network in Aqueous Glycerol Aerosols

Weeraratna

Amarasinghe

et al. 2021

J. Phys. Chem. Lett.

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“…The average number of intermolecular hydrogen bonds increases with the increase in molecular size of the osmolyte in the following order: ethanol < urea < glycerol < sorbitol ∼ α-glucose ∼ β-glucose < trehalose (Table ). The values of 15.8 for trehalose and 5.9 for glycerol are comparable to the experimentally determined hydration number of 16–18 for trehalose and 5.58 for glycerol . We find a urea molecule on average to form 5.3–5.5 hydrogen bonds, in close agreement with the value of 5.7 estimated from the empirical potential structure refinement (EPSR) simulation characterizing neutron scattering data of urea solutions.…”

Section: Resultssupporting

confidence: 84%

“…The values of 15.8 for trehalose and 5.9 for glycerol are comparable to the experimentally determined hydration number of 16−18 for trehalose 74 and 5.58 for glycerol. 75 We find a urea molecule on average to form 5.3−5.5 hydrogen bonds, in close agreement with the value of 5.7 estimated from the empirical potential structure refinement (EPSR) simulation characterizing neutron scattering data 38 of urea solutions.…”

Section: ■ Introductionsupporting

confidence: 85%

Unraveling the Influence of Osmolytes on Water Hydrogen-Bond Network: From Local Structure to Graph Theory Analysis

Sundar

Sandilya

Priya

2021

J. Chem. Inf. Model.

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Water structure in aqueous osmolyte solutions, deduced from the slight alteration in the water−water radial distribution function, the decrease in water−water hydrogen bonding, and tetrahedral ordering based only on the orientation of nearest water molecules derived from the molecular dynamics simulations, appears to have been perturbed. A careful analysis, however, reveals that the hydrogen bonding and the tetrahedral ordering around a water molecule in binary solutions remain intact as in neat water when the contribution of osmolyte−water interactions is appropriately incorporated. Furthermore, the distribution of the water binding energies and the water excess chemical potential of solvation in solutions are also pretty much the same as in neat water. Osmolytes are, therefore, well integrated into the hydrogen-bond network of water. Indeed, osmolytes tend to preferentially hydrogen bond with water molecules and their interaction energies are strongly correlated to their hydrogen-bonding capability. The graph network analysis, further, illustrates that osmolytes act as hubs in the percolated hydrogen-bond network of solutions. The degree of hydrogen bonding of osmolytes predominantly determines all of the network properties. Osmolytes like ethanol that form fewer hydrogen bonds than a water molecule disrupt the water hydrogen-bond network, while other osmolytes that form more hydrogen bonds effectively increase the connectivity among water molecules. Our observation of minimal variation in the local structure and the vitality of osmolyte−water hydrogen bonds on the solution network properties clearly imply that the direct interaction between protein and osmolytes is solely responsible for the protein stability. Further, the relevance of hydrogen bonds on solution properties suggests that the hydrogen-bonding interaction among protein, water, and osmolyte could be the key determinant of the protein conformation in solutions.

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“…[9,11,12] While experimental evidence does reveal features such as longer residence times and restricted rotational dynamics of water molecules at the interface with ionic solutes, there is little evidence to support the claim that such water molecules are immobilized to the extent that they cannot participate in ice formation even at low temperatures. [14][15][16][17][18][19] Furthermore, while some have observed that the appearance of bulk-like water within a polymer substantially impacts its physical properties, the specific relationship between the amount of melting water and the bulk properties of the hydrated polymer remains poorly understood. [20,21] Fourier transform infrared spectroscopy (FTIR) is another experimental method that has been used to probe the behavior of water in hydrated polymers.…”

Section: Introductionmentioning

confidence: 99%

On the Nature of Freezing/Melting Water in Ionic Polysulfones

Vondrasek,

Wen,

Cheng

et al. 2021

Preprint

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We investigate the behavior of hydrated sulfonated polysulfones over a range of ion contents through differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and molecular dynamics (MD) simulations. Experimental evidence shows that at comparable ion contents, the spacing between the ionic groups along the polymer backbone can significantly impact the amount of melting water present in the polymer. When we only consider water molecules that can hydrogen bond to four neighboring water molecules as the melting water, the MD simulation results are found to agree with the experimental data. The states of water measured by DSC can therefore be described as "aggregated" (or bulk-like) for the melting component, and "isolated" for the nonmelting part. Using this physical picture, a polymer with more aggregated ions has a higher content of melting water, while a polymer at the same ion content but with more dispersed ions has a lower content of melting water. Therefore, ions should be well dispersed to minimize the amount of bulk-like water in ionic polymer membranes.

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Insights into Hydration Dynamics and Cooperative Interactions in Glycerol–Water Mixtures by Terahertz Dielectric Spectroscopy

Cited by 37 publications

References 51 publications

A Direct Probe of the Hydrogen Bond Network in Aqueous Glycerol Aerosols

A Direct Probe of the Hydrogen Bond Network in Aqueous Glycerol Aerosols

Unraveling the Influence of Osmolytes on Water Hydrogen-Bond Network: From Local Structure to Graph Theory Analysis

On the Nature of Freezing/Melting Water in Ionic Polysulfones

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