How Is Diffusion of Neutral and Charged Tracers Related to the Structure and Dynamics of a Room-Temperature Ionic Liquid? Large Deviations from Stokes–Einstein Behavior Explained

Araque, Juan C.; Yadav, Sharad Kumar; Shadeck, Michael; Maroncelli, Mark; Margulis, Claudio J.

doi:10.1021/acs.jpcb.5b01093

Cited by 167 publications

(210 citation statements)

References 80 publications

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“…In contrast, a less specific coordination behavior, as found for EMIM/TFSI, might increase the mobility of the solute. These assumptions are in accordance with literature results, where it has been shown that solvent–solvent interactions significantly influence the diffusion behavior of solutes …”

Section: Numerical Resultssupporting

confidence: 93%

Properties of Apolar Solutes in Alkyl Imidazolium‐Based Ionic Liquids: The Importance of Local Interactions

et al. 2015

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The solvation and the dynamic properties of apolar model solutes in alkyl imidazolium-based ionic liquids (IL) are studied by using all-atom molecular dynamics simulations. In regards to specific IL effects, we focused on the often used 1-ethyl-3-methyl imidazolium cation in combination with the anions tetrafluoroborate, acetate, and bis(trifluoromethanesulfonyl)imide. Our findings reveal that the size of the anion crucially influences the accumulation behavior of the cations, which results in modified IL solvation properties. Deviations between the different alkyl imidazolium-based IL combinations can be also observed with regard to the results for the radial distribution functions, the number of surrounding molecules, and the molecular orientation. The analysis of the van Hove function further shows pronounced differences in the dynamic behavior of the solutes. The simulations verify that the solute mobilities are mainly influenced by the composition of the local solvent shell and the properties of the underlying Lennard-Jones interactions. Additional simulations with regard to modified short-range dispersion energies for alkyl imidazolium-based ILs validate our conclusions.

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Section: Numerical Resultssupporting

confidence: 93%

Properties of Apolar Solutes in Alkyl Imidazolium‐Based Ionic Liquids: The Importance of Local Interactions

et al. 2015

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“…We can connect these observations with ideas we recently introduced in a set of articles. 138,139 In these, we proposed that ionic liquids can be described as composed of frictionally stiff (high electrostriction) and frictionally soft (charge depleted) regions. Stiff and soft regions are associated with distinct local friction, high friction in the charge enhanced region, and low friction in the charge depleted region.…”

Section: -39mentioning

confidence: 99%

Communication: Nanoscale structure of tetradecyltrihexylphosphonium based ionic liquids

Hettige

Araque

Kashyap

et al. 2016

The Journal of Chemical Physics

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“…[70][71][72][73] Despite noting that charge-charge interactions are much more relevant for ionic liquids as for the diffusivity of water in presence of proteins, the deviations from SE behavior are similar in origin. [70][71][72][73] Despite noting that charge-charge interactions are much more relevant for ionic liquids as for the diffusivity of water in presence of proteins, the deviations from SE behavior are similar in origin.…”

Section: Sh3 and Bsa In Mixturesmentioning

confidence: 99%

Transient binding accounts for apparent violation of the generalized Stokes–Einstein relation in crowded protein solutions

Rothe

Gruber

Gröger

et al. 2016

Phys. Chem. Chem. Phys.

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The effect of high concentration, also referred to as crowding conditions, on Brownian motion is of central relevance for the understanding of the physical, chemical and biological properties of proteins in their native environment. Specifically, the simple inverse relationship between the translational diffusion coefficient and the macroscopic solution viscosity as predicted by the generalized Stokes-Einstein (GSE) relation has been the subject of many studies, yet a consensus on its applicability has not been reached. Here, we use isotope-filtered pulsed-field gradient NMR to separately assess the μm-scale diffusivity of two proteins, BSA and an SH3 domain, in mixtures as well as single-protein solutions, and demonstrate that transient binding can account for an apparent violation of the GSE relation. Whereas GSE behavior applies for the single-protein solutions, it does not hold for the protein mixtures. Transient binding behavior in the concentrated mixtures is evidenced by calorimetric experiments and by a significantly increased apparent activation energy of diffusion. In contrast, the temperature dependence of the viscosity, as well as of the diffusivity in single-component solutions, is always dominated by the flow activation energy of pure water. As a practically relevant second result, we further show that, for high protein concentrations, the diffusion of small molecules such as dioxane or water is not generally a suitable probe for the viscosity experienced by the diffusing proteins.

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How Is Diffusion of Neutral and Charged Tracers Related to the Structure and Dynamics of a Room-Temperature Ionic Liquid? Large Deviations from Stokes–Einstein Behavior Explained

Cited by 167 publications

References 80 publications

Properties of Apolar Solutes in Alkyl Imidazolium‐Based Ionic Liquids: The Importance of Local Interactions

Properties of Apolar Solutes in Alkyl Imidazolium‐Based Ionic Liquids: The Importance of Local Interactions

Communication: Nanoscale structure of tetradecyltrihexylphosphonium based ionic liquids

Transient binding accounts for apparent violation of the generalized Stokes–Einstein relation in crowded protein solutions

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