Non-monotonic composition dependence of the breakdown of Stokes-Einstein relation for water in aqueous solutions of ethanol and 1-propanol: explanation using translational jump-diffusion approach.

A series of experimental and simulation studies examined the validity of the Stokes-Einstein relationship (SER) of water in binary water/alcohol mixtures of different mixture compositions. These studies revealed a strong non-monotonic composition dependence of the SER with maxima at the specific alcohol mole fraction where the non-idealities of the thermodynamic and transport properties are observed. The translational jump-diffusion (TJD) approach elucidated the breakdown of the SER in pure supercooled water as caused by the jump translation of molecules. The breakdown of SER in the supercooled water/methanol binary mixture was successfully explained using the same TJD approach. To further generalize the picture, here we focus on the non-monotonic composition dependence of SER breakdown of water in two water/alcohol mixtures (water/ethanol and water/propanol) for a broad temperature range. In agreement with previous studies, maximum breakdown of SER is observed for the mixture with alcohol mole fraction x = 0.2. Diffusion of the water molecules at the maximum SER breakdown point is largely contributed by jump-diffusion. The residual-diffusion, obtained by subtracting the jump-diffusion from the total diffusion, approximately follows the SER for different compositions and temperatures. We also performed hydrogen (H-)bond dynamics and observed that the contribution of jump-diffusion is proportional to the total free energy of activation of breaking all H-bonds that exist around a molecule. This study, therefore, suggests that the more a molecule is trapped by H-bonding, the more likely it is to diffuse through the jump-diffusion mechanism, eventually leading to an increasing degree of SER breakdown.

Absorption of Volatile Organic Compounds Toluene and Acetaldehyde in Choline Chloride-Based Deep Eutectic Solvents.

Unrestricted emission of volatile organic compounds (VOCs)─a threat to human health and the environment─can be controlled to a large extent by the capturing mechanism. Few recent experimental studies explored the efficacy of the deep eutectic solvent (DES), a designer solvent with some fascinating properties, as a VOC-capturing medium. Through the partition coefficient measurement, it was found that the choline chloride-based DESs exhibit excellent VOC-capturing potencies. However, a molecular picture of the above absorption process is still lacking. Here, we study the molecular mechanism of the absorption of two commonly occurring VOCs, toluene and acetaldehyde, in two different choline chloride-based DESs with varying donor molecules, urea, and levulinic acid via the molecular dynamics simulation technique. Strong absorption of the VOCs is observed in both the DESs. The free energy profile for the absorption process has been explored using the umbrella sampling method. The VOCs are preferentially solvated near the liquid/vapor interface. The simulated partition coefficients for the VOCs from the vapor to the liquid phase show good agreement with the experimental results. Detailed analyses of the spatial and orientational structure of the VOCs and different components of DESs are performed to elucidate the interaction among them. The above analyses have indicated that DES is a better VOC-capturing medium compared to a room-temperature ionic liquid, which is more extensively studied in the literature.

Understanding the Origin of the Breakdown of the Stokes-Einstein Relation in Supercooled Water at Different Temperature-Pressure Conditions.

A recent experiment has measured the viscosity of water down to approximately 244 K and up to 300 MPa. The correct viscosity and translational diffusivity data at various temperature-pressure (T-P) state points allowed for checking the validity of the Stokes-Einstein (SE) relation, which accounts for the coupling between translational self-diffusion and medium viscosity. The diffusion-viscosity decoupling increases with decreasing temperature, but the increasing pressure reduces the extent of the decoupling. Earlier simulation studies explained the breakdown of the SE relation in terms of the location of the Widom line, emanating from the liquid-liquid critical point (LLCP). Although these studies made a significant contribution to the current understanding of the above phenomena, a detailed molecular picture is still lacking. Recently, our group has explained the diffusion-viscosity decoupling from a jump-diffusion perspective. The jump-diffusion coefficient, emanating from the jump translation of water molecules, is calculated using a quantitative approach for different temperatures at ambient pressure. It has been observed that jump-diffusion is the key factor for diffusion-viscosity decoupling in supercooled water. The same method is adopted in the present work to estimate the jump-diffusion coefficient for different T-P state points and, thereby, explains the role of jump-diffusion for the different extents of the SE relation breakdown at different pressures. The residual diffusion coefficient, the other component of the total diffusion that originates from small step displacement and that is calculated by subtracting the jump-diffusion coefficient from the total diffusion, is seen to be fairly coupled to the viscosity at the entire range of temperature and pressure. Furthermore, we have calculated the average number of H-bonds per water molecule and the tetrahedral order for different T-P state points and investigated an approximate correlation between the average local structure and the contribution of the jump-diffusion to the total diffusion of water. This study, therefore, puts forward a new perspective for explaining the SE relation breakdown in supercooled water under different pressure conditions.

How Heterogeneous Are Trehalose/Glycerol Cryoprotectant Mixtures? A Combined Time-Resolved Fluorescence and Computer Simulation Investigation.

Heterogeneity and molecular motions in representative cryoprotectant mixtures made of trehalose and glycerol are investigated in the temperature range 298 ≤ T (K) ≤ 353, via time-resolved fluorescence Stokes shift and anisotropy measurements, and molecular dynamics simulations of four-point density-time correlations and H-bond relaxations. Mixtures containing 5 and 20 wt % of trehalose along with neat glycerol are studied. Viscosity coefficients for these systems lie in the range 0.30 < η (P) < 23. Measured solute (Coumarin 153) rotation and solvation times reveal a substantial departure from the hydrodynamic viscosity dependence, suggesting the strong microheterogeneous nature of these systems. Fluorescence anisotropy decays are highly nonexponential, reflecting a non-Markovian character of the medium friction. A complete missing of the Stokes shift dynamics in these systems at 298 K but partial detection of it at other higher temperatures (shift magnitude being ∼400-600 cm-1) indicates rigid solute environments. An amorphous solid-like feature emerges in the simulated radial distribution functions at these temperatures. Analyses of mean squared displacements reveal rattling-in-a-cage motion, non-Gaussian displacement distributions, and strong dynamic heterogeneity features. Simulated dynamic structure factors and four-point correlations hint, respectively, at very long α-relaxation and correlated time scales at 298 K. This explains the long solute rotation times (∼80-200 ns) measured at 298 K. Stretched exponential decay of the simulated H-bond relaxations with long time scales further highlights the strong temporal heterogeneity and slow dynamics inherent to these systems. In summary, this work provides the first insight into the molecular motions and interspecies interaction in a representative cryoprotectant mixture, and stimulates further study to investigate the interconnection between cryoprotection and dynamic heterogeneity.

Structural anomaly and dynamic heterogeneity in cycloether/water binary mixtures: Signatures from composition dependent dynamic fluorescence measurements and computer simulations.

We have performed steady state UV-visible absorption and time-resolved fluorescence measurements and computer simulations to explore the cosolvent mole fraction induced changes in structural and dynamical properties of water/dioxane (Diox) and water/tetrahydrofuran (THF) binary mixtures. Diox is a quadrupolar solvent whereas THF is a dipolar one although both are cyclic molecules and represent cycloethers. The focus here is on whether these cycloethers can induce stiffening and transition of water H-bond network structure and, if they do, whether such structural modification differentiates the chemical nature (dipolar or quadrupolar) of the cosolvent molecules. Composition dependent measured fluorescence lifetimes and rotation times of a dissolved dipolar solute (Coumarin 153, C153) suggest cycloether mole-fraction (X(THF)/Diox) induced structural transition for both of these aqueous binary mixtures in the 0.1 ≤ X(THF)/Diox ≤ 0.2 regime with no specific dependence on the chemical nature. Interestingly, absorption measurements reveal stiffening of water H-bond structure in the presence of both the cycloethers at a nearly equal mole-fraction, X(THF)/Diox ∼ 0.05. Measurements near the critical solution temperature or concentration indicate no role for the solution criticality on the anomalous structural changes. Evidences for cycloether aggregation at very dilute concentrations have been found. Simulated radial distribution functions reflect abrupt changes in respective peak heights at those mixture compositions around which fluorescence measurements revealed structural transition. Simulated water coordination numbers (for a dissolved C153) and number of H-bonds also exhibit minima around these cosolvent concentrations. In addition, several dynamic heterogeneity parameters have been simulated for both the mixtures to explore the effects of structural transition and chemical nature of cosolvent on heterogeneous dynamics of these systems. Simulated four-point dynamic susceptibility suggests formation of clusters inducing local heterogeneity in the solution structure.

Heterogeneity in (2-butoxyethanol + water) mixtures: Hydrophobicity-induced aggregation or criticality-driven concentration fluctuations?

Micro-heterogeneity in aqueous solutions of 2-butoxyethanol (BE), a system with closed loop miscibility gap, has been explored via absorption and time-resolved fluorescence measurements of a dissolved dipolar solute, coumarin 153 (C153), in the water-rich region at various BE mole fractions (0 ≤ XBE ≤ 0.25) in the temperature range, 278 ≤ T/K ≤ 320. Evidences for both alcohol-induced H-bond strengthening and subsequent structural transition of H-bond network have been observed. Analyses of steady state and time-resolved spectroscopic data for these aqueous mixtures and comparisons with the results for aqueous solutions of ethanol and tertiary butanol indicate that alcohol aggregation in BE/water mixtures is driven by hydrophobic interaction with no or insignificant role for criticality-driven concentration fluctuations preceding phase separation. Excitation energy dependence of fluorescence emission of C153 confirms formation of aggregated structures at very low BE mole fractions. No asymptotic critical power law dependence for relaxation rates of the type, k ∝ (|T - Tc|/Tc)(γ), with γ denoting universal critical constant, has been observed for both solute's rotational relaxation and population relaxation rates in these mixtures upon either approaching to critical concentration or critical temperature. Estimated activation energies for rotational relaxation rate of C153 and solution viscosity have been found to follow each other with no abrupt changes in either of them at any mixture composition. In addition, measured C153 rotation times at various compositions and temperatures reflect near-hydrodynamic viscosity coupling through the dependence,〈τr〉∝ (η/T)(p), with p = 0.8-1.0, suggesting solute's orientational relaxation dynamics being, on an average, temporally homogeneous.