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Water mobility in cancer cells could be a powerful parameter to predict the progression or remission of tumors. In the present descriptive work, new insight into this concept was achieved by combining neutron scattering and thermal analyses. The results provide the first step to untangle the role played by water dynamics in breast cancer cells (MCF-7) after treatment with a chemotherapy drug. By thermal analyses, the cells were probed as micrometric reservoirs of bulk-like and confined water populations. Under this perspective we showed that the drug clearly alters the properties of the confined water. We have independently validated this idea by accessing the cellular water dynamics using inelastic neutron scattering. Finally, analysis of the quasi-elastic neutron scattering data allows us to hypothesize that, in this particular cell line, diffusion increases in the intracellular water in response to the action of the drug on the nanosecond timescale.

The (meta)stability of low water activity sodium hydroxide/aluminate (Na + OH - /Al(OH) 4 - ) electrolytes dictates kinetics in the Bayer process for aluminum refining and high-level nuclear waste processing. We utilized quasi-elastic neutron scattering (QENS) and proton nuclear magnetic resonance spectroscopy ( 1 H NMR) in extremely concentrated sodium aluminate solutions to investigate the picosecond (ps) to microsecond (ms) timescale motions of H-bearing species (Al(OH) 4 - monomers/clusters, OH - and H 2 O). In the QENS data, in contrast to typical liquids, no short-time translational diffusion was observed at 293 K, but two types of localized motions were found: (i) local backbone tumbling or a formation of large hydrated ion clusters on the order of 40-60 ps; and (ii) much slower, complex, and collective dynamics of the ensemble of H-bearing species on the order of 350-750 ps. Variable temperature, pulsed field gradient, diffusion-ordered 1 H NMR was used to determine the ensemble translational motion along with relaxometry to calculate rotational correlation coefficients. The ensemble rotational correlation times were on the order of 184-300 ps from 1 H NMR, which is consistent with the timescale of the QENS components. Complementary molecular dynamics simulation of NaOH solutions exhibit extensive ion networks potentially responsible for the observed dynamical coupling of water with the motion of large hydrated ion clusters. Understanding these collective motions will aid in predicting the behavior of complex solutions during aluminum production and during nuclear waste processing.

A detailed understanding of the diffusion mechanisms of ions in pure and doped ionic liquids remains an important aspect in the design of new ionic-liquid electrolytes for energy storage. To gain more insight into the widely used imidazolium-based ionic liquids, the relationship between viscosity, ionic conductivity, diffusion coefficients, and reorientational dynamics in the ionic liquid 3-methyl-1-methylimidazolium bis(trifluoromethanesulfonyl)imide (DMIM-TFSI) with and without lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) was examined. The diffusion coefficients for the DMIM + cation and the role of ion aggregates were investigated by using the quasielastic neutron scattering (QENS) and neutron spin echo techniques. Two diffusion mechanisms are observed for the DMIM + cation with and without Li-TFSI, that is, translational and local. The data additionally suggest that Li + ion transport along with ion aggregates, known as the vehicle mechanism, may play a significant role in the ion diffusion process. These dielectric-spectroscopy investigations in a broad temperature and frequency range reveal a typical α-β-relaxation scenario. The α relaxation mirrors the glassy freezing of the dipolar ions, and the β relaxation exhibits the signatures of a Johari-Goldstein relaxation. In contrast to the translational mode detected by neutron scattering, arising from the decoupled faster motion of the DMIM + ions, the α relaxation is well coupled to the dc charge transport, that is, the average translational motion of all three ion species in the material. The local diffusion process detected by QENS is only weakly dependent on temperature and viscosity and can be ascribed to the typical fast dynamics of glass-forming liquids., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Highly efficient proton conductors, polyoxometalate-poly(ethylene glycol) (POM-PEG) hybrid nanocomposites, have been synthesized by encapsulating a single PEG chain inside the 1D nanochannel defined by the frameworks of POMs. By employing two types of neutron scattering techniques complemented by thermal analysis, we prove that in a nanochannel a single PEG chain stays as a distorted helix. More importantly, we reveal that the PEG segments perform a localized longitudinal random walk and quantitatively show the strong correlation between the local motion of PEG and the macroscopic proton conduction of the material. On the basis of these spatial-temporal characteristics, a microscopic picture for the proton conduction process of POM-PEG hybrid materials is proposed.

We probe, for the first time, quantum tunneling in the methyl groups of the ionic liquid [DMIm][TFSI] facilitated by the presence of Bis(trifluoromethane)sulfonimide lithium salt. The observation of tunneling is made possible by crystallization, rather than vitrification, of [DMIm][TFSI] at low temperature. Neutron scattering measurements detect quantum tunneling excitations at ~27 μeV at temperatures below 30 K in the presence of LiTFSI at a concentration of 1 mol/kg, but not in salt-free [DMIm][TFSI]. This indicates that the methyl rotational potential barrier is reduced by the presence of LiTFSI, thus bringing the tunneling excitations into the measurable range. The salt-induced reduction of the rotational barrier is corroborated by quasi-elastic scattering data associated with stochastic re-orientation of methyl groups measured between 40 and 60 K.

Dynamics of hydration water is essential for the function of biomacromolecules. Previous studies have demonstrated that water molecules exhibit subdiffusion on the surface of biomacromolecules; yet the microscopic mechanism remains vague. Here, by performing neutron scattering, molecular dynamics simulations, and analytic modeling on hydrated perdeuterated protein powders, we found water molecules jump randomly between trapping sites on protein surfaces, whose waiting times obey a broad distribution, resulting in subdiffusion. Moreover, the subdiffusive exponent gradually increases with observation time towards normal diffusion due to a many-body volume-exclusion effect.

Interactions of water with cellulose are of both fundamental and technological importance. Here, we characterize the properties of water associated with cellulose using deuterium labeling, neutron scattering and molecular dynamics simulation. Quasi-elastic neutron scattering provided quantitative details about the dynamical relaxation processes that occur and was supported by structural characterization using small-angle neutron scattering and X-ray diffraction. We can unambiguously detect two populations of water associated with cellulose. The first is "non-freezing bound" water that gradually becomes mobile with increasing temperature and can be related to surface water. The second population is consistent with confined water that abruptly becomes mobile at ~260 K, and can be attributed to water that accumulates in the narrow spaces between the microfibrils. Quantitative analysis of the QENS data showed that, at 250 K, the water diffusion coefficient was 0.85 ± 0.04 × 10 -10  m 2 sec -1 and increased to 1.77 ± 0.09 × 10 -10  m 2 sec -1 at 265 K. MD simulations are in excellent agreement with the experiments and support the interpretation that water associated with cellulose exists in two dynamical populations. Our results provide clarity to previous work investigating the states of bound water and provide a new approach for probing water interactions with lignocellulose materials.

We explore the influence of the solvent dipole moment on cation-anion interactions and transport in 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl), [BMIM + ][Tf2N - ]. Free energy profiles derived from atomistic molecular dynamics (MD) simulations show a correlation of the cation-anion separation and the equilibrium depth of the potential of mean force with the dipole moment of the solvent. Correlations of the ion diffusivity with the dipole moment and the concentration of the solvent were further demonstrated by classical MD simulations. Quasi-elastic neutron scattering experiments with deuterated solvents reveal a complex picture of nanophase separation into the ionic liquid-rich and solvent-rich phases. The experiment corroborates the trend of concentration- and dipole moment-dependent enhancement of ion mobility by the solvent, as suggested by the simulations. Despite the considerable structural complexity of ionic liquid-solvent mixtures, we can rationalize and generalize the trends governing ionic transport in these complex electrolytes.

Encapsulation behavior, as well as the presence of internal catalytically active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo132 } as an encapsulation host and a nanoreactor. Due to its well-defined and tunable cluster structures, and nanoscaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under nanoconfinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton of the internal ligands. NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Using quasielastic neutron scattering, we have investigated diffusion dynamics of protons in the protic ionic liquid, N,N,N',N'-tetramethylguanidinium bis(perfluoroethylsulfonyl)imide, a promising new compound for application as an electrolyte in proton-conducting fuel cells. A temperature range of 30-360 K has been studied. The melting temperature of N,N,N',N'-tetramethylguanidinium bis(perfluoroethylsulfonyl)imide is about 290 K. We have found four distinct dynamic processes. First, the methyl group rotations exhibit broadly distributed dynamics which, on the nanosecond time scale, become visible above approximately 100 K. Second, there is a localized process with a characteristic confinement radius of about 1.6 A, which likely involves protons of the -NH(2) groups. These two processes take place in both solid and liquid phases, even though the methyl group rotations in the liquid phase are likely too fast to be detected in our experiment. Above the melting temperature, there are two new diffusion processes contributing to the dynamics of the liquid phase. Both of them appear to be of translational character. However, only the slower process represents unrestricted translation diffusion. The faster process is better described as spatially restricted translational diffusion with a characteristic confinement radius of about 8 A. It is likely that the long-range proton transfer in N,N,N',N'-tetramethylguanidinium bis(perfluoroethylsulfonyl)imide is associated primarily with the unrestricted translational diffusion process, which is characterized by a diffusion coefficient varying from 0.4 x 10(-10) to 1.4 x 10(-10) m(2)/s in the temperature range of 320-360 K.