Observation of a Plastic Crystal in Water-Ammonia Mixtures under High Pressure and Temperature.

Solid mixtures of ammonia and water, the so-called ammonia hydrates, are thought to be major components of solar and extra-solar icy planets. We present here a thorough characterization of the recently reported high pressure (P)-temperature (T) phase VII of ammonia monohydrate (AMH) using Raman spectroscopy, X-ray diffraction, and quasi-elastic neutron scattering (QENS) experiments in the ranges 4-10 GPa, 450-600 K. Our results show that AMH-VII exhibits common structural features with the disordered ionico-molecular alloy (DIMA) phase, stable above 7.5 GPa at 300 K: both present a substitutional disorder of water and ammonia over the sites of a body-centered cubic lattice and are partially ionic. The two phases however markedly differ in their hydrogen dynamics, and QENS measurements show that AMH-VII is characterized by free molecular rotations around the lattice positions which are quenched in the DIMA phase. AMH-VII is thus a peculiar crystalline solid in that it combines three types of disorder: substitutional, compositional, and rotational.

Vibrational dynamics of confined supercooled water.

The quest for a possible liquid-liquid coexistence line in supercooled water below its homogeneous nucleation temperature is faced by confining water within a porous silica substrate (MCM-41). This system is investigated by synchrotron radiation infrared spectroscopy, exploring both the intramolecular and the intermolecular vibrational dynamics, in the temperature range from ambient down to ∼120 K, along several isobaric paths between 0.7 kbar and 3.0 kbar. Upon lowering the temperature, the OH-stretching band shows that the intramolecular vibrational dynamics continuously evolves from predominantly liquidlike to predominantly icelike. An abrupt change in the line shape of the intermolecular vibrational band between 220 K and 240 K, depending on the pressure, is the signature of nucleation of ice within the MCM-41 pores. These findings do not support the presence of two liquid phases and provide evidence for the coexistence of liquid water and ice in water confined in MCM-41.

Ice crystallization observed in highly supercooled confined water.

We investigate the state of water confined in the cylindrical pores of MCM-41 type mesoporous silica, with pore diameters of 2.8 nm and 4.5 nm, over the temperature range 160-290 K by combining small angle neutron scattering and wide angle diffraction. This allows us to observe simultaneously the intermolecular correlations in the local water structure (which shows up in a main water peak around Q = 1.7 Å-1), the two-dimensional hexagonal arrangement of water cylinders in the silica matrix (which gives rise to a pronounced Bragg peak around Q = 0.2 Å-1), and the so-called Porod scattering at smaller Q, which arises from larger scale interfacial scattering within the material. In the literature, the temperature evolution of the intensity of the Bragg peak has been interpreted as the signature of a density minimum in confined water at approximately 210 K. Here we show that, under the conditions of our experiment, a fraction of freezable water coexists with a layer of non-freezable water within the pore volume. The overall temperature dependence of our data in the different Q regions, as well as the comparison of the data for the two pore sizes, leads us to conclude that the observed variation in the intensity of the Bragg diffraction peak is actually caused by a liquid to ice transition in the freezable fraction of confined water.

Probing ice VII crystallization from amorphous NaCl-D2O solutions at gigapascal pressures.

We probe the possible inclusion of salt (NaCl) in the ice VII lattice over the pressure range from 2 to 4 gigapascal. We combine data from neutron diffraction experiments under pressure and from computational structure searches based on density functional theory. We observe that the high density amorphous precursor (NaCl·10.2D2O) crystallises during annealing at high pressure in the vicinity of the phase boundary between pure ices VII and VIII. The structure formed is very similar to that of pure ice VII. Our simulations indicate that substituting water molecules in the ice VII lattice with Na+ and Cl- ions would lead to a significant expansion of the lattice parameter. Since this expansion was not observed in our experiments, the ice crystallised is likely to be pure D2O or contains only a small fraction of the ions from the salt solution.

Ice VII from aqueous salt solutions: From a glass to a crystal with broken H-bonds.

It has been known for decades that certain aqueous salt solutions of LiCl and LiBr readily form glasses when cooled to below ≈160 K. This fact has recently been exploited to produce a « salty ¼ high-pressure ice form: When the glass is compressed at low temperatures to pressures higher than 4 GPa and subsequently warmed, it crystallizes into ice VII with the ionic species trapped inside the ice lattice. Here we report the extreme limit of salt incorporation into ice VII, using high pressure neutron diffraction and molecular dynamics simulations. We show that high-pressure crystallisation of aqueous solutions of LiCl∙RH2O and LiBr∙RH2O with R = 5.6 leads to solids with strongly expanded volume, a destruction of the hydrogen-bond network with an isotropic distribution of water-dipole moments, as well as a crystal-to-amorphous transition on decompression. This highly unusual behaviour constitutes an interesting pathway from a glass to a crystal where translational periodicity is restored but the rotational degrees of freedom remaining completely random.

Structural characterization of eutectic aqueous NaCl solutions under variable temperature and pressure conditions.

The structure of amorphous NaCl solutions produced by fast quenching is studied as a function of pressure, up to 4 GPa, by combined neutron diffraction experiments and classical molecular dynamics simulations. Similarly to LiCl solutions the system amorphizes at ambient pressure in a dense phase structurally similar to the e-HDA phase in pure water. The measurement of the static structure factor as a function of pressure allowed us to validate a new polarizable force field developed by Tazi et al., 2012, never tested under non-ambient conditions. We infer from simulations that the hydration shells of Na(+) cations form well defined octahedra composed of both H2O molecules and Cl(-) anions at low pressure. These octahedra are gradually broken by the seventh neighbour moving into the shell of first neighbours yielding an irregular geometry. In contrast to LiCl solutions and pure water, the system does not show a polyamorphic transition under pressure. This confirms that the existence of polyamorphism relies on the tetrahedral structure of water molecules, which is broken here.

Picosecond acoustics method for measuring the thermodynamical properties of solids and liquids at high pressure and high temperature.

Based on the original combination of picosecond acoustics and diamond anvils cell, recent improvements to accurately measure hypersonic sound velocities of liquids and solids under extreme conditions are described. To illustrate the capability of this technique, results are given on the pressure and temperature dependence of acoustic properties for three prototypical cases: polycrystal (iron), single-crystal (silicon) and liquid (mercury) samples. It is shown that such technique also enables the determination of the density as a function of pressure for liquids, of the complete set of elastic constants for single crystals, and of the melting curve for any kind of material. High pressure ultrafast acoustic spectroscopy technique clearly opens opportunities to measure thermodynamical properties under previously unattainable extreme conditions. Beyond physics, this state-of-the-art experiment would thus be useful in many other fields such as nonlinear acoustics, oceanography, petrology, in of view. A brief description of new developments and future directions of works conclude the article.

Pressure-induced transformations in LiCl-H2O at 77 K.

A systematic study of the properties of high-density amorphous ice (HDA) in the presence of increasing amounts of salt is missing, especially because it is challenging to avoid ice crystallization upon cooling the pressurized liquid. In order to be able to study HDA also in the presence of small amounts of salt, we have investigated the transformation behaviour of quenched aqueous LiCl solutions (mole fraction x < 0.25) upon pressurization in a piston-cylinder setup at 77 K. The sample properties were characterized by in situ dilatometry under high pressure conditions and after recovery by ex situ powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC) at ambient pressure. Two regimes can be identified, with a rather sharp switch at about x = 0.12. At x < 0.12 the samples show the phenomenology also known for pure water samples. They are composed mainly of hexagonal ice (Ih) and experience pressure-induced amorphization to HDA at P > 1 GPa. The observed densification is consistent with the idea that a freeze concentrated LiCl solution of x = 0.14 (R = 6) segregates, which transforms to the glassy state upon cooling, and that the densification is only due to the Ih → HDA transition. Also the XRD patterns and DSC scans are almost unaffected by the presence of the segregated glassy LiCl solution. Upon heating at ambient pressure HDA experiences the polyamorphic transition to low-density amorphous ice (LDA) at ∼120 K, even at x ∼ 0.10. Based on the latent heat evolved in the transition we suggest that almost all water in the sample transforms to an LDA-like state, even the water in the vicinity of the ions. The glassy LiCl solution acts as a spectator that does not shift the transformation temperature significantly and experiences a glass-to-liquid transition at ∼140 K prior to the crystallization to cubic ice. By contrast, at x > 0.12 the phenomenology completely changes and is now dominated by the salt. Hexagonal ice no longer forms upon quenching the LiCl solution, but instead LDA forms. A broad pressure-induced transformation at >0.6 GPa can be attributed to the densification of LDA, the glassy LiCl solution and/or glassy hydrates.

Equation of state of liquid mercury to 520 K and 7 GPa from acoustic velocity measurements.

Ultrafast acoustics measurements on liquid mercury have been performed at high pressure and temperature in a diamond anvil cell using picosecond acoustic interferometry. We extract the density of mercury from adiabatic sound velocities using a numerical iterative procedure. We also report the pressure and temperature dependence of the thermal expansion, isothermal and adiabatic compressibility, bulk modulus, and pressure derivative of the latter up to 7 GPa and 520 K. We finally show that the sound velocity follows a scaling law as a function of density in the overall measured metallic state.

Translational and rotational diffusion in water in the Gigapascal range.

First measurements of the self-dynamics of liquid water in the GPa range are reported. The GPa range has here become accessible through a new setup for the Paris-Edinburgh press specially conceived for quasielastic neutron scattering studies. A direct measurement of both the translational and rotational diffusion coefficients of water along the 400 K isotherm up to 3 GPa, corresponding to the melting point of ice VII, is provided and compared with molecular dynamics simulations. The translational diffusion is observed to strongly decrease with pressure, though its variation slows down for pressures higher than 1 GPa and decouples from that of the shear viscosity. The rotational diffusion turns out to be insensitive to pressure. Through comparison with structural data and molecular dynamics simulations, we show that this is a consequence of the rigidity of the first neighbors shell and of the invariance of the number of hydrogen bonds of a water molecule under high pressure. These results show the inadequacy of the Stokes-Einstein-Debye equations to predict the self-diffusive behavior of water at high temperature and high pressure, and challenge the usual description of hot dense water behaving as a simple liquid.

Observation of nanophase segregation in LiCl aqueous solutions from transient grating experiments.

Transient grating experiments performed on supercooled LiCl, RH2O solutions with R > 6 reveal the existence of well resolved, short time, extra signal which superposes to the normal signal observed for the R = 6 solution and for homogenous glass forming systems. This extra signal shows up below 190 K, its shape and the associated timescale depend only on temperature, while its intensity increases with R. We show that the origin of this signal is a phase separation between clusters with a low solute concentration and the remaining, more concentrated, solution. Our analysis demonstrates that these clusters have a nanometer size and a composition which are rather temperature independent, while increasing R simply increases the density of these clusters.

Pressure-induced polyamorphism in salty water.

We investigated the metastable phase diagram of an ionic salt aqueous solution, LiCl:6D2O, at high pressure and low temperature by neutron diffraction measurements and computer simulations. We show that the presence of salt triggers a stepwise transformation, under annealing at high pressure, to a new very high-density amorphous form. The transition occurs abruptly at 120 K and 2 GPa, is reversible, and is characterized by a sizeable enthalpy release. Simulations suggest that the polyamorphic transition is linked to a local structural reorganization of water molecules around the Li ions.

Structural study of low concentration LiCl aqueous solutions in the liquid, supercooled, and hyperquenched glassy states.

Neutron diffraction experiments on a solution of LiCl in water (R = 40) at ambient conditions and in the supercooled and hyperquenched states are reported and analyzed within the empirical potential structure refinement framework. Evidence for the modifications of the microscopic structure of the solvent in the presence of such a small amount of salt is found at all investigated thermodynamic states. On the other hand, it is evident that the structure of the hyperquenched salty sample is similar to that of pure low density amorphous water, although all the peaks of the radial distribution functions are broader in the present case. Changes upon supercooling or hyperquenching of the ion's hydration shells and contacts are of limited size and evidence for segregation phenomena at these states does not clearly show up, although the presence of water separated contacts between ion of the same sign is intriguing.

The low frequency dynamics of supercooled LiBr, 6H2O.

We present results of a series of experiments performed on LiBr, 6H(2)0 from room temperature down to 172 K ≈ 1.2T(g). These ultrasound, Brillouin and depolarized light scattering, and transient grating experiments show that, above 215 K, this solution behaves like supercooled water: its zero frequency sound velocity C(0) continuously decreases with decreasing temperature, and the reorientational dynamics of the water molecules can be directly detected at some temperatures of this domain. Conversely, below 215 K, a new regime sets in, where the apparent C(0) is practically temperature independent and where a ß, Arrenhius like, relaxation process coexists with the usual, Vogel-Fulcher like, α relaxation process of the supercooled liquid. These results are similar to those recently obtained in LiCl, 6H(2)O. The onset of the new regime is possibly due to an increase of the interaction of the water molecules with a neighboring Li(+) ion when lowering the temperature. We also compare our results with published dielectric data on water solutions of glass forming polyalcohols. Some of them present a low temperature splitting of their relaxation time similar to what is found in LiBr, 6H(2)O.

Vitamin E neuroprotection for cisplatin neuropathy: a randomized, placebo-controlled trial.

OBJECTIVE: The clinical use of cisplatin chemotherapy is limited by severe peripheral neurotoxicity reported in up to 90% of patients receiving a cumulative dose higher than 300 mg/m(2). The present study evaluates the neuroprotective effect of antioxidant supplementation (vitamin E) in patients treated with cisplatin chemotherapy. METHODS: A total of 108 patients treated with cisplatin chemotherapy were randomly assigned to receive vitamin E supplementation (alpha-tocopherol 400 mg/day) or placebo. Treatment was started orally before chemotherapy and continued for 3 months after the suspension of cisplatin. RESULTS: Of 108 randomized patients, 68 received at least one clinical and neurophysiologic examination after cisplatin CT; 41 patients received a cumulative dose of cisplatin higher than 300 mg/m(2) and were eligible for statistical analysis: 17 in the vitamin E group (group 1) and 24 in the placebo group (group 2). The incidence of neurotoxicity was significantly lower in group 1 (5.9%) than in group 2 (41.7%) (p < 0.01). The severity of neurotoxicity, measured with a validated neurotoxicity score (Total Neuropathy Score [TNS]), was significantly lower in patients receiving vitamin E than those receiving placebo (mean TNS 1.4 vs 4.1; p < 0.01). CONCLUSIONS: This phase III study confirms the neuroprotective role of vitamin E against cisplatin peripheral neurotoxicity. Vitamin E supplementation should be adopted in patients receiving cisplatin-based chemotherapy. CLASSIFICATION OF EVIDENCE: This study provides Class II evidence that vitamin E supplementation significantly reduces the relative risk of developing signs or symptoms of neurotoxicity (relative risk = 0.14) (95% confidence interval = 0.02-1.00, p < 0.05).

A regular or an intermittent treatment for asthma: the long-term effect.

OBJECTIVES: Many asthmatics take therapy intermittently because of their scarce compliance. It is not known if this is effective in controlling and slowing down the lung function decline in asthma. Our aim was to compare the effect of a regular treatment and an intermittent one on some clinical aspects and on the forced expiratory volume 1 (FEV1) decline in 165 persistent asthmatics with FEV1 > 70% (60 men; age 40.87 +/- 14.05; FEV1 95.03 +/- 13.1%), in a retrospective way over 4 years. PATIENTS AND METHODS: Eighty-four patients took inhaled corticosteroids (ICSs) plus long-acting bronchodilator agents (LABAs) regularly (regular) and 81 patients took ICSs plus LABAs intermittently for short periods when symptoms appeared (intermittent). RESULTS: Less patients (p < 0.05) took oral corticosteroids, short-acting bronchodilators as needed in regular compared to intermittent. More patients increased the therapy (step-up) in intermittent (p < 0.01) More patients reported a subjective improvement while fewer reported a worsening in regular (p < 0.05). After 4 years, the variation in maximal mid expiratory flow (FEF25-75) was lower in regular (-159.40 +/- 472.79 ml/sec; CI 95% -261.99, 56.82) than in intermittent (-324.44 +/- 569.97 ml/sec; CI 95% -450.48, -198.41); whereas the FEV1 decline was similar between regular (-276.97 +/- 199.37 ml; CI 95% -316.24, -229.71) and Intermittent (-317.65 +/- 194.05 ml; CI 95% -360.56, -274.74). In males and females, in smokers and non-smokers no differences were found in the FEV1 decline. CONCLUSIONS: In conclusion, the regular use of ICSs plus LABAs is better than the irregular use of them in controlling asthma over a long period of time. Whereas, after 4 years the regular treatment may not decrease the FEV1 decline more effectively than the intermittent therapy.

Anomalous proton dynamics in ice at low temperatures.

We present incoherent quasielastic neutron scattering measurements on ice Ih (ordinary ice) and Ic (cubic ice) which show the existence of nonharmonic motion of hydrogen at low temperatures, down to 5 K. We show that this dynamics is localized, nonvibrational, and related to the hydrogen disorder since it is absent in ordered ice VIII. A main jump distance of 0.75 A is identified, hence close to the distance between the two possible proton sites along the oxygen-oxygen bond. The dynamics is non-Arrhenius, has a large time rate of 2.7x10(11) s-1, and affects only a few percent of the total number of hydrogen atoms in the crystal. These results give evidence for the existence of concerted proton tunneling in these ice phases.

The low frequency phonons dynamics in supercooled LiCl, 6 H2O.

We report the results of a series of ultrasound, Brillouin scattering, and optical heterodyne detected transient grating experiments performed on a LiCl, 6H(2)O solution from room temperature down to the vicinity of its liquid-glass transition, T(g) approximately 138 K. Down to T approximately 215 K, the supercooled liquid has a behavior similar to what is expected for supercooled water: its zero frequency sound velocity, C(0), continuously decreases while the corresponding infinite frequency velocity, C(infinity), sharply increases, reflecting the increasing importance of H bonding when temperature is lowered. Below 215 K, specific aspects of the solution, presumably related to the role of the Li(+) and Cl(-) ions, modify the thermal behavior of C(0), while a beta relaxation process also appears and couples to the sound propagation. The origin of those two effects is briefly discussed.

Neutron investigation of the ion dynamics in liquid mercury: evidence for collective excitations.

The ion dynamics of liquid mercury was investigated by inelastic neutron scattering. By exploiting an optimized high-resolution ( approximately 1 meV) experimental configuration, the dynamic response function was accurately measured. Collective excitations extending up to 0.6 A(-1) were observed with an associated velocity of 2100+/-80 m/s. This value is notably greater than the sound velocity, but it is provided by a simple Bohm-Staver calculation. The latter finding emphasizes those electron-related features in the ion dynamics, which are common to systems as different as polyvalent and alkali metals.