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The hydrogen bonding ability of both water and methanol, together with the occurrence of hydrophobic interactions, makes their solutions nonideal. This nonideality is reflected in both dynamic and thermodynamic quantities at different extent depending on temperature and concentration. The thermal behavior in terms of transport quantities is investigated for different methanol molar fractions by using the concepts of the Stokes-Einstein relation. Starting from the pure compounds, we compare self-diffusion and viscosity data as a function of the temperature for methanol molar fractions XMeOH = 0.22, 0.5, and 0.7. The results are interpreted within the scenario of the mode coupling theory and show that the Stokes-Einstein relation is violated in a different way depending on the solution concentration. [ABSTRACT FROM AUTHOR]

The use of nanostructured materials is increasingly widespread thanks to their particular properties that can improve the performance of devices in various scientific applications. One of them is in the architecture of perovskite solar cells characterized by high photoconversion efficiency values that make them able to compete with silicon solar cells. In this framework, we deposited TiO 2 sponges by reactive sputtering based on a grazing-incidence geometry combined with the local oxidation of species. The deposited material gains 50% porosity in volume through depths of hundreds of nanometers and consists of a forest of uniform rods separated by mesopores (pipelines) arising from the grazing geometry. Many previous studies showed how TiO 2 can improve the efficiency of perovskite solar cells. In this article, we investigated the change of the wettability values of the TiO 2 samples before and after a postdeposition thermal annealing treatment. For comparison, the influence of the annealing on the wettability of the glass substrate is also reported. [ABSTRACT FROM AUTHOR]

By means of a nuclear magnetic resonance experiment, we give evidence of the existence of a fragile-to-strong dynamic crossover transition (FST) in confined water at a temperature TL=223±2 K. We have studied the dynamics of water contained in 1D cylindrical nanoporous matrices (MCM-41-S) in the temperature range 190–280 K, where experiments on bulk water were so far hampered by crystallization. The FST is clearly inferred from the T dependence of the inverse of the self-diffusion coefficient of water (1/D) as a crossover point from a non-Arrhenius to an Arrhenius behavior. The combination of the measured self-diffusion coefficient D and the average translational relaxation time ≤sτT>, as measured by neutron scattering, shows the predicted breakdown of Stokes-Einstein relation in deeply supercooled water [ABSTRACT FROM AUTHOR]

The bulk liquid water density data (ρ) are studied in a very large temperature pressure range including also the glass phases. A thorough analysis of their isobars, together with the suggestions of recent thermodynamical studies, gives evidence of two crossovers at T * and P * above which the hydrogen bond interaction is unable to arrange the tetrahedral network that is at the basis of the liquid polymorphism giving rise to the low density liquid (LDL). The curvatures of these isobars, as a function of T, are completely different: concave below P * (where maxima are) and convex above. In both the cases, a continuity between liquid and glass is observed with P * as the border of the density evolution toward the two different polymorphic glasses (low and high density amorphous). The experimental data of the densities of these two glasses also show a markedly different pressure dependence. Here, on the basis of these observations in bulk water and by considering a recent study on the growth of the LDL phase, by decreasing temperature, we discuss the water liquid-liquid transition and evaluate the isothermal compressibility inside the deep supercooled regime. Such a quantity shows an additional maximum that is pressure dependent that under ambient conditions agrees with a recent X-ray experiment. In particular, the present analysis suggests the presence of a liquid-liquid critical point located at about 180 MPa and 197 K.

Using nuclear magnetic resonance we study the dynamics of the hydrogen bond (HB) sub-domains in bulk and emulsified water across a wide temperature range that includes the supercooled regime. We measure the proton spin-lattice T 1 and spin-spin T 2 relaxation times to understand the hydrophilic interactions that determine the properties of water. We use (i) the Bloembergen, Purcell, and Pound approach that focuses on a single characteristic correlation time τ c , and (ii) the Powles and Hubbard approach that measures the proton rotational time τ θ . We find that when the temperature is low both relaxation times are strongly correlated when the HB lifetime is long, and that when the temperature is high a decrease in the HB lifetime destroys the water clusters and decouples the dynamic modes of the system.

We study the relaxation times tα in the water-methanol system. We examine new data and data from the literature in the large temperature range 163 < T < 335 K obtained using different experimental techniques and focus on how tα affects the hydrogen bond structure of the system and the hydrophobicity of the alcohol methyl group. We examine the relaxation times at a fixed temperature as a function of the water molar fraction XW and observe two opposite behaviors in their curvature when the system moves from high to low T regimes. This behavior differs from that of an ideal solution in that it has excess values located at different molar fractions (XW = 0.5 for high T and 0.75 in the deep supercooled regime). We analyze the data and find that above a crossover temperature T ∼ 223 K, hydrophobicity plays a significant role and below it the water tetrahedral network dominates. This temperature is coincident with the fragile-to-strong dynamical crossover observed in confined water and supports the liquid-liquid phase transition hypothesis. At the same time, the reported data suggest that this crossover temperature (identified as the Widom line temperature) also depends on the alcohol concentration.

We study the self-diffusion coefficient and viscosity of a water-glycerol mixture for several glycerol molar fractions as a function of temperature well inside the metastable supercooled regime. We perform NMR experiments and verify that the system has at different concentration a fragile-to-strong crossover accompanied by the violation of the Stokes-Einstein relation. We observe that the crossover temperature depends on the water amount. Studying the fractional representation of the Stokes-Einstein relation, we find that in these systems dynamical arrest does not exhibit criticality and the transport parameters have a universal behavior.

We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature.

The thermodynamic response functions of water display anomalous behaviors. We study these anomalous behaviors in bulk and confined water. We use nuclear magnetic resonance (NMR) to examine the configurational specific heat and the transport parameters in both the thermal stable and the metastable supercooled phases. The data we obtain suggest that there is a behavior common to both phases: that the dynamics of water exhibit two singular temperatures belonging to the supercooled and the stable phase, respectively. One is the dynamic fragile-to-strong crossover temperature (T(L) ≃ 225 K). The second, T* ∼ 315 ± 5 K, is a special locus of the isothermal compressibility K(T)(T, P) and the thermal expansion coefficient α(P)(T, P) in the P-T plane. In the case of water confined inside a protein, we observe that these two temperatures mark, respectively, the onset of protein flexibility from its low temperature glass state (T(L)) and the onset of the unfolding process (T*).

The "dynamic" or "glass" transition in biomolecules is as important to their functioning as the folding process. This transition occurs in the low temperature regime and has been related to the onset of biochemical activity that is dependent on the hydration level. This protein transition is believed to be triggered by the strong hydrogen bond coupling in the hydration water. We study the vibrational bending mode and measure it using Fourier Transform Infrared spectroscopy. We demonstrate that at the molecular level the hydration water bending mode bonds the C=O and N-H peptide groups, and find that the temperature of the "dynamic" protein transition is the same as the fragile-to-strong dynamic transition in confined water. The fragile-to-strong dynamic transition in water governs the nature of the H bonds between water and peptides and appears to be universal in supercooled glass-forming liquids.

We study the dynamical arrest in an adhesive hard-sphere colloidal system. We examine a micellar suspension of the Pluronic-L64 surfactant in the temperature (T) and volume fraction (φ) phase diagram. According to mode-coupling theory (MCT), this system is characterized by a cusp-like singularity and two glassy phases: an attractive glass (AG) phase and a repulsive glass (RG) phase. The T - φ phase diagram of this system as confirmed by a previous series of scattering data also exhibits a Percolation Threshold (PT) line, a reentrant behavior (AG-liquid-RG), and a glass-to-glass transition. The AG phase can be generated out of the liquid phase by using T and φ as control parameters. We utilize viscosity and nuclear magnetic resonance (NMR) techniques. NMR data confirm all the characteristic properties of the colloidal system phase diagram and give evidence of the onset of a fractal-like percolating structure at a precise threshold. The MCT scaling laws used to study the shear viscosity as a function of φ and T show in both cases a fragile-to-strong liquid glass-forming dynamic crossover (FSC) located near the percolation threshold where the clustering process is fully developed. These results suggest a larger thermodynamic generality for this phenomenon, which is usually studied only as a function of the temperature. We also find that the critical values of the control parameters, coincident with the PT line, define the locus of the FSC. In the region between the FSC and the glass transition lines the system dynamics are dominated by clustering effects. We thus demonstrate that it is possible, using the conceptual framework provided by extended mode-coupling theory, to describe the way a system approaches dynamic arrest, taking into account both cage and hopping effects.

We study the dynamics of hydration water in the protein lysozyme in the temperature range 180 K