Nanostructured fluids for polymeric coatings removal: Surfactants affect the polymer glass transition temperature.

Hypothesis: Nanostructured fluids (NSFs) based on water, organic solvents and surfactants are a valid alternative to the use of neat unconfined organic solvents for polymer coatings removal in art conservation. The physico-chemical processes underpinning their cleaning effectiveness in terms of swelling/dewetting of polymer films were identified as key in this context. The role of surfactants on polymers' dewetting was considered to be mainly restricted to the lowering of interfacial tensions.

Hydrophilic and Hydrophobic Effects on the Structure and Themodynamic Properties of Confined Water: Water in Solutions.

NMR spectroscopy is used in the temperature range 180-350 K to study the local order and transport properties of pure liquid water (bulk and confined) and its solutions with glycerol and methanol at different molar fractions. We focused our interest on the hydrophobic effects (HE), i.e.

Tailoring Chitosan/LTA Zeolite Hybrid Aerogels for Anionic and Cationic Dye Adsorption.

Chitosan (CS) is largely employed in environmental applications as an adsorbent of anionic dyes, due to the presence in its chemical structure of amine groups that, if protonated, act as adsorbing sites for negatively charged molecules. Efficient adsorption of both cationic and anionic dyes is thus not achievable with a pristine chitosan adsorbent, but it requires the combination of two or more components. Here, we show that simultaneous adsorption of cationic and anionic dyes can be obtained by embedding Linde Type A (LTA) zeolite particles in a crosslinked CS-based aerogel.

Functionalised nanoclays as microstructure modifiers for calcium and magnesium silicate hydrates.

Calcium silicate hydrate (C-S-H) is the main binding product of ordinary Portland concrete (OPC). Unfortunately, OPC production generates ∼5% of all anthropomorphic CO2. Among the most promising green alternatives, magnesium silicate hydrate (M-S-H) is a colloidal gel equivalent to C-S-H which exhibits weaker mechanical properties.

Some Aspects of the Liquid Water Thermodynamic Behavior: From The Stable to the Deep Supercooled Regime.

Liquid water is considered to be a peculiar example of glass forming materials because of the possibility of giving rise to amorphous phases with different densities and of the thermodynamic anomalies that characterize its supercooled liquid phase. In the present work, literature data on the density of bulk liquid water are analyzed in a wide temperature-pressure range, also including the glass phases. A careful data analysis, which was performed on different density isobars, made in terms of thermodynamic response functions, like the thermal expansion αP and the specific heat differences CP-CV, proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis.

Specific Heat and Transport Functions ofWater.

Numerous water characteristics are essentially ascribed to its peculiarity to form stronghydrogen bonds that become progressively more stable on decreasing the temperature. However, thestructural and dynamical implications of the molecular rearrangement are still subject of debate andintense studies. In this work, we observe that the thermodynamic characteristics of liquid water arestrictly connected to its dynamic characteristics.

The Proton Density of States in Confined Water (HO).

The hydrogen density of states (DOS) in confined water has been probed by inelastic neutron scattering spectra in a wide range of its - phase diagram. The liquid-liquid transition and the dynamical crossover from the fragile (super-Arrhenius) to strong (Arrhenius) glass forming behavior have been studied, by taking into account the system polymorphism in both the liquid and amorphous solid phases. The interest is focused in the low energy region of the DOS ( E < 10 meV) and the data are discussed in terms of the energy landscape (local minima of the potential energy) approach.

Some considerations on the water polymorphism and the liquid-liquid transition by the density behavior in the liquid phase.

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.

Nanoscale dynamics of water confined in ordered mesoporous carbon.

The single particle dynamics of water confined within two ordered mesoporous carbon matrices was investigated in the temperature range from 290 K to 170 K by quasielastic neutron scattering using three high resolution neutron spectrometers. Thus, it was possible to investigate the mobility of water confined in model hydrophobic cavities at the nanoscale. Models developed for the nanoscale dynamics of supercooled water and water confined within hydrophilic matrices were able to describe the collected data but remarkable differences with analogous silica confined matrices were observed in these carbon samples.

Hydration-dependent dynamics of water in calcium-silicate-hydrate: A QENS study by global model.

Hypothesis: In a saturated cement paste, there are three different types of water: the structural water chemically reacted with cement, the constrained water absorbed to the surface of the pores, and the free water in the center of the pores. Each type has different physicochemical state and unique relation to cement porosity. The different water types have different dynamics which can be detected using quasi-elastic neutron scattering (QENS).

The evaluation of the hydrophilic-hydrophobic interactions and their effect in water-methanol solutions: A study in terms of the thermodynamic state functions in the frame of the transition state theory.

Aqueous solutions of amphiphilic molecules are characterized by the competition between hydrophilic and hydrophobic interactions. These interactions have a different energetic dependence with the temperature. Whereas hydrophilic interactions have been well characterized, a complete theory for the hydrophobic ones is still lacking as well as the comprehension of the effect that the solvent exerts on the solute and vice versa.

Water as a Probe of the Colloidal Properties of Cement.

Cement is produced by mixing mineral phases based on calcium silicates and aluminates with water. The hydration reaction of the mixture leads to a synthetic material with outstanding properties that can be used as a binder for construction applications. Despite the importance of cement in society, for a long time, the chemical reactions involved in its hydration remained poorly understood as a result of the complexity of hydration processes, nanostructure, and transport phenomena.

Characterization of colloidal structures during intestinal lipolysis using small-angle neutron scattering.

Hypothesis: Bile micelles are thought to mediate intestinal absorption, in part by providing a phase into which compounds can partition. Solubilizing capacity of bile micelles is enhanced during the digestion of fat rich food. We hypothesized that the intestinal digestion of triglycerides causes an increase in volume of micelles that can be quantitatively monitored over the course of digestion using small-angle neutron scattering (SANS), and that SANS can enable evaluation of the contribution of each of the components present during digestion to the size of micelles.

Energy landscape in protein folding and unfolding.

We use (1)H NMR to probe the energy landscape in the protein folding and unfolding process. Using the scheme ⇄ reversible unfolded (intermediate) → irreversible unfolded (denatured) state, we study the thermal denaturation of hydrated lysozyme that occurs when the temperature is increased. Using thermal cycles in the range 295 < T < 365 K and following different trajectories along the protein energy surface, we observe that the hydrophilic (the amide NH) and hydrophobic (methyl CH3 and methine CH) peptide groups evolve and exhibit different behaviors.

Dynamical behaviors of structural, constrained and free water in calcium- and magnesium-silicate-hydrate gels.

Hypothesis: The mechanical properties of cement pastes depend strongly on their porosities. In a saturated paste, the porosity links to the free water volume after hydration. Structural water, constrained water, and free water have different dynamical behavior.

Pressure Effect on the Boson Peak in Deeply Cooled Confined Water: Evidence of a Liquid-Liquid Transition.

The boson peak in deeply cooled water confined in nanopores is studied to examine the liquid-liquid transition (LLT). Below ∼180  K, the boson peaks at pressures P higher than ∼3.5  kbar are evidently distinct from those at low pressures by higher mean frequencies and lower heights.

Dynamic crossover in deeply cooled water confined in MCM-41 at 4 kbar and its relation to the liquid-liquid transition hypothesis.

With quasi-elastic neutron scattering, we study the single-particle dynamics of the water confined in a hydrophilic silica material, MCM-41, at 4 kbar. A dynamic crossover phenomenon is observed at 219 K. We compare this dynamic crossover with the one observed at ambient pressure and find that (a) above the crossover temperature, the temperature dependence of the characteristic relaxation time at ambient pressure exhibits a more evident super-Arrhenius behavior than that at 4 kbar.

Liquid-Liquid Phase Transition and Its Phase Diagram in Deeply-Cooled Heavy Water Confined in a Nanoporous Silica Matrix.

Using neutron diffraction technique, we measure the average density of the heavy water confined in a nanoporous silica matrix, MCM-41, over the pressure-temperature plane. The result suggests the existence of a line of liquid-liquid phase transition with its end point at 1.29 ± 0.

Some thermodynamical aspects of protein hydration water.

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.

Translational and rotational dynamics of water contained in aged Portland cement pastes studied by quasi-elastic neutron scattering.

Cement is a widely used construction material in the world. The quality and durability of aged cement pastes have a strong relationship with the water contained in it. The translational and rotational dynamics of water in ordinary Portland cement (OPC) pastes cured for 7, 14 and 30days were studied by analyzing Quasi-elastic Neutron Scattering (QENS) data.

Hydration-dependent dynamic crossover phenomenon in protein hydration water.

The characteristic relaxation time τ of protein hydration water exhibits a strong hydration level h dependence. The dynamic crossover is observed when h is higher than the monolayer hydration level hc=0.2-0.

The influence of water on protein properties.

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.

Evidence of the existence of the high-density and low-density phases in deeply-cooled confined heavy water under high pressures.

The average density of D2O confined in a nanoporous silica matrix (MCM-41-S) is studied with neutron scattering. We find that below ~210 K, the pressure-temperature plane of the system can be divided into two regions. The average density of the confined D2O in the higher-pressure region is about 16% larger than that in the lower-pressure region.

Boson peak in deeply cooled confined water: a possible way to explore the existence of the liquid-to-liquid transition in water.

The boson peak in deeply cooled water confined in nanopores is studied with inelastic neutron scattering. We show that in the (P, T) plane, the locus of the emergence of the boson peak is nearly parallel to the Widom line below ∼ 1600 bar. Above 1600 bar, the situation is different and from this difference the end pressure of the Widom line is estimated.