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In the recent years a considerable effort has been devoted to foster the understanding of the basic mechanisms underlying the dynamical arrest that is involved in glass forming in supercooled liquids and in the sol-gel transition. The elucidation of the nature of such processes represents one of the most challenging unsolved problems in the field of material science. In this context, two important theories have contributed significantly to the interpretation of these phenomena: the Mode-Coupling theory (MCT) and the Percolation theory (PT). These theories are rooted on the two pillars of statistical physics, universality and scale laws, and their original formulations have been subsequently modified to account for the fundamental concepts of Energy Landscape (EL) and of the universality of the fragile to strong dynamical crossover (FSC). In this review, we discuss experimental and theoretical results, including Molecular Dynamics (MD) simulations, reported in the literature for colloidal and polymer systems displaying both glass and sol-gel transitions. Special focus is dedicated to the analysis of the interferences between these transitions and on the possible interplay between MCT and PT. By reviewing recent theoretical developments, we show that such interplay between sol-gel and glass transitions may be interpreted in terms of the extended F13 MCT model that describes these processes based on the presence of a glass-glass transition line terminating in an A3 cusp-like singularity (near which the logarithmic decay of the density correlator is observed). This transition line originates from the presence of two different amorphous structures, one generated by the inter-particle attraction and the other by the pure repulsion characteristic of hard spheres. We show here, combining literature results with some new results, that such a situation can be generated, and therefore experimentally studied, by considering colloidal-like particles interacting via a hard core plus an attractive square well potential. In the final part of this review, scaling laws associated both to MCT and PT are applied to describe, by means of these two theories, the specific viscoelastic properties of some systems.

This contribution aims at providing a critical overview of experimental results for the sorption of low molecular weight compounds in the Cu-BTC Metal–Organic Framework (MOF) and of their interpretation using available and new, specifically developed, theoretical approaches. First, a literature review of experimental results for the sorption of gases and vapors is presented, with particular focus on the results obtained from vibrational spectroscopy techniques. Then, an overview of theoretical models available in the literature is presented starting from semiempirical theoretical approaches suitable to interpret the adsorption thermodynamics of gases and vapors in Cu-BTC. A more detailed description is provided of a recently proposed Lattice Fluid approach, the Rigid Adsorbent Lattice Fluid (RALF) model. In addition, to deal with the cases where specific self- and cross-interactions (e.g., H-bonding, Lewis acid/Lewis base interactions) play a role, a modification of the RALF model, i.e., the RALFHB model, is introduced here for the first time. An extension of both RALF and RALFHB is also presented to cope with the cases in which the heterogeneity of the rigid adsorbent displaying a different kind of adsorbent cages is of relevance, as it occurs for the adsorption of some low molecular weight substances in Cu-BTC MOF.

Interactions between nanoparticles (NPs) determine their self-organization and dynamic processes. In these systems, a quantitative description of the interparticle forces is complicated by the presence of the hydrophobic effect (HE), treatable only qualitatively, and due to the competition between the hydrophobic and hydrophilic forces. Recently, instead, a sort of crossover of HE from hydrophilic to hydrophobic has been experimentally observed on a local scale, by increasing the temperature, in pure confined water and studying the occurrence of this crossover in different water–methanol solutions. Starting from these results, we then considered the idea of studying this process in different nanoparticle solutions. By using photon correlation spectroscopy (PCS) experiments on dendrimer with OH terminal groups (dissolved in water and methanol, respectively), we show the existence of this hydrophobic–hydrophilic crossover with a well defined temperature and nanoparticle volume fraction dependence. In this frame, we have used the mode coupling theory extended model to evaluate the measured time-dependent density correlation functions (ISFs). In this context we will, therefore, show how the measured spectra are strongly dependent on the specificity of the interactions between the particles in solution. The observed transition demonstrates that just the HE, depending sensitively on the system thermodynamics, determines the hydrophobic and hydrophilic interaction properties of the studied nanostructures surface.

We discuss a phenomenon regarding water that was until recently a subject of scientific interest: i.e., the dynamical crossover, from the fragile to strong glass forming material, for both bulk and protein hydration water. Such crossover is characterized by a temperature TL in which significant dynamical changes like the decoupling (or the violation of the Stokes-Einstein relation) of homologous transport parameters, e.g., the density relaxation time τ and the viscosity η, occur in the system. On this respect we considered the dynamic properties of water-protein systems. More precisely, we focused our study on proteins and their hydration water, as far as bulk and confined water. In order to clarify the effects of the water dynamical crossover on the protein properties we considered and discussed in a comparative way previous and new experimental data, obtained from different techniques and molecular dynamic simulation (MD). We pointed out the reasons for different dynamical findings from the use of different experimental techniques.

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. In particular, we compare the thermal behaviourof the isobaric specific heat of water, measured in different confinement conditions at atmosphericpressure (and evaluated by means of theoretical studies) with its configurational contribution obtainedfrom the values of the measured self-diffusion coefficient through the use of the Adam&ndash, Gibbsapproach. Our results confirm the existence of a maximum in the specific heat of water at about 225K and indicate that especially at low temperature the configurational contributions to the entropy aredominant.

Neurodegenerative diseases such as Alzheimer’s are characterized by neuritic plaques throughout the brain gray matter, associated with neurofibrillary tangles and neuron loss. These plaques are formed by abnormal aggregation of amyloid beta (A β ) peptide into insoluble fibrils. In the present work we study the A β 1 − 40 peptide in the three aggregations states – monomers, oligomers and fibrils – via small angle neutron scattering (SANS) technique. The size of the three forms as well as their fractal nature are investigated at physiologic conditions. Our results evidence that the A β 1 − 40 peptide has a good aggregation capability but can also adopt an unfolded conformation in particular conditions, as for example, when incubated in DMSO.

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. In order to optimize dye removal ability of the hybrid aerogel, we target the crosslinker concentration so that crosslinking is mainly activated during the thermal treatment after the fast freezing of the CS/LTA mixture. The adsorption of isotherms is obtained for different CS/LTA weight ratios and for different types of anionic and cationic dyes. Irrespective of the formulation, the Langmuir model was found to accurately describe the adsorption isotherms. The optimal tradeoff in the adsorption behavior was obtained with the CS/LTA aerogel (1:1 weight ratio), for which the maximum uptake of indigo carmine (anionic dye) and rhodamine 6G (cationic dye) is 103 and 43 mg g−1, respectively. The behavior observed for the adsorption capacity and energy cannot be rationalized as a pure superposition of the two components, but suggests that reciprocal steric effects, chemical heterogeneity, and molecular interactions between CS and LTA zeolite particles play an important role.

The diffusion process of water molecules within a polyetherimide (PEI) glassy matrix has been analyzed by combining the experimental analysis of water sorption kinetics performed by FTIR spectroscopy with theoretical information gathered from Molecular Dynamics simulations and with the expression of water chemical potential provided by a non-equilibrium lattice fluid model able to describe the thermodynamics of glassy polymers. This approach allowed us to construct a convincing description of the diffusion mechanism of water in PEI providing molecular details of the process related to the effects of the cross- and self-hydrogen bonding established in the system on the dynamics of water mass transport.

In this review we discuss the role of hydrophilic/hydrophobic interplay in several processes involving water–surface interactions. For this purpose, we describe the self-organization architecture of biomacromolecules, the design of artificial biocompatible nano-devices able to deliver poorly water-soluble drugs, and the engineering of packaging materials capable to preserve food from water, dust, and microorganisms contamination. Material properties together with mutual-cooperative interactions play a crucial role to match the complexity of biological environments and desired functional products. Therefore, the comprehension and description of hydrophilic/hydrophobic interactions at molecular level represent the main steps towards the development of new biosystems with improved functionality.

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., the competition between hydrophilic and hydrophobic interactions. Nowadays, compared to hydrophilicity, little is known about hydrophobicity. Therefore, the main purpose of this study is to gain new information about hydrophobicity. As the liquid water properties are dominated by polymorphism (two coexisting liquid phases of high and low density) due to hydrogen bond interactions (HB), creating (especially in the supercooled regime) the tetrahedral networking, we focused our interest to the HE of these structures. We measured the relaxation times (T1 and T2) and the self-diffusion (DS). From these times, we took advantage of the NMR property to follow the behaviors of each molecular component (the hydrophilic and hydrophobic groups) separately. In contrast, DS is studied in terms of the Adam–Gibbs model by obtaining the configurational entropy (Sconf) and the specific heat contributions (CP,conf). We find that, for the HE, all of the studied quantities behave differently. For water–glycerol, the HB interaction is dominant for all conditions, water–methanol, two different T-regions above and below 265 K are observable, dominated by hydrophobicity and hydrophilicity, respectively. Below this temperature, where the LDL phase and the HB network develops and grows, with the times and CP,conf change behaviors leading to maxima and minima. Above it, the HB becomes weak and less stable, the HDL dominates, and hydrophobicity determines the solution.

NMR spectroscopic literature data are used, in a wide temperature-pressure range (180–350 K and 0.1–400 MPa), to study the water polymorphism and the validity of the liquid–liquid transition (LLT) hypothesis. We have considered the self-diffusion coefficient DS and the reorientational correlation time τθ (obtained from spin-lattice T1 relaxation times), measured, respectively, in bulk and emulsion liquid water from the stable to well inside the metastable supercooled region. As an effect of the hydrogen bond (HB) networking, the isobars of both these transport functions evolve with T by changing by several orders of magnitude, whereas their pressure dependence become more and more pronounced at lower temperatures. Both these transport functions were then studied according to the Adam–Gibbs model, typical of glass forming liquids, obtaining the water configurational entropy and the corresponding specific heat contribution. The comparison of the evaluated CP,conf isobars with the experimentally measured water specific heat reveals the full consistency of this analysis. In particular, the observed CP,conf maxima and its diverging behaviors clearly reveals the presence of the LLT and with a reasonable approximation the liquid–liquid critical point (LLCP) locus in the phase diagram.

Molecular mechanisms for N2 fixation (solar NH3) and CO2 conversion to C2+ products in enzymatic conversion (nitrogenase), electrocatalysis, metal complexes and plasma catalysis are analyzed and compared. It is evidenced that differently from what is present in thermal and plasma catalysis, the electrocatalytic path requires not only the direct coordination and hydrogenation of undissociated N2 molecules, but it is necessary to realize features present in the nitrogenase mechanism. There is the need for (i) a multi-electron and -proton simultaneous transfer, not as sequential steps, (ii) forming bridging metal hydride species, (iii) generating intermediates stabilized by bridging multiple metal atoms and (iv) the capability of the same sites to be effective both in N2 fixation and in COx reduction to C2+ products. Only iron oxide/hydroxide stabilized at defective sites of nanocarbons was found to have these features. This comparison of the molecular mechanisms in solar NH3 production and CO2 reduction is proposed to be a source of inspiration to develop the next generation electrocatalysts to address the challenging transition to future sustainable energy and chemistry beyond fossil fuels.

Molecular mechanisms for N2 fixation (solar NH3) and CO2 conversion to C2+ products in enzymatic conversion (Nitrogenase), electrocatalysis, metal-complexes and plasma-catalysis are analysed and compared. It is evidenced that differently from what present in thermal and plasma-catalysis, the electrocatalysis path requires not only the direct coordination and hydrogenation of undissociated N2 molecule, but to realize a series of features present in the Nitrogenase mechanism. There is the need of i) a multi-electron and -proton simultaneous transfer, not as sequential steps, ii) forming bridging metal hydride species, iii) generate intermediates stabilized by bridging multiple metal atoms, iv) have the capability of the same sites to be effective both in N2 fixation and in COx reduction to C2+ products. Only iron oxide/hydroxide stabilized at defective sites of nanocarbons was found to have these features. This comparison of the molecular mechanisms in solar NH3 production and relations with CO2 reduction is proposed to be a source of inspiration to develop the next generation electrocatalysts to address the challenging transition to a future sustainable energy and chemistry beyond fossil fuels.

Molecular mechanisms for N2 fixation (solar NH3) and CO2 conversion to C2+ products in enzymatic conversion (nitrogenase), electrocatalysis, metal complexes and plasma catalysis are analyzed and compared. It is evidenced that differently from what is present in thermal and plasma catalysis, the electrocatalytic path requires not only the direct coordination and hydrogenation of undissociated N2 molecules, but it is necessary to realize features present in the nitrogenase mechanism. There is the need for (i) a multi-electron and -proton simultaneous transfer, not as sequential steps, (ii) forming bridging metal hydride species, (iii) generating intermediates stabilized by bridging multiple metal atoms and (iv) the capability of the same sites to be effective both in N2 fixation and in COx reduction to C2+ products. Only iron oxide/hydroxide stabilized at defective sites of nanocarbons was found to have these features. This comparison of the molecular mechanisms in solar NH3 production and CO2 reduction is proposed to be a source of inspiration to develop the next generation electrocatalysts to address the challenging transition to future sustainable energy and chemistry beyond fossil fuels.

Water is a fascinating material. Its composition is simple—one oxygen andtwo hydrogen atoms—but its chemistry and physics are extremely complex andexhibit 75 documented anomalies. Although these anomalies and theirmolecular origin are not completely understood, we know that hydrogen bondsplay key roles in all of the phases of water. Moreover, there isexperimental evidence that the polymorphism of the ice structure extendsinto the liquid phase and is associated with a liquid-liquid coexistenceline. This is currently a topic of great interest in water research becausethere are indications that the end point of the coexistence line correspondsto a second critical point inside the supercooled liquid regime. We examinethe recent progress in understanding water anomalies and the liquid-liquidphase transition hypothesis, including the results of recent experimentalwork and molecular simulations of both bulk and confined water. We examineexperimental results that test whether the behavior of liquid water isconsistent with the textquotedblleft liquid polymorphismtextquotedblrighthypothesis that liquid water can exist in two distinct phases of differingdensities. We also examine recent research on the anomalies of nanoconfinedwater and, in particular, on water in biological environments. We find thatthe concept of liquid polymorphism can also describe the properties of otherliquids that have two characteristic length scales.

Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food samples. Nevertheless, to date only a few internationally agreed guidelines have been reported on the use of NMR for quantitative analysis. The main goal of the present study is to provide a methodological pipeline to assess the reproducibility of NMR data produced for a given matrix by spectrometers from different manufacturers, with different magnetic field strengths, age and hardware configurations. The results have been analyzed through a sequence of chemometric tests to generate a community-built calibration system which was used to verify the performance of the spectrometers and the reproducibility of the predicted sample concentrations.

The thermal properties of an extra Virgin Olive Oil (eVOO) depend on its composition and indeed characterize its quality. Many studies have shown that the freezing and melting behaviors of eVOOs can serve for geographical or chemical discrimination. We use Nuclear Magnetic Resonance spectroscopy to study the evolution of the fatty acids bands as a function of temperature during freezing and melting processes. In such a way we can follow separately the variations in the thermal properties of the different molecular groups during these thermodynamic phase transitions. The data indicate that the methyl group which is at the end of every fatty chain displays the major changes during both freezing and melting processes.

A modern approach to the diagnosis of artistic heritage makes use of non-destructive techniques which avoid damage to artworks or signs of interaction with the analytical technique used. For this reason, today, the employment of X-rays to study artistic heritage is quite widespread. Computed tomography (CT) Imaging was first used as specialized medical diagnostic tool in the early 1970s. Today, CT scanners have become more common, and non-destructive three-dimensional imaging has found an increasing number of uses in different areas such as materials research, geology, archaeology, and museum conservation. In this work, a new generation of clinical CT (based on the Dual Energy and multi-slice acquisition principle) is used to investigate an Egyptian wooden mummy board with a total acquisition time of 93.23 seconds and a voxel size of 0.078 × 0.078 × 1.5 mm. The use of two distinct techniques of image post-processing, the two-dimensional multi-planar reconstruction (MPR) and the three-dimensional volume rendering technique (VRT) allowed us to: evaluate the state of conservation of the mummy board, determine how the wooden object was implemented, recognize a nineteenth-century intervention of consolidation, and advance the hypothesis that the wooden planks were reused. In particular, we highlight the use of the cardiovascular and pulmonary filter with VRT reconstruction, which allows a virtual elimination of different parts of the mummy board to investigate those areas otherwise accessible only by removing parts of the board and thus damaging the work.

A study of the rotation dynamics of the spin probe TEMPO by electron spin resonance (ESR) spectroscopy in a series of six short- and medium-sized n-alkanes is presented. In addition to the usual crossover effects connected with solid-liquid phase transitions at temperature Tm and the solid-solid transition at Tss, we find a strong correlation between the change in reorientation at the characteristic ESR temperature TfastX1 < Tss and/or Tm with the ratio TfastX1/Tm = 0.76 ± 0.03 and the characteristic dynamic temperature, TX, obtained from the viscosity data. This indicates the presence of local disordered regions in the crystalline structure which is indeed sensitive to dynamic change at the crossover temperature TX ≅ TfastX1.

The hydrogen density of states (DOS) in confined water has been probed by inelastic neutron scattering spectra in a wide range of its P&ndash, T phase diagram. The liquid&ndash, 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 &lt, 10 meV) and the data are discussed in terms of the energy landscape (local minima of the potential energy) approach. In this latest research, we consider a unit scale energy (EC) linked to the water local order governed by the hydrogen bonding (HB). All the measured spectra, scaled according to such energy, evidence a universal power law behavior with different exponents ( &gamma, ) in the strong and fragile glass forming regions, respectively. In the first case, the DOS data obey the Debye squared-frequency law, whereas, in the second one, we obtain a value predicted in terms of the mode-coupling theory (MCT) ( &gamma, ≃ 1.6 ).

The hydrogen density of states (DOS) in confined water has been probed by inelastic neutron scattering spectra in a wide range of its P–T 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

The aim of this research is the identification of main and common physical-chemical parameters which induce paper degradation. A simple protocol to monitor the quality and molecular structure of ancient papers under natural degradation processes was proposed. Two-dimensional micro-Raman mapping were carried out. Then, point to point, the changes of both the cellulose Raman signature and fluorescence signal intensity were analysed. Modern papers were artificially aged to simulate the natural degradation and a comparison with the trend found for the ancient paper was presented and discussed. Cellulose degradation involves different mechanisms such as dehydration, cleaving of cellulose-glycosidic bonds and glucopyranose rings oxidation, that induce a reduction in the polymerization degree. As shown by the changes of Raman and fluorescence signals and NMR relaxation times, the rate of each processes depends on the initial amount of glycosidic bonds in the cellulose amorphous and crystalline regions, respectively. All these informations are useful both to define procedures to restore old documents and also to preserve the quality of modern papers for a long-term time.

We study the evolution of the Boson peak for water confined in cement paste obtained by means of Inelastic Neutron Scattering from room temperature to the deep supercooled regime. We analyze the data in terms of a universal-like model, developed for glass forming liquids in the frame of the energy landscape. In such a way it is possible to discriminate between the fragile and strong glass forming character of supercooled liquids and the dynamical crossover, fragile to strong, between them. Hence, we confirm the linkbetween the Boson peak and the water polymorphism. In particular, the main result is represented by a crossover from a local energetic minima configuration to that characteristic of saddle points on going towards the deep supercooled regime up to the dynamical arrest.

We study the hydrogen bonds effect on the water density as a function of temperature and pressure from the supercritical region to the metastable supercooled and amorphous phases. We identify two important thermodynamic thresholds, that is $P^{\ast~}\simeq2~{~\rm~kbar}$ and $T^{\ast~}\simeq~315~{~\rm~K}$, that separate two different water behaviors in terms of hydrogen bonding capability. For $T

Spectroscopic non-targeted methods are gaining ever-growing importance in quality control and authenticity assessment of food products because of their strong potential for identification of specific features of the products by data-driven classifiers. One of the factors hampering the diffusion of spectroscopic non-targeted methods and data-driven classifiers is the lack of harmonized guidelines for their development and validation. In particular, to date, neither conditions to directly compare spectra recorded by different spectrometers nor studies demonstrating the statistical equivalence of the spectra are available. Among the spectroscopic analytical techniques suitable for the development of non-targeted methods, nuclear magnetic resonance (NMR) offers the unique opportunity to generate statistically equivalent signals. In this paper, the feasibility of NMR spectroscopy to generate statistically equivalent NMR signals from a number of different spectrometers was demonstrated for complex mixtures (aqueous extracts of wheat and flour) by organizing an inter-laboratory comparison involving 36 NMR spectrometers. Univariate statistics along with multivariate analysis were exploited to establish unbiased criteria for assessing the statistical equivalence of the NMR signals. The aspects affecting the signal equivalence were investigated, and possible solutions to reduce the extent of the human error were proposed and applied with satisfactory results. This study furnishes the scientific community with an appropriate and easy procedure to validate non-targeted NMR methods and provides error values to be used as a reference for future studies.

Here we investigate to what extent X-ray absorption (XAS) and emission (XES) spectroscopy, the oxygen-oxygen radial distribution function and σ(1H) and σ(17O) NMR shielding can be represented by a common set of model structures of liquid water. This is done by using a Monte Carlo-based fitting technique which fits the spectra based on a library of ~1400 precomputed spectra and assigns weights to contributions from different model structures. These are then used to reweight the contributions from the structures in the library to reveal classes of structures that are over- or under-represented in the library. The goal is to include different experimental data sets which are sensitive to different aspects of liquid water structure and thus narrow down which types of structures must exist in the real liquid.

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 &alpha, P and the specific heat differences CP&minus, CV, proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis. The study confirms that supercooled bulk water is a mixture of two liquid &ldquo, phases&rdquo, namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the CP&minus, CV isobars behaviors clearly support the existence of both a liquid&ndash, liquid transition and of a liquid&ndash, liquid critical point.

Herein we study the different microscopic interactions occurring in wa- ter/methanol solutions at different methanol molar fractions, using NMR spctroscopy. Temperature was found to determine which interaction domi- nates. It was found that the mixing between water and methanol is non-ideal because of the presence of interactions like hydrophobicity and hydrophilic- ity. These results indicate that the competition between hydrophilic and hydrophobic interactions is different in different thermal regions, and that the physical properties of the solution are determined by the character of the solution itself, which in turn depends on the mole fraction of methanol and on the temperature.

The degradation process of cellulose-made materials was investigated by means of nuclear magnetic resonance (NMR) spectroscopy, with particular emphasis on the role of water and on the hydration mechanism of cellulose fibrils. To accomplish this, the structure and dynamics of water within ancient and modern samples with different aging histories were investigated. The results mainly indicated that hydrolytic and oxidative reactions provoked the formation of acidic by-products. Furthermore, degradation processes were enhanced by higher amounts of water because of the progressive consumption of the amorphous regions of the cellulose. We propose NMR experiments as a benchmark for characterization of the degradation state of paper, as well as for investigating the effectiveness of restoration treatments.

The biological activity of proteins depends on their three-dimensional structure, known as the native state. The main force driving the correct folding mechanism is the hydrophobic effect and when this folding kinetics is altered, aggregation phenomena intervene causing the occurrence of illnesses such as Alzheimer and Parkinson’s diseases. The other important effect is performed by water molecules and by their ability to form a complex network of hydrogen bonds whose dynamics influence the mobility of protein amino acids. In this work, we review the recent results obtained by means of spectroscopic techniques, such as Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopies, on hydrated lysozyme. In particular, we explore the Energy Landscape from the thermal region of configurational stability up to that of the irreversible denaturation. The importance of the coupling between the solute and the solvent will be highlighted as well as the different behaviors of hydrophilic and hydrophobic moieties of protein amino acid residues.

The dynamics of a hierarchical colloid solution, dendrimer in methanol, has been studied using photon-correlation spectroscopy (PCS). The obtained relaxation curves are analyzed according to the mode-coupling theory (MCT). The main results are: i) the occurrence of a fragile to strong dynamical crossover as a function of the packing fraction at ϕ c ≃ 0.39, and ii) the observation of a secondary relaxation ( β ) that has its onset just at the dynamical crossover and is correlated with the primary α -relaxation. Finally we discuss the obtained findings in comparison with recent experiments in similar systems characterized by an attractive interaction obtaining a confirmation on the primary role of the dynamical crossover in the physics of the dynamical arrest.

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. In this paper from the measured relaxation time, we evaluated the thermodynamic state functions of water–methanol solutions in the frame of the transition state theory. In particular we study the behavior of the Gibbs free energy, enthalpy and entropy of water, methanol and some of their solutions as a function of both temperature and water molar fraction. Our results indicate that the temperature of about 280 K represents a crossover between two regions dominated by hydrophobicity (high T) and hydrophilicity (low T).

The thermal properties of many organic extra Virgin Olive Oils (eVOOs) coming from different countries of the world were investigated by Differential Scanning Calorimetry (DSC). This technique, through a series of heating and cooling cycles, provides a specific curve, i.e., a thermogram, which represents the fingerprint of each eVOO sample. In fact, variations due to the different cultivars, geographical origin or chemical composition can be highlighted because they produce changes in the corresponding thermogram. In particular, in this work, we show the results of an unsupervised multivariate statistical analysis applied to the DSC thermograms of many organic eVOOs. This analysis allows us to discriminate the geographical origin of the different studied samples in terms of the peculiar features shown by the melting profiles of the triacylglycerol moieties. (C) 2017 Published by Elsevier B.V.

We study by means of the infrared bending vibrational mode the microscopic mechanisms that are at the base of protein irreversible denaturation. In particular, we follow the thermal evolution of the Amide I and II vibrational modes of lysozyme residuals from ambient temperature toward the temperature of irreversible unfolding. Our results indicate that the thermal changes of the coupling, by means of the hydrogen bond, between hydration water molecules and the different chemical groups of the protein are the main microscopic mechanisms underlying the unfolding process. (C) 2014 Elsevier B.V. All rights reserved.

We have studied by means of High Resolution Magic Angle Spinning Nuclear Magnetic Resonance the metabolic profile of the famous Sicilian cherry tomato of Pachino. Thanks to its organoleptic and healthy properties, this particular foodstuff was the first tomato accredited by the European PGI (Protected Geographical Indication) certification of quality. Due to the relatively high price of the final product commercial frauds originated in the Italian and international markets. Hence, there is a growing interest to develop analytical techniques able to predict the origin of a tomato sample, indicating whether or not it originates from the area of Pachino, Sicily (Italy). In this paper we have determined the molar concentration of the metabolites constituent the PGI cherry tomato of Pachino. Furthermore, by means of a multivariate statistical analysis we have identified which metabolites are relevant for sample differentiation.

The bulk liquid water density data (rho) 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.

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.

Research in the field of emotions has highlighted that men and women differ as regards the perception and reaction to disgust. The aim of our study was to analyse, by means of a questionnaire on disgust, any gender differences regarding this feeling in its various dimensions, viewed both individually and globally. For this purpose a synthetic indicator was developed to evaluate the expression of disgust and identify any individual differences. The sample of 1587 subjects were given a questionnaire on disgust that contained items to elicit disgust. Statistical analysis was performed on the items and on the scores via a synthetic indicator, the Synthetic Disgust Index (SDI).The analysis revealed a different trend in different types of disgust for age and sex. In males. The oral disgust and contamination showed a reduction of SDI in the age group between 18 and 39 years (p