The time dependence dynamics of hydration water changes upon crossing T∗

We carry out a Nuclear Magnetic Resonance (NMR) spectroscopy study on the dynamics of lysozyme hydration water. We consider a hydration level corresponding to a single water monolayer. We investigate the thermodynamical region from 295K to 355 K, at temperatures below and above the “magic” temperature T∗ ≈ 320 K. In particular, we focus our attention on hydration water mean-square displacement (MSD) as a function of the diffusion time at different temperatures. Our results suggest the occurrence of a smooth anomalous diffusion from a sub-diffusive state (T < T ∗) to a super-diffusive one (T > T∗). These conclusions confirm the importance of the temperature T∗ as the border for water behavior

Water and lysozyme: Some results from the bending and stretching vibrational modes

The dynamic or glass transition in biomolecules is important to their functioning. Also essential is the transition between the protein native state and the unfolding process. To better understand these transitions, we use Fourier transform infrared spectroscopy to study the vibrational bending and stretching modes of hydrated lysozymes across a wide temperature range. We find that these transitions are triggered by the strong hydrogen bond coupling between the protein and hydration water. More precisely, we demonstrate that in both cases the water properties dominate the evolution of the system. We find that two characteristic temperatures are relevant: in the supercooled regime of confined water, the fragile-to-strong dynamic transition occurs at T[subscript L], and in the stable liquid phase, T* ≈ 315 ± 5 K characterizes the behavior of both isothermal compressibility K[subscript T] (T,P) and the coefficient of thermal expansion a[subscript P] (T,P)

The local order of supercooled water in solution with LiCl studied by NMR proton chemical shift

We study by means of Nuclear Magnetic Resonance (NMR) spectroscopy the local order of water molecules in solution with lithium chloride at eutectic concentration. In particular, by measuring the proton chemical shift as a function of the temperature in the interval 203K < T < 320K, we observe a net change at about 235 K. We ascribe this result to the increase of the hydrogen bond interaction that on decreasing the temperature favors the formation of the network that characterizes the low density liquid phase of water. Furthermore, the Gaussian deconvolution of the NMR peak allows the investigation of the mutual difference between the chemical shift of water solvating lithium and chlorine individually. The thermal behavior of this quantity confirms previous results about the role of the temperature in the solvation mechanisms down to about 225 K. This temperature coincides with that of the so-called Widom line for water supporting the liquid-liquid transition hypothesis

Molecular degradation of ancient documents revealed by 1H^1H HR-MAS NMR spectroscopy

For centuries mankind has stored its knowledge on paper, a remarkable biomaterial made of natural cellulose fibers. However, spontaneous cellulose degradation phenomena weaken and discolorate paper over time. The detailed knowledge of products arising from cellulose degradation is essential in understanding deterioration pathways and in improving durability of cultural heritage. In this study, for the first time, products of cellulose degradation were individually detected in solid paper samples by means of an extremely powerful proton HR-MAS NMR set-up, in combination to a wise use of both ancient and, as reference, artificially aged paper samples. Carboxylic acids, in addition to more complex dicarboxylic and hydroxy-carboxylic acids, were found in all samples studied. Since these products can catalyze further degradation, their knowledge is fundamental to improve conservation strategies of historical documents. Furthermore, the identification of compounds used in ancient production techniques, also suggests for artifacts dating, authentication and provenance

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. The study confirms that supercooled bulk water is a mixture of two liquid “phases”, namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the CP − CV isobars behaviors clearly support the existence of both a liquid–liquid transition and of a liquid–liquid critical point

Complex viscosity behavior and cluster formation in attractive colloidal systems

The increase of the viscosity, which is observed in attractive colloidal systems by varying the temperature or the volume fraction, can be related to the formation of structures due to particle aggregation. In particular we have studied the non trivial dependence of the viscosity from the temperature and the volume fraction in the copolymer-micellar system L64. The comparison of the experimental data with the results of numerical simulations in a simple model for gelation phenomena suggests that this intriguing behavior can be explained in terms of cluster formation and that this picture can be quite generally extended to other attractive colloidal systems.Comment: 5 pages, 4 figure

Two dynamical crossovers in protein hydration water revealed by the NMR spin-spin relaxation time

Hydration water is essential in determining the optimal conditions for the development of the biological activity of biological systems. Indeed the physical properties of hydration water are responsible for and determine the region of biological stability of proteins. By means of Nuclear Magnetic Resonance, we probe some thermodynamical properties of the first hydration shell of lysozyme from 200K to 360 K. In particular, we study the thermal behavior of the nuclear magnetization and of the apparent spin-spin relaxation time (T∗2). We find the existence of two thermal borders with two corresponding evident crossovers at low and high temperatures signaling the thresholds of the native state of lysozyme and therefore of its functionality

A singular thermodynamically consistent temperature at the origin of the anomalous behavior of liquid water

The density maximum of water dominates the thermodynamics of the system under ambient conditions, is strongly P-dependent, and disappears at a crossover pressure P[subscript cross] ~ 1.8 kbar. We study this variable across a wide area of the T–P phase diagram. We consider old and new data of both the isothermal compressibility K[subscript T](T, P) and the coefficient of thermal expansion αP(T, P). We observe that KT(T) shows a minimum at T* ~ 315±5 K for all the studied pressures. We find the behavior of αP to also be surprising: all the αP(T) curves measured at different P cross at T*. The experimental data show a “singular and universal expansivity point” at T* ~ 315 K and αP(T*) ≃ 0.44 10[superscript −3] K[superscript −1]. Unlike other water singularities, we find this temperature to be thermodynamically consistent in the relationship connecting the two response functions.Fulvio Frisone FondazioneNational Science Foundation (U.S.) (NSF Chemistry Division (grant CHE 0911389))National Science Foundation (U.S.) (NSF Chemistry Division CHE 1213217))Italy. Ministero dell'istruzione, dell'università e della ricerca (MIUR-PRIN2008

A molecular interpretation of the dynamics of diffusive mass transport of water within a glassy polyetherimide

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