4,870 research outputs found
The fragile-to-strong dynamical crossover and the system viscoelasticity in attractive glass forming colloids
No full textThis paper is dedicated to Professor Heinz Hoffmann on the occasion of his 80th birthday in celebration of his long-time friendship with both of us (Professors Sow-Hsin Chen and Francesco Mallamace).The dynamical arrest phenomena of an adhesive hard-sphere (AHS) colloid, L64-D 2O system has been studied by using calorimetry and the complex shear modulus. This system is characterized by a rich temperature (T) and volume fraction (ϕ) phase diagram with a percolation line (PT). According to the mode-coupling theory (MCT), a cusp-like singularity and two glassy phases, one attractive (AG) and one repulsive (RG), are supposed to coexist in the phase diagram. The MCT scaling laws used to study the shear viscosity with ϕ and T as control parameters propose the existence of fragile-to-strong dynamic crossover (FSDC) analogous to that observed in molecular supercooled liquid glass formers. The measured critical values of the control parameters, coincident with the PT line, where the clustering process generates the AG phase, define the FSDC locus. This is in agreement with the extended mode-coupling theory that takes into account both cage and inter-cluster hopping effects. In this work, we demonstrate, by considering the frequency dependence of the complex moduli, that there is the onset of a system viscoelasticity as an effect of the clustering accompanying the FSDC. We will show as the measured frequency-dependent complex moduli satisfy the scaling relations predicted by the scalar elasticity percolation theory and well account for the system evolution toward the glass transition process.United States. Dept. of Energy (DOE Grant No. DE-FG02-90ER45429
The Role of Hydrogen Bonding in the Folding/Unfolding Process of Hydrated Lysozyme: A Review of Recent NMR and FTIR Results
No full textThe 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. Keywords: protein denaturation; FTIR; NMR; hydration water; hydrogen bonding; energy landscap
Molecular degradation of ancient documents revealed by HR-MAS NMR spectroscopy
Full text linkFor 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
The Water Polymorphism and the Liquid–Liquid Transition from Transport Data
No full textNMR 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
The Hydrophobic Effect Studied by Using Interacting Colloidal Suspensions
Full text linkInteractions 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
Water and lysozyme: Some results from the bending and stretching vibrational modes
Full text linkThe 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)
Erratum to: The fragile-to-strong dynamical crossover and the system viscoelasticity in attractive glass forming colloids
No full textErratum to: Colloid Polym Sci http://dx.doi.org/10.1007/s00396-015-3713-6 The original version of this article, unfortunately, contained errors
The Time–Temperature Superposition of Polymeric Rubber Gels Treated by Means of the Mode-Coupling Theory
No full textViscoelastic relaxation measurements on styrene-butadiene rubbers (SBRs) doped with carbon nanotube (CNT) at different concentrations around the sol-gel transition show the time–temperature superposition (TTS). This process is described in terms of the mode coupling theory (MCT) approach to viscoelasticity by considering the frequency behavior of the loss modulus E″(ω) and showing that the corresponding TTS is linked to ω1/2 decay. From the analysis of the obtained data, we observe that the interaction between SBRs and CNT determines different levels of decay according to their concentration. Systems with the lowest CNT concentration are only characterized in the studied T-range by their fragile glass-forming behavior. However, at a specific temperature TL, those with the highest CNT concentration show a crossover towards pure Arrhenius that, according to the MCT, indicates the presence of kinetic glass transition (KGT), where system response functions are characterized by scaling behaviors
Specific Heat and Transport Functions of Water
Full text linkNumerous water characteristics are essentially ascribed to its peculiarity to form strong hydrogen bonds that become progressively more stable on decreasing the temperature. However, the structural and dynamical implications of the molecular rearrangement are still subject of debate and intense studies. In this work, we observe that the thermodynamic characteristics of liquid water are strictly connected to its dynamic characteristics. In particular, we compare the thermal behaviour of the isobaric specific heat of water, measured in different confinement conditions at atmospheric pressure (and evaluated by means of theoretical studies) with its configurational contribution obtained from the values of the measured self-diffusion coefficient through the use of the Adam-Gibbs approach. Our results confirm the existence of a maximum in the specific heat of water at about 225 K and indicate that especially at low temperature the configurational contributions to the entropy are dominant
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