Water response to ganglioside GM1 surface remodelling.

BACKGROUND: Gangliosides are biological glycolipids participating in rafts, structural and functional domains of cell membranes. Their headgroups are able to assume different conformations when packed on the surface of an aggregate, more lying or standing. Switching between different conformations is possible, and is a collective event. Switching can be induced, in model systems, by concentration or temperature increase, then possibly involving ganglioside-water interaction. In the present paper, the effect of GM1 ganglioside headgroup conformation on the water structuring and interactions is addressed. METHODS: Depolarized Rayleigh Scattering, Raman Scattering, Quasielastic Neutron Scattering and NMR measurements were performed on GM1 ganglioside solutions, focusing on solvent properties. RESULTS: All used techniques agree in evidencing differences in the structure and dynamics of solvent water on different time-and-length scales in the presence of either GM1 headgroup conformations. CONCLUSIONS: In general, all results indicate that both the structural properties of solvent water and its interactions with the sugar headgroups of GM1 respond to surface remodelling. The extent of this modification is much higher than expected and, interestingly, ganglioside headgroups seem to turn from cosmotropes to chaotropes upon collective rearrangement from the standing- to the lying-conformation. SIGNIFICANCE: In a biological perspective, water structure modulation could be one of the physico-chemical elements contributing to the raft strategy, both for rafts formation and persistence and for their functional aspects. In particular, the interaction with approaching bodies could be favoured or inhibited or triggered by complex-sugar-sequence conformational switch. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo.

The role of the dynamic crossover temperature and the arrest in glass-forming fluids.

We discuss the role of the dynamic glass-forming fragile-to-strong crossover (FSC) in supercooled liquids. In the FSC, significant dynamic changes such as the decoupling (the violation of the Stokes-Einstein relation) of homologous transport parameters, e.g., the density relaxation time τ and the viscosity η, occur at a characteristic temperature T(c). We study the FSC using a scaling law approach. In particular, we use both forms of the mode-coupling theory (MCT): the original (ideal) and the extended form, which explicitly describes energy hopping processes. We demonstrate that T(c) plays the most important physical role in understanding dynamic arrest processes.

Liquid polymorphism: water in nanoconfined and biological environments.

We demonstrate some recent progress in understanding the anomalous behavior of liquid water, by combining information provided by recent experiments and simulations on water in bulk, nanoconfined, and biological environments. We interpret evidence from recent experiments designed to test the hypothesis that liquid water may display 'polymorphism' in that it can exist in two different phases--and discuss recent work on water's transport anomalies as well as the unusual behavior of water in biological environments. Finally, we will discuss how the general concept of liquid polymorphism may prove useful in understanding anomalies in other liquids, such as silicon, silica, and carbon, as well as metallic glasses which have in common that they are characterized by two characteristic length scales in their interactions.

A possible scenario for the fragile-to-strong dynamic crossover predicted by the extended mode-coupling theory for glass transition.

It is argued that the extended mode-coupling theory for glass transition predicts a dynamic crossover in the α-relaxation time and in the self-diffusion constant as a general implication of the structure of its equations of motion. This crossover occurs near the critical temperature T(c) of the idealized version of the theory, and is caused by the change in the dynamics from the one determined by the cage effect to that dominated by hopping processes. When combined with a model for the hopping kernel deduced from the dynamical theory for diffusion-jump processes, the dynamic crossover can be identified as the fragile-to-strong crossover (FSC) in which the α-relaxation time and the self-diffusion constant cross over from a non-Arrhenius to an Arrhenius behavior. Since the present theory does not resort to the existence of the so-called Widom line, to which the FSC in confined water has been attributed, it provides a possible explanation of the FSC observed in a variety of glass-forming systems in which the existence of the Widom line is unlikely. In addition, the present theory predicts that the Stokes-Einstein relation (SER) breaks down in different ways on the fragile and strong sides of the FSC, in agreement with the experimental observation in confined water. It is also demonstrated that the violation of the SER in both the fragile and strong regions can be fitted reasonably well by a single fractional relation with an empirical exponent of 0.85.

Evidence of dynamic crossover phenomena in water and other glass-forming liquids: experiments, MD simulations and theory.

In a recent quasi-elastic neutron scattering experiment on water confined in a Portland cement paste, we find that this 3D confined water shows a dynamic crossover phenomenon at T(L) = 227 ± 5 K. The DSC heat-flow scan upon cooling and an independent measurement of specific heat at constant pressure of confined water in silica gel show a prominent peak at the same temperature. We show in this paper that this type of behavior is common to many other glassy liquids, which also show the crossover temperature in coincidence with the temperature of a small specific heat peak. We also demonstrate with MD simulations that the dynamic crossover phenomenon in confined water is an intrinsic property of bulk water, and is not due to the confinement effect. Recently, an extended version of the mode coupling theory (MCT) including the hopping effect was developed. This theory shows that, instead of a structural arrest transition at T(C) predicted by the idealized MCT, a fragile-to-strong dynamic crossover phenomenon takes place instead at T(C), confirming both the experimental and the numerical results. The coherent and incoherent α relaxation times can be scaled with the calculated viscosity, showing the same crossover phenomenon. We thus demonstrated with experiments, simulations and theory that a genuine change of dynamical behavior of both water and many glassy liquids happens at the crossover temperature T(L), which is 10-30% higher than the calorimetric glass transition temperature T(g).

Heterogeneities in confined water and protein hydration water.

We report recent efforts to understand a broad range of experiments on confined water and protein hydration water, many initiated by a collaboration between workers at the University of Messina and MIT-the editors of this special issue. Preliminary calculations are not inconsistent with one tentative interpretation of these experiments as resulting from the system passing from the high-temperature high-pressure 'HDL' side of the Widom line (where the liquid might display non-Arrhenius behavior) to the low-temperature low-pressure 'LDL' side of the Widom line (where the liquid might display Arrhenius behavior). The Widom line-defined to be the line in the pressure-temperature plane where the correlation length has its maximum-arises if there is a critical point. Hence, interpreting the Messina-MIT experiments in terms of a Widom line is of potential relevance to testing, experimentally, the hypothesis that water displays a liquid-liquid critical point.

NMR evidence of a sharp change in a measure of local order in deeply supercooled confined water.

Using NMR, we measure the proton chemical shift delta, of supercooled nanoconfined water in the temperature range 195 K < T < 350 K. Because delta is directly connected to the magnetic shielding tensor, we discuss the data in terms of the local hydrogen bond geometry and order. We argue that the derivative -( partial differential ln delta/ partial differentialT)(P) should behave roughly as the constant pressure specific heat C(P)(T), and we confirm this argument by detailed comparisons with literature values of C(P)(T) in the range 290-370 K. We find that -( partial differential ln delta/ partial differentialT)(P) displays a pronounced maximum upon crossing the locus of maximum correlation length at approximately 240 K, consistent with the liquid-liquid critical point hypothesis for water, which predicts that C(P)(T) displays a maximum on crossing the Widom line.

The fragile-to-strong dynamic crossover transition in confined water: nuclear magnetic resonance results.

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 T(L)=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 (1D) 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 tau(T), as measured by neutron scattering, shows the predicted breakdown of Stokes-Einstein relation in deeply supercooled water.

Complex viscosity behavior and cluster formation in attractive colloidal systems.

The increase in viscosity that 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 nontrivial 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.

Observation of a re-entrant kinetic glass transition in a micellar system with temperature-dependent attractive interaction.

We detect in a tri-block co-polymer micellar system an ergodic-to-nonergodic-to-ergodic transition, as a function of temperature, in a range of concentrations, by photon correlation measurements. The shear viscosity is also shown to jump two order of magnitude at these transition temperatures. Surprisingly, the structure factor as measured by small angle neutron scattering shows a marked narrowing at the structural arrest state. Rationalization of these results with the existence of an attractive branch in the phase diagram of an attractive colloid system predicted by mode coupling theory is made.

Separation of scattering and absorption contributions in UV/visible spectra of resonant systems.

Resonance light scattering (RLS) is a phenomenon due to an enhancement of the scattered light in close proximity to an absorption band. The effect is easily detectable in the case of strongly absorbing chromophores, which are able to interact, thus leading to large aggregates (Pasternack, R. F.; Collings, P. J. Science 1995, 269, 935). The measurement of absorption spectra from solutions containing such resonant systems can lead to misleading results. In this paper, a simple method is described to obtain absorption spectra of aggregated species with a fairly good correction of the scattering component. The RLS spectrum, obtained using a common spectrofluorimeter, is correlated to the extinction spectrum of the same sample, allowing for an estimation of the scattering contribution to the total extinction spectrum. The method has been successfully applied both on real samples containing aggregated chromophores, such as porphyrins, chlorophyll a and gold colloids, and by simulating extinction spectra.

Kinetic glass transition in a micellar system with short-range attractive interaction

We show that percolation and structural arrest transitions coexist in different regions of the phase diagram of a copolymer-micellar system and relate them to short-range intermicellar attraction. The intermediate scattering function shows a nonergodic transition along a temperature and concentration dependent line. Analyses show a logarithmic time dependence, attributed to a higher-order glass transition singularity predicted by mode-coupling theory, followed by a power law.

Interaction and percolation in the L64 triblock copolymer micellar system.

We present results of analyses of an extensive set of static light scattering (SLS), small angle neutron scattering (SANS), and viscoelastic (frequency dependent complex moduli) measurements of aqueous solutions of a triblock copolymer micellar system. We investigate Pluronic L64 (PEO(13)PPO(30)PEO(13))-water system in a wide range of composition and temperature. We determine phase diagram of the disordered micellar phase, including a cmc-cmt curve, a cloud point curve, the critical concentration, and the critical temperature by means of SLS and SANS. The microstructure and interaction between micelles are determined by analyses of SANS intensities. SANS intensity distributions are well described by combining the cap-and-gown model for the polymer segmental distribution within a micelle and the sticky hard sphere model for the intermicellar structure factor. The existence of percolation loci at well defined poins in the temperature-concentration plane is inferred from an abrupt increase of the stickiness parameter extracted from SANS data and from two order of magnitude jump of the complex moduli at the percolation point. Study of temperature dependence of real (storage) and imaginary (loss) part of the complex modulus at fixed concentration and frequency lends further support to the existence of a percolation line. We observe an increase of some order of magnitude of the real and imaginary part of viscosity at certain temperature and composition, a phenomenon usually ascribed to a gelation process in a polymer solution. The definitive confirmation of the percolation process is obtained by frequency dependent complex viscosity measured in a frequency range 0-160 (rad/sec). From these measurements we clearly observe a well defined frequency scaling behavior of the complex moduli and a loss angle (delta) independent of the frequency. Scaling exponents, determined for frequency-dependent complex moduli satisfy the scaling relations predicted by the scalar elasticity percolation theory.