Search

The measurements of steady shear viscosity (eta(sub 8)(super 0)), longitudinal elastic modulus (M'), and ultrasonic absorption (alpha) in the one-phase isotropic liquid region of the non-ionic surfactant C12E8 aqueous solutions are presented. In the surfactant-rich region viscoelasticity and glass-like properties govern the behavior of the solutions and an additional low-frequency contribution is ascribed to the exchange of water molecules and/or surfactant monomers between the aggregates and the bulk solvent region.

Two independent series of calculations are performed simulating spherical and cylindrical C12E6micelles in a temperature range around the experimental sphere-to-rod transition temperature for surfactant concentrations less than 20% by weight. A comparative analysis of these systems helps to shed light on the microscopic details of the micelle sphere-to-rod transition. In agreement with theoretical models, we find that spherical and cylindrical micelles have a different oil core packing; the core radius of a cylindrical micelle is reduced by a factor of 0.87 with respect to the core radius of a spherical micelle. Despite this contraction, the specific volume of the alkyl tails is larger in a cylindrical micelle than in a spherical micelle. In both geometries, this specific volume follows the same linear increase with temperature. Density measurement experiments are also performed in order to evaluate the specific volume of the hydrophobic tail of surfactants of the C12Ejfamily with jranging from 5 to 8. We observe a good agreement between experimental data and simulation results. Our simulations also show that the spatial distribution of the head groups in the interface is more effective in screening the oil core in the cylindrical aggregate than in the spherical aggregate, reducing by a factor of 2 the oil surface per monomer exposed to water. This screening accounts for a free-energy difference of Δfs= fssph− fscyl≃ +2.5kBTper monomer and mirrors the essential role that the hydrophobic interactions have on the shape transition. We also find that the different interface packing correlates with different conformations and flexibility of the hydrophilic fragments E6, that appear as an entropicreservoir for the transition. Finally, comparing the degree of hydration of a spherical micelle at T= 283 K with that of a cylindrical micelle at T= 318 K, we observe an amount of dehydration in agreement with reported experimental data across the sphere-to-rod transition. However, for aggregates of fixed shape, we find a much smaller amount of dehydration with temperature, suggesting that the shape transition is not a consequence of the measured temperature dehydration but rather the opposite. [ABSTRACT FROM AUTHOR]

Three homologous proteins with mesophilic, thermophilic and hyperthermophilic character have been studied via molecular dynamics simulations at four different temperatures in order to investigate how water controls thermostability. The water-exposed surface of the protein is shown to increase with the degree of thermophilicity, and the role of water in enhancing the protein internal flexibility and structural robustness is elucidated. The presence of water-water hydrogen bond clusters enveloping the macromolecule is shown to correlate with thermal robustness when going from the mesophilic to the hyperthermophilic variants. Our analysis indicates that essential contributions to thermostability stem from protein-water surface effects whereas the protein internal packing plays a minor role.

A spherical micelle of C12E6 is simulated at different pressures, from 0.001 to 3 kbar, by molecular dynamics. On increasing the pressure the alkyl tails of the surfactants pack tightly and stretch. At 3 kbar we observe dynamical slowing down of the oil core of the micelle. At that pressure the core is characterized by a high oil density, rho oil approximately 0.85 g/cm(3), regular density oscillation, and low chain entropy. Pressure affects the interfacial region as well. Dehydration, induced by the collapse of the hydrophilic head groups, is observed in the inner part of the interface. Such dehydration resembles temperature dehydration but differs in details. Our results support the interpretation of recent experiments on micellar solutions at high pressure.

We present an extensive set of radio wave dielectric relaxation spectroscopy measurements of aqueous suspensions of different size unilamellar L-alpha-dipalmitoylphosphatidylcholine (DPPC) vesicles, in a temperature range between 15 and 55 C, where the lipidic bilayer experiences structural transitions from the gel to the rippled phase (at the pretransition temperature) and from the rippled to the liquid phase (at the main transition temperature). The dielectric spectra have been analyzed in the light of the Cole-Cole relaxation function, and the main dielectric parameters-the dielectric increment Deltaepsilon and the mean relaxation frequency omega(0)--have been evaluated as a function of temperature. These parameters display a very complex phenomenology, depending on the structural arrangement of the lipid-water interface. The structural parameters that govern the dielectric behavior of these systems associated with the lipid bilayer have been recognized within a recent dynamic mean-field model we have proposed, aimed to predict the dipolar relaxation of an array of strongly interacting dipoles anchored to a flat or corrugated surface. They are the prefactor A(T) of the distance-dependent part of the effective dipolar interaction energy, the term Gamma(vis), that takes into account the damping of the dipolar motion, the average dipolar distance related to the area a(0) per polar head, and the bilayer thickness. The present analysis furnishes, from a phenomenological point of view, the dependence of these parameters on the temperature and on the vesicle size.

The temperature dehydration of a C(12)E(6) spherical micelle is characterized through the study of the structure and dynamics of the hydrogen bonds formed by water within the micellar interface. Water molecules in proximity of the hydrophilic fragment of the C(12)E(6) surfactants form strong H-bonds with the oxyethilene units E and with the polar alcoholic heads. The activation energies of such H-bonds fall in the range 2-3 Kcal mol(-1). On the exposed oil core, the number of water-water H-bonds decreases as an effect of dehydration. The dynamics of such bonds exhibits a slow relaxation with respect to the bulk, and two time scales can be discerned: the first one, tau approximately 3-6 ps, is typical of water-water H-bonds around small hydrophobic molecules, whereas the second one, tau approximately 40-80 ps, is probably due to the confining effect of the long hydrophilic fragments which reduces the probability of a water molecule to leave the hydration layer of the exposed oil core. Water molecules around the core form H-bond clusters whose size and distribution change with temperature. From a cluster analysis, the system appears to be below the percolation threshold, suggesting that the exposed oily surface is formed by disconnected patches of size around 1 nm(2), close to the estimate of the solvated hydrophobic patches on protein surfaces. The network connectivity is also considered for concentric hydration shells along the interface: it turns out that near the oil core, the cluster size is larger than elsewhere in the interface demonstrating a strong structural effect induced by the exposed hydrocarbon tails. Temperature affects the cluster size only in the innermost shell.

We present an extensive set of measurements of steady shear viscosity (eta degrees(s)), longitudinal elastic modulus (M'), and ultrasonic absorption (alpha) in the one-phase isotropic liquid region of the non-ionic surfactant C12E8 aqueous solutions. Within a given temperature interval, this phase extends along the entire surfactant concentration range that could be fully covered in the experiments. In agreement with previous studies, the overall results support the presence of two separated intervals of concentration corresponding to different structural properties. In the surfactant-rich region the temperature dependence of eta degrees(s) follows an equation characteristic of glass-like systems. The ultrasonic absorption spectra show unambiguous evidence of viscoelastic behavior that can be described by a Cole-Cole relaxation formula. In this region, when both the absorption and the frequency are scaled by the static shear viscosity (eta degrees(s)), the scaled attenuation reduces to a single universal curve for all temperatures and concentrations. In the water-rich region the behavior of eta degrees(s), M', and alpha are more complex and reflect the presence of dispersed aggregates whose size increases with temperature and concentration. At these concentrations the ultrasonic spectra are characterized by a multiple decay rate. The high-frequency tail falls in the same frequency range seen at high surfactant content and exhibits similar behaviors. This contribution is ascribed to the mixture of hydrophilic terminations and water present at the micellar interfaces that resembles the condition of a concentrated polymer solution. An additional low-frequency contribution is also observed, which is ascribed to the exchange of water molecules and/or surfactant monomers between the aggregates and the bulk solvent region.