It is now well admitted that hydrophobic interactions and hydrogen bonds are the main forces driving protein folding and stability. However, because of the complex structure of a protein, it is still difficult to separate the different energetic contributions and have a reliable estimate of the hydrogen bond part. This energy can be quantified on simpler systems such as surfaces bearing hydrogen-bonding groups. Using the surface force apparatus, we have directly measured the interaction energy between monolayers of lipids whose headgroups can establish hydrogen bonds in water: nitrilotriacetate, adenosine, thymidine, and methylated thymidine lipids. From the adhesion energy between the surfaces, we have deduced the energy of a single hydrogen bond in water. We found in each case an energy of 0.5 kcal/mol. This result is in good agreement with recent experimental and theoretical studies made on protein systems showing that intramolecular hydrogen bonds make a positive contribution to protein stabilization.

The collapse of monolayers of 10,12-pentacosadiyonic acid at the air/water interface has been studied by measurements of isotherms as a function of temperature, compression speed, and spreading solvent. Films on the water surface have been examined by X-ray reflectivity, and atomic force microscopy (AFM) images have been obtained of films transferred to mica by the Langmuir−Blodgett method. At constant temperature, collapse occurs at constant pressure, which increases with the logarithm of the compression speed, suggesting an activation controlled process. Both the AFM and reflectivity measurements are consistent with the formation of a trilayer upon collapse. A mechanical model for collapse is discussed.

Friction forces measurements between smooth surfaces across two layers of linear alkanes over five decades of speeds are presented. A maximum friction dissipation is observed at a characteristic speed. This behaviour is described by a new approach: the formation and destruction of molecular bridges between confined alkane layers. These bridges which interdigitate between the layers exhibit a thermally activated resistance to shear. An analytical model involving activation barriers accounts for the overall behaviour of the speed dependence of the forces over four decades. This first simple semi-quantitative description sheds new light on the subtle mechanisms of friction at the nanoscale level and shows how the molecular length influences the tribological properties of the liquid.

We use dynamic light scattering (DLS) and fluorescence recovery after pattern photobleaching (FRAPP) to investigate the dynamics of a model transient network made of an oil-in-water droplet microemulsion to which small amounts of a telechelic polymer are added. The DLS correlation functions exhibit three relaxation modes. The two first modes can be interpreted quantitatively in the frame of the classical De Gennes–Brochard theory of DLS in viscoelastic system. The third, slower mode is diffusive and arises from the ternary character (droplets, polymers, and water) of the system. By contrast, the pattern relaxation in FRAPP exhibits a single-, slow-exponential decay with a characteristic time proportional to the squared inverse scattering vector: the corresponding self-diffusion coefficient of the droplets is found to be close to the diffusion coefficient characterizing the third mode in DLS. We interpret these results in terms of the coupled relaxation of the concentration fluctuations of the polymers and the droplets.

Hydrophobically modified poly(ethylene oxide), HMPEO, was studied in concentrated salt solutions. The influence of salts was compared to the effect of temperature on poly(ethylene oxide), PEO. As expected, the addition of monovalent cations (Na(+), K(+)) has the same effect as an increase in temperature in agreement with the thermodynamic properties of PEO: a decrease in solubility, micelle size, and viscosity was observed. Moreover, the intensity of neutron scattering peaks (characteristic of the semi-dilute solutions of these associative polymers) increases due to the collapse of PEO coronae in micelles. Very peculiar behavior was observed in the presence of divalent cations (Ca(2+), Mg(2+)): larger micelle aggregates and higher viscosities, relaxation times, and activation energies were observed by dynamic rheology. This behavior is attributed to interactions between divalent cations and oxygen in PEO backbones close to the micelle core, which may reinforce intermicellar bridges.