Friction force 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. The behaviour is described by a new approach: the formation and destruction of molecular bridges between confined alkane layers. The bridges interdigitated between the layers exhibit a thermally activated resistance to shear. An analytical model involving activation barriers accounts for the overall behaviour of the forces over four decades of speed. 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.

In mixed alcohol-water solvents, bovine beta-lactoglobulin undergoes a cooperative transition from beta-sheet to a high alpha-helix content conformer. We report here the characterization of beta-lactoglobulin by compressibility and spectroscopy measurements during this transconformation. Both the volume and compressibility increase as a function of alcohol concentration, up to maximal values which depend on the chemical nature of the three alcohols used: hexafluoroisopropanol, trifluoroethanol, and isopropanol. The order of effectiveness of alcohols in inducing the compressibility transition is identical to that previously reported for circular dichroism and thus independent of the observation technique. The highly cooperative sigmoidal curves found by compressibility determination match closely those obtained by circular dichroism at 222 nm, indicating a correlation between the two phenomena measured by the two different techniques. The presence of an equilibrium intermediate form was shown by the interaction of beta-lactoglobulin with 8-anilino-1-naphthalene sulfonic acid, a probe widely used to detect molten-globule states of proteins. It was correlated with the plateau region of the volume curves and with the inflexion points of the sigmoidal compressibility curves. Ultrasound characterization of proteins can be carried out in optically transparent or nontransparent media.

We present a high precision ultrasonic velocimeter for a small volume sample (1 cm3) for a path length of 1 cm achieved. The method used is based on the time of flight measurement with an original signal processing technique: the barycenter method. With our system, we have measured the sound velocity with an accuracy of 10(-5). The detection of a difference in velocity between two liquids of about 2 cm/s is achieved. The compressibility of the reference liquid can then be deduced with an accuracy better than 0.2%. Using this custom-made system, we have studied and characterized complex fluids, systems biomimetic of biological membranes, as well as proteins included in nanometric water droplets. Under these experimental conditions, we have reached the value of protein compressibilities with an accuracy better than 10%.

Poly-12-hydroxystearic acid (PHSA) is widely used as a coating on colloidal spheres to provide a “hard-sphere-type” interaction. These hard spheres have been widely used in fundamental studies of nucleation, crystallization, and glass formation. Most authors describe the interaction as “nearly” hard sphere. In this paper we directly measure this interaction, using layers of PHSA adsorbed onto mica sheets in a surfaces force apparatus. We find that the layers, in appropriate solvents, have no long-range interaction. When the solvent is decahydronaphthalene (decalin), the repulsion rises from zero to the maximum measurable over a distance range of 15–20 nm. The data is converted to equivalent forces between spheres of different diameters, and modeled using a hard core potential. Using zeroth-order perturbation theory and computer simulation, we demonstrate that the equation of state does not deviate from that of a perfect hard-sphere system under any relevant experimental conditions.