HypothesisAlthough the dynamics of colloids in the vicinity of a solid interface has been widely characterized in the past, experimental studies of Brownian diffusion close to an air–water interface are rare and limited to particle-interface gap distances larger than the particle size. At the still unexplored lower distances, the dynamics is expected to be extremely sensitive to boundary conditions at the air–water interface. There, ad hoc experiments would provide a quantitative validation of predictions.ExperimentsUsing a specially designed dual wave interferometric setup, the 3D dynamics of 9 μm diameter particles at a few hundreds of nanometers from an air–water interface is here measured in thermal equilibrium.FindingsIntriguingly, while the measured dynamics parallel to the interface approaches expected predictions for slip boundary conditions, the Brownian motion normal to the interface is very close to the predictions for no-slip boundary conditions. These puzzling results are rationalized considering current models of incompressible interfacial flow and deepened developing an ad hoc model which considers the contribution of tiny concentrations of surface active particles at the interface. We argue that such condition governs the particle dynamics in a large spectrum of systems ranging from biofilm formation to flotation process.

In this article, we present the mobilities of prolate ellipsoidal micrometric particles close to an air–water interface measured by dual wave reflection interference microscopy. Particle's position and orientation with respect to the interface are simultaneously measured as a function of time. From the measured mean square displacement, five particle mobilities (3 translational and 2 rotational) and two translational–rotational cross-correlations are extracted. The fluid dynamics governing equations are solved by the finite element method to numerically evaluate the same mobilities, imposing either slip and no-slip boundary conditions to the flow at the air–water interface. The comparison between experiments and simulations reveals an agreement with no-slip boundary conditions prediction for the translation normal to the interface and the out-of-plane rotation, and with slip ones for parallel translations and in-plane rotation. We rationalize these evidences in the framework of surface incompressibility at the interface.

Food transition requires the replacement in human diet of animal-based proteins by alternative sources of proteins including plant-based proteins. This calls for a detailed knowledge of the functional properties of plant-based proteins, including their surface activity. In this framework, we provide here a comparative study of the interfacial properties of two plant proteins, extracted respectively from wheat and sunflower. We combine time- and concentration-dependent measurements of the surface tension and the surface rheology, as measured with a pendant-drop set-up, and of the surface excess concentration, as measured by ellipsometry, of plant protein interfacial films. We demonstrate a time-concentration superposition principle for the surface pressure and surface excess concentration, showing that the kinetics for the building of the interfacial films is essentially governed by the diffusion of the proteins from the bulk to the interface. We find that the rheological and structural properties of the interfacial protein films show markedly different behaviors for the two classes of protein, which is encoded in the structural features of the individual proteins: wheat proteins are more surface active than sunflower proteins, are keen to compress and re-arrange at an air-water interface, whereas sunflower proteins do not. This work provides qualitative and quantitative analysis of the comparative interfacial behavior of flexible and rigid plant proteins extracted respectively from wheat and sunflower, and demonstrates that a combination of several experimental techniques is necessary to obtain insightful information on the interfacial properties of any species.

The adsorption of a sunflower protein extract at two air− water and oil−water interfaces is investigated using tensiometry, dilational viscoelasticity, and ellipsometry. For both interfaces, a three step mechanism was evidenced thanks to master curve representations of the data taken at different aging times and protein concentrations. At short times, a diffusion limited adsorption of proteins at interfaces is demonstrated. First, a two-dimensional protein film is formed with a partition of the polypeptide chains in the two phases that depends strongly on the nature of the hydrophobic phase: most of the film is in the aqueous phase at the air−water interface, while it is mostly in the organic phase at the oil−water interface. Then a three-dimensional saturated monolayer of proteins is formed. At short times, adsorption mechanisms are analogous to those found with typical globular proteins, while strong divergences are observed at longer adsorption times. Following the saturation step, a thick layer expands in the aqueous phase and appears associated with the release of large objects in the bulk. The kinetic evolution of this second layer is compatible with a diffusion limited adsorption of the minor population of polymeric complexes with hydrodynamic radius R H ∼ 80 nm, evidenced in equilibrium with hexameric globulins (R H ∼ 6 nm) in solution. These complexes could result from the presence of residual polyphenols in the extract and raise the question of the role of these compounds in the interfacial properties of plant protein extracts.