Cédric Gaillard

Self-Assembly of Bilayer Vesicles Made of Saturated Long Chain Fatty Acids

Saturated long chain fatty acids (sLCFA, e.g., C14:0, C16:0, and C18:0) are potentially the greenest and cheapest surfactants naturally available. However, because aqueous sodium soaps of sLCFA are known to crystallize, the self-assembly of stable bilayer vesicles has not been reported yet. Here, by using such soaps in combination with guanidine hydrochloride (GuHCl), which has been shown recently to prevent crystallization, we were capable of producing stable bilayer vesicles made of sLCFA. The phase diagrams were established for a variety of systems showing that vesicles can form in a broad range of composition and pH. Both solid state NMR and small-angle neutron scattering allowed demonstrating that in such vesicles sLCFA are arranged in a bilayer structure which exhibits similar dynamic and structural properties as those of phospholipid membranes. We expect these vesicles to be of interest as model systems of protocells and minimal cells but also for various applications since fatty acids are potentially substitutes to phospholipids, synthetic surfactants, and polymers.

Smart Nonaqueous Foams from Lipid-Based Oleogel

Oil foams are composed of gas bubbles dispersed in an oil phase. These systems are scarcely studied despite their great potential in diverse fields such as the food and cosmetic industries. Contrary to aqueous foams, the production of oil foams is difficult to achieve due to the inefficiency of surfactant adsorption at oil-air interfaces. Herein, we report a simple way to produce oil foams from oleogels, whose liquid phase is a mixture of sunflower oil and fatty alcohols. The temperature at which the oleogel formed was found to depend on both fatty alcohol chain length and concentration. The air bubbles in the oleogel foam were stabilized by fatty alcohol crystals. Below the melting temperature of the crystals, oleogel foams were stable for months. Upon heating, these ultrastable foams collapsed within a few minutes due to the melting of the crystal particles. The transition between crystal formation and melting was reversible, leading to thermoresponsive nonaqueous foams. The reversible switching between ultrastable and unstable foam depended solely on the temperature of the system. We demonstrate that these oleogel foams can be made to be photoresponsive by using internal heat sources such as carbon black particles, which can absorb UV light and dissipate the absorbed energy as heat. This simple approach for the formulation of responsive oil foams could be easily extended to other oleogel systems and could find a broad range of applications due to the availability of the components in large quantities and at low cost.

Mechanical properties of membranes composed of gel-phase or fluid-phase phospholipids probed on liposomes by atomic force spectroscopy

In many liposome applications, the nanomechanical properties of the membrane envelope are essential to ensure, e.g., physical stability, protection, or penetration into tissues. Of all factors, the lipid composition and its phase behavior are susceptible to tune the mechanical properties of membranes. To investigate this, small unilamellar vesicles (SUV; diameter < 200 nm), referred to as liposomes, were produced using either unsaturated 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) or saturated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) in aqueous buffer at pH 6.7. The respective melting temperatures of these phospholipids were -20 and 41 °C. X-ray diffraction analysis confirmed that at 20 °C DOPC was in the fluid phase and DPPC was in the gel phase. After adsorption of the liposomes onto flat silicon substrates, atomic force microscopy (AFM) was used to image and probe the mechanical properties of the liposome membrane. The resulting force-distance curves were treated using an analytical model based on the shell theory to yield the Youngs modulus (E) and the bending rigidity (kC) of the curved membranes. The mechanical investigation showed that DPPC membranes were much stiffer (E = 116 ± 45 MPa) than those of DOPC (E = 13 ± 9 MPa) at 20 °C. The study demonstrates that the employed methodology allows discrimination of the respective properties of gel- or fluid-phase membranes when in the shape of liposomes. It opens perspectives to map the mechanical properties of liposomes containing both fluid and gel phases or of biological systems.

Transition from fractal to spherical aggregates of globular proteins: Brownian-like activation and/or hydrodynamic stress?

We report on the structure of whey protein aggregates formed by a short heating coupled to shear at high temperatures (80-120) and neutral pH in scale-up processing conditions, using gel filtration chromatography, light scattering, small angle neutron scattering, and cryogenic transmission electron microscopy. The results are interpreted in terms of coexistence of residual non-aggregated proteins and aggregates. The characteristics of aggregates such as the size, the aggregation number and the shape evidence two different morphologies. Whereas aggregates formed at 80 °C show a selfsimilar structure down to a length scale of the monomer with a fractal dimension typical for reaction limited cluster aggregation (D~2.2), aggregates formed at higher temperature show a spherical morphology, with the structure from small angle neutron scattering data best modelled with the form factor of a polydisperse sphere. We compare the structure of these aggregates to that of aggregates formed in quiescent conditions at lab scale. The structure transition is interpreted in terms of a non-trivial interplay between three perturbation factors: interparticle interaction, temperature and shear.