6 pagesInternational audienceUltrastable foams with an optimal foamability have been obtained using hydroxyl fatty acids tubes. The stabilization results from the adsorption of monomers at the air-water interface preventing coalescence and coarsening and from the presence of tubes in the Plateau borders limiting the drainage. Upon heating, tubes transit to micelles, which induces foam destabilization. Such foams are thus the first to have a temperature tunable stability

There is considerable interest in constructing supramolecular hollow tube architectures based on amphiphilic molecules. This can be achieved by using relatively expensive synthetic lipids. Herein, we report on the facile preparation of self-assembled microtubes from a novel low-cost lipid mixture that does not require a previous chemical synthesis step and consists of the ethanolamine salt of 12-hydroxy-stearic acid in water. Tubes of more than 10 microm in length spontaneously form upon cooling from an isotropic solution. They exhibit inner and outer diameters of 400 and 600 nm, respectively, and their walls consist of concentric stacked bilayers of fatty acid salts, each separated by a layer of water.

We report the dispersions of a fatty acid and hydroxyl derivative salts in aqueous solutions that were further used to produce foams and emulsions. The tetrabutyl-ammonium salts of palmitic acid, 12-hydroxy stearic acid, and omega-hydroxy palmitic acid formed isotropic solutions of micelles, whereas the ethanolamine salts of the same acids formed turbid birefringent lamellar solutions. The structure and dimension of those phases were confirmed by small-angle neutron scattering and NMR. Micelles exhibited a surprisingly small radius of about 20 A, even for hydroxyl fatty acids, suggesting the formation of hydrogen bonds between lipids in the core of the micelles. In the case of ethanolamine salts of palmitic and 12-hydroxy stearic acids, the lipids were arranged in bilayers, with a phase transition from gel to fluid upon heating, whereas for omega-hydroxy palmitic acid, monolayers formed in accordance with the bola shape of this lipid. Foams and emulsions produced from ethanolamine salt solutions were more stable than those obtained from tetrabutyl-ammonium salt solutions. We discuss these results in terms of counterion size, lipid molecular shape, and membrane curvature.

A new method for analysis of scattering data from lamellar bilayer systems is presented. The method employs a form‐free description of the cross‐section structure of the bilayer and the fit is performed directly to the scattering data, introducing also a structure factor when required. The cross‐section structure (electron density profile in the case of X‐ray scattering) is described by a set of Gaussian functions and the technique is termed Gaussian deconvolution. The coefficients of the Gaussians are optimized using a constrained least‐squares routine that induces smoothness of the electron density profile. The optimization is coupled with the point‐of‐inflection method for determining the optimal weight of the smoothness. With the new approach, it is possible to optimize simultaneously the form factor, structure factor and several other parameters in the model. The applicability of this method is demonstrated by using it in a study of a multilamellar system composed of lecithin bilayers, where the form factor and structure factor are obtained simultaneously, and the obtained results provided new insight into this very well known system.

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Encapsulating biological materials in lipid vesicles is of interest for mimicking cells; however, except in some particular cases, such processes do not occur spontaneously. Herein, we developed a simple and robust method for encapsulating proteins in fatty acid vesicles in high yields. Fatty acid based, membrane-free coacervates spontaneously sequester proteins and can reversibly form membranous vesicles upon varying the pH value, the precrowding feature in coacervates allowing for protein encapsulation within vesicles. We then produced enzyme-enriched vesicles and show that enzymatic reactions can occur in these micrometric capsules. This work could be of interest in the field of synthetic biology for building microreactors.

Long-chain fatty acids are insoluble in aqueous solution and form crystal precipitates. It is then of particular importance to determine the physicochemical parameters allowing their dispersion in water to improve their bioavailability and their utilization as surfactants. Herein, we report a study on salt-free catanionic systems in aqueous solution made of mixtures between palmitic or stearic fatty acids and alkylboladiamines (Abd's) differing by their alkyl chain length. Phase contrast microscopy, solid-state NMR, Fourier transform infrared spectroscopy, and small-angle neutron scattering were used to characterize the phase behavior of these systems at molar ratio of fatty acid to Abd of 1 and 2. Whatever the Abd and the molar ratio, fatty acids were embedded at low temperature in a bilayer gel phase which crystallizes after a period of rest. At an equimolar ratio, the gel phases transited upon raising the temperature to an isotropic phase made of worm-like micelles except in the case of the ethylenediamine chain for which a lamellar fluid phase was observed. At a molar ratio of 2 and high temperature, fatty acids were embedded in a lamellar fluid phase which self-orients with its stacking axis perpendicular to the magnetic field. However, for a long alkylboladiamine such as spermine, worm-like micelles formed. The phase behavior at high temperature is discussed in terms of molecular volume.

It is known that 12-hydroxystearic acid coupled via ion-pairing with a counterion, such as ethanolamine, self-assembles into supramolecular multilayer tubes that exhibit a peculiar temperature-tunable diameter variation. At a given temperature threshold (T(Ø↑)), there is a large increase of the tube diameter by almost a factor of 10. We investigate here the nature of the counterion on the self-assembly of such tubes and the variation of their diameter with the temperature. Eight different counterions are used to produce tubes via ion-pairing with 12-hydroxystearic acid. We systematically measure structural parameters at different scales coupling phase contrast microscopy and small-angle neutron scattering (SANS), in combination with thermodynamic studies using differential scanning calorimetry (DSC). The temperature T(Ø↑) is found to depend sensitively on the nature of the counterion. One could not identify any DSC peak associated with the diameter variation. However, a detailed line-shape analysis of the SANS spectra reveals that a significant softening of the elastic properties of the multilayer tube walls occurs at T(Ø↑), for all counterions investigated. Depending on both the temperature and the nature of the counterion, the interlayer spacing in the multilayered structure (respectively, the bilayer thickness) varies in a range from 240 to 440 Å (respectively, from 22 to 42 Å), but those variations appear not to be related to T(Ø↑). Altogether, our results show that the variation of the diameter is correlated to the nature of the counterion and to the elastic properties of the bilayer stack.