A phase of liposomes with entangled tubular vesicles

An equilibrium phase belonging to the family of bilayer liposomes in ternary mixtures of dimyristoylphosphatidylcholine (DMPC), water, and geraniol (a biological alcohol derived from oil-soluble vitamins that acts as a cosurfactant) has been identified. Electron and optical microscopy reveal the phase, labeled Ltv, to be composed of highly entangled tubular vesicles. In situ x-ray diffraction confirms that the tubule walls are multilamellar with the lipids in the chain-melted state. Macroscopic observations show that the Ltv phase coexists with the well-known L4 phase of spherical vesicles and a bulk L alpha phase. However, the defining characteristic of the Ltv phase is the Weissenberg rod climbing effect under shear, which results from its polymer-like entangled microstructure

Adsorption of MultiLamellar tubes with a temperature tunable diameter at the air-water interface: a process driven by the bulk properties

The behavior at the air/water interface of multilamellar tubes made of the ethanolamine salt of the 12-hydroxy stearic acid as a function of the temperature has been investigated using Neutron Reflectivity. Those tubes are known to exhibit a temperature tunable diameter in the bulk. We have observed multilamellar tubes adsorbed at the air/water interface by specular neutron reflectivity. Interestingly, at the interface, the adsorbed tubes exhibit the same behavior than in the bulk upon heating. There is however a peculiar behavior at around 50\degree for which the increase of the diameter of the tubes at the interface yields an unfolding of those tubes into a multilamellar layer. Upon further heating, the tubes re-fold and their diameter re-decrease after what they melt as observed in the bulk. All structural transitions at the interface are nevertheless shown to be quasi-completely reversible. This provides to the system a high interest for its interfacial properties because the structure at the air/water interface can be tuned easily by the temperature

Confined Multilamellae Prefer Cylindrical Morphology

By evaporating a drop of lipid dispersion we generate the myelin morphology often seen in dissolving surfactant powders. We explain these puzzling nonequilibrium structures using a geometric argument: The bilayer repeat spacing increases and thus the repulsion between bilayers decreases when a multilamellar disk is converted into a myelin without gain or loss of material and with number of bilayers unchanged. Sufficient reduction in bilayer repulsion can compensate for the cost in curvature energy, leading to a net stability of the myelin structure. A numerical estimate predicts the degree of dehydration required to favor myelin structures over flat lamellae.Comment: 6 pages, 3 figures, submitted to Euro. Phys. J.

Polyelectrolyte-induced peeling of charged multilamellar vesicles

We study mixtures of charged surfactants, which alone in solution form uni- and multilamellar vesicles, and oppositely charged polyelectrolytes (PEs). The phase behavior is investigated at fixed surfactant concentration as a function of the PE-to-surfactant charge ratio $x$. We find that, for $x>0$, aggregates form. Light microscopy and X-ray scattering experiments show that the isoelectric point plays a crucial role since the morphology and the microscopic structure of the aggregates are different before ($x\leq1$) and after the isoelectric point ($x>1$). To better understand the dynamics for the formation of PE/surfactant complexes, we perform light microscopy experiments where we follow in real-time the effect of a PE solution on one multilamellar vesicle (MLV). We find that the PE induces a peeling of the bilayers of the MLV one by one. The peeling is accompanied by strong shape fluctuations of the MLV and leads ultimately to a pile of small aggregates. This novel phenomenon is analyzed in detail and discussed in terms of PE-induced tension, and pore formation and growth in a surfactant bilayer.Comment: to appear in Langmui

Transient and steady-state shear banding in a lamellar phase as studied by Rheo-NMR

Flow fields and shear-induced structures in the lamellar (L-alpha) phase of the system triethylene glycol mono n-decyl ether (C10E3)/water were investigated by NMR velocimetry, diffusometry, and H-2 NMR spectroscopy. The transformation from multilamellar vesicles (MLVs) to aligned planar lamellae is accompanied by a transient gradient shear banding. A high-shear-rate band of aligned lamellae forms next to the moving inner wall of the cylindrical Couette shear cell while a low-shear-rate band of the initial MLV structure remains close to the outer stationary wall. The band of layers grows at the expense of the band of MLVs until the transformation is completed. This process scales with the applied strain. Wall slip is a characteristic of the MLV state, while aligned layers show no deviation from Newtonian flow. The homogeneous nature of the opposite transformation from well aligned layers to MLVs via an intermediate structure resembling undulated multilamellar cylinders is confirmed. The strain dependence of this transformation appears to be independent of temperature. The shear diagram, which represents the shear-induced structures as a function of temperature and shear rate, contains a transition region between stable layers and stable MLVs. The steady-state structures in the transition region show a continuous change from layer-like at high temperature to MLV-like at lower temperature. These structures are homogeneous on a length scale above a few micrometers

On the stability and growth of single myelin figures

Myelin figures are long thin cylindrical structures that typically grow as a dense tangle when water is added to the concentrated lamellar phase of certain surfactants. We show that, starting from a well-ordered initial state, single myelin figures can be produced in isolation thus allowing a detailed study of their growth and stability. These structures grow with their base at the exposed edges of bilayer stacks from which material is transported into the myelin. Myelins only form and grow in the presence of a driving stress; when the stress is removed, the myelins retract.Comment: 4 pages, 8 figures. Revised version, 1 new figure, additional reference

Cochleates derived from Vibrio cholerae O1 proteoliposomes : The impact of structure transformation on mucosal immunisation

Cochleates are phospholipid-calcium precipitates derived from the interaction of anionic lipid vesicles with divalent cations. Proteoliposomes from bacteria may also be used as a source of negatively charged components, to induce calcium-cochleate formation. In this study, proteoliposomes from V. cholerae O1 (PLc) (sized 160.7±1.6 nm) were transformed into larger (16.3±4.6 µm) cochleate-like structures (named Adjuvant Finlay Cochleate 2, AFCo2) and evaluated by electron microscopy (EM). Measurements from transmission EM (TEM) showed the structures had a similar size to that previously reported using light microscopy, while observations from scanning electron microscopy (SEM) indicated that the structures were multilayered and of cochleate-like formation. The edges of the AFCo2 structures appeared to have spaces that allowed penetration of negative stain or Ovalbumin labeled with Texas Red (OVA-TR) observed by epi-fluorescence microscopy. In addition, freeze fracture electron microscopy confirmed that the AFCo2 structures consisted of multiple overlapping layers, which corresponds to previous descriptions of cochleates. TEM also showed that small vesicles co-existed with the larger cochleate structures, and in vitro treatment with a calcium chelator caused the AFCo2 to unfold and reassemble into small proteoliposome-like structures. Using OVA as a model antigen, we demonstrated the potential loading capacity of a heterologous antigen and in vivo studies showed that with simple admixing and administration via intragastric and intranasal routes AFCo2 provided enhanced adjuvant properties compared with PLc