Lipid tubule self-assembly: length dependence on cooling rate through a first-order phase transition.

The formation kinetics and self-assembly of multilamellar tubules of the diacetylenic phospholipid 1,2-bis(tricosa-10,12-diynoyl)-sn-glycerol-3-phosphocholine formed under controlled cooling rates were studied by x-ray diffraction and optical, atomic force, and scanning electron microscopy. Tubule formation was driven by a reversible first-order phase transition from an intralamellar, chain-melted L(alpha) phase to a chain-frozen L(beta), phase. These observations are the basis of a highly efficient method of tubule production in which tubule lengths can be controlled, between 1 and 100 micrometers, by varying the cooling rate. These tubules can be made in suspensions with 10 percent lipid by mass, far exceeding the lipid solubility limit.

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.

Structure of membrane surfactant and liquid crystalline smectic lamellar phases under flow.

Synchrotron x-ray scattering studies were performed to probe the nonequilibrium structures of two layered systems at high shear rates: the smectic-A phase of the thermotropic liquid crystal 4-cyano-4'-octylbiphenyl (8CB) and the lamellar L(alpha) phases of surfactant membranes composed of sodium dodecyl sulfate and pentanol. Whereas the lamellar surfactant phases oriented primarily with their layers parallel to the shearing plates, as expected intuitively, in the corresponding high shear regime, the smectic-A liquid crystalline material oriented with the layers perpendicular to the shearing plates. A careful numerical study revealed that this surprising layer orientation results from nonlinear dynamics of the liquid crystal director and is caused by the flow distortion of thermal fluctuations.

X-ray Scattering Studies of Aligned, Stacked Surfactant Membranes.

X-ray scattering studies were performed to understand the structure and correlations in the lamellar phases of thick, freely suspeded films of (i) the hydrated phospholipid dimyristoylphosphotidylcholine (DMPC) and (ii) the ternar system consisting of the surfactant sodium dodecyl sulfate (SDS), cosurfactant (pentanol), and water. The films were drawn in a temperature- and humidity-controlled environment, where the layers were oriented to within 0.1 degrees . In the DMPC system, this made it possible to directly observe the orientation of the P(beta') modulation and to identify phase L(beta') as three distinct phases distinguished by the direction of chain tilt with respect to the lattice. In the L(alpha) phase of the ternary system, power law behavior of the (0,0,L) structure factor arising from the algebraic decay of layer correlatios was observed in single crystals.