Stripes of Partially Fluorinated Alkyl Chains: Dipolar Langmuir Monolayers

Stripe-like domains of Langmuir monolayers formed by surfactants with partially fluorinated lipid anchors (F-alkyl lipids) are observed at the gas-liquid phase coexistence. The average periodicity of the stripes, measured by fluorescence microscopy, is in the micrometer range, varying between 2 and 8 microns. The observed stripe-like patterns are stabilized due to dipole-dipole interactions between terminal -CF3 groups. These interactions are particularly strong as compared with non-fluorinated lipids due to the low dielectric constant of the surrounding media (air). These long-range dipolar interactions tend to elongate the domains, in contrast to the line tension that tends to minimize the length of the domain boundary. This behavior should be compared with that of the lipid monolayer having alkyl chains, and which form spherical micro-domains (bubbles) at the gas-liquid coexistence. The measured stripe periodicity agrees quantitatively with a theoretical model. Moreover, the reduction in line tension by adding traces (0.1 mol fraction) of cholesterol results, as expected, in a decrease in the domain periodicity.Comment: 20 pages, 4 fig

Effect of dipolar moments in domain sizes of lipid bilayers and monolayers

Lipid domains are found in systems such as multi-component bilayer membranes and single component monolayers at the air-water interface. It was shown by Andelman et al. (Comptes Rendus 301, 675 (1985)) and McConnell et al. (Phys. Chem. {\bf 91}, 6417 (1987)) that in monolayers, the size of the domains results from balancing the line tension, which favors the formation of a large single circular domain, against the electrostatic cost of assembling the dipolar moments of the lipids. In this paper, we present an exact analytical expression for the electric potential, ion distribution and electrostatic free energy for different problems consisting of three different slabs with different dielectric constants and Debye lengths, with a circular homogeneous dipolar density in the middle slab. From these solutions, we extend the calculation of domain sizes for monolayers to include the effects of finite ionic strength, dielectric discontinuities (or image charges) and the polarizability of the dipoles and further generalize the calculations to account for domains in lipid bilayers. In monolayers, the size of the domains is dependent on the different dielectric constants but independent of ionic strength. In asymmetric bilayers, where the inner and outer leaflets have different dipolar densities, domains show a strong size dependence with ionic strength, with molecular-sized domains that grow to macroscopic phase separation with increasing ionic strength. We discuss the implications of the results for experiments and briefly consider their relation to other two dimensional systems such as Wigner crystals or heteroepitaxial growth.Comment: 13 pages, 5 figues in eps Replaced with new version, one citation added and a few statements corrected. The results of the paper are unchange

Line tension and structure of smectic liquid crystal multilayers at the air-water interface

At the air/water interface, 4,-8-alkyl[1,1,-biphenyl]-4-carbonitrile (8CB) domains with different thicknesses coexist in the same Langmuir film, as multiple bilayers on a monolayer. The edge dislocation at the domain boundary leads to line tension, which determines the domain shape and dynamics. By observing the domain relaxation process starting from small distortions, we find that the line tension is linearly dependent on the thickness difference between the coexisting phases in the film. Comparisons with theoretical treatments in the literature suggest that the edge dislocation at the boundary locates near the center of the film, which means that the 8CB multilayers are almost symmetric with respect to the air/water interface.Comment: 21 pages, 6 figure

Standing-wave-excited multiplanar fluorescence in a laser scanning microscope reveals 3D information on red blood cells

Standing-wave excitation of fluorescence is highly desirable in optical microscopy because it improves the axial resolution. We demonstrate here that multiplanar excitation of fluorescence by a standing wave can be produced in a single-spot laser scanning microscope by placing a plane reflector close to the specimen. We report that the relative intensities in each plane of excitation depend on the Stokes shift of the fluorochrome. We show by the use of dyes specific for the cell membrane how standing-wave excitation can be exploited to generate precise contour maps of the surface membrane of red blood cells, with an axial resolution of ~90 nm. The method, which requires only the addition of a plane mirror to an existing confocal laser scanning microscope, may well prove useful in studying diseases which involve the red cell membrane, such as malaria.Comment: 15 pages, 4 figures; changed the discussion of narrow-band detected fringes (Fig. 3) to describe the phenomenon as a moire pattern between the excitation and emission standing-wave fields, rather than a beats pattern; added DiI(5)-labelled red blood cell in Fig. 4 to show that standing-wave fringes are present even when the dye excitation wavelength is outside the haemoglobin absorption ban

Fluorescence resonance energy transfer between organic dyes adsorbed onto nano-clay and Langmuir-Blodgett (LB) films

In this communication we investigate two dyes N,N' -dioctadecyl thiacyanine perchlorate (NK) and octadecyl rhodamine B chloride (RhB) in Langmuir and Langmuir-Blodgett (LB) films with or with out a synthetic clay laponite. Observed changes in isotherms of RhB in absence and presence of nano-clay platelets indicate the incorporation of clay platelets onto RhB-clay hybrid films. AFM image confirms the incorporation of clay in hybrid films. FRET was observed in clay dispersion and LB films with and without clay. Efficiency of energy transfer was maximum in LB films with clay.Comment: 15 pages 5 figures, 1 tabl

Lamellar and inverse micellar structures of skin lipids: Effect of templating

The outermost layer of skin, the stratum corneum (SC), comprises rigid corneocytes in a layered lipid matrix. Using atomistic simulations we find that the equilibrium phase of the SC lipids is inverse micellar. A model of the corneocyte is used to demonstrate that lamellar layering is induced by the patterned corneocyte wall. The inverse micellar phase is consistent with in vivo observations in the lacunar spaces and at the stratum granulosum - SC boundary region, and suggests a functional role in the lipid synthesis pathway in vivo.Comment: pdflatex 5 pages, 10 page supplementary material. Published Physical Review Letters. Added link to website with animation

Particles adsorbed at various non-aqueous liquid-liquid interfaces

Particles adsorbed at liquid interfaces are commonly used to stabilise water-oil Pickering emulsions and water-air foams. The fundamental understanding of the physics of particles adsorbed at water-air and water-oil interfaces is improving significantly due to novel techniques that enable the measurement of the contact angle of individual particles at a given interface. The case of non-aqueous interfaces and emulsions is less studied in the literature. Non-aqueous liquid-liquid interfaces in which water is replaced by other polar solvents have properties similar to those of water-oil interfaces. Nanocomposites of non-aqueous immiscible polymer blends containing inorganic particles at the interface are of great interest industrially and consequently more work has been devoted to them. By contrast, the behaviour of particles adsorbed at oil-oil interfaces in which both oils are immiscible and of low dielectric constant (ε < 3) is scarcely studied. Hydrophobic particles are required to stabilise these oil-oil emulsions due to their irreversible adsorption, high interfacial activity and elastic shell behaviour