Growth of large liquid crystalline domains of phospholipids at air-water interfaces

Abstract The fusion of condensed phase domains in a fluid environment in monolayers is studied. A system of electrodes permits the non-invasive and predetermined movement of single domains while the film is observed by fluorescence microscopy. Two domains fuse when they are brought into contact with special positions of their borderlines. The experiment yields information about the molecular structure of the domains and allows us to fabricate very large domains. The equilibrium size is estimated and verified.

Influence of chirality on the structure of phospholipid monolayers.

Structure, energy and charge transport in two-dimensional crystals of cyanine dyes

Abstract In order to develop systems with controlled energy or charge transfer across molecular dimensions it is highly desirable to build two-dimensional crystals of functional dye molecules: they can be addressed from the third dimension and the lateral intermolecular interactions can be well characterized due to a fixed and defined geometry. In an effort to study these possibilities we prepared crystals of different, negatively charged cyanine dyes, formed after adsorption from a water subphase to a positively charged monolayer. These crystals are one monolayer thick, of uniform dimensions between 10 and 100 μm (depending on nucleation conditions) and of rectangular shape. Single crystal…

Dynamics of Structure Formation in Model Membranes and in Adsorbed Layers

Unconventional and new ways to prepare ultrathin films with defined lateral distribution of components are described. These methods make use of two different principles: (1) Films with two coexisting phases are prepared and an active component preferentially partitions into one of the phases. Domain formation and interdomain distance largely depend on the kinetics of nucleation and growth and can thus be controlled. This is demonstrated by fluorescence microscopy with monolayers on water surfaces as well as with monolayers formed by co-adsorption of a fatty acid and a dye on silicon. (2) The support is structured by conventional techniques, in our case by photolithography. Adsorption or des…

The influence of counterions and hydrophobic moieties on the thermostability of Langmuir-Blodgett multilayers

Abstract Langmuir-Blodgett (LB) multilayers with various counterions and different organic moieties (one- and two-chain fatty acids, polymeric acid) are prepared to investigate on line temperature-dependent structural changes and desorption by small-angle X-ray scattering (SAXS), interference-enhanced reflection and Nomarsky microscopy. On temperature increase a sequence of phase transitions can be observed. A crystalline LB film melts to a fluid phase and eventually desorbs either from droplets or from a homogeneous film. The phase sequence depends on the counterion: nickel stearate and magnesium stearate melt while the layered structure is conserved; SAXS measurements reveal a continuous,…

CEMS/XPS study of iron stearate Langmuir-Blodgett layers

Langmuir-Blodgett mono- and multilayers of ferric stearate have been formed on oxidized silicon wafers. Thermodesorption of these layers was investigated by conversion electron Mossbauer and photoelectron spectroscopy and some complementary methods. Heating of samples in air up to 523 K leads to a desorption of the fatty acid chains, while the ferric ions are left on the substrate surface. These ions do not cluster laterally like it was found for Cd ions. They form a rather homogeneous, closed oxidic layer. This well defined layer may be used afterwards for further studies of surface reactions as well as interface and intra-layer interactions. The surface iron ions were found to exhibit a r…

Behenic Acid as a Structural Model for Fatty Acid Monolayers at the Air/Water Interface: An X-Ray Diffraction Study

We present an X-ray diffraction study of behenic (docosanoic) acid films at the air/water interface. Analysis of the rod profiles parallel and perpendicular to the surface provides detailed information on the unit cells of five different phases.

Domain shapes and monolayer structures of triple-chain phospholipids on water

Two triple-chain phospholipid isomers were investigated at the air-water interface by means of fluorescence microscopy and grazing incidence X-ray diffraction (GID). The two lipids differ only in the position of the branched chain at the glycerol backbone. Fluorescence microscopy shows different domain sharp-edged domains. In the case of dendritic domains the chains are more tilted, the deviation from hexagonal symmetry is more pronounced and hence the lattice anisotropy is larger.

Two-dimensional dye crystals with controllable optical properties

The structure, molecular ordering and optical properties of single crystals of cyanine dyes grown by adsorption from a water subphase to a positively charged lipid monolayer are discussed. These crystals are one monolayer thick, of uniform dimensions between 10 and 100μm (depending on nucleation conditions) and of rectangular shape. Single crystals were studied by transmission electron diffraction and by polarized absorption and emission spectroscopy. We show that the crystals consist of two rows of densely stacked molecules with two different orientations of the long molecular axes. This leads to two perpendicularly polarized absorption bands. The measured splitting is in accordance with r…

An X-ray scattering study of lipid monolayers at the air-water interface and on solid supports

Abstract Monolayers of the lipid arachidic acid (C20) and of the phospholid dimyristolyphosphatidic acid (PMDA) have been studied by X-ray reflection and diffraction technique, using a purpose-built Langmuir trough installed at the sample stage of our high-resolution X-ray diffractometer at the DORIS synchroton X-ray source in Hamburg. For comparison we also report data for monolayers of C20 on a solid support using a 10 kW rotating anode X-ray source. By the X-ray reflection method, the density profile across the interface is probe, while in-plane diffraction measurements gauge the two-dimensional crystalline properties of the monolayers. Flourescence microscopy experiments of DMPA monolay…

The Phases of Phosphatidyl Ethanolamine Monolayers

For the first time phospholipid monolayers at the air/water interface have been studied by X-ray diffraction and reflection along the whole isotherm from the isotropic fluid to the ordered phases [1]. The model used to analyze the data — and the accuracy of the parameters deduced — were tested by comparing the results obtained with two lipids having the same head group but different chain lengths.

Miscibility of cyanine dyes in two-dimensional aggregates

Mixed aggregates of cyanine dyes at a charged lipid monolayer surface are studied by absorption spectroscopy, fluorescence microscopy and electron diffraction. We show that slight variations of the molecular structure can convert a system from being fully miscible to being immiscible, and also that the concentrations of dyes in the solution and in the crystal may deviate considerably. The different concentration in the solution and crystal was observed for a molecule where force field calculations indicated the existence of two isomers in solution and where probably only one fits into the lattice.

Monolayers of Amphiphilic Molecules

There are good reasons why the organizers have placed this lecture at the beginning of a conference on the multip1e aspects of membranes. In many respects the monolayer may be considered half of a membrane and it obviously is the most simple and best-defined model system. Yet we will show that the system is more complex than many have anticipated. On the other hand, there are many general features which can be discussed without looking into chemical details.

Thin Liquid Films. Edited byI. B. Ivanov. Marcel Dekker Inc, New York 1988. 1160 pp., bound, US $ 295.—ISBN 0-8247-7763-8

Protein interactions with ordered lipid films: Specific and unspecific binding

Structural Characterization of Monolayers at the air-water interface

J-aggregates prepared by adsorption at monolayer/water interfaces

By adsorption of anionic cyanine dyes at positivly charged lipid monolayers large J-aggregates are formed. Absorption and fluorescence spectra are measured at the air/water interface during the crystallization process. The influence of the lipid/dye interaction on the aggregate structure is studied for two different systems. It is shown that the aggregate structure can be improved by growing crystals from a seed.

Pressure dependent arrangement of a protein in two-dimensional crystals specifically bound to a monolayer

Abstract The arrangement of streptavidin bound to a biotinylated monolayer of a polymeric amphiphile at the air-water interface is studied as a function of lateral pressure or ligand density. Closely packed domains are observed by fluorescence microscopy. The arrangement of the protein in these domains is sensitively detected by X-ray reflectivity and an especially thorough data analysis yields the following: the distance of the protein from the air-monolayer interface varies with lateral pressure by 10 A; the interfaces involving the protein are much rougher than expected due to capillary waves; the electron density of the protein layer increases considerably on compression, which can be u…

Fluorescence Microscopy Studies of Structure Formation in Surfactant Monolayers

Monolayers of water-insoluble surfactants (Langmuir monolayers) are important model system in basic research for studying the self-organization of organic molecules into two-dimensional layers [1, 2]. These floating films are also the basis for the build-up of complex multilayered structures on solid substrates, so-called Langmuir—Blodgett films (LB-films), which are of considerable interest in fundamental science and promise some future practical applications [3].

Comparative optical reflection and mass spectrometry analysis of thermodesorption of Langmuir-Blodgett films

Abstract Thermodesorption of cadmium arachidate multilayers is studied by optical surface analysis and by mass spectrometry measurements. The optical reflection technique has been improved to discriminate signal contributions from desorption and light scattering. The scattering arises from film heterogeneities that are also observed by Nomarsky microscopy. The assessment of these heterogeneities is important to understand mass spectrometry data. Both the optical technique and mass spectrometry are sensitive to observing the multilayer phase transition at 110 °C and the desorption near 200 °C (at the heating rate applied). The mass spectrometry analysis yields detailed information on the des…

Thermodesorption of LB-multilayers of metal stearates

Thermodesorption of stearate multilayers containing different metal ions was investigated by Interference-enhanced Reflection (IeR) and Nomarsky microscopy. Heating of samples in air leads to desorption of stearyl chains and to formation of metal oxide clusters. A new approach to build controlled structures was made by preparing a surface with neighbouring hydrophobic and hydrophilic areas. It is shown that arranging inorganic particles in a predetermined way is possible.

Thickness and temperature dependent structure of Cd arachidate Langmuir-Blodgett films

Abstract The structure of monolayers of Cd arachidate on water and on solid support, and the thickness dependent changes when building up a multilayer via the LB technique are studied by means of grazing incidence diffraction of X-ray. In monolayers the perpendicularly oriented amphiphilic molecules are arranged in a hexagonal lattice, whereas for thicker layers (even for three layers) they crystallize in an orthorhombic unit cell with a reduced molecular are ( A = 18.2 A 2 ) compared to that of the monolayer ( A = 19.7 A 2 ). In-plane diffraction measurements with wave vector transfer perpendicular to the surface (rod scans) could prove for multilayers a maximum tilt angle of 2°. The data …

Separation of Enantiomers in a Monolayer of Racemic 3-Hexadecyl-oxy-propane-1,2-diol

Monolayers of a racemic mixture and of the pure S enantiomer of 3-hexadecyloxy-propane-1,2-diol have been characterized by thermodynamic measurements at the air/water interface as well as by fluorescence microscopy. The critical temperatire T c , the limiting molecular area at high pressure and the pressure π c corresponding to the observed main phase transition, derived from the isotherms, slightly depend on chiral purity

Organized systems in eilat

X-ray scattering studies of fatty acid films on water and on Cdcl2 solutions

X-ray diffraction methods for Langmuir films on the surface of water are briefly presented, together with recent results for docosanoic acid monolayers on pure water and for eicosanoic acid monolayers on an ionic subphase.

Phospholipid and phospholipid-protein monolayers at the air/water interface.

Chemical modification of Topaz surfaces

In chemisorption, one is typically faced with the problem that the two-dimensional structure of the organic layer does not match the structure of the inorganic substrate. This work describes the first steps toward an induced epitaxial correlation of organic compounds on an inorganic surface. The idea of this work was to use a single crystal with a two-dimensional surface structure, Topaz (001), that matches an alkyl chain lattice better than existing substrates. X-ray reflectivity and FTIR experiments prove the surface modification of the Topaz, which is probably an etherification of the reactive OH-groups on the Topaz (001) surface.

Thermostability of polymeric langmuir-blodgett films

Monolayers of dipalmitoylphosphatidylcholine at the oil-water interface

Abstract Monolayers of dipalmitoylphosphatidylcholine at the interfaces waterbicylohexyl, waterdodecane and waterhexadecane were studied by fluorescence microscopy and thermodynamic measurements. The experiments show that the oil also partitions in the liquid condensed (LC) monolayer phase with concentration depending on the type of oil and the lateral pressure. In contrast to monolayers of dipalmitoylphosphatidylethanolamine the larger molecular area per head group enables oil partitioning in the LC phase even if there is a mismatch between the aliphatic tails of liquid and alkane.

Thin liquid films. Edited byI. B. Ivanov. Marcel Dekker Inc, New York 1988. 1160 pp., bound, US $ 295.- ISBN 0-8247-7763-8

Local control of antibody binding to hapten-presenting interfaces: Steric and electrostatic interaction

The binding of labeled antibodies to hapten substituted monolayers at the air/water interface has been studied by means of fluorescence microscopy. Haptens with various spacer lengths between the epitope and a hydrocarbon chain, anchoring the molecule to the interface, have been synthesized. With DMPC,a unspecific binding has been shown to predominate over specific binding due to electrostatic interactions. At high surface pressures the bound antibody is detached because of steric interference with the lipid head groups. Due to a reduction of electrostatic interactions, no unspecific binding is observed to monolayers of cholesterol, which carries a small dipole moment. Mixed monolayers of c…

X-Ray Scattering Studies of Organic Monolayers on Electrolytic Solutions: Arachidic Acid on CdCl2

The interaction between a charged monolayer of fatty acid molecules on the surface of a CdCl2 aqueous solution and the ions below has been investigated by means of X-ray Reflection and Grazing-Incidence Diffraction. A stoichiometric, localised layer of Cd++ ions forms an epitaxial 2×3 superstructure below the 2D-crystalline fatty acid monolayer.

Ultrathin metal films and inorganic clusters via thermodesorption of LB films

Langmuir-Blodgett multilayers of cadmium arachidate and ferric stearate were investigated during heating in order to derive information on processes involved in thermodesorption and on the inorganic microstructures left on the substrate after thermodesorption. We studied these processes by X-ray induced photoelectron spectroscopy (XPS), interference enhanced reflection (IeR), Nomarsky microscopy, electron microprobe analysis and in the case of Fe57-ions by conversion electron Mossbauer spectroscopy (CEMS). Two different mechanisms of desorption were observed. In the case of cadmium arachidate multilayers it is shown that before desorption the film ruptures laterally and then forms droplets.…

Tail and Head Group Interactions in Phospholipid Monolayers

Abstract The order/disorder transition of the phospholipid 1,2-dihexadecyl-sn-glycero-3-phosphocholine and its derivatives was studied by X-ray reflection and thermodynamic measurements. We find that increasing the length of an ethylene oxide spacer (zero to three EO groups) between the phosphate group and the hydrophobic chains (i) induces a slight shift of the main transition, (ii) reduces the influence of the head groups on the chain lattice, and (iii) increases the head group length and promotes its hydration. For DH(EO)3PC in the ordered phase we find that the small phosphate groups (which are the main source of contrast in X-ray reflectivity) are homogeneously distributed within the h…

Structure and optical properties of a monolayer single crystal of a cyanine dye

Abstract Molecularly thin single crystals of a cyanine dye prepared by adsorption at a charged surfactant monolayer are studied by polarized optical spectroscopy and electron diffraction. Both techniques independently show a herringbone arrangement of the dye with the long axes of translationally inequivalent molecules forming an angle of 80°. The dye arranges in a primitive rectangular unit cell (a=21.2 A, b=6.14 A) adjacent to an epitaxially related hexagonal cell of the aliphatic tails of the surfactant.

Polymorphic domains in monolayers of isomeric triple-chain phospholipids

Monolayers of two isomeric branched chain phosphatidyl cholines at the air/water interface have been studied by means of fluorescence microscopy. The lipids differ in the position of the branched chain at the glycerol backbone and carry three chains per headgroup of almost equal length. Most qualitative features of the compression isotherms are similar except a difference of 4 A2/molecule in the minimum molecular area at high lateral pressures. This indicates a more condensed solid phase of compound C2 and is also reflected in the shapes of domains observed in the LE/LC phase coexistence range: domains with sharp edges and a mostly hexagonal shape are formed. On the other hand, the compound…