0000000000181315
AUTHOR
Helmut Möhwald
X-ray diffraction of a protein crystal anchored at the air/water interface
We report the first successful in situ x-ray diffraction experiment with a 2D protein array at the lipid/water interface and demonstrate that the order can be controlled via lateral pressure or density. A protein (streptavidin) was bound to a monolayer of biotinylated lipid at the air/water interface, and diffraction of the protein layer could be measured to many orders. Compression of the monolayer changed the diffraction pattern drastically, indicating that the protein structure can be strongly influenced by external parameters like lateral pressure or density. From the width of the peaks, we find that aggregates consisting of as few as 100 monomers contribute to the diffraction. This ind…
Structure features and phase behaviour of amphiphilic N-tetradecyl-β-hydroxy-propionic acid amide monolayers
Abstract Two phase transitions of N-tetradecyl-β-hydroxy-propionic acid amide monolayers at the air/water interface were studied by means of pressure/surface area ( π A ) isotherms, Brewster angle microscopy (BAM) and synchrotron X-ray grazing-incidence diffraction (GID). At T≤15 °C the π A isotherms show two plateau regions indicating two first-order phase transitions. In the first main transition from the lowdensity fluid-like phase to a condensed phase, dendritic growth of condensed phase domains with six main growth directions was observed by BAM. A second transition from a condensed phase with large tilt angle to a condensed phase with smaller tilt angle and a denser arrangement of mol…
Condensed phases in monolayers of a triple-chain lecithin on water
Abstract A triple-chain phospholipid monolayer at the air-water interface is investigated by means of grazing incidence X-ray diffraction (GID). Analysis of the diffraction spot profiles parallel and perpendicular to the surface yields different ordered phases. On increasing the lateral pressure at different temperatures the hydrocarbon chains form tilted phases with a tilt toward the nearest neighbors and eventually a hexagonal lattice with vertical chain orientation.
Influence of a hydrophilic spacer on the structure of a phospholipid monolayer
We present the results of thermodynamical and X-ray grazing incidence diffraction experiments performed on Langmuir monolayers of ether lipids with hydrophilic spacers between the glycerol backbone and the phosphatidylcholine head group: DHPC, DH-E01-PC, and DH-E02-PC. As a spacer the oxy-ethylene group is used, which is a typical hydrophilic unit of non-ionic tensides. It turns out that the introduction of the hydrophilic spacers leads to a fluidization of the monolayer and reduces the tilt angle of the chains.
Cluster growth with long-range interactions
Abstract Growth models in which the morphology depends on interactions of the type V(r) = C r n are presented. The growth algorithms are generalizations of DLA. The particles diffuse on a triangular lattice and eventually either stick to the cluster or are lost. Several processes are simulated in this way: in one case only pure sticking is taken into account, in another case evaporation and rearrangement are also allowed to occur. In the former case (with attractive interactions) the clusters exhibit a highly symmetric shape (a sixfold star) whose detailed structure depends on n , C kT , and time. In the latter case (studied with repulsive dipolar interactions) the tendency to ramification …
Chirality effects on 2D phase transitions
Monolayers of the racemate and pure enantiomers of 1-hexadecyl-glycerol were investigated by grazing incidence X-ray diffraction (GID) at 5 and 20 °C on compression from 0 mN m−1 to pressures greater than 30 mN m−1. The racemate lattice is centred-rectangular for both temperatures at all investigated pressures. However, at both temperatures, there is a sharp phase transition from a low-pressure phase, in which the molecules are tilted towards nearest neighbours (NN) and the distortion azimuth also points towards NN, to a high-pressure phase, in which the molecules are tilted towards next-nearest neighbours (NNN) and an NNN-distorted lattice is observed. At 5 °C, the transition pressure is 1…
Nonlinear hairy layer theory of electrophoretic fingerprinting applied to consecutive layer by layer polyelectrolyte adsorption onto charged polystyrene latex particles
The consecutive layer-by-layer adsorption of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate) (PSS) on colloidal charged latex particles is investigated by measuring the electrophoretic mobility as a function of pH and ionic strength over a broad range (electrophoretic fingerprinting). Meaningful interpretation of the data required the development of a nonlinear approach to hairy particle electrophoresis including dissociation, adsorption, and association. Steric and electrostatic exclusion of mobile ions from the hairy layer has been considered. Also, the surface conductivity correction is extended to the case of charged hairy layer particles. We deposited up to three polyel…
Low temperature plasma treatment of monomolecular Langmuir-Blodgett films
Abstract The structure of the surface layer of materials is usually quite different from the bulk. Detailed information about the surface structure is often not available. This, together with the complex nature of low temperature plasma treatment, hinders the investigations of plasma chemical processes on solid surfaces. Monomolecular Langmuir-Blodgett (LB) structures offer a unique opportunity to prepare model surfaces with known thickness and molecular architecture. From the data obtained, the depth of the Ar plasma influence on solid organic surfaces was estimated to be about 400–1000 A depending on the nature of the surface layer. An oxygen plasma penetrates deeper with a penetration li…
Domain formation in monolayers
For phospholipids at the air/water interface we demonstrate that molecular chirality in some, but not in all, cases influences the domain shapes. In other cases chirality in the head group region can cause a chiral structure considering the tail arrangement. This indicates head group ordering. Minute changes of the molecular structure may change domain morphology from circular to dendritic. This can be related to slight changes of the lattice structure. In case of a dendritic domain the chains are more tilted, the deviation from hexagonal symmetry is more pronounced, and hence the lattice anisotropy is larger. This can be understood also in view of recent simulations considering diffusion-l…
Head-group variations and monolayer structures of diol derivatives
Monolayers of 5 chemically modified diols varying the headgroup (nonadecane-1,2-diol (C1), hexadecyl-propane-1,3-diol (C2), hexadecyl-oxy-propane-1,2-diol (C3), hexadecyl-oxy-butane-1,2-diol (C4), hexadecanoyl-oxy-propane-1,2-diol (C5)) have been investigated by grazing incidence x-ray diffraction at 20°C and at different lateral pressures. C1 and C5 exhibit a centred-rectangular lattice with NN (nearest neighbour) tilt and NN distortion directions. In the case of C1 on increasing the lateral pressure the distortion changes to NNN (next-nearest neighbour direction) without a change in tilt direction (NN). This behaviour could not be observed for the other compounds. C3 and C4 display a phas…
Surface properties of valine-gramicidin A at the air-water interface
Abstract Fluorescence microscopy, X-ray reflectivity and ellipsometry have been applied to the study of a monolayer of valine-gramicidin A (VGA) at the air-water interface to obtain insight into the conformation and orientation of VGA, and to clarify the shoulder observed in its π - A curve (12.5–16 mN m −1 , 240 – 175 A 2 molecule −1 ). At low molecular areas, the X-ray reflectivities are consistent with formation of a single layer of tubular-shaped dimers. Fluorescence microscopy yielded homogeneous pictures suggesting that on the macroscopic scale the shoulder cannot be attributed to domain formation. Thicknesses calculated from the ellipsometric isotherm are consistent with the X-ray da…
Brewster angle microscopy and X-ray GID studies of morphology and crystal structure in monolayers of N-tetradecyl-γ,δ-dihydroxypentanoic acid amide
First-order phase transitions from the low-density fluidlike phase to the condensed phase of monolayers of N-tetradecyl-γ,δ-dihydroxypentanoic acid amides at the air−water interface have been studied by π−A isotherms, Brewster angle microscopy (BAM), and synchrotron X-ray grazing incidence diffraction (GID). The thermodynamic differences between enantiomeric and racemic monolayers are too small to be measured. However, chiral discrimination is observable in the macroscopic domain morphology by BAM. The domains of the condensed phase grow dendritically. The characteristic shapes of domains of the pure S and R enantiomers are mirror images of each other. The domains of the racemic mixture are…