Fine-Tuning of the film thickness of ultrathin multilayer films composed of consecutively alternating layers of anionic and cationic polyelectrolytes

We have recently introduced a new method of creating ultrathin films [1–3] based on the electrostatic attraction between opposite charges. Consecutively, alternating adsorption of anionic and cationic polyelectrolytes leads to the formation of multilayer assemblies. Multilayer buildup is easily monitored by small angle x-ray scattering (SAXS). The total thickness of the multilayer assemblies increases linearly with the number of adsorbed layers, indicating a stepwise and regular deposition process. — Here, we report on the fine-tuning of the total film thickness by changing the ionic strength of the solvent from which the polyelectrolytes are adsorbed. When the anionic polyelectrolyte is ad…

Proof of multilayer structural organization in self-assembled polycation-polyanion molecular films

Abstract Multilayer organization of ultrathin polycation-polyanion self-assembled films is demonstrated using two approaches. (1) Fabrication of polyion superlattices with alternation of three different polyelectrolytes in (ABCB) n fashion, which gives rise to a Bragg peak in X-ray reflectivity. The spacing d=93.4 A corresponds to the repeat unit (ABCB) n . (2) Drying-induced manipulation of the film surface at regular intervals. Normally the layer-by-layer adsorption is carried out by keeping the film wet throughout all deposition cycles. Alternatively the film surface can be manipulated by gently drying the film in a stream of nitrogen or air after the adsorption of every layer. When the …

Preparation and Thermal Behavior of Freely-Suspended and Transferred Films Composed of a Single Compound, the Liquid Crystal 707PP

We have recently introduced a new method for the preparation of ultrathin smectic films on solid supports by transferring freely-suspended liquid-crystalline films [1, 2]. Here we report on the preparation, structural properties and thermal behavior of freely-suspended and transferred films of 2-(4'-Heptyloxyphenyl)-5-heptylpyridine (707PP). Freely-suspended and transferred films were investigated using optical microscopy and X-ray diffraction. Both types of films exhibit reversible phase transitions comparable to bulk values.

An Introduction to Ultrathin Organic Films from Langmuir-Blodgett to Self-Assembly. VonA. Ulman. Academic Press, New York, 1991. XIII, 442 S., geb. $ 65.00. — ISBN 0-12-708230-1

The supramolecular self-organization of an amphotropic cholesterol derivative Micelles, liposomes and liquid-crystalline phases

Abstract The cholesterol derivative tetraethoxycholesteryl semisuccinate is both a mesogen and an amphiphile. This combination of both molecular prerequisites permits two types of supramolecular self-organization: the formation of a thermotropic liquid-crystalline phase and of various forms of aggregates in contact with water or other solvents. Depending on the pH of the aqueous medium the compound self organizes in micelles or liposomes. At high concentrations lyotropic liquid-crystalline phases are obtained. The formation of liposomes and lyotropic phases is not restricted to water as a solvent but can also be induced in pure organic media such as water-free diethyleneglycol. Due to the b…

New amphiphilic terphenyl liquid crystals for the preparation of highly ordered ultrathin films

Four new amphiphilic liquid crystals have been synthesized, in which terphenyl was used as the mesogenic unit. In order to enable the formation of Langmuir Monolayers at the air/water-interface, the molecules were equipped with slightly polar headgroups such as esters or a carboxylic acid group. All compounds can be transferred onto solid substrates. In addition, it is possible to prepare freely suspended films of at least one compound in the temperature range of the smectic phases. The phases of the different states, bulk, monolayer, freely suspended film, and Langmuir-Blodgett multilayers have been investigated by means of monolayer isotherms, optical textures, differential scanning calor…

Reversible swelling of polyanion/polycation multilayer films in solutions of different ionic strength

Immersion of consecutively adsorbed polyanion/polycation multilayer films in solutions of different ionic strength causes reversible thickness changes. Swelling of the films up to 18% was observed after soaking the films in aqueous solutions of NaCl at concentrations up to 1.0 mol/l. X-ray reflectivity clearly shows that the thickness changes are reversible within experimental error and that the films seem to get smoother after several cycles of immersion in salt solutions and in pure water. The extent of swelling depends on the internal film structure, namely on the number of polyanion/polycation interfaces in a film of a given thickness. Interestingly, the swelling levels off at salt conc…

Membranes and More. Membrane-Mimetic Approach to Advanced Materials. ByJ. H. Fendler, Advances in Polymeric Science, Vol. 113, Springer, Berlin 1994, X, 326 pp., hardcover, DM 168.00, ISBN 3-540-57237-6

Photo-crosslinking in freely-suspended films of ferroelectric lc-polymers

Optical Studies of Amphiphilic Molecules with Interesting Electro-Optical and Non-Linear Optical Properties

Structural control is a major issue in both life science, investigating the function of the biological machinery, and in materials science, aiming at the design of novel devices. In part one, recent electro-optical investigations of the primary event of photosynthesis on purified protein preparations are described. Part two focuses on structural studies of monolayers at an air/water interface, and of Langmuir-Blodgett multilayers from a new molecule designed for nonlinear optical applications.

Metal nanoparticle/polymer superlattice films: Fabrication and control of layer structure

Layer-by-layer deposited multilayer assemblies of polyelectrolytes and proteins: from ultrathin films to protein arrays

We have recently introduced a new method of creating ultrathin films of polyelectrolytes based on the electrostatic attraction between opposite charges. Multilayer assemblies are adsorbed in a layer-by-layer fashion from aqueous solutions of the polymers. The total film thickness can easily be adjusted by varying the ionic strength of the solution. Here, we report on the temperature stability and the water content of the multilayer assemblies. Furthermore, we have extended our concept to the incorporation of protein layers into films of synthetic polyelectrolytes. The well established system biotin/streptavidin was used to construct such multilayers, also by biospecific recognition. Adsorpt…

Book Review: An Introduction to Ultrathin Organic Films from Langmuir-Blodgett to Self-Assembly. By A. Ulman

Spectroscopic studies of the stability of monolayers of 2-docosylamino-5-nitropyridine at the air/water interface

Monolayers of 2-docosylamino-5-nitropyridine (DCANP) at the air/water interface were investigated by UV/Vis spectroscopy. The combination of this method with the classic constant-area relaxation technique yields insight into the longtime stability and the collapse behavior of monolayers. We have demonstrated that monolayers of DCANP are certainly stable under standard deposition conditions. At surface pressures above 20 mN/m monolayer instabilities lead to the formation of a three-dimensional head-to-head multilayered structure.

Characterization of Zirconium Phosphate/Polycation Thin Films Grown by Sequential Adsorption Reactions

Monolayer and multilayer thin films consisting of anionic α-zirconium phosphate (α-ZrP) sheets and polycations (poly(allylamine hydrochloride) (PAH), cytochrome c) were characterized by transmission electron microscopy (TEM), ellipsometry, UV−visible absorbance spectroscopy, reflectance FT-IR, XPS, and X-ray diffraction. Titration and powder X-ray diffraction experiments confirm that exfoliation of α-ZrP begins to occur when enough tetra(n-butylammonium) hydroxide (TBA+OH-) has been added to exceed single-layer packing of TBA+ ions (x ≈ 0.50) in the intercalation compound Zr(HPO4)2-x(TBA+PO4-)x·nH2O. The identical contrast of many sheets in TEM micrographs suggests that the suspension is un…

Giant liposomes as model membranes for immunological studies: spontaneous insertion of purified K1-antigen (poly-alpha-2,8-NeuAc) of Escherichia coli.

A flow chamber has been constructed to use giant liposomes (diameter 5-50 microns) as model membranes for immunological studies and other experiments involving the interaction with water-soluble compounds. As an example of immunological importance, the insertion of purified K-antigen from Escherichia coli K1 has been studied. Despite its large hydrophilic part (poly-alpha-2,8-NeuAc), which is capped at its potential reducing end with phosphatidic acid acting as a lipid anchor group, this water-soluble material is readily incorporated into liposomal membranes of dimyristoylphosphatidylcholine (DMPC). The incorporation has been proven by immunofluorescence using a FITC-labeled monoclonal anti…

Buildup of ultrathin multilayer films by a self-assembly process: III. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces

A solid substrate with a positively charged planar surface is immersed in a solution containing an anionic polyelectrolyte and a monolayer of the polyanion is adsorbed. Since the adsorption is carried out at relatively high concentrations of polyelectrolyte, a large number of ionic residues remain exposed to the interface with the solution and thus the surface charge is effectively reversed. After rinsing in pure water the substrate is immersed in the solution containing a cationic polyelectrolyte. Again a monolayer is adsorbed but now the original surface charge is restored. By repeating both steps in a cyclic fashion, alternating multilayer assemblies of both polymers are obtained. The bu…

Layer-by-Layer Adsorption: The Solid/Liquid-Interface as a Template for the Controlled Growth of Well-Defined Nanostructures of Polyelectrolytes, Proteins, DNA and Polynucleotides

This report describes the construction of ultrathin films whose structure can be tailored on the molecular scale. The resulting supramolecular film architectures may include functional biological macromolecules such as proteins or polynucleotides. The average distances of two functional layers can be adjusted on the nanometer scale (from less than lnm to several tens of nanometers), with a precision of approximately 0.1 nm. This control is achieved by varying the number and the thickness of the polyelectrolyte interlayers and requires the capability of steering each adsorption step with high accuracy. A crucial factor is the fabrication and manipulation of the film surface at each adsorptio…

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.

Layer-by-layer assembled protein/polymer hybrid films: nanoconstruction via specific recognition

Abstract In the present study it is shown that streptavidin-containing multilayer films with varying numbers of polyelectrolyte spacer layers can be fabricated reproducibly using optimized deposition conditions. Direct alternation of streptavidin and PLB leads to multilayer systems with an average streptavidin thickness of 5.3 nm which is in good agreement with the dimensions of the protein. When the streptavidin layers are spacered by more polyelectrolyte layers the distance between the protein sheets is increased up to e.g. 6.5 nm in the case of (PLB/PSS/PAH/PSS/PLB) as spacer layer. X-ray reflectivity reveals that streptavidin increases the surface roughness of the films probably due to …

Highly-ordered ultrathin lc multilayer films on solid substrates

Freely-Suspended and Transferred Freely-Suspended Films of Polymeric Liquid Crystals

Freely-suspended (FS) liquid-crystal (LC) films of a polymethylsiloxane homo- and a copolymer with different mesogenic side groups have been prepared and investigated. For both substances the preparation of the films succeeded only in the isotropic phase but the higher ordered phases were reached after cooling. The films of the homopolymer have only been obtained with thicknesses estimated to be in the pm-range and with an unusual “Book-Shelf” orientation of the smectic layers. In contrast, the films of the copolymer were thinner and showed a homeotropic orientation of the mesogens in the smectic A phase. Interestingly, this material exhibited a different layer spacing in film and bulk, alt…