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The possibilities and limits of structure refinement of Langmuir-Blodgett films by means of symmetrical reflection of X- rays are described using the example of a stearic acid multilayer. Three different techniques for the determiantion of the electron density profile from reflectivity data are compared; a Fourier method, a Patterson method, and model calculations. The important role of the a priori information for finding the besft structure model is outlined.
For bilayer stacks of non-centrosymmetrical molecules, formed by the Langmuir-Blodgett (LB) technique (Y deposition), 00l peaks for the bilayer period are usually observed in the X-ray specular reflectivity curve, in this study, we show that the introduction of stacking disorder at lower transfer ratios and the subsequent partial repair of defects by a parallel shift of oppositely oriented molecules into the vacancies may result in the formation of antiphase domains and in an increase in the average monolayer symmetry followed by quenching of the bilayer peaks. The X-ray reflectivity data, obtained for multilayers of penta-alkynes, are used to demonstrate this real structural effect, which is expected to be of general importance for X-ray and neutron reflectivity data reduction and for the structural modelling of multilayers.
The structure of mono- and multilayers of amphiphilic disc-shaped pentaynes wa inbestigated by Brewsterangle microscopy, X-ray specular reflection and grazing incidence diffraction (GID). X-ray specular reflection experiments confirm the "edge on" arrangement of the molecular discs. The molecular modelling of the Langmuir-Blodgett (LB)- multilayers predicts a columnar in-plane packing of the molecules. A GID experiment with monochromatic synchrotron radiation was used to verify the predicted multilayer structure on molecular level, while the Brewsterangle microscopy gave a deeper insight in the monolayer in-plane structure on micron scale.
Changes of the molecular arrangenemt that can be induced by means of the LB technique in the multilayers of a disc-shaped multialkynyl amphiphile are monitored by means of small angle X-ray diffraction. Studies of the monolayers at the air-water interface reveal "edge-on" orientation of the discs. Specific effects of the counter- ions (Na+, Cd²+, Pb²+, and Ba²+) and sub-solution pH on the monolayer collapse pressure, transfer efficiency and molecular order in the multilayers are found. A correlation between the monolayer properties and the ability for formation of periodic discotic structures in the presence of divalent counterions is established. The discotic molecules retain their "edge-on" arrangement in the highly compressed transferred films with slight irregular interdigtation of the flexible wings and inclination to the substrate normal. The tilt and the inter- digitation are reduced when the discotic monolayers are deposited in alternating LB films with barium arachidate spacer layers.
Langmuir monolayer degradation (LMD) experiments with polymers possessing outstanding biomedical application potential yield information regarding the kinetics of their hydrolytic or enzymatic chain scission under well-defined and adjustable degradation conditions. A brief review is given of LMD investigations, including the author's own work on 2-dimensional (2D) polymer systems, providing chain scission data, which are not disturbed by simultaneously occurring transport phenomena, such as water penetration into the sample or transport of scission fragments out of the sample.
A knowledge-based approach for the description and simulation of polymer hydrolytic and enzymatic degradation based on a combination of fast LMD experiments and computer simulation of the water penetration is briefly introduced. Finally, the advantages and disadvantages of this approach are discussed.
Langmuir-Blodgett(LB) multilayers were prepared from disc-shaped multiyne mesogens based on amphiphilic alkyl pentakis(aryl-ethynyl)benzene ethers. The two compounds used are characterized by five hydrophobic flexible chains and one hydrophilic substituent at the terminal position of the alkoxy chain. The LB films were analysed by X-ray scattering and spectroscopic measurements. An edge-on arrangement of the two discotic pentaalkynes within Y-type bilayers with a different packing density proved to be possible for the LB films of both compounds.
Einfluss des Transferverhältnisses auf die Monoschichtsymmetrie in Y-Typ Langmuir-Blodgett-Schichten
(1995)
Grazing incidence x-ray diffraction (GIXD) measurements of uranyl arachidate (UO2A2) LB films
(1998)
Investigation of molecular diffusion across organic multilayers using neutron specular reflectivity
(1999)
Amphiphilic disc-shaped penta-alkynes were studied with regard to their molecular organization in Langmuir-Blod- gett (LB) mono- and multilayers. It was found that each compound investigated forms edge-on arranged stable monolayers at the air-water interface. LB-multilayers derived from fivefold pentyl-substituted pentaynes are characterized by an edge-on ordering of the molecules within Y-type bilayers. One of these compounds, containing a hydoxy substituent as hydrophilic head group, is exemplified and two possible rectangular molecular assemblies perpendicular to the substrate, each with a columnar in-plane packing, will be discussed as a result of molecular modelling. Based on the experimental results, hexagonal layer packing in the LB-film of a disc-shaped penta-alkynyl carboxylic acid without lateral substituents proved to be possible, which, furthermore, could be confirmed by molecular mechanics simulation.
Langmuir monolayers of arachidic acid have been prepared on a subphase containing uranyl ions (O-U-O)ý+. The interaction between the uranyl ions and the monolayer of arachidic acid has been studied by means of surface pressure and surface potential isotherms and Brewster angle microscopy at different pH values (ranging from 1.5 to 8). A similar systematic study has been carried out in the presence of Cdý+ ions for comparison purposes. The surface pressure and surface potential isotherms demonstrate that the acid to salt conversion of arachidic acid in the presence of uranyl ions occurs at lower bulk pH values (pH=3.5) as compared with other bivalent metal counterions such as Cdý+. Changes in the surface morphology of the monolayer induced by the interaction with uranyl- and cadmium ions are analyzed and the correlation between the surface potential change and the morphology of the films is discussed.
In this second paper we describe the comprehensive structure investigations on multilayers of uranyl arachidate formed by Langmuir-Blodgett deposition from subphases of different pH on solid substrates by means of a combination of infrared spectroscopy, X-ray specular reflection, ellipsometry, and scanning force microscopy, The structure of these multilayers and their stability are obviously influenced by the subphase pH. The pH range of the acid to salt conversion determined for the Langmuir films is confirmed by the infrared spectroscopic data of the multilayers. While arachidic acid films, deposited from an uranyl acetate subphase of low pH, are found to have strongly distorted rough surface, the films of uranyl structure, The influence of the counterions on the alkyl chain conformation, chain packing, reorganization probability, and stability of the multilayer is discussed.
The molecular in-plane structure of uranyl arachidate Langmuir-Blodgett (LB) films formed at different subphase pH values was analysed by means of X-ray grazing-incidence diffraction. For multilayers formed at low subphase pH a reorganisation of the arachidic acid film structure is confirmed. At appropriate subphase pH values, reorganisation of the film structure, e.g. via the formation of three-dimensional crystallites, is prevented by the presence of the uranyl ions and by the subsequent introduction of conformational disorder (gauche defects) in the alkyl chains. The observation of a macroscopic flow-induced in-plane texture in these uranyl arachidate LB films has profound implications for the design of ordered, supramolecular structures by the Langmuir-Blodgett technique.
We have formed Y layers of perfluorododecanoic acid CF3(CF2)10COOH by thermal evaporation in vacuo and of perfluorotetradecanoic acid CF3(CF2)12COOH by thermal evaporation and by the Langmuir-Blodgett (LB) technique. We have obtained the bilayer spacing of both these materials by X-ray diffraction and have also studied the in-plane structure of these materials by means of grazing incidence diffraction (GID). Computer modelling was used to interpret the results obtained. For the perfluorododecanoic acid, we find two stable untwisted phases at 25°C and a combination of these two predicts both the Bragg peaks arising from the layer structure and the GID results. Our experimental results show that the perfluorotetradecanoic acid exists in the generally accepted helical structure. Computer modelling leads to the conclusion that closely packed perfluorinated chains with 12 or less carbon atoms should exist in an untwisted state while molecules having more than 12 carbon atoms show the onset of the helical conformation.
The surfaces of ordered films formed from an amphiphilic derivative of 2,5-diphenyl-1,3,4-oxadiazole by the Langmuir-Blodgett (LB) technique and organic molecular beam deposition (OMBD) were investigated by the use of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. For the assignment of the spectral features of the C, N, and O K- edge absorption spectra, fingerprint spectra of poly(p-phenylene terephthalamide)(Kevlar), poly(ethylene terephthalate), poly(p-phenylene-1,3,4-oxadiazole), and 2,5-di- (pentadecyl)-1,3,4-oxadiazole, which contain related chemical moieties, were recorded. Ab initio molecular orbital calculations, performed with explicit treatment of the core hole, are used to support the spectral interpretations. Angle-resolved NEXAFS spectroscopy at the C, N, and O K-edges suggests a preferentially upright orientation of the oxadiazole derivative in the outermost layer of the films. X-ray specular reflectivity data and molecular modeling results suggest a similar interpretation.
Amphiphilic discotic pentakis (arylethynyl) benzene compounds 1 and 2 containing an enlarged aromatic core functioning as a chromophoric p-electron system were studied with regard to their photophysical properties within Langmuir-Blodgett (LB) films. The results obtained from steady-state absorption as well as fluorescence excitation and emission measurements will be discussed with regard to interchromophoric interactions in the LB films. Time-resolved fluorescence inves6igations revealed the formation of a ground-state complex as well as excimer formation. Thermal treatment causes irreversible destruction of the LB film structure of the discotic amphiphiles. Within droplets the reorganization of the original nematic-discotic (ND) mesophase of the bulk materials was found for the alcohol 2 as indicated by a Maltese Cross texture, whereas the acid 1 remained isotopic.
Polypropylene membranes with deposited ultrathin "siin" layers are attractive for separation and cleaning of gaseous mixtures. In the present study, the surface morphology and wetting hysteresis of composite membranes consisting of a microporous polypropylene support and Langmuir-Blodgett ("skin") films, are investigated. The effect of the interlayer molecular interactions and the substrate features on the integrity and homogeneity of the "skin" layers is examined. Langmuir-Blodgett films of arachidic acid and cadmium and calcium arachidate are characterized both on smooth silicon and on porous polypropylene supports. Contact angle measurements and scanning force microscopy (SFM) are applied for investigations of the membrane surface modification upon transfer of a different number of monolayers. It was found that the contact angle hysteresis of the bare membrane decreases after the LB-deposition of close-packed monolayers. Smoothing of the membrane surface is also evidenced by the SFM images, on different length scales, confirming a good coverage of the membrane pores.
Langmuir-Blodgett films of zinc 11,18,25-tri(tert-butyl)-4-sulfo-phthalocyanine (ZNPctSO3Na) have been deposited onto hydrophilic and hydrophobic silicon wafers. Y-type films were formed on both types of substrate, and the transfer ratio was very close to unity. The organization of the films on the molecular level was probed by X-ray specular reflectivity.
The complexation of highly ordered fatty acid monolayers with polyelectrolytes is expected to yield well- ordered Langmuir films suitable for the formation of Langmuir-Blodgett multilayers with improved long-term stability. Studies of the surface pressure-area isotherms and of the surface potential kinetics yield detailed information regarding the influence of these polymeric counterions on the monolayer properties. The injection of bivalent metal salts into the subphase after the complexation was used to improve the order and stability of the mono- and multilayers. The corresponding Langmuir-Blodgett films were investigated by means of X-ray reflectivity measurements and scanning force microscopy. The polyion complex multilayers show a strongly increased mechanical stability compared with films of fatty acid salts formed with bivalent metal ions. These structures are expected to be suitable as ultrathin separation layer for gas separation or ultrafiltration membranes.
Langmuir-Blodgett films of bolaamphiphiles with reactive head groups can be used for the surface modification of composite membranes for gas separation processes. The scope of our investigations was to get a detailed insight in the monolayer behaviour and LB film structure of previously synthesized bisaroyl azide bolaamphiphiles. The layers have been analyses by means of surface potential measurements and Brewster angle microscopy. Furthermore parameters for a successful LB Film deposition were found. As expected for a molecule with two hydrophilic ends the transfer ratio on upstroke was close to one and on downstroke no transfer occurred. The multilayer structure was analysed by scanning force microscopy and X-ray reflectivity measurements. The SFM images revealed a periodic in plane structure on molecular level. Based on a combination of the X-ray data with results of other methods two possible models of the multilayer structure are presented
Langmuir floating layers of two phthalocyanine derivatives, ytterbium bisphthalocyanine and tetra-tert-butyl nickel phthalocyanine, were investigated by means of compression isotherms, surface potential kinetics and Brewster angle microscopy (BAM) in order to study the influence of peripheral substituents on the structure and stability of these films and on their suitability for a subsequent transfer onto solid substrates. Specific substitutions that may lead to amphiphilic molecular units seem to play a key role in the development of well organised thin films prepared with this technique.
The thermal treatment of Y-type Langmuir-Blodgett (LB) films formed from the amphiphilic derivative of 2,5- diphenyl-1,3,4-oxadiazole 1 results in changes of the molecular packing. These changes have been analysed by a combination of X-ray specular reflectivity data, X-ray grazing incidence diffraction data and scanning force microscopy images, On the basis of these experimental data we have simulated possible supramolecular structures, These simulations provide insight into the intermolecular interactions giving rise to the observed structural transitions. The crystalline structure induced by thermal treatment of the LB films is characterized by a uniaxial texture, which is correlated with the dipping direction during deposition of the LB film.
Study of gas transport through composite membranes with a stabilised Langmuir-Blodgett skin layer
(1995)
The Langmuir-Blodgett (LB-) technique is used to deposit molecular reinforced separation layers on porous polymer substrates resulting in composite membranes for gas separation. The adsorption of a polycation to the arachidic acid Langmuir layer and the subsequent transfer of the highly ordered and stabilised monolayer onto a polypropylene membrane (Cellgard 2400) yields a laminated separation layer combining the advantageous high degree of order of fatty acid films and the stability of thin polymeric films. X-ray reflectivity data of these films confirm the transfer of the assembled polymer layer together with the fatty acid monolayer and the formation of ordered Y-type LB-films. SFM pictures show a dense film without pinholes completely covering the porous support. Gas permeation measurements are used to study the transport process of different gases through the composite membrane.
This paper describes the formation and structure investigation of Langmuir monolayers and Langmuir-Blodgett multilayers formed from amphiphilic derivatives of 2,5-diphenyl-1,3,4-oxadiazole. The 2,5-diphenyl-1,3,4-oxadiazole group as a functional unit with interesting physical and chemical properties is maintained, while the head group, the length of the alkyl chain and the structure of the coupling unit between aromatic and aliphatic part of these linear short-chain amphiphiles is systematically varied in order to explore the influence of this change on the film forming properties and the stability of Langmuir and Langmuir-Blodgett films. Molecular mechanics simulations are shown by these systematic variations to be suitable for the prediction of optimal chemical structures allowing for a stable stratified molecular packing. The combination of a detailed structure investigation of the multilayers based on scanning force microscopy and X-ray data with molecular mechanics simulations yields an insight into the packing of the molecules and the intermolecular interactions.