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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.