Refine
Has Fulltext
- no (55)
Year of publication
Document Type
- Article (55) (remove)
Is part of the Bibliography
- yes (55)
New amphiphilic compounds 1-9 that feature a construction with dendronized hydrophilic and hydrophobic segment groups connected to a specific aromatic or aliphatic spacer unit have been synthesized, following a modular building block strategy. The hydrophilic dendrons are typically branched elements with peripheral carboxylic groups, unlike the hydrophobic dendrons that contain peripheral alkyl chains as part of respective amide functions. The hydrophilic dendrons are in different generations of branching, while the hydrophobic dendrons are all in the first generation of branching (three terminal branching), but differ in the length of the alkyl chains, thus giving rise to designed structure and amphiphilic properties in the new compounds. The resulting surfactants are capable of forming well-defined Langmuir films of remarkable stability when spread from a solution onto an aqueous subphase. Nevertheless, specific packing behaviour and orientation of the amphiphilic molecules were found, depending on the molecular structure, as determined using analysis of the surface pressure-area (pi-A) isotherms. Langmuir-Blodgett transfer of the first monolayer from a pure water subphase to a clean silicon wafer proved possible for the amphiphiles of peripheral alkyl chain length C-12, while the amphiphiles with the longer alkyl chains failed, possibly due to the more rigid monolayers they form, impeding the transfer.
The influence of the subphase temperature on the stripe pattern formation during Langmuir-Blodgett transfer (LB patterning) is investigated in a combined experimental and theoretical study. According to our experiments on the LB transfer of dipalmitoylphosphatidylcholine (DPPC) on planar mica substrates, even small temperature changes between 21.5 and 24.5 degrees C lead to significant changes in the monolayer patterns. For a constant surface pressure and dipper speed, the width of the stripes and the overall spatial period of the patterns increase with increasing subphase temperature. Because the stripe patterns are ascribed to alternating monolayer domains in the liquid-expanded and the liquid-condensed phases, the working regime for the formation of stripes is found to depend strongly on the respective surface pressure-area isotherm. These experimental findings are in accordance with the results of a theoretical investigation based on a model that takes hydrodynamics and the monolayer thermodynamics into account.
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.
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.
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.
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.