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.
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.
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.
If not oriented perfectly isotropically, the strong dipole moment of polar organic semiconductor materials such as tris-(8-hydroxyquinolate)aluminum (Alq3) will lead to the buildup of a giant surface potential (GSP) and thus to a macroscopic dielectric polarization of the organic film. Despite this having been a known fact for years, the implications of such high potentials within an organic layer stack have only been studied recently. In this work, the influence of the GSP on hole injection into organic layers is investigated. Therefore, we apply a concept called dipolar doping to devices consisting of the prototypical organic materials N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) as nonpolar host and Alq3 as dipolar dopant with different mixing ratios to tune the GSP. The mixtures are investigated in single-layer monopolar devices as well as bilayer metal/insulator/semiconductor structures. Characterization is done electrically using current-voltage (I-V) characteristics, impedance spectroscopy, and charge extraction by linearly increasing voltage and time of flight, as well as with ultraviolet photoelectron spectroscopy. We find a maximum in device performance for moderate to low doping concentrations of the polar species in the host. The observed behavior can be described on the basis of the Schottky effect for image-force barrier lowering, if the changes in the interface dipole, the carrier mobility, and the GSP induced by dipolar doping are taken into account.
Biomaterials are used in regenerative medicine for induced autoregeneration and tissue engineering. This is often challenging, however, due to difficulties in tailoring and controlling the respective material properties. Since functionalization is expected to offer better control, in this study gelatin chains were modified with physically interacting groups based on tyrosine with the aim of causing the formation of physical crosslinks. This method permits application-specific properties like swelling and better tailoring of mechanical properties. The design of the crosslink strategy was supported by molecular dynamic (MD) simulations of amorphous bulk models for gelatin and functionalized gelatins at different water contents (0.8 and 25 wt.-%). The results permitted predictions to be formulated about the expected crosslink density and its influence on equilibrium swelling behavior and on elastic material properties. The models of pure gelatin were used to validate the strategy by comparison between simulated and experimental data such as density, backbone conformation angle distribution, and X-ray scattering spectra. A key result of the simulations was the prediction that increasing the number of aromatic functions attached to the gelatin chain leads to an increase in the number of physical netpoints observed in the simulated bulk packing models. By comparison with the Flory-Rehner model, this suggested reduced equilibrium swelling of the functionalized materials in water, a prediction that was subsequently confirmed by our experimental work. The reduction and control of the equilibrium degree of swelling in water is a key criterion for the applicability of functionalized gelatins when used, for example, as matrices for induced autoregeneration of tissues.
This open access book presents a topical, comprehensive and differentiated analysis of Germany’s public administration and reforms. It provides an overview on key elements of German public administration at the federal, Länder and local levels of government as well as on current reform activities of the public sector. It examines the key institutional features of German public administration; the changing relationships between public administration, society and the private sector; the administrative reforms at different levels of the federal system and numerous sectors; and new challenges and modernization approaches like digitalization, Open Government and Better Regulation. Each chapter offers a combination of descriptive information and problem-oriented analysis, presenting key topical issues in Germany which are relevant to an international readership.
Context. On March 4, 2013 the Fermi-EAT and AGILE reported a flare from the direction of the Crab nebula in which the high-energy (HE; E > 100 MeV) flux was six times above its quiescent level. Simultaneous observations in other energy bands give us hints about the emission processes during the flare episode and the physics of pulsar wind nebulae in general.
Aims. We search for variability in the emission of the Crab nebula at very-high energies (VHF,; E > 100 GeV), using contemporaneous data taken with the H.E.S.S. array of Cherenkov telescopes.
Methods. Observational data taken with the H.E.S.S. instrument on five consecutive days during the flare were analysed for the flux and spectral shape of the emission from the Crab nebula. Night-wise light curves are presented with energy thresholds of 1 TeV and 5 TeV.
Results. The observations conducted with H.E.S.S. on March 6 to March 10, 2013 show no significant changes in the flux. They limit the variation in the integral flux above 1 TeV to less than 63% and the integral flux above 5 TeV to less than 78% at a 95% confidence level.