Hyperverzweigte Lacton-Copolymere: enzymatische Synthese, Charakterisierung und Darstellung strukturierter Polymernetzwerke = (Hyperbranched lactone copolymers by enzyme catalysis: synthesis, characterization and preparation of structured polymer networks)

Hyperverzweigte Polymere erfuhren in den letzten Jahren immer mehr Beachtung, da sie im Vergleich zu ihren linearen Analoga besondere Eigenschaften besitzen. Im Jahre 2002 wurde die erste enzymkatalysierte Darstellung hyperverzweigter Poly(epsilon-caprolacton)e (hb-PCL) beschrieben. Hier ermöglichte das Konzept der konkurrierenden ringöffnenden Polymerisation und Polykondensation die Kontrolle der Eigenschaften des dargestellten Polymers. Detaillierte Untersuchungen in Hinblick auf Grenzen und Möglichkeiten, aber auch die Synthese im Technikumsmaßstab sind wesentliche Aspekte dieser Arbeit. Außerdem wird ein neues Konzept eingeführt, das Reknitting genannt wurde. Ziel desselben ist das Recycling kommerziellen, linearen PCLs mittels Umesterung zu hb-PCL durch Enzymkatalyse. Diese hb-PCLs zeigen vergleichbare Eigenschaften zu den aus den Comonomeren dargestellten. Ausgehend von hb-PCL sollte eine geeignete Route zu methacrylierten Vernetzerverbindungen entwickelt werden. Aus Mischungen derselben mit 2-Hydroxyethylmethacrylat wurden komplexe Netzwerkarchitekturen durch Copolymerisation erhalten. Diese Netzwerke wurden in Hinblick auf ihre mechanisch physikalischen Eigenschaften untersucht. Zuletzt wurden Screeningexperimente an anderen zyklischen Estern durchgeführt, da ein Transfer des oben vorgestellten Konzepts angestrebt wurde. Zwei neue hyperverzweigte Polymerklassen, hb-Poly(delta-valerolacton) und hb-Polytrimethylencarbonat wurden detaillierter untersucht und in Ihren Eigenschaften mit hb-PCL verglichen.

Nanomechanical and phononic properties of structured soft materials

Significant interest in nanotechnology, is stimulated by the fact that materials exhibit qualitative changes of properties when their dimensions approach ”finite-sizes”. Quantization of electronic, optical and acoustic energies at the nanoscale provides novel functions, with interests spanning from electronics and photonics to biology. The present dissertation involves the application of Brillouin light scattering (BLS) to quantify and utilize material displacementsrnfor probing phononics and elastic properties of structured systems with dimensions comparable to the wavelength of visible light. The interplay of wave propagation with materials exhibiting spatial inhomogeneities at sub-micron length scales provides information not only about elastic properties but also about structural organization at those length scales. In addition the vector nature of q allows, for addressing the directional dependence of thermomechanical properties. To meet this goal, one-dimensional confined nanostructures and a biological system possessing high hierarchical organization were investigated. These applications extend the capabilities of BLS from a characterization tool for thin films to a method for unravelingrnintriguing phononic properties in more complex systems.

Parametric editors for structured documents

Lo scopo di questa dissertazione è di identificare le tecnologie più appropriate per la creazione di editor parametrici per documenti strutturati e di descrivere LIME, un editor di markup parametrico e indipendente dal linguaggio. La recente evoluzione delle tecnologie XML ha portato ad un utilizzo sempre più consistente di documenti strutturati. Oggigiorno, questi vengono utilizzati sia per scopi tipografici sia per l’interscambio di dati nella rete internet. Per questa ragione, sempre più persone hanno a che fare con documenti XML nel lavoro quotidiano. Alcuni dialetti XML, tuttavia, non sono semplici da comprendere e da utilizzare e, per questo motivo, si rendono necessari editor XML che possano guidare gli autori di documenti XML durante tutto il processo di markup. In alcuni contesti, specialmente in quello dell’informatica giuridica, sono stati introdotti i markup editor, software WYSIWYG che assistono l’utente nella creazione di documenti corretti. Questi editor possono essere utilizzati anche da persone che non conoscono a fondo XML ma, d’altra parte, sono solitamente basati su uno specifico linguaggio XML. Questo significa che sono necessarie molte risorse, in termini di programmazione, per poterli adattare ad altri linguaggi XML o ad altri contesti. Basando l’architettura degli editor di markup su parametri, è possibile progettare e sviluppare software che non dipendono da uno specifico linguaggio XML e che possono essere personalizzati al fine di utilizzarli in svariati contesti.

Structured antibody surfaces for bio-recognition and a label-free detection of bacteria

Antibody microarrays are of great research interest because of their potential application as biosensors for high-throughput protein and pathogen screening technologies. In this active area, there is still a need for novel structures and assemblies providing insight in binding interactions such as spherical and annulus-shaped protein structures, e.g. for the utilization of curved surfaces for the enhanced protein-protein interactions and detection of antigens. Therefore, the goal of the presented work was to establish a new technique for the label-free detection of bio-molecules and bacteria on topographically structured surfaces, suitable for antibody binding.rnIn the first part of the presented thesis, the fabrication of monolayers of inverse opals with 10 μm diameter and the immobilization of antibodies on their interior surface is described. For this purpose, several established methods for the linking of antibodies to glass, including Schiff bases, EDC/S-NHS chemistry and the biotin-streptavidin affinity system, were tested. The employed methods included immunofluorescence and image analysis by phase contrast microscopy. It could be shown that these methods were not successful in terms of antibody immobilization and adjacent bacteria binding. Hence, a method based on the application of an active-ester-silane was introduced. It showed promising results but also the need for further analysis. Especially the search for alternative antibodies addressing other antigens on the exterior of bacteria will be sought-after in the future.rnAs a consequence of the ability to control antibody-functionalized surfaces, a new technique employing colloidal templating to yield large scale (~cm2) 2D arrays of antibodies against E. coli K12, eGFP and human integrin αvβ3 on a versatile useful glass surface is presented. The antibodies were swept to reside around the templating microspheres during solution drying, and physisorbed on the glass. After removing the microspheres, the formation of annuli-shaped antibody structures was observed. The preserved antibody structure and functionality is shown by binding the specific antigens and secondary antibodies. The improved detection of specific bacteria from a crude solution compared to conventional “flat” antibody surfaces and the setting up of an integrin-binding platform for targeted recognition and surface interactions of eukaryotic cells is demonstrated. The structures were investigated by atomic force, confocal and fluorescence microscopy. Operational parameters like drying time, temperature, humidity and surfactants were optimized to obtain a stable antibody structure.

Essays in Media and Finance

This Ph.D. thesis consists in three research papers focused on the relationship between media industry and the financial sector. The importance of a correct understanding what is the effect of media on financial markets is becoming increasingly important as long as fully informed markets hypothesis has been challenged. Therefore, if financial markets do not have access to complete information, the importance of information professionals, the media, follows. On the other side, another challenge for economic and finance scholar is to understand how financial features are able to influence media and to condition information disclosure. The main aim of this Ph.D. dissertation is to contribute to a better comprehension for both the phenomena. The first paper analyzes the effects of owning equity shares in a newspaper- publishing firm. The main findings show how for a firm being part of the ownership structure of a media firm ends to receive more and better coverage. This confirms the view in which owning a media outlet is a source of conflicts of interest. The second paper focuses on the effect of media-delivered information on financial markets. In the framework of IPO in the U.S. market, we found empirical evidence of a significant effect of the media role in the IPO pricing. Specifically, increasing the quantity and the quality of the coverage increases the first-day returns (i.e. the underpricing). Finally the third paper tries to summarize what has been done in studying the relationship between media and financial industries, putting together contributes from economic, business, and financial scholars. The main finding of this dissertation is therefore to have underlined the importance and the effectiveness of the relationship between media industry and the financial sector, contributing to the stream of research that investigates about the media role and media effectiveness in the financial and business sectors.

Der vertragliche Nachrang von Forderungen : über Rechtsnatur und Rechtsfolgen der Forderungssubordination bei Nachrangdarlehen, Finanzplankredit, Mezzanine-Finance und Rangrücktritt

Die Arbeit behandelt den vertraglichen Nachrang von Forderungen. Sie beleuchtet unter Einbeziehung rechtsvergleichender Erkenntnisse zum us-amerikanischen und englischen Recht Inhalt und Reichweite der Rangvereinbarung und beschreibt die vertragliche Rangvereinbarung als einheitliches Institut einer schuldändernden Verfügung. Der Rangrücktritt zur Vermeidung der Überschuldung und die Rangvereinbarung im Rahmen von Mezzanine-Finanzierungen werden zueinander in Bezug gesetzt, die mit dem Rangrücktritt im Vertrags-, Gesellschafts- Insolvenz-, Bilanz- und Steuerrecht verbundenen Probleme werden erörtert.