Numerical analysis of control surface effects on AUV

Computational fluid dynamics, CFD, is becoming an essential tool in the prediction of the hydrodynamic efforts and flow characteristics of underwater vehicles for manoeuvring studies. However, when applied to the manoeuvrability of autonomous underwater vehicles, AUVs, most studies have focused on the de- termination of static coefficients without considering the effects of the vehicle control surface deflection. This paper analyses the hydrodynamic efforts generated on an AUV considering the combined effects of the control surface deflection and the angle of attack using CFD software based on the Reynolds-averaged Navier–Stokes formulations. The CFD simulations are also independently conducted for the AUV bare hull and control surface to better identify their individual and interference efforts and to validate the simulations by comparing the experimental results obtained in a towing tank. Several simulations of the bare hull case were conducted to select the k –ω SST turbulent model with the viscosity approach that best predicts its hydrodynamic efforts. Mesh sensitivity analyses were conducted for all simulations. For the flow around the control surfaces, the CFD results were analysed according to two different methodologies, standard and nonlinear. The nonlinear regression methodology provides better results than the standard methodology does for predicting the stall at the control surface. The flow simulations have shown that the occurrence of the control surface stall depends on a linear relationship between the angle of attack and the control surface deflection. This type of information can be used in designing the vehicle’s autopilot system.

Constraint handling rules. Compositional semantics and program transformation

This thesis intends to investigate two aspects of Constraint Handling Rules (CHR). It proposes a compositional semantics and a technique for program transformation. CHR is a concurrent committed-choice constraint logic programming language consisting of guarded rules, which transform multi-sets of atomic formulas (constraints) into simpler ones until exhaustion [Frü06] and it belongs to the declarative languages family. It was initially designed for writing constraint solvers but it has recently also proven to be a general purpose language, being as it is Turing equivalent [SSD05a]. Compositionality is the first CHR aspect to be considered. A trace based compositional semantics for CHR was previously defined in [DGM05]. The reference operational semantics for such a compositional model was the original operational semantics for CHR which, due to the propagation rule, admits trivial non-termination. In this thesis we extend the work of [DGM05] by introducing a more refined trace based compositional semantics which also includes the history. The use of history is a well-known technique in CHR which permits us to trace the application of propagation rules and consequently it permits trivial non-termination avoidance [Abd97, DSGdlBH04]. Naturally, the reference operational semantics, of our new compositional one, uses history to avoid trivial non-termination too. Program transformation is the second CHR aspect to be considered, with particular regard to the unfolding technique. Said technique is an appealing approach which allows us to optimize a given program and in more detail to improve run-time efficiency or spaceconsumption. Essentially it consists of a sequence of syntactic program manipulations which preserve a kind of semantic equivalence called qualified answer [Frü98], between the original program and the transformed ones. The unfolding technique is one of the basic operations which is used by most program transformation systems. It consists in the replacement of a procedure-call by its definition. In CHR every conjunction of constraints can be considered as a procedure-call, every CHR rule can be considered as a procedure and the body of said rule represents the definition of the call. While there is a large body of literature on transformation and unfolding of sequential programs, very few papers have addressed this issue for concurrent languages. We define an unfolding rule, show its correctness and discuss some conditions in which it can be used to delete an unfolded rule while preserving the meaning of the original program. Finally, confluence and termination maintenance between the original and transformed programs are shown. This thesis is organized in the following manner. Chapter 1 gives some general notion about CHR. Section 1.1 outlines the history of programming languages with particular attention to CHR and related languages. Then, Section 1.2 introduces CHR using examples. Section 1.3 gives some preliminaries which will be used during the thesis. Subsequentely, Section 1.4 introduces the syntax and the operational and declarative semantics for the first CHR language proposed. Finally, the methodologies to solve the problem of trivial non-termination related to propagation rules are discussed in Section 1.5. Chapter 2 introduces a compositional semantics for CHR where the propagation rules are considered. In particular, Section 2.1 contains the definition of the semantics. Hence, Section 2.2 presents the compositionality results. Afterwards Section 2.3 expounds upon the correctness results. Chapter 3 presents a particular program transformation known as unfolding. This transformation needs a particular syntax called annotated which is introduced in Section 3.1 and its related modified operational semantics !0t is presented in Section 3.2. Subsequently, Section 3.3 defines the unfolding rule and prove its correctness. Then, in Section 3.4 the problems related to the replacement of a rule by its unfolded version are discussed and this in turn gives a correctness condition which holds for a specific class of rules. Section 3.5 proves that confluence and termination are preserved by the program modifications introduced. Finally, Chapter 4 concludes by discussing related works and directions for future work.

Expressiveness in biologically inspired languages

A very recent and exciting new area of research is the application of Concurrency Theory tools to formalize and analyze biological systems and one of the most promising approach comes from the process algebras (process calculi). A process calculus is a formal language that allows to describe concurrent systems and comes with well-established techniques for quantitative and qualitative analysis. Biological systems can be regarded as concurrent systems and therefore modeled by means of process calculi. In this thesis we focus on the process calculi approach to the modeling of biological systems and investigate, mostly from a theoretical point of view, several promising bio-inspired formalisms: Brane Calculi and k-calculus family. We provide several expressiveness results mostly by means of comparisons between calculi. We provide a lower bound to the computational power of the non Turing complete MDB Brane Calculi by showing an encoding of a simple P-System into MDB. We address the issue of local implementation within the k-calculus family: whether n-way rewrites can be simulated by binary interactions only. A solution introducing divergence is provided and we prove a deterministic solution preserving the termination property is not possible. We use the symmetric leader election problem to test synchronization capabilities within the k-calculus family. Several fragments of the original k-calculus are considered and we prove an impossibility result about encoding n-way synchronization into (n-1)-way synchronization. A similar impossibility result is obtained in a pure computer science context. We introduce CCSn, an extension of CCS with multiple input prefixes and show, using the dining philosophers problem, that there is no reasonable encoding of CCS(n+1) into CCSn.

Kinetische Untersuchungen zur Synthese von Blockcopolymeren mit Methacrylatsegmenten durch neue anionische Polymerisationssysteme

Ein metallfreies Reaktionssystem mit Bis(triphenylphosphoranyliden)ammonium-Kationen als Gegenionen sowie das Additiv Lithium-2-methoxyethoxid wurden auf ihre Eignung zur anionischen Synthese von Blockcopolymeren mit (Meth)acrylatsegmenten bei moderaten Temperaturen im Strömungsrohr-Reaktor untersucht. Das metallfreie System ist zur lebenden Polymerisation von Methacrylaten in THF mit engen Molekulargewichtsverteilungen bei Reaktionszeiten < 1 s bis zu Temperaturen von 0 °C geeignet. In Gegenwart von Metallionen (Li+) findet eine Verlangsamung der Polymerisation unter Verlust der Reaktionskontrolle statt, Lithiumenolate verursachen nun breite, multimodale Molekulargewichtsverteilungen. Eine lebende Polymerisation von Acrylaten ist nicht möglich, massenspektroskopische Untersuchungen der Produkte weisen auf einen komplexen Reaktionsmechanismus mit Abbruch- und Übertragungsreaktionen hin. Die Synthese von Poly(styrol)-block-Poly(1,4-butadien)-block-Poly(methylmethacrylat)-Copolymeren in Toluol ist mit Lithium-2-methoxyethoxid als Additiv für die MMA-Polymerisation bei moderaten Mischtemperaturen (T < 0 °C) im Strömungsrohr-Reaktor möglich, die Effektivität des Wechselschritts von Polybutadien zu PMMA beträgt im Durchschnitt ca. 50 %. Untersuchungen verschiedener Reaktionsparameter, wie z.B. der Endfunktionalisierung des Polybutadiens mit 1,1-Diphenylethylen und der Temperatur während der Verkappung und der MMA-Polymerisation, geben keine eindeutigen Hinweise auf die Ursache dieses Phänomens. MALDI-TOF-Massenspektren des unreagierten Polybutadien Precursors zeigen die Anlagerung von 1-3 Molekülen Methylmethacrylat und keinen Abbruch durch Backbiting, was auf die Ausbildung stabiler Aggregate hindeutet.

Geological and Structural evolution of the Eurasia Africa plate boundary in the Gulf of Cadiz Central Eastern Atlantic Sea.

Iberia Africa plate boundary, cross, roughly W-E, connecting the eastern Atlantic Ocean from Azores triple junction to the Continental margin of Morocco. Relative movement between the two plate change along the boundary, from transtensive near the Azores archipelago, through trascurrent movement in the middle at the Gloria Fracture Zone, to transpressive in the Gulf of Cadiz area. This study presents the results of geophysical and geological analysis on the plate boundary area offshore Gibraltar. The main topic is to clarify the geodynamic evolution of this area from Oligocene to Quaternary. Recent studies have shown that the new plate boundary is represented by a 600 km long set of aligned, dextral trascurrent faults (the SWIM lineaments) connecting the Gloria fault to the Riff orogene. The western termination of these lineaments crosscuts the Gibraltar accretionary prism and seems to reach the Moroccan continental shelf. In the past two years newly acquired bathymetric data collected in the Moroccan offshore permit to enlighten the present position of the eastern portion of the plate boundary, previously thought to be a diffuse plate boundary. The plate boundary evolution, from the onset of compression in the Oligocene to the Late Pliocene activation of trascurrent structures, is not yet well constrained. The review of available seismics lines, gravity and bathymetric data, together with the analysis of new acquired bathymetric and high resolution seismic data offshore Morocco, allows to understand how the deformation acted at lithospheric scale under the compressive regime. Lithospheric folding in the area is suggested, and a new conceptual model is proposed for the propagation of the deformation acting in the brittle crust during this process. Our results show that lithospheric folding, both in oceanic and thinned continental crust, produced large wavelength synclines bounded by short wavelength, top thrust, anticlines. Two of these anticlines are located in the Gulf of Cadiz, and are represented by the Gorringe Ridge and Coral Patch seamounts. Lithospheric folding probably interacted with the Monchique – Madeira hotspot during the 72 Ma to Recent, NNE – SSW transit. Plume related volcanism is for the first time described on top of the Coral Patch seamount, where nine volcanoes are found by means of bathymetric data. 40Ar-39Ar age of 31.4±1.98 Ma are measured from one rock sample of one of these volcanoes. Analysis on biogenic samples show how the Coral Patch act as a starved offshore seamount since the Chattian. We proposed that compression stress formed lithospheric scale structures playing as a reserved lane for the upwelling of mantle material during the hotspot transit. The interaction between lithospheric folding and the hotspot emplacement can be also responsible for the irregularly spacing, and anomalous alignments, of individual islands and seamounts belonging to the Monchique - Madeira hotspot.

InSAR deformation measurements of the earthquake cycle in transcurrent tectonic domains, analytical and analog modeling

I applied the SBAS-DInSAR method to the Mattinata Fault (MF) (Southern Italy) and to the Doruneh Fault System (DFS) (Central Iran). In the first case, I observed limited internal deformation and determined the right lateral kinematic pattern with a compressional pattern in the northern sector of the fault. Using the Okada model I inverted the observed velocities defining a right lateral strike slip solution for the MF. Even if it fits the data within the uncertainties, the modeled slip rate of 13-15 mm yr-1 seems too high with respect to the geological record. Concerning the Western termination of DFS, SAR data confirms the main left lateral transcurrent kinematics of this fault segment, but reveal a compressional component. My analytical model fits successfully the observed data and quantifies the slip in ~4 mm yr-1 and ~2.5 mm yr-1 of pure horizontal and vertical displacement respectively. The horizontal velocity is compatible with geological record. I applied classic SAR interferometry to the October–December 2008 Balochistan (Central Pakistan) seismic swarm; I discerned the different contributions of the three Mw > 5.7 earthquakes determining fault positions, lengths, widths, depths and slip distributions, constraining the other source parameters using different Global CMT solutions. A well constrained solution has been obtained for the 09/12/2008 aftershock, whereas I tested two possible fault solutions for the 28-29/10/08 mainshocks. It is not possible to favor one of the solutions without independent constraints derived from geological data. Finally I approached the study of the earthquake-cycle in transcurrent tectonic domains using analog modeling, with alimentary gelatins like crust analog material. I successfully joined the study of finite deformation with the earthquake cycle study and sudden dislocation. A lot of seismic cycles were reproduced in which a characteristic earthquake is recognizable in terms of displacement, coseismic velocity and recurrence time.

DNA block copolymers – from micelles to machines

DNA block copolymer, a new class of hybrid material composed of a synthetic polymer and an oligodeoxynucleotide segment, owns unique properties which can not be achieved by only one of the two polymers. Among amphiphilic DNA block copolymers, DNA-b-polypropylene oxide (PPO) was chosen as a model system, because PPO is biocompatible and has a Tg < 0 °C. Both properties might be essential for future applications in living systems. During my PhD study, I focused on the properties and the structures of DNA-b-PPO molecules. First, DNA-b-PPO micelles were studied by scanning force microscopy (SFM) and fluorescence correlation spectroscopy (FCS). In order to control the size of micelles without re-synthesis, micelles were incubated with template-independent DNA polymerase TdT and deoxynucleotide triphosphates in reaction buffer solution. By carrying out ex-situ experiments, the growth of micelles was visualized by imaging in liquid with AFM. Complementary measurements with FCS and polyacrylamide gel electrophoresis (PAGE) confirmed the increase in size. Furthermore, the growing process was studied with AFM in-situ at 37 °C. Hereby the growth of individual micelles could be observed. In contrast to ex-situ reactions, the growth of micelles adsorbed on mica surface for in-situ experiments terminated about one hour after the reaction was initiated. Two reasons were identified for the termination: (i) block of catalytic sites by interaction with the substrate and (ii) reduced exchange of molecules between micelles and the liquid environment. In addition, a geometrical model for AFM imaging was developed which allowed deriving the average number of mononucleotides added to DNA-b-PPO molecules in dependence on the enzymatic reaction time (chapter 3). Second, a prototype of a macroscopic DNA machine made of DNA-b-PPO was investigated. As DNA-b-PPO molecules were amphiphilic, they could form a monolayer at the air-water interface. Using a Langmuir film balance, the energy released owing to DNA hybridization was converted into macroscopic movements of the barriers in the Langmuir trough. A specially adapted Langmuir trough was build to exchange the subphase without changing the water level significantly. Upon exchanging the subphase with complementary DNA containing buffer solution, an increase of lateral pressure was observed which could be attributed to hybridization of single stranded DNA-b-PPO. The pressure versus area/molecule isotherms were recorded before and after hybridization. I also carried out a series of control experiments, in order to identify the best conditions of realizing a DNA machine with DNA-b-PPO. To relate the lateral pressure with molecular structures, Langmuir Blodgett (LB) films were transferred to highly ordered pyrolytic graphite (HOPG) and mica substrates at different pressures. These films were then investigated with AFM (chapter 4). At last, this thesis includes studies of DNA and DNA block copolymer assemblies with AFM, which were performed in cooperation with different group of the Sonderforschungsbereich 625 “From Single Molecules to Nanoscopically Structured Materials”. AFM was proven to be an important method to confirm the formation of multiblock copolymers and DNA networks (chapter 5).

New methods for the functionalization of metathesis polymers

Two general strategies for the functionalization of metathesis polymers are presented in this dissertation. Introducing Sacrificial Synthesis, many of the limitations of ruthenium-catalyzed ROMP have been overcome. Here, the living ROMP polymer to be functionalized was turned into a diblock copolymer by polymerizing dioxepine monomers onto the desired first polymer block. The second block was then later removed to leave “half-a-dioxepin”, i.e. exactly one hydroxyl group, at the chain-end. The efficiency of Sacrificial Synthesis is also studied. Thiol groups were also placed by a sacrificial strategy based on cyclic thioacetals. 2-Phenyl-1,3-dithiepin could be polymerized and subsequently cleaved by hydrogenation with Raney-Nickel. The presence of thiol groups on the chain end has been proven by chemical means (derivatization) and by coating gold-nanoparticles. The second strategy, vinyl lactone quenchingv is a termination reaction based on vinyl esters. After a metathesis step, an inactive Fischer-type carbene is formed. Such acyl carbenes are unstable and self-decompose to set an inactive ruthenium complex and the functional group free without changing the reaction conditions. The two compounds vinylene carbonate and 3H-furanone gave rise to the placement of aldehydes and carboxylic acids at the polymer chain ends without the necessity to perform any deprotection steps after the functionalization. The development of those two functionalization methods led to several applications. By reacting hydroxyl-functionalized ROMP-polymers with norbornene acid, macromonomers were formed which were subsequently polymerized to the respective graft-copolymers. Also, the derivatization of the same functionalized polymers with propargylic acid gave rise to alkyne-functionalized polymers which were conjugated with azides. Furthermore, “ugly stars”, i.e. long-chain branched structures were synthesized by polycondensation of ABn-type macromonomers and telechelic polymers were accessed combining the described functionalization techniques.

Project Financing nelle Infrastrutture del Trasporto

L’elaborato ha avuto ad oggetto l’analisi delle sofisticate soluzioni normative proposte dall’ordinamento nazionale in relazione all’evoluzione della finanza di progetto. In particolare, è stata condotto un dettagliato studio delle fasi che compongono il project financing, nonché dei soggetti che, a diverso titolo e ragione, vi partecipano. L’elaborato contiene, poi, recenti esempi concreti di project financing nelle infrastrutture primarie (autostrade) tra cui il progetto di costruzione e la successiva gestione dell’autostrada regionale Medio Padana veneta, dell’autostrada regionale Cispadana, e dell’autostrada “Nogara-mare”. L’ultimo parte della tesi è stata infine incentrata sull’analisi delle più recenti pronunce giurisprudenziali in materia di project financing. In particolare, si ha avuto modo di analizzare il fenomeno dello jus poenitendi dell’amministrazione aggiudicatrice, nonché, più in generale gli eventi che possono negativamente incidere sulla finanza di progetto (mancata aggiudicazione, risoluzione del contratto di gestione, ecc.).

Mathematical aspects of Feynman integrals

In the present dissertation we consider Feynman integrals in the framework of dimensional regularization. As all such integrals can be expressed in terms of scalar integrals, we focus on this latter kind of integrals in their Feynman parametric representation and study their mathematical properties, partially applying graph theory, algebraic geometry and number theory. The three main topics are the graph theoretic properties of the Symanzik polynomials, the termination of the sector decomposition algorithm of Binoth and Heinrich and the arithmetic nature of the Laurent coefficients of Feynman integrals.rnrnThe integrand of an arbitrary dimensionally regularised, scalar Feynman integral can be expressed in terms of the two well-known Symanzik polynomials. We give a detailed review on the graph theoretic properties of these polynomials. Due to the matrix-tree-theorem the first of these polynomials can be constructed from the determinant of a minor of the generic Laplacian matrix of a graph. By use of a generalization of this theorem, the all-minors-matrix-tree theorem, we derive a new relation which furthermore relates the second Symanzik polynomial to the Laplacian matrix of a graph.rnrnStarting from the Feynman parametric parameterization, the sector decomposition algorithm of Binoth and Heinrich serves for the numerical evaluation of the Laurent coefficients of an arbitrary Feynman integral in the Euclidean momentum region. This widely used algorithm contains an iterated step, consisting of an appropriate decomposition of the domain of integration and the deformation of the resulting pieces. This procedure leads to a disentanglement of the overlapping singularities of the integral. By giving a counter-example we exhibit the problem, that this iterative step of the algorithm does not terminate for every possible case. We solve this problem by presenting an appropriate extension of the algorithm, which is guaranteed to terminate. This is achieved by mapping the iterative step to an abstract combinatorial problem, known as Hironaka's polyhedra game. We present a publicly available implementation of the improved algorithm. Furthermore we explain the relationship of the sector decomposition method with the resolution of singularities of a variety, given by a sequence of blow-ups, in algebraic geometry.rnrnMotivated by the connection between Feynman integrals and topics of algebraic geometry we consider the set of periods as defined by Kontsevich and Zagier. This special set of numbers contains the set of multiple zeta values and certain values of polylogarithms, which in turn are known to be present in results for Laurent coefficients of certain dimensionally regularized Feynman integrals. By use of the extended sector decomposition algorithm we prove a theorem which implies, that the Laurent coefficients of an arbitrary Feynman integral are periods if the masses and kinematical invariants take values in the Euclidean momentum region. The statement is formulated for an even more general class of integrals, allowing for an arbitrary number of polynomials in the integrand.

The calcite(10-14) surface: a versatile substrate for molecular self-assembly

This thesis presents a detailed and successful study of molecular self-assembly on the calcite CaCO3(10-14) surface. One reason for the superior applicability of this particular surface is given by reflecting the well-known growth modes. Layer-by-layer growth, which is a necessity for the formation of templated two-dimensional (2D) molecular structures, is particularly favoured on substrates with a high surface energy. The CaCO3(10-14) surface is among those substrates and, thus, most promising. rnrnAll experiments in this thesis were performed using the non-contact atomic force microscope (NC-AFM) under ultra-high vacuum conditions. The acquisition of drift-free data became in this thesis possible owing to the herein newly developed atom-tracking system. This system features a lateral tip-positioning precision of at least 50pm. Furthermore, a newly developed scan protocol was implemented in this system, which allows for the acquisition of dense three-dimensional (3D) data under room-temperature conditions. An entire 3D data set from a CaCO3(10-14) surface consisting of 85x85x500 pixel is discussed. rnrnThe row-pairing and (2x1) reconstructions of the CaCO3(10-14) surface constitute most interesting research subjects. For both reconstructions, the NC-AFM imaging was classified to a total of 12 contrast modes. Eight of these modes were observed within this thesis, some of them for the first time. Together with literature findings, a total of 10 modes has been observed experimentally to this day. Some contrast modes presented themselves as highly distance-dependent and at least for one contrast mode, a severe tip-termination influence was found. rnrnMost interestingly, the row-pairing reconstruction was found to break a symmetry element of the CaCO3(10-14) surface. With the presence of this reconstruction, the calcite (10-14) surface becomes chiral. From high-resolution NC-AFM data, the identification of the enantiomers is here possible and is presented for one enantiomer in this thesis. rnrnFive studies of self-assembled molecular structures on calcite (10-14) surfaces are presented. Only for one system, namely HBC/CaCO3(10-14), the formation of a molecular bulk structure was observed. This well-known occurence of weak molecule-insulator interaction hinders the investigation of two-dimensional molecular self-assembly. It was, however, possible to force the formation of an island phase for this system upon following a variable-temperature preparation. rnFor the C60/CaCO3(10-14) system it is most notably that no branched island morphologies were found. Instead, the first C60 layer appeared to wet the calcite surface. rnrnIn all studies, the molecules arranged themselves in ordered superstructures. A templating effect due to the underlying calcite substrate was evident for all systems. This templating strikingly led either to the formation of large commensurate superstructures, such as (2x15) with a 14 molecule basis for the C60/CaCO3(10-14) system, or prevented the vast growth of incommensurate molecular motifs, such as the chicken-wire structure in the trimesic acid (TMA)/CaCO3(10-14) system. rnrnThe molecule-molecule and the molecule-substrate interaction was increased upon choosing molecules with carboxylic acid moieties in the third, fourth and fifth study, using terephthalic acid, TMA and helicene molecules. In all these experiments, hydrogen-bonded assemblies were created. rnrnDirected hydrogen bond formation combined with intermolecular pi-pi interaction is employed in the fifth study, where the formation of uni-directional molecular "wires" from single helicene molecules succeeded. Each "wire" is composed of heterochiral helicene pairs, well-aligned along the [01-10] substrate direction and stabilised by pi-pi interaction.

Kurzzeit-Orientierungsstrategien in Drosophila melanogaster

Tiere müssen Nahrung, Fortpflanzungspartner oder eine angenehme Umgebung finden und gleichzeitig eventuellen Gefahren aus dem Weg gehen. Eine effektive Orientierungsstrategie stellt für sie einen enormen Vorteil dar, vor allem wenn sie sich in einer komplexen Umwelt bewegen. Eine bisher unbekannte Art, die Orientierung zu optimieren, wird in dieser Arbeit vorgestellt. Sie analysiert, wie sich Taufliegen in einem Temperatur- Gradienten sowie in einer visuell geprägten Umwelt orientieren. Die dabei gefundene Orientierungsstrategie wird als „Memotaxis“ bezeichnet. Sie basiert auf der Integration von Informationen entlang der Wegstrecke, was dazu führt, dass die eingeschlagene Richtung proportional zum positiven Feedback immer stereotyper beibehalten wird. Obwohl die Memotaxis perfekt für die Orientierung in verrauschten Gradienten geeignet ist, wurde ihre Existenz in Situationen mit wenig Rauschen nachgewiesen. Die Strategie führt im Temperaturgradienten dazu, dass Fliegen umso weiter über ein Temperaturoptimum hinweg laufen, je weiter sie vorher darauf zuliefen. Beim Anlauf visueller Stimuli zeigen sie ein ähnliches Verhalten. Je weiter sie auf eine Landmarke zulaufen, desto länger dauert es, bis sie nach deren Verschwinden von dieser Richtung abweichen. Dies gilt auch dann, wenn man gleichzeitig mit dem Verschwinden der Landmarke der Fliege eine andere anbietet. Memotaxis sollte bei vielen Tieren eine gewichtige Rolle spielen, bei der Taufliege können durch die verfügbaren genetischen Methoden zusätzlich die dafür relevanten Gehirnzentren und die biochemischen Komponenten gefunden werden. Der Ellipsoidkörper des Zentralkomplexes ist für die Memotaxis in visuellen Umgebungen notwendig.rnDas Verhalten auf einem vertikalen Laufband wurde analysiert, vor allem im Hinblick auf die adaptive Termination dieses Verhaltens. Die Fliegen erkannten lange Zeit nicht, dass ihr Verhalten nicht zielführend ist und liefen stereotyp und ohne voranzukommen nach oben. Dieses Verhalten wird sogar noch verstärkt, wenn man das visuelle Feedback für die Bewertung ihres Verhaltens verstärkt. rn

Synthese und Charakterisierung zylindrischer Poly(2-oxazolin)bürsten als Nanocarrier für Drug Delivery Systeme

Inspiriert durch natürlich vorkommende Peptide, sind Poly(2-oxazoline) vielversprechende Kandidaten für Anwendungen in Bereichen des kontrollierten Wirkstoff- bzw. Gentransportes, wie die moderne Biomedizin dies fordert. Da Polyoxazoline als strukturisomere Amide von natürlichen Polypeptiden aufgefasst werden können, zeigen diese synthetischen Polymere in direktem Vergleich erhebliche Vorteile etwa hinsichtlich Zytotoxizät und Effizienz, was wesentlich dazu beitragen kann, aktuelle Hürden biomedizinischer Fragestellungen hinsichtlich Transport und Targeting zu überwinden. Darüber hinaus sollten zylindrische Polymerbürsten aufgrund ihrer molekularen, architekturbedingten Formanisotropie und jüngsten Ergebnissen insbesondere zur formabhängigen Endozytose sehr aussichtsreiche Kandidaten für den Einsatz zum Wirkstofftransport sein.rnrnDie vorliegende Arbeit widmete sich deshalb der Synthese und Charakterisierung von biokompatiblen zylindrischen Poly(2-oxazolin)bürsten als potentielle Nanotransporter von Wirkstoffen, Biomolekülen oder genetischem Material. Als Monomer wurde zunächst 2-Isopropyloxazolin gewählt, da das Polymer eine Phasenübergangstemperatur von 37 °C besitzt, was für Konjugatsynthesen wie auch diverse biomedizinische Applikationen interessant sein kann. Durch terminierende Methacrylamid Funktionalisierung der lebenden kationischen Oxazolinpolymerisation bzw. nachfolgende Endgruppen Transferreaktionen sind Makromonomere im Bereich 1000-5000 g/mol zugänglich. Erstmals gelang es so 2-Oxazolin basierte, hochmolekulare zylindrische Bürsten mit Konturlängen im Bereich von 250 nm mittels „Grafting Through“ Technik in freier radikalischer Polymerisation herzustellen.rnrnAusgehend von der entwickelten Syntheseroute konnten so neben Homo- und Blockcopolymerbürsten von 2-Ethyl-2-oxazolin und 2-Isopropyl-2-oxazolin auch Bürstenmoleküle aus statistischen Copolymeren von 2-Ethyl-2-oxazolin und unsubstituiertem 2-Oxazolin hergestellt werden. Während letztere die Einführung kationischer Gruppen durch selektivere Abspaltmethoden der Formylreste erlauben und so etwa DNA/RNA Komplexierungen ermöglichen können, bietet andererseits der in dieser Arbeit erstmalig demonstrierte Einsatz Azid-funktionalisierter Initiatoren zur kationischen Oxazolinpolymerisation unter Beibehaltung aller anderen sonstigen Reaktionsschritte auch die Möglichkeit der Synthese Azid-Endgruppen-funktionalisierter Makromonomere. Die „Grafting Through“ Methodik der freien radikalischen Makromonomer Polymerisation ist selbst bei diesen funktionalisierten Systemen von großem Vorteil, erlaubt sie auch hier den Zugang zu hochmolekularen Substraten mit einem Pfropfungs- bzw. Funktionalisierungsgrad von 100 %, da jede Seitenkette dieser zylindrischen Bürsten die aussenliegende, und damit sterisch leichter zugängliche funktionale Gruppe trägt. Dabei gelang es die Syntheseroute so zu gestalten, dass es möglich war alle vorgestellten Polymerbürsten mittels statischer und dynamischer Lichtstreuung hinsichtlich absoluter Molmasse und molekularer Dimension zu charakterisieren.rnIn weitereren Reaktionen konnten dann reaktive Fluoreszenzfarbstoffe mit Hilfe kupferfreier 1,3 dipolarerer Addition (kupferfreie „Click-Chemie“) an die Azid-funktionalisierten Polymerbürsten angebunden werden, so dass eine wesentliche Voraussetzung für die Detektion in in vivo und in vitro Experimenten erfüllt werden kann. Darüber hinaus gelingt die quantitative polymeranaloge Umsetzung der Azid- zu Aminogruppen durch eine polymeranalog geführte Reduktion nach Staudinger; damit können an diesen Systemen auch etablierte Konjugationstechniken an Aminogruppen durchgeführt werden. Zudem erlauben die Aminogruppen-haltigen Polymerbürsten durch Protonierung schon bei physiologischem pH die Komplexierung von DNA oder RNA. rnrnErste Lichtstreumessungen in Blutserum zeigen im Falle der kationischen Aminogruppen tragenden Polymerbürsten zwar Aggregation, was aber durch entsprechende Umsetzung nach Konjugation wahrscheinlich unterdrückt werden kann, zeigen doch die entsprechenden Precursorpolymerbürsten mit Azidgruppen in Serum keinerlei Aggregation.rnrnZellaufnahmestudien in dendritische Zellen zeigen nur im Falle einer Azid-funktionalisierten Poly(2-isopropyl-2-oxazolin)bürste eine unspezifische Aufnahme. Die hydrophileren Poly(2-oxazolin)bürsten weise keine unspezifische Aufnahme auf, was eine wichtige Anfoderung für die Verwendung als Polymercarrier in der Krebsimmuntherapie ist.rn

From anionic polymerization in continuous flow to macromolecular architectures and stimuli-responsive surfaces

The thesis can be divided in four parts and summarized as follows:(i) The investigation and development of a continuous flow synthesis procedure affording end-functional polymers by anionic polymerization and subsequent termination in one reaction step and on a multigram scale was carried out. Furthermore, the implementation of not only a single hydroxyl but multiple orthogonal functionalities at the chain terminus was achieved by utilizing individually designed, functional epoxide-based end-capping reagents.(ii) In an additional step, the respective polymers were used as macroinitiators to prepare in-chain functionalized block copolymers and star polymers bearing intriguing novel structural and material properties. Thus, the second part of this thesis presents the utilization of end-functional polymers as precursors for the synthesis of amphiphilic complex and in some cases unprecedented macromolecular architectures, such as miktoarm star polymers based on poly(vinyl pyridine), poly(vinyl ferrocene) and PEO.(iii) Based on these structures, the third part of this thesis represents a detailed investigation of the preparation of stimuli-responsive ultrathin polymer films, using amphiphilic junction point-reactive block copolymers. The single functionality at the block interface can be employed as anchor group for the covalent attachment on surfaces. Furthermore, the change of surface properties was studied by applying different external stimuli.(iv) An additional topic related to the oxyanionic polymerizations carried out in the context of this thesis was the investigation of viscoelastic properties of different hyperbranched polyethers, inspired by the recent and intense research activities in the field of biomedical applications of multi-functional hyperbranched materials.

Sistema di terminazione forzata del volo per APR

Questo elaborato presenta le fasi di progettazione e realizzazione di un sistema di terminazione forzata del volo per Aeromobili a Pilotaggio Remoto. Tale sistema ha lo scopo di evitare il potenziale impatto di un APR con cose e persone in caso di perdita di controllo dello stesso, provocandone la caduta all'interno di un’area sicura. Questo dispositivo è ormai indispensabile per l’utilizzo degli APR in ambito professionale e sperimentale in quanto previsto dalla normativa vigente, e dato il crescente sviluppo del settore sarà sempre più richiesto. Dopo una breve rassegna dei sistemi di terminazione attualmente presenti sul mercato viene illustrata la linea di progetto seguita, e successivamente vengono descritti i componenti principali utilizzati per la realizzazione. Sono quindi presentati i vari prototipi ideati fino ad arrivare al modello definitivo, che è stato costruito e poi testato sia al banco prova sia nell'effettivo utilizzo in volo.