Le trafic vésiculaire joue un rôle crucial dans la sécrétion et l'internalisation des composantes extracellulaires ou membranaires. De plus, il contrôle la distribution spatio-temporelle de nombreuses protéines. En outre, ce processus peut contrôler la livraison de protéines à divers domaines des membranes plasmiques. Mes travaux de recherche se sont centrés sur l'étude des protéines Rab11-Family of Interacting Proteins de classe I (Rab11FIPs), plus précisément de Rab11FIP1 et de sa fonction dans différents processus cellulaires nécessitant le trafic vésiculaire, tels que la mitose, la cytokinèse, l'établissement de la polarité cellulaire et de la migration cellulaire, individuelle ou collective. En effet, ces processus nécessitent un contrôle vésiculaire finement régulé, par exemple, la mitose/cytokinèse nécessite le recrutement de différents complexes protéiques contenant des cargaisons liées aux vésicules. L'établissement de la polarité cellulaire nécessite le tri et la livraison de complexes protéiques à des membranes spécifiques et la migration cellulaire nécessite une polarisation complète de la cellule pour permettre un mouvement directionnel. Mes travaux ont élucidé une voie impliquant Rab11FIP1 et Rab35 dans le contrôle à la fois de la cytokinèse et de l'établissement de la polarité. En effet, alors que d'autres groupes ont publié que Rab35 est essentiel pour l'élimination de l'actine située au pont intercellulaire via le recrutement de MICAL1 et OCRL, j'ai montré que Rab11FIP1 est critique pour maintenir Rab35 dans cette région. De plus, j'ai montré que l'absence de Rab11FIP1 et la mauvaise localisation subséquente de Rab35 peuvent conduire à des phénotypes similaires à ceux observés lors de la dérégulation de l'abscission, tels que la binucléation et le retard de la cytokinèse, qui sont des défauts qui contribuent au développement de cancers. Ces défauts peuvent cependant être rétablies en utilisant de faibles doses de Latrunculin A pour dépolymériser de l'actine. De plus, j'ai montré que Rab11FIP1 et Rab35 semblent avoir des fonctions dans la polarité apico-basale des cellules Caco-2 et MCF-10a. Enfin, j'ai aussi montré que Rab35 est impliquée dans la régulation de la migration collective. En conclusion, mes données établissent Rab11FIP1 et Rab35 comme des régulateurs importants de divers processus cellulaires. Ces résultats constituent un point de départ important pour une étude plus approfondie de l'abscission, de l'établissement de la polarité cellulaire, de la formation du Apical Membrane Initiation Site (AMIS) et de la migration cellulaire collective. Cela aura des implications de grande envergure, car ces cascades de signalisation peuvent avoir un impact sur pratiquement tous les processus cellulaires. / Vesicular trafficking plays a crucial role in the secretion and internalization of extracellular or plasma membrane components. Moreover, it controls the spatiotemporal distribution of many proteins during different processes. Also, it can control the delivery of proteins to various domains of the plasma membranes. With this in mind, my research focused on the Rab11 Family of Interacting Proteins of Class I (Rab11FIPs), more specifically of Rab11FIP1 and its function in different cellular processes that require vesicular trafficking, those being mitosis, cytokinesis, establishment of cell polarity and cellular migration, both single and collective. Indeed, these processes require exquisite vesicular control, for example, mitosis/cytokinesis require the recruitment of different protein complexes containing vesicle-bound cargoes. Cell polarity establishment requires the sorting and delivery of protein complexes and cell migration requires fine-tuned polarization of the entire cell to allow for directional movement. My work has elucidated one such pathway involving Rab11FIP1 and Rab35 in the control of both cytokinesis and the establishment of polarity. Indeed, while others have shown that Rab35 is critical for the removal of actin in the intercellular bridge via recruitment of its cargoes MICAL1 and OCRL, I showed that Rab11FIP1 is vital for maintaining Rab35 in the midbody. In fact, I showed that lack of Rab11FIP1 and subsequent mislocalization of Rab35 can lead to similar phenotypes observed during dysregulated abscission, such as binucleation and cytokinesis delay, which are hallmarks of cancer. These phenotypes however, can be rescued using low doses of an actin depolymerizing drug called Latrunculin A. Furthermore, I showed that both Rab11FIP1 and Rab35 seem to have functions in the establishment of apico-basal polarity of both Caco-2 and MCF-10a. Finally, I showed that Rab35 seems to regulate the collectiveness of migrating cells. Altogether, these data establish Rab11FIP1 and Rab35 as important regulators of various cellular processes. These results will be an important stepping stone for further studies into abscission, establishment of cellular polarity, Apical Membrane Initiation Site (AMIS) formation, and collective cell migration. This will have far reaching implications, as these signaling cascades can impact virtually all cellular processes.

<p> In Part I the one-electron charge distribution in the water molecule is obtained by demanding that this distribution balance the nuclear forces of repulsion and reproduce the observed dipole moment. Parameters contained in the molecular orbital description are then related to such concepts as hybridisation and bond polarities. </p> <p> In Part II the electronic forces of attraction and the one-electron charge distribution, calculated from near Hartree-Fock wave functions, are used to interpret the binding in the first-row diatomic hydrides. </p> / Thesis / Doctor of Philosophy (PhD)

In den letzten Jahren gab es Fortschritte im Verständnis der Gefäßbildung bei Ereignissen wie Keimen, Lumenbildung und Gefäßstabilisierung. Nach der Bildung eines primitiven Plexus ist die Gefäßoptimierung und hierarchische Umwandlung der morphologischen Gefäße in einen reifen Plexus durch vaskuläres "Pruning" wenig verstanden. Unterschiedliche Blutflussprofile in nebeneinander angeordneten Gefäßen können Asymmetrien in der Scherspannung verursachen, was die Zellmigration in Bereichen mit höherem Fluss fördert und die Destabilisierung von Segmenten mit geringem Fluss induziert. Diese Studie basiert auf der Hypothese, dass funktionelle Gefäßnetzwerke und Umbildung durch flussgesteuerte Endothelzellmigration ausgelöst werden. Wie die zelluläre Erfassung physikalischer Kräfte integriert ist, um Informationen zu übertragen und das Verhalten von Zellen zu modifizieren, ist noch unbekannt. Die Studie untersucht die Regulation und Koordination durch RhoGTPase-Signale während der kollektiven endothelialen Migration aufgrund von Flüssigkeitskräften. RhoGTPasen ermöglichen die räumlich-zeitliche Koordination, langfristige Anpassung an den Fluss und morphologische Umgestaltung. Beeinträchtigungen von RhoGTPasen zeigen Defekte bei Zellmigration und kollektiver Koordination in Umgebungen mit freiem Rand und strömungsgetriebener Migration. Die Studie erläutert den Einfluss der RhoGTPase-Regulation der Verbindungsdynamik in Verbindung mit der Aktinorganisation, die für die mechanische Kopplung und endotheliale Reaktionsfähigkeit erforderlich ist. Insgesamt betont die Studie die Relevanz der räumlich-zeitlichen RhoGTPase-Kontrolle und der Aufrechterhaltung der mechanischen Kopplung zwischen Strömung und Migration für die kollektive Koordination als Reaktion auf hämodynamische Kräfte. / In recent years, there have been significant advances in understanding how new vessels form during events like sprouting, lumen formation, and vessel stabilization. Yet, after the formation of a basic network, the crucial step of rearranging vessels into a mature structure, known as vascular pruning, needs further investigation. It's suggested that different blood flow profiles in nearby vessels create imbalances in shear stress, leading to cell migration toward higher flow regions, destabilizing low-flow segments, and causing the collapse of redundant segments. This study, in line with existing literature, proposes that functional vascular networks and remodeling result from the flow-driven migration of endothelial cells. However, how cells precisely sense physical forces to regulate their behavior and coordinate migration in response to flow remains unknown. I explore the regulation and coordination of Rho GTPases during collective endothelial migration under fluid forces. Rho GTPases' coordination allows long-term adaptation to flow and morphological remodeling. Impairments in Rho GTPases reveal defects in cell migration and collective coordination during free-edge and flow-driven migration. Finally, I explain how Rho GTPases' regulation influences junctional dynamics and actin organization, crucial for mechanical coupling and endothelial responsiveness to flow. Overall, this study emphasizes the importance of controlling Rho GTPases over time and maintaining mechanical coupling between flow and migration for collective coordination in response to fluid forces.

No description available.

Our society demands for increasingly powerful and efficient microprocessors. However, the conventional method to achieve this, i.e. by reducing the device dimensions and operation voltage of field-effect transistors (FETs), is approaching physical limits. This state of things is driving science and industry to consider new approaches for the generation of efficient logic devices. An emerging solution is the use of reconfigurable FETs (RFETs) that – unlike conventional CMOS transistors – do not need doping but can be toggled between p- and n-type behavior in runtime. For this to be possible, it is necessary to employ an intrinsic channel with Schottky junctions at source and drain. A program gate then toggles the polarity of the device at the Schottky junction on the drain side while one or more additional control gates switch the transistor on or off. This allows to create compact and delay-efficient logic gates that can switch their functionality dynamically, e.g. to save area or to prevent the disclosure of the circuit functionality. Additionally, the ability to include multiple gates in a single transistor to implement a wired-AND functionality allows to create power- and delay-efficient circuits. This thesis demonstrates that such devices can be created by means of a lithographic top-down technology based on commercial silicon-on-insulator (SOI) wafers. In order to ensure a compatibility with future CMOS process lines, the channels are created from silicon nanosheets and nanowires, which will most likely substitute the current FinFET and FD-SOI technology in the future. Nano-dimensional channels allow for ideal electrostatic control by the gates especially if the gates surround them. For this purpose, a process employing multiple oxide etching and oxidation steps, nickel silicide formation and the structuring of conformal metal gates is developed to create shrank and omega-gated nanosheets and nanowires with atomically sharp source and drain Schottky junctions. The resulting RFETs feature high on-current densities, high on/off current ratios and up to four individual gates that realize a wired-AND functionality. More importantly, in contrast to top-down fabricated RFETs in earlier works, these RFETs provide symmetrical electrical characteristics for p- and n-configuration but only need a single supply voltage. These properties will allow to create circuits of cascaded, static logic gates with polarity-independent signal delay times and no need for interposed buffers to refresh the signals. Additionally, the use of ferroelectric materials to create RFETs with nonvolatile programming has been tested at a Schottky-barrier MOSFET. Unfortunately, contact fabrication by self-aligned silicidation can lead to some difficulties: The silicide intrusion length varies widely even between similar nanowires on the same chip, which makes the fabrication of short channels and the application of narrow gates particularly challenging. Detailed analyses in this work show that the variation is mainly caused by the variable amount of nickel supplied. Several material-, temperature- and geometry-based methods to gain a more homogeneous silicidation length are tested. One of these methods employs the layout freedom of the top-down technology to create novel structures of nanowires with local volume extensions. When using a single nickel source, these structures allow to study the impact of wire geometry on silicidation dynamics independently from the nickel contact quality. The gained findings have implications well beyond the application in RFETs, as nickel silicidation is widely used in state-of-the-art semiconductor technology.:Abstract Kurzzusammenfassung 1 Introduction 2 Fundamentals and state-of-the-art of reconfigurable field-effect transistors 2.1 Schottky junction 2.2 Schottky-barrier field-effect transistor 2.3 Current control by the gate voltage 2.4 Reconfigurable FETs 2.4.1 Working principle 2.4.2 Architectures and channel materials of RFETs in prior works 2.4.3 Applications 2.4.4 Requirements for the use in circuits 3 Transistor fabrication 3.1 Electron-beam lithography 3.2 Top-down nanowire fabrication 3.3 Nanowire oxidation and underetch 3.3.1 Oxidation of nanowires 3.3.2 Oxidation processes 3.4 Top-gate fabrication 3.4.1 Basic process for tri-gate 3.4.2 Advanced process for omega-gate 3.4.3 Integration of ferroelectric hafnium-zirconium oxide 3.5 Contact formation by nickel silicidation 3.5.1 Contact metal selection 3.5.2 Nickel deposition and silicide formation 3.5.3 Influences on nickel silicidation in nanowires 3.5.3.1 General 3.5.3.2 Silicide and void formation in different nanowire orientations 3.5.3.3 Influence of nanowire width on silicidation length 3.5.3.4 Importance of an oxide shell 3.5.3.5 Titanium interlayer and exhaustible nickel source 3.5.3.6 Influence of the contact to the nickel supply 3.5.3.7 Effect of temperature on silicidation length homogeneity 3.6 Gate-first and gate-last approach 3.7 RFET circuit realization 3.7.1 Logic gate layout 3.7.2 Mix-and-match technology 4 Nickel silicidation in extended wire geometries 4.1 Silicidation into areas 4.2 Control of silicide growth regime by extensions to nanowires 4.3 Polder extensions for controlled silicidation lengths 4.3.1 Concept and model 4.3.2 Experimental verification 5 Transistor characteristics 5.1 Measurement setup 5.2 Single gate Schottky-barrier MOSFET 5.2.1 Back-gate control 5.2.2 Single top-gate control 5.3 Double top-gate RFET 5.3.1 Tri-gate architecture by gate-last fabrication 5.3.2 Omega-gate architecture by gate-first fabrication 5.4 Multiple independent top-gate RFET 5.4.1 Value of multiple independent gates 5.4.2 Single channel MIG-RFET 5.4.3 Multiple channel MIG-RFET 5.5 Towards nonvolatile RFETs using ferroelectric gate dielectric 5.5.1 Fundamentals and applications of ferroelectric materials in FETs 5.5.2 Schottky-barrier MOSFET with ferroelectric gate 5.6 Performance comparison to state-of-the-art RFETs 6 Conclusion 7 Outlook 7.1 Enhanced understanding, performance and yield of RFETs 7.2 RFETs with split channels 7.3 Silicidation control 8 Appendix 8.1 Analysis of unsuccessful silicidation on circuit chips Bibliography Own publications List of constants and symbols List of abbreviations Acknowledgments Curriculum Vitae / Unsere Gesellschaft verlangt nach immer leistungsfähigeren und effizienteren Mikroprozessoren. Die herkömmlichen Methoden, d.h. das Reduzieren der Bauelementabmessungen und der Betriebsspannung von Feldeffekttransistoren (FETs), nähern sich jedoch physikalischen Grenzen. Diese Tatsache veranlasst Forschung und Industrie dazu, neue Ansätze bei der Erzeugung von effizienten logischen Schaltkreisen zu verfolgen. Auf großes Interesse stößt dabei die Verwendung von rekonfigurierbaren Feldeffekttransistoren (RFETs), die im Gegensatz zu herkömmlichen FETs keine Dotierung benötigen, sondern jederzeit zwischen p- und n-Typ Verhalten umgeschaltet werden können. Dazu wird ein intrinsischer Kanal mit Schottky-Kontakten an den Drain- und Source-Anschlüssen benötigt. Außerdem wird ein Programmier-Gate verwendet um die Polarität des Bauelements festzulegen, und ein oder mehrere weitere Kontroll-Gates schalten den Transistor ein oder aus. Dies ermöglicht es kompakte und laufzeiteffiziente Logikgatter zu konstruieren, die ihrer Funktionalität dynamisch verändern können, zum Beispiel um den Flächenverbrauch zu reduzieren oder um eine Enthüllung der Schaltkreisfunktionalität zu verhindern. Außerdem können in einem einzelnen Transistor mehrere Gates angelegt werden. Die sich ergebende nicht-komplementäre UND-Verkettung kann dazu genutzt werden, um energie- und laufzeit-sparende Schaltkreise zu generieren. Diese Arbeit weist nach, dass solche Bauelemente mit einem lithographischen Top-Down-Ansatz auf Basis von kommerziellen Silizium-auf-Isolator Substraten (sog. SOI-Wafern) realisierbar sind. Um eine Kompatibilität mit zukünftigen CMOS-Prozesslinien sicherzustellen, wurden die Kanäle aus nanometer-dünnen Silizium-Drähten oder -Bändern gebildet. Es wird erwartet, dass solche Kanalgeometrien bald die heutigen FinFET und FD-SOI Technologien ablösen werden, weil sie insbesondere mit umschließendem Gate eine optimale elektrostatische Gate-Kontrolle über den Kanal aufweisen. Der in dieser Arbeit entwickelte Prozess umfasst daher mehrfache Oxid-Ätzungen und Oxidationen zur Schrumpfung und teilweisen Unterätzung der Kanäle, die Bildung von abrupten Schottky-Kontakten aus Nickel-Silizid und die Strukturierung umschließender Metall-Gates. Die erzeugten RFETs weisen besonders hohe Stromdichten im An-Zustand und sehr hohe Verhältnisse von An- zu Aus-Strom auf. Außerdem besitzen sie bis zu vier unabhängige Gates, deren Eingänge somit quasi UND-verknüpft sind. Vor allem aber weisen diese RFETs im Gegensatz zu vorangegangenen Arbeiten symmetrische elektrische Charakteristiken für p- und n-Konfiguration auf, wozu sie sogar nicht mehr als eine Betriebsspannung benötigen. Diese Eigenschaften ermöglichen die Erzeugung von Schaltkreisen aus verkoppelten Logikgattern, bei denen die Signal-Laufzeit nicht von der Polarität der Transistoren abhängt und bei denen die Signale nicht durch zwischengeschaltete Pufferschaltungen aufgefrischt werden müssen. Darüber hinaus wurde in einem Schottky-Barrieren FET die Verwendung ferroelektrischer Materialien erprobt, mit denen zukünftig RFETs mit nichtflüchtiger Programmierung erzeugt werden könnten. Leider bereitet die Kontaktbildung durch die selbst-ausgerichtete Silizidierung häufig Probleme: Die Silizid-Eindringlänge schwankt stark, selbst zwischen ähnlichen Nanodrähten auf demselben Chip, was die Herstellung kurzer Kanäle und die Verwendung schmaler Gates besonders erschwert. Detaillierte Analysen in dieser Arbeit zeigen, dass insbesondere der ungleiche Nachschub von Nickel diese Varianz verursacht. Verschiedene material-, temperatur- und geometrie-basierte Ansätze wurden getestet um homogenere Silizid-Eindringlängen zu erreichen. Einer dieser Ansätze macht sich zunutze, dass mit der Top-Down-Technologie beliebige Strukturen definiert werden können, sodass Nanodrähte lokal erweitert werden können. Wenn solche Strukturen mit nur einer einzelnen Nickelquelle verbunden sind, kann der Einfluss der Drahtgeometrie auf den Silizidierungsprozess unabhängig von der Güte des Nickel-Kontakts beobachtet werden. Die auf diese Weise gewonnenen Erkenntnisse sind über die Arbeit an RFETs hinaus von Relevanz, da die Nickel-Silizidierung in vielen modernen Halbleiterprozessen zum Einsatz kommt.:Abstract Kurzzusammenfassung 1 Introduction 2 Fundamentals and state-of-the-art of reconfigurable field-effect transistors 2.1 Schottky junction 2.2 Schottky-barrier field-effect transistor 2.3 Current control by the gate voltage 2.4 Reconfigurable FETs 2.4.1 Working principle 2.4.2 Architectures and channel materials of RFETs in prior works 2.4.3 Applications 2.4.4 Requirements for the use in circuits 3 Transistor fabrication 3.1 Electron-beam lithography 3.2 Top-down nanowire fabrication 3.3 Nanowire oxidation and underetch 3.3.1 Oxidation of nanowires 3.3.2 Oxidation processes 3.4 Top-gate fabrication 3.4.1 Basic process for tri-gate 3.4.2 Advanced process for omega-gate 3.4.3 Integration of ferroelectric hafnium-zirconium oxide 3.5 Contact formation by nickel silicidation 3.5.1 Contact metal selection 3.5.2 Nickel deposition and silicide formation 3.5.3 Influences on nickel silicidation in nanowires 3.5.3.1 General 3.5.3.2 Silicide and void formation in different nanowire orientations 3.5.3.3 Influence of nanowire width on silicidation length 3.5.3.4 Importance of an oxide shell 3.5.3.5 Titanium interlayer and exhaustible nickel source 3.5.3.6 Influence of the contact to the nickel supply 3.5.3.7 Effect of temperature on silicidation length homogeneity 3.6 Gate-first and gate-last approach 3.7 RFET circuit realization 3.7.1 Logic gate layout 3.7.2 Mix-and-match technology 4 Nickel silicidation in extended wire geometries 4.1 Silicidation into areas 4.2 Control of silicide growth regime by extensions to nanowires 4.3 Polder extensions for controlled silicidation lengths 4.3.1 Concept and model 4.3.2 Experimental verification 5 Transistor characteristics 5.1 Measurement setup 5.2 Single gate Schottky-barrier MOSFET 5.2.1 Back-gate control 5.2.2 Single top-gate control 5.3 Double top-gate RFET 5.3.1 Tri-gate architecture by gate-last fabrication 5.3.2 Omega-gate architecture by gate-first fabrication 5.4 Multiple independent top-gate RFET 5.4.1 Value of multiple independent gates 5.4.2 Single channel MIG-RFET 5.4.3 Multiple channel MIG-RFET 5.5 Towards nonvolatile RFETs using ferroelectric gate dielectric 5.5.1 Fundamentals and applications of ferroelectric materials in FETs 5.5.2 Schottky-barrier MOSFET with ferroelectric gate 5.6 Performance comparison to state-of-the-art RFETs 6 Conclusion 7 Outlook 7.1 Enhanced understanding, performance and yield of RFETs 7.2 RFETs with split channels 7.3 Silicidation control 8 Appendix 8.1 Analysis of unsuccessful silicidation on circuit chips Bibliography Own publications List of constants and symbols List of abbreviations Acknowledgments Curriculum Vitae

Drawing especially on Donna Haraway's notion of the cyborg, this thesis argues that Eoin Colfer's Artemis Fowl novels, through their depiction of the cyborg and their use of metafiction, intertextuality, and irony, subvert binaries and hierarchies that cause social injustice. Chapter one argues that Colfer's characters disrupt the oppressive binary opposition between innocence and experience that characterizes children's literature. Chapter two argues that Colfer's fairy hierarchy satirizes the human hierarchy. Chapter three argues that Colfer's cyborg, by disrupting the boundary between machine and organism, breaches the wall around the pervasive garden hierarchy of childhood innocence. Chapter four argues against the traditional textual hierarchies which classify children's literature as inferior, and which give adult writers power over child readers.

Indiana University-Purdue University Indianapolis (IUPUI) / While breast cancer is the second most commonly diagnosed cancer worldwide, its causes and natural history are not well defined. The female mammary organ is unique in that it does not reach full maturity until the lactation cycle following pregnancy. This cycle entails extensive growth and reorganization of the primitive epithelial ductal network. Following lactation, these same epithelial cells undergo an equally extensive program of apoptosis and involution. The mammary gland's sensitivity to pro-growth and pro-apoptotic signals may partly explain its proclivity to develop cancers. For epithelial cells to become transformed they must lose intracellular organization known as polarity as differentiated epithelial tissues are refractory to aberrant growth. One essential component of epithelial to mesenchymal transition is the intrinsic capacity of cells to repurpose polarity constituents to promote growth. Recently, a novel mechanism of organ size control has been shown to repurpose the apical junctional associated protein Yap into the nucleus where it functions as a transcriptional coactivator promoting growth and dedifferentiation. The focus of my work has been on a family of adaptor proteins termed Amots that have been shown to scaffold Yap and inhibit growth signaling. Specifically, I have shown that the 80KDa form of Amot, termed Amot80, acts as a dominant negative to the other Amot proteins to promote cell growth while reducing cell differentiation. Amot80 was found to promote the prolonged activation of MAPK signaling. Further, Amot80 expression was also found to enhance the transcriptional activity of Yap. This effect likely underlies the ability of Amot80 to drive disorganized overgrowth of MCF10A cells grown in Matrigel̈™. Overall, these data suggest a mechanism whereby the balance of Amot proteins controls the equilibrium between growth and differentiation within mammary epithelial tissues.

This thesis describes stereospecific fluorination reactions, and addresses the synthesis of fluorosugars. In Chapter 1, the influence of fluorine on the physical properties of organic molecules, as well as its stereoelectronic effects, are introduced. Furthermore, an overview of nucleophilic and electrophilic fluorination reactions is given. Chapter 2 describes the dehydroxyfluorination of allylic alcohol diastereoisomers 155a and 155b, which can proceed either by direct or allylic fluorination. The regio- and stereo- selectivities were also assessed. Chapter 3 outlines the synthesis of the novel trifluoro D-glucose analogue 193 and trifluoro D-altrose analogue 216. The transport of these hexose analogues across the red blood cell membranes was then explored, to investigate the influence of polarity versus hydrogen bonding ability in carbohydrate-protein interactions. Chapter 4 describes the development and optimisation of Bio’s methodology, to promote stereospecific dehydroxyfluorination of benzylic alcohols (R)-213 and (R)-227 by addition of TMS-amine additives 226 and 229. And finally Chapter 5 reports the experimental procedures as well as the characterisation and the crystallographic data of the molecules prepared in this thesis.

No description available.

Cosa determina la stabilità di un sistema politico internazionale? L’anarchia sistemica determina sempre una minaccia alla sopravvivenza? Il modello strutturale qui proposto integra le variabili della concentrazione del potere e della localizzazione geografica delle Grandi Potenze, per dimostrare come specifiche configurazioni strutturali contribuiscano a plasmare le motivazioni che stanno alla base dei comportamenti statali, condizionando i risultati sistemici osservabili. Viene, inoltre, inquadrato il processo di socializzazione come variabile interveniente, attivata da specifiche condizioni strutturali, in grado di inibire la ricorrenza della tendenza sistemica al bilanciamento attraverso la riduzione delle opzioni di politica estera a disposizione degli Stati. Dal punto di vista teorico, concentrandosi sul ruolo svolto dal potere e dalla geografia nell’orientare le motivazioni di base degli attori, il modello modifica l’assunto realista di incentivi strutturali costanti all’azione degli Stati, ipotizzando che questi varino al variare dei livelli di concentrazione del potere. Inoltre, mitiga il carattere meccanicistico del realismo strutturale, considerando il bilanciamento come una tra tante opzioni disponibili. Dal punto di vista empirico, il modello viene applicato a tre casi di studio, nel tentativo di evidenziare come la stabilità o l’instabilità sistemica siano determinate dall’esistenza di strutture di potere diffuse o concentrate. / What does effectively determine systemic stability? Does international anarchy always determine a threat to survival? The structural model introduced in this work focuses on two main variables, power concentration and geography, to demonstrate how structural constraints shape States’ base motivations to action, and how the resulting behaviors condition the observable systemic outcomes. Furthermore, I introduce the socialization process as an intervening variable, enabled by specific structural conditions. Socialization could inhibit the systemic balancing tendency by narrowing States’ foreign policy options. From the theoretical point of view, the model modifies the realist assumption towards constant structural incentives to action. By focusing on the role played by power concentration and geography in shaping States’ motivations, it is possible to link together the shifts in international power distribution with shifts in structural incentives. Nonetheless, the model loses the rather mechanistic character of structural realism, making balancing one among many viable options. From the empirical point of view, I apply the model against three case studies, trying to demonstrate how the existence of concentrated or diffused power structures determines systemic stability or instability.