I sistemi multipolari. Analisi storica e teorica.

This research undertakes to provide a typology of multipolar systems. Multipolarity plays a key role in IR theory, for it is strictly associated with the history of European politics since the seventeenth century to the end of World War Two. Despite wide investigation, one can doubt the matter has received a definitive treatment. Trouble is that current studies often consider multipolarity as a one-dimensional concept. They obviously reckon that multipolarism is substantially different from other systems and deserves attention, but generally fail to distinguish between different types of multipolar systems (the few exceptions are listed in chapter one). The history of international politics tells us a different story. Multipolar power systems may share some general characteristics, but they also show a wide array of difference, and understanding this difference requires a preliminary work of classification. That is the purpose of the present study. The work is organized as follows. In chapter one, we provide a cursory review of the literature on multipolarity, with particular reference to the work of Duncan Snidal and Joseph Grieco. Then we propose a four-cell typology of multipolar systems to be tested via historical analysis. The first type, hegemony, is best represented by European international system to the time of Napoleonic France, and is discussed in chapter two. Type number two is the traditional concert of Europe, which history is detailed in chapter three. Type number three is the reversal of alliances, which closest example, the diplomatic revolution of 1756, is discussed in chapter four. Finally, chapter five is devoted to the chain-gang system, and the European politics from Bismarck’s late years to World War One represents a good illustration of how it works. In chapter six we proceed to draw a first evaluation of the main results achieved in the previous chapters, in order to see if, and to what extent, our typology serves the purpose of explaining the nature of multipolar systems.

Enantioselective Reactions Promoted by Organocatalytic Species From The Natural Chiral Pool

During the course of my Ph.D. in the laboratories directed by Prof. Alfredo Ricci at the Department of Organic Chemistry “A. Mangini” of the University of Bologna, I was involved in the study and the application of a number of organocatalytic systems, all coming from the natural chiral pool. The first part of this thesis will be devoted to new homogeneous organocatalytic reactions promoted by Cinchona alkaloid-based organocatalysts. Quinine based catalysts were found to be a very effective catalyst for Diels-Alder reactions involving 3-vinylindoles. Excellent results in terms of yields and enantioselectivities were achieved, outlining also a remarkable organocatalytic operational mode mimicking enzymatic catalysis. The same reaction with 2-vinylindoles showed a completely different behaviour resulting in an unusual resolution-type process. The asymmetric formal [3+2] cycloaddition with in situ generated N-carbamoyl nitrones using Cinchona-derived quaternary ammonium salts as versatile catalysts under phase transfer conditions, outlines another application in organocatalysis of this class of alkaloids. During the seven months stage in the Prof. Helma Wennemers’ group at the Department of Chemistry of the University of Basel (Switzerland) I have been involved in organocatalysis promoted by oligopeptides. My contribution regarded the 1,4-addition reaction of aldehydes to nitroolefins. In the work performed at the Department of Organic Chemistry “A. Mangini” of the University of Bologna, in collaboration with the ‘Institut Charles Gerhardt-Montpellier, of Montpellier (France) the possibility of performing for the first time heterogeneous organocatalysis by using a natural polysaccharide biopolymer as the source of chirality was disclosed. With chitosan, derived from deacetylation of chitin, a highly enantioselective heterogeneous organocatalytic aldol reaction could be performed. The use of an eco-friendly medium such as water, the recyclability of the catalytic specie and the renewable nature of the polysaccharide are assets of this new approach in organocatalysis and open interesting perspectives for the use of biopolymers.

Origini dell'ucronia. La letteratura contro la storia

L’ucronia (Alternate History) è un fenomeno letterario ormai popolare e molto studiato, ma non lo sono altrettanto lo sue origini e i suoi rapporti con la storia “fatta con i se” (Counterfactual History), che risale a Erodoto e a Tito Livio. Solo nell’Ottocento alcuni autori, per vie largamente autonome, fecero della storia alternativa un genere di fiction: Louis Geoffroy con Napoléon apocryphe (1836), storia «della conquista del mondo e della monarchia universale», e Charles Renouvier con Uchronie. L’utopie dans l’histoire (1876), storia «della civiltà europea quale avrebbe potuto essere» se il cristianesimo fosse stato fermato nel II secolo. Questi testi intrattengono relazioni complesse con la letteratura dell’epoca di genere sia realistico, sia fantastico, ma altresì con fenomeni di altra natura: la storiografia, nelle sue forme e nel suo statuto epistemico, e ancor più il senso del possibile - o la filosofia della storia - derivato dall’esperienza della rivoluzione e dal confronto con le teorie utopistiche e di riforma sociale. Altri testi, prodotti in Inghilterra e negli Stati Uniti nello stesso periodo, esplorano le possibilità narrative e speculative del genere: tra questi P.s’ Correspondence di Nathaniel Hawthorne (1845), The Battle of Dorking di George Chesney (1871) e Hands Off di Edward Hale (1881); fino a una raccolta del 1931, If It Had Happened Otherwise, che anticipò molte forme e temi delle ucronie successive. Queste opere sono esaminate sia nel contesto storico e letterario in cui furono prodotte, sia con gli strumenti dell’analisi testuale. Una particolare attenzione è dedicata alle strategie di lettura prescritte dai testi, che subordinano i significati al confronto mentale tra gli eventi narrati e la serie dei fatti autentici. Le teorie sui counterfactuals prodotte in altri campi disciplinari, come la storia e la psicologia, arricchiscono la comprensione dei testi e dei loro rapporti con fenomeni extra-letterari.

Silica-Supported Gold Nanoparticles: Synthesis, Characterization and Reactivity

The main aim of this work was the synthesis and applications of functionalized-silica-supported gold nanoparticles. The silica-anchored functionalities employed, e.g. amine, alkynyl carbamate and sulfide moieties, possess a notable affinity with gold, so that they could be able to capture the gold precursor, to spontaneously reduce it (possibly at room temperature), and to stabilize the resulting gold nanoparticles. These new materials, potentially suitable for heterogeneous catalysis applications, could represent a breakthrough among the “green” synthesis of supported gold nanoparticles, since they would circumvent the addition of extra reducing agent and stabilizers, also allowing concomitant absorption of the active catalyst particles on the support immediately after spontaneous formation of gold nanoparticles. In chapter 4 of this thesis is also presented the work developed during a seven-months Marco Polo fellowship stay at the University of Lille (France), regarding nanoparticles nucleation and growth inside a microfluidic system and the study of the corresponding mechanism by in situ XANES spectroscopy. Finally, studies regarding the reparation and reactivity of gold decorated nanodiamonds are also described. Various methods of characterization have been used, such as ultraviolet-visible spectroscopy (UV-Vis), Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS), X-ray Fluorescence (XRF), Field Emission Gun Scanning Electron Microscopy (SEM-FEG), X-ray Photoionization (XPS), X ray Absorption Spectroscopy (XAS).