N-Heterocyclic carbene complexes of silver, rhodium and iron: structures, dynamics and catalysis

The research performed in the framework of this Master Thesis has been directly inspired by the recent work of an organometallic research group led by Professor Maria Cristina Cassani on a topic related to the structures, dynamics and catalytic activity of N-heterocyclic carbene-amide rhodium(I) complexes1. A series of [BocNHCH2CH2ImR]X (R = Me, X = I, 1a’; R = Bz, X = Br, 1b’; R = trityl, X = Cl, 1c’) amide-functionalized imidazolium salts bearing increasingly bulky N-alkyl substituents were synthetized and characterized. Subsequently, these organic precursors were employed in the synthesis of silver(I) complexes as intermediate compounds on a way to rhodium(I) complexes [Rh(NBD)X(NHC)] (NHC = 1-(2-NHBoc-ethyl)-3-R-imidazolin-2-ylidene; X = Cl, R = Me (3a’), R = Bz (3b’), R = trityl (3c’); X = I, R = Me (4a’)). VT NMR studies of these complexes revealed a restricted rotation barriers about the metal-carbene bond. However, while the rotation barriers calculated for the complexes in which R = Me, Bz (3a’,b’ and 4a) matched the experimental values, this was not true in the trityl case 3c’, where the experimental value was very similar to that obtained for compound 3b’ and much smaller with respect to the calculated one. In addition, the energy barrier derived for 3c’ from line shape simulation showed a strong dependence on the temperature, while the barriers measured for 3a’,b’ did not show this effect. In view of these results and in order to establish the reasons for the previously found inconsistency between calculated and experimental thermodynamic data, the first objective of this master thesis was the preparation of a series of rhodium(I) complexes [Rh(NBD)X(NHC)] (NHC = 1-benzyl-3-R-imidazolin-2-ylidene; X = Cl, R = Me, Bz, trityl, tBu), containing the benzyl substituent as a chiral probe, followed by full characterization. The second objective of this work was to investigate the catalytic activity of the new rhodium compounds in the hydrosilylation of terminal alkynes for comparison purposes with the reported complexes. Another purpose of this work was to employ the prepared N-heterocyclic ligands in the synthesis of iron(II)-NHC complexes.

IEEE 802.21: Media Independent Handover

In questo lavoro, dopo un'introduzione sul panorama contemporaneo, si è analizzato lo standard IEEE 802.21, illustrandone i motivi che hanno portato al suo sviluppo, la timeline del processo di standardizzazione, gli obbiettivi del working group, l'architettura del sistema specificato e le sue funzionalità, con particolare riguardo all'utilità in applicazioni reali, al fine di darne un giudizio completo sulla sua effettiva efficacia. Dopo aver citato qualche esempio di possibile applicazione dello standard e descritto lo stato attuale dell'arte, si è studiata una sua implementazione cross-platform chiamata ODTONE, descrivendone i vari componenti e le loro funzionalità, ma anche sottolineando le attuali mancanze per arrivare ad una implementazione completa sotto tutti i punti di vista. Successivamente si è studiata ed implementata un'applicazione, MIH-proxy, che potesse sfruttare in modo costruttivo i servizi specificati dallo standard per creare un proxy che potesse scegliere su quale interfaccia instradare i pacchetti a seconda dello stato attuale di tutti i collegamenti, realizzato in versione unidirezionale e bidirezionale. In particolare questa applicazione è in grado di restare in ascolto di cambiamenti di stato delle interfacce di rete, e.g. quando viene stabilita una connessione oppure cade, e, di conseguenza, stabilire di volta in volta quali collegamenti utilizzare per inviare dati. Nella versione bidirezionale è anche possibile far comunicare tra loro applicazioni che normalmente utilizzerebbero il protocollo di trasporto TCP attraverso un ulteriore componente, phoxy, che si preoccupa di convertire, in modo trasparente, un flusso TCP in datagrammi UDP eventualmente cifrati. Sarà quindi possibile creare un collegamento criptato ad alta affidabilità tra le applicazioni che possa sfruttare tutte le interfacce disponibili, sia per inviare, sia per ricevere.

The Presence of Words in Visual Art from Surrealism to Conceptualism

Without a doubt, one of the biggest changes that affected XXth century art is the introduction of words into paintings and, in more recent years, in installations. For centuries, if words were part of a visual composition, they functioned as reference; strictly speaking, they were used as a guideline for a better perception of the subject represented. With the developments of the XXth century, words became a very important part of the visual composition, and sometimes embodied the composition itself. About this topic, American art critic and collector Russell Bowman wrote an interesting article called Words and images: A persistent paradox, in which he examines the American and the European art of the XXth century in almost its entirety, dividing it up in six “categories of intention”. The aforementioned categories are not based on the art history timeline, but on the role that language played for specific artists or movements. Taking inspiration from Bowman's article, this paper is structured in three chapters, respectively: words in juxtaposition and free association, words as means of exploration of language structures, and words as means for political and personal messages. The purpose of this paper is therefore to reflect on the role of language in contemporary art and on the way it has changed from artist to artist.

Detecting social patterns within 20th century documentary photos: a deep learning based approach

The job of a historian is to understand what happened in the past, resorting in many cases to written documents as a firsthand source of information. Text, however, does not amount to the only source of knowledge. Pictorial representations, in fact, have also accompanied the main events of the historical timeline. In particular, the opportunity of visually representing circumstances has bloomed since the invention of photography, with the possibility of capturing in real-time the occurrence of a specific events. Thanks to the widespread use of digital technologies (e.g. smartphones and digital cameras), networking capabilities and consequent availability of multimedia content, the academic and industrial research communities have developed artificial intelligence (AI) paradigms with the aim of inferring, transferring and creating new layers of information from images, videos, etc. Now, while AI communities are devoting much of their attention to analyze digital images, from an historical research standpoint more interesting results may be obtained analyzing analog images representing the pre-digital era. Within the aforementioned scenario, the aim of this work is to analyze a collection of analog documentary photographs, building upon state-of-the-art deep learning techniques. In particular, the analysis carried out in this thesis aims at producing two following results: (a) produce the date of an image, and, (b) recognizing its background socio-cultural context,as defined by a group of historical-sociological researchers. Given these premises, the contribution of this work amounts to: (i) the introduction of an historical dataset including images of “Family Album” among all the twentieth century, (ii) the introduction of a new classification task regarding the identification of the socio-cultural context of an image, (iii) the exploitation of different deep learning architectures to perform the image dating and the image socio-cultural context classification.