Al giorno d’oggi, la tecnologia GNSS può essere uno strumento utile, non solo in ambito di navigazione, ma anche per applicazioni di posizionamento di precisione come il monitoraggio di strutture o del territorio. Questa tecnica permette un controllo in continuo, anche da remoto, e ha un costo relativamente basso sia per quanto riguarda le strumentazioni che per gli aspetti di materializzazione e mantenimento. Nell’ottica di utilizzare la tecnologia GNSS per applicazioni di monitoraggio, il problema, nella sua interezza, può essere suddiviso in due grandi ambiti: l’ambito tecnologico (strumentazioni e apparati da adottare per un problema di monitoraggio anche in tempo reale) e l’ambito scientifico legato al problema del trattamento del dato che può, o deve, essere separato a sua volta in due aree legate alla tipologia di monitoraggio che si intende compiere. Il monitoraggio di movimenti lenti per analisi di stabilità (volto principalmente allo studio dell’evoluzione del quadro deformativo nel lungo periodo) o il monitoraggio per possibili applicazioni nell’ambito dell’early warning (che richiedono la valutazione di un movimento in tempo reale). Per le sperimentazioni sia di natura tecnologica che di trattamento del dato sono stati individuati due siti su cui sono stati installate stazioni permanenti GNSS di classe geodetica. Il primo sito è collocato sul tetto della scuola di Ingegneria ed Architettura dell’Università di Bologna, il secondo sito è la sommità della Torre Garisenda di Bologna (oggetto di particolare rilevanza culturale). Sul tetto di Ingegneria è stata collocata anche una slitta micrometrica che ha consentito l’imposizione di movimenti calibrati nelle tre direzioni. Per ciascun aspetto sono stati compiuti numerosi test sperimentali volti ad individuare le tecniche migliori per il monitoraggio con GNSS a partire dalle problematiche di trasferimento dati e finendo con lo sviluppo di particolari algoritmi per migliorare le prestazioni del sistema in condizioni di monitoraggio statico. / Nowadays, GNSS technology can be a useful tool, not only for navigation and location aspects, but also for precise positioning applications, such as structures and environmental monitoring. This technique allows a continuous control, even remotely, and has a relatively low cost both regarding the instrumentation, the monumentation and the maintenance. In order to use the GNSS technology for monitoring applications, two main problems can be identified: (a) the technological one is represented by instrumentation and equipment that are used in order to provide data in real time. The scientific one (b) is related to the issue of data processing. It can be in turn separated in two fields, which are related to the type of monitoring. In detail, (b1) the monitoring of slow movements for stability analysis (aimed mainly at the study of the long time evolution of these phenomena) or (b2) the monitoring for possible applications in early warning systems. For this study two sites were considered. In each one, a GNSS geodetic class permanent station was installed. The first site is located on the roof of the School of Engineering and Architecture, University of Bologna, while the second one is on the top of the Garisenda Tower in Bologna. Moreover, in the first site, a micrometric sledge which allowed the imposition of calibrated movements in the three directions, has also been placed. For each aspect, several experimental tests have been carried out. They were aimed at identifying the best techniques for GNSS monitoring, starting from the data transfer problems and ending with the development of algorithms to improve system performance in static monitoring conditions.

Over the last decades the impact of natural disasters to the global environment is becoming more and more severe. The number of disasters has dramatically increased, as well as the cost to the global economy and the number of people affected. Among the natural disaster, flood catastrophes are considered to be the most costly, devastating, broad extent and frequent, because of the tremendous fatalities, injuries, property damage, economic and social disruption they cause to the humankind. In the last thirty years, the World has suffered from severe flooding and the huge impact of floods has caused hundreds of thousands of deaths, destruction of infrastructures, disruption of economic activity and the loss of property for worth billions of dollars. In this context, satellite remote sensing, along with Geographic Information Systems (GIS), has become a key tool in flood risk management analysis. Remote sensing for supporting various aspects of flood risk management was investigated in the present thesis. In particular, the research focused on the use of satellite images for flood mapping and monitoring, damage assessment and risk assessment. The contribution of satellite remote sensing for the delineation of flood prone zones, the identification of damaged areas and the development of hazard maps was explored referring to selected cases of study.

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).

The Notch1 signaling pathway has a pivotal role in cell fate regulation and has been found to be critically deranged in different cancers, including colorectal cancer (CRC). Inflammation is known to play an important role in the pathogenesis of CRC and a prominent function of Notch1 during inflammation has been recently demonstrated. Epithelial to Mesenchymal Transition (EMT), a crucial process in the malignant transformation, is modulated by inflammation and Metalloproteinase-9 (MMP9) is involved in this interaction. Eicosapentaenoic Acid is an omega-3 polyunsaturated fatty acid (omega-3 PUFA) known for its anti-inflammatory properties as well as for its capability in preventing colon cancer development both in sporadic and in hereditary settings. In particular, our group has demonstrated that an extra-pure formulation of Eicosapentaenoic Acid as the free fatty acid (EPA-FFA) protects from CRC development in a mouse model of colitis-associated cancer (CAC) by modulating the Notch signaling pathway. In the present work, we re-created an in vitro model of inflammatory-driven CRC by exposing colon cancer cells to a cytokine-enriched conditioned medium (CM) obtained from THP-1-differentiated macrophages. We found, for the first time, that CM strongly induces Notch1 signaling and EMT markers, increasing the capability of cells to invade. Importantly we found that, upon CM exposure, Notch1 signaling is dependent on MMP9 expression. Finally, we show that a non-cytotoxic pre-treatment with 50 μM of EPA-FFA for 72h counteracts the effect of inflammation on Notch1 signaling and EMT, leading to a reduction of invasiveness. Taken together, our data demonstrate that in CRC inflammation up-regulates Notch1 signaling through MMP9 and that this mechanism can be effectively counteracted by EPA-FFA.

This PhD research project deals with the synthesis and characterization of supramolecular photoresponsive systems based on the azobenzene unit. 1)Azobenzene-cyclodextrin inclusion complexes: the aim of this study was to obtain relatively simple, water-soluble derivatives, whose self-assembly could be reversibly controlled by light. On the basis of previous results, this opens the possibility of directly converting light into mechanical energy via osmosis. Several new azobenzene functionalized cyclodextrins have been synthesized, fully characterized and studied The inclusion complexes thus formed and their light-driven disassembly were studied by means of several complementary techniques including NMR, UV, CD, ICT, mass spectroscopy. The most suitable systems were used in experiments, still in progress, of light-to-mechanical energy conversion. 2)Azobenzene-guanosine hybrids: several novel azobenzene-guanosine hybrids were synthesized for the purpose of investigating the effect of cis-trans photoisomerization on guanosine self-assembly. Lipophilic guanosines in organic solvents can form either ribbon-like supramolecular polymers or, in the presence of alkali metal ions, G-quartet based supramolecular complexes. These complexes were fully characterized for newly synthesized azobenzene-guanosine hybrids. In the absence of ions, the ribbon-like supramolecular polymer gives rise to a gel-like system, which turned out to be a lyotropic liquid crystalline phase. Photoisomerization to cis form induces the transition to an isotropic solution, in a reversible fashion. In addition, the G-quartet structure obtained in the presence of alkali metal ions can be disassembled by light. 3) Oligoazobenzenes’s project. While several examples of electron-rich conjugated polymers are known and find application e.g. as electron donors in “plastic” photovoltaics, no examples are reported on the use of electron-poor conjugated polymers as acceptor counterpart. In particular, no polyazobenzenes having the (-C6H4-N=N-) repeat unit have ever been reported. Although no polymeric has been obtained yet, we succeeded in synthesizing several homologues up to a tetramer. The compounds were subjected to photophysical, photochemical and electrochemical characterization.

In this thesis the results of a Computational Organic Chemistry Ph.D. work course ranging from organometallic to metal-free and enzymatic catalysis is discussed. Various energetic and mechanistic aspects of organic reactions in catalysis are the key-issues which are addressed. A multidisciplinary approach allowed the development of several research projects in collaboration with experimental groups and combined experimental-theoretical works were carried out. Notes and comments concerning the theoretical models used and the experimental work carried out by the research groups who cooperated with us, are reported. The thesis comprises four main sections. The first section provides basic information on the computational methods used in the present work. In the subsequent sections (Part II, Part III and Part IV) we focus on different aspects of organic catalysis. In Part II the results of computational studies on the mechanism of various metal-catalyzed reactions are presented. In particular we describe organic reactions catalyzed by Gold(I) complexes. We consider some synthetically important processes in organic chemistry. The purpose of these studies was to discover some general rules to rationalize the role of gold complexes in different classes of organic reactions. Furthermore, at the end of this section we describe a mechanistic investigation of an example of organo-catalysis, thus not involving metal complexes. In Part III we focus on an emerging and promising area of "metal-free" catalysis, based on carbon nanostructures such as graphite, graphene, graphene oxide, fullerenes and carbon nanotubes (CNTs). This “metal-free” catalysis is usually denoted as Carbocatalysis. The energy contributions that may influence the course of a reaction inside a CNT, have been elucidated by means of computational methods. In Part IV the computational approach is used to elucidate the mechanism of an enzymatic reaction. We describe the results obtained in the study of tyrosine O-sulfonation catalyzed by human Tyrosylprotein Sulfotransferases-2.

The increasing occurrence of CRC developing in young patients with no identified genetic predisposition, defined as sporadic early onset colorectal cancers (EOCRCs), demands maintaining a high index of suspicion when people below 50 years of age present with symptoms. To define the clinicopathological features and the stage at presentation of EOCRCs, as well as to understand whether the histological, immunohistochemical and molecular analyses were associated with particular clinicopathological parameters and oncologic outcome, a total of 94 cases of EOCRCs diagnoses between 2006 and 2014 at the Sant’Orsola University Hospital were studied. Indeed, EOCRCs appear frequently as an aggressive disease located in the sigmoid colon and rectum, and most patients are symptomatic at the time of presentation, mainly presenting with rectal bleeding, haematochezia or abdominal pain. The genetic basis in the majority of early onset colorectal carcinomas remains unknown, however, most EOCRCs, not related hereditary syndromes, appear to arise through the same pathways as sporadic CRCs, such as the classical adenoma-carcinoma sequence, but with only rare involvement of the methylator pathway. Taken together, the analyses described in this study suggest that, in the absence of screening programs for patients under 50 years of age, the risk factor of a family history and the presence of symptoms may be considered as an indication for prompt endoscopic investigation in these patients, since this may reduce the stage of disease at diagnosis and likely have an impact on improving survival.

During my PhD I was involved in many studies concerning the nucleophilic (SNAr) and electrophilic (SEAr) aromatic substitution reactions. My research activity was focused on the study of different electrophile/nucleophile combinations between strongly activated species, with the purpose to investigate on their reactivity, to detect new intermediates of the aromatic substitution reaction and to obtain new higly conjugated structures bearing contemporaneously electron donor and acceptor moieties on the same unit for application in different fields. Different reactions between both neutral or charged electrophilic and nucleophilic species were performed and from their combinations new products for applications in different fields (e.g. medicine, biology and materials) were obtained and new intermediates of the aromatic substitution reactions [e.g. Wheland (W), Meisenheimer (M), and even Wheland-Meisenheimer (WM)], were detected and characterized, mainly using NMR spectroscopic techniques. In particular the involved nucleophilic species were: tri- and diaminobenzene derivatives, trihydroxybenzene, trimethoxybenzene, anisole derivatives and aminothiazole derivatives; whereas the selected electrophilic species were: aryldiazonium ions, benzofuroxan and benzofurazan derivatives, thiophene derivatives and benzhydrylium ions. Furthermore, the last year of my PhD course, I spent a period in the Department of Chemistry, Ludwig-Maximilians-University of Munich, in collaboration with Prof. Herbert Mayr’s group, with the aim to investigate on the nucleophilic reactivities of di- and triaminobenzene derivatives performing their combination with different reference electrophiles, selected from the Mayr’s reactivity scales.

Questa tesi è mirata ad essere un lavoro che racchiude alcuni dei vari aspetti rilevanti che collegano la Green Chemistry alla sostenibilità ambientale. La tesi riguarda lo sviluppo sostenibile attraverso capitoli che concorrono alla progettazione di processi chimici eco-compatibili innovativi e approcci verdi per ridurre al minimo e/o rimediare l'inquinamento ambientale. In questo contesto, il mio progetto di dottorato ha affrontato tre temi principali: 1. Progettazione, sintesi e caratterizzazione di nuove molecole di tensioattivo che impiegano materie prime rinnovabili, acido itaconico e ammine lipofile, come materiali di partenza; il Capitolo 2 descrive questo argomento. 2. Sviluppo di una procedura sostenibile finalizzata alla sintesi multicomponente a cascata di biarilcalconi in acqua pura o in condizioni di catalisi micellare; in quest'ultimo caso, uno dei tensioattivi precedentemente sintetizzati è stato ampiamente impiegato; il Capitolo 5 descrive questo argomento. Capitolo 3 e Capitolo 4 descrivono il contesto scientifico e le innovazioni più importanti che hanno aperto la strada a i risultati conseguiti durante il 2 ° anno del corso di dottorato; il primo è una panoramica sull'uso dell'acqua come solvente per reazioni organiche; il secondo è una panoramica sulle reazioni di cross-coupling e lo sfruttamento in questo contesto della catalisi micellare. 3. Progettazione, sintesi e impiego di ligandi di tipo fenantrolinico deuterati per l'ossidazione aerobica palladio catalizzata del metil-glucoside, consentendo un elevato miglioramento della prestazione in questa reazione impegnativa; il Capitolo 7 raccoglie i risultati ottenuti, mentre il capitolo 6 riassume i più importanti progressi ottenuti negli ultimi anni nelle ossidazioni aerobiche di alcoli palladio-catalizzate. / This thesis is intended to be a work that encompasses some of the various relevant aspects linking the Green Chemistry practice to environmental sustainability. The thesis covers sustainable development through chapters that contribute to the design of novel environmentally benign chemical processes and green approaches to minimize and/or remediate environmental pollution. In this context, my PhD project has faced three main topics: 1. Design, synthesis and characterization of new surfactant molecules employing renewable feedstocks, itaconic acid and fatty amines, as starting materials; Chapter 2 describes this topic. 2. Development of a sustainable procedure aimed to the multicomponent cascade synthesis of biaryl-based chalcones in pure water or under micellar catalysis conditions; in the latter case, one of the surfactants previously synthesized has been widely employed; Chapter 5 describes this topic. Chapter 3 and Chapter 4 describe the scientific context and the most important innovations that have paved the way to the results achieved during the 2nd year of PhD course; the former is an overview on the use of water as solvent for organic reactions; the latter is an overview on cross-coupling reactions and the exploitation in this context of micellar catalysis. 3. Design, synthesis and exploitation of deuterated phenanthroline-type ligands for the aerobic palladium-catalyzed oxidation of methyl glucoside, allowing a high performance improvement in this challenging reaction; Chapter 7 collects the obtained results, while Chapter 6 summarizes the most important advances obtained in the last years in the palladium-catalyzed aerobic oxidations of alcohols.

During the last fifteen years organocatalysis emerged as a powerful tool for the enantioselective functionalization of the most different organic molecules. Both C-C and C-heteroatom bonds can be formed in an enantioselective fashion using many types of catalyst and the field is always growing. Many kind of chiral catalysts have emerged as privileged, but among them Proline, cinchona alkaloids, BINOL, and their derivatives showed to be particularly useful chiral scaffolds. This thesis, after a short presentation of many organocatalysts and activation modes, focuses mainly on cinchona alkaloid derived primary amines and BINOL derived chiral Brønsted acids, describing their properties and applications. Then, in the experimental part, these compounds are used for the catalysis of new transformations. The enantioselective Friedel-Crafts alkylation of cyclic enones with naphthols using cinchona alkaloid derived primary amines as catalysts is presented and discussed. The results of this work were very good and this resulted also in a publication. The same catalysts are then used to accomplish the enantioselective addition of indoles to cyclic enones. Many catalysts in combination with many acids as co-catalysts were tried and the reaction was fully studied. Selective N-alkylation was obtained in many cases, in combination with quite good to good enantioselectivities. Also other kind of catalysis were tried for this reaction, with interesting results. Another aza-Michael reaction between OH-free hydroxylamines and nitrostyrene using cinchona alkaloid derived thioureas is briefly discussed. Then our attention focused on Brønsted acid catalyzed transformations. With this regard, the Prins cyclization, a reaction never accomplished in an enantioselective fashion until now, is presented and developed. The results obtained are promising. In the last part of this thesis the work carried out abroad is presented. In Prof. Rueping laboratories, an enantioselective Nazarov cyclization using cooperative catalysis and the enantioselective desymmetrization of meso-hydrobenzoin catalyzed by Brønsted acid were studied.