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Design, realization, and characterization of complex reaction networks in dynamic mechanically interlocked molecules
Get PDFThe experimental projects discussed in this thesis are all related to the field of artificial molecular machines, specifically to systems composed of pseudorotaxane and rotaxane architectures. The characterization of the peculiar properties of these mechano-molecules is frequently associated with the analysis and elucidation of complex reaction networks; this latter aspect represents the main focus and central thread tying my thesis work. In each chapter, a specific project is described as summarized below: the focus of the first chapter is the realization and characterization of a prototype model of a photoactivated molecular transporter based on a pseudorotaxane architecture; in the second chapter is reported the design, synthesis, and characterization of a [2]rotaxane endowed with a dibenzylammonium station and a novel photochromic unit that acts as a recognition site for a DB24C8 crown ether macrocycle; in the last chapter is described the synthesis and characterization of a [3]rotaxane in which the relative number of rings and stations can be changed on command
Robust Adaptive Control with Applications to Multi-Agent Systems and Mobile Robotics
Get PDFThis thesis deals with robust adaptive control and its applications, and it is divided into three main parts. The first part is about the design of robust estimation algorithms based on recursive least squares. First, we present an estimator for the frequencies of biased multi-harmonic signals, and then an algorithm for distributed estimation of an unknown parameter over a network of adaptive agents. In the second part of this thesis, we consider a cooperative control problem over uncertain networks of linear systems and Kuramoto systems, in which the agents have to track the reference generated by a leader exosystem. Since the reference signal is not available to each network node, novel distributed observers are designed so as to reconstruct the reference signal locally for each agent, and therefore decentralizing the problem. In the third and final part of this thesis, we consider robust estimation tasks for mobile robotics applications. In particular, we first consider the problem of slip estimation for agricultural tracked vehicles. Then, we consider a search and rescue application in which we need to drive an unmanned aerial vehicle as close as possible to the unknown (and to be estimated) position of a victim, who is buried under the snow after an avalanche event.
In this thesis, robustness is intended as an input-to-state stability property of the proposed identifiers (sometimes referred to as adaptive laws), with respect to additive disturbances, and relative to a steady-state trajectory that is associated with a correct estimation of the unknown parameter to be found
Insolvency proceedings in the field of international maritime transport
Get PDFLa presente trattazione affronta le principali problematiche giuridiche derivanti dall’apertura di una procedura concorsuale, esaminando le questioni di maggiore rilievo giuridico e operativo per il settore del trasporto marittimo in base ai due sistemi che, a livello sovranazionale, regolano l’insolvenza transfrontaliera, i.e. quello ispirato alla UNCITRAL Model Law e il Regolamento UE 848/2015.
Le cornici normative UNCITRAL e UE hanno rappresentato, quindi, il punto di partenza dello scrutinio delle possibili aree di conflitto tra il trasporto marittimo e le procedure di insolvenza: sono emerse numerose zone di potenziale collisione, soprattutto in relazione ai criteri di collegamento tipici della navigazione (in primis, la bandiera quale elemento distintivo della nazionalità della nave) e, dunque, all’individuazione del centro degli interessi principali del debitore/armatore, soprattutto se – come di fatto avviene frequentemente in ambito internazionale – organizzato sotto forma di shipping group.
Il secondo capitolo è dedicato, in senso lato, ai privilegi marittimi e al loro rapporto con le procedure di insolvenza, con precipuo riferimento all’ipoteca navale e ai maritime liens.
A tale proposito, sono analizzate le principali problematiche correlate all’attuazione dei privilegi marittimi, segnatamente in relazione all’istituto del sequestro di nave di cui alla Convenzione di Bruxelles del 1952 nel contesto dell’insolvenza transfrontaliera.
Il terzo e ultimo capitolo è dedicato alla limitazione di responsabilità quale istituto tipico del settore di riferimento, dalla prospettiva delle possibili interferenze tra la costituzione dei fondi di cui alle Convenzioni LLMC e CLC ed eventuali procedimenti concorsuali.
La ricerca svolta ha dimostrato che l’universalità a cui ambiscono il Regolamento 848/2015 (già 1346/2000) e il sistema UNCITRAL risulta minata dalla coesistenza di una molteplicità di differenti interpretazioni e implementazioni, tali per cui l’insolvenza transfrontaliera delle compagnie di trasporto marittimo non risulta regolata in maniera uniforme, con conseguente possibilità di diverso trattamento di fattispecie e situazioni analoghe.This research addresses the main legal problems deriving from the opening of an insolvency procedure, examining the issues of greater legal and operational importance for the maritime transport sector, referring to the two systems which, at a supranational level, regulate cross-border insolvency, i.e. the one inspired by the UNCITRAL Model Law and EU Regulation 848/2015.
The UNCITRAL and EU regulatory frameworks therefore represented the starting point of the scrutiny of the possible areas of conflict between maritime transport and insolvency proceedings: many areas of potential collision emerged, especially in relation to the typical connection criteria of navigation (first and foremost, the flag as a distinctive element of the nationality of the ship) and, therefore, for what concerns the identification of the COMI of the debtor/shipowner, especially if – as it happens frequently at the international level - organized as a shipping group.
The second chapter is dedicated, in a broad sense, to maritime privileges and their relationship with insolvency proceedings, with particular reference to ship mortgages and maritime liens.
In this regard, the main issues related to the implementation of maritime privileges have been analyzed, especially in relation to the legal institution of the arrest of ships in the context of cross-border insolvency.
The third and final chapter is dedicated to the limitation of liability as a typical institution of the maritime sector, from the perspective of possible interference between the establishment of the funds referred to in the LLMC and CLC Conventions and insolvency proceedings.
The research has shown that the universality which aims Regulation 848/2015 and the UNCITRAL system is jeopardized by the coexistence of different interpretations and implementations, such that the cross-border insolvency of shipping companies is not regulated in a uniform manner, with the consequent possibility of different treatment of similar cases and situations
Structural and biophysical characterization of RAD52 as novel pharmacological target for synthetic lethality
Get PDFRAD52 is a protein involved in various DNA reparation mechanisms. In the last few years, RAD52 has been proposed as a novel pharmacological target for cancer synthetic lethality strategies. Hence, this work has the purpose to investigate RAD52 protein, with biophysical and structural tools to shed light on proteins features and mechanistic details that are, up to now poorly described, and to design novel strategies for its inhibition.
My PhD work had two goals: the structural and functional characterization of RAD52 and the identification of novel RAD52 inhibitors. For the first part, RAD52 was characterized both for its DNA interaction and oligomerization state together with its propensity to form high molecular weight superstructures. Moreover, using EM and Cryo-EM techniques, additional RAD52 structural hallmarks were obtained, valuable both for understanding protein mechanism of action and for drug discovery purpose.
The second part of my PhD project focused on the design and characterization of novel RAD52 inhibitors to be potentially used in combination therapies with PARPi to achieve cancer cells synthetic lethality, avoiding resistance occurrence and side effects. With this aim we selected and characterized promising RAD52 inhibitors through three different approaches: 19F NMR fragment-based screening; virtual screening campaign; aptamers computational design. Selected hits (fragments, molecules and aptamers) were investigated for their binding to RAD52 and for their mechanism of inhibition. Collected data highlighted the identification of hits worthy to be developed into more potent and selective RAD52 inhibitors.
Finally, a side project carried out during my PhD is reported. GSK-3β protein, an already validated pharmacological target was investigated using biophysical and structural biology tools. Here, an innovative and adaptable drug discovery screening pipeline able to directly identify selective compounds with binding affinities not higher than a reference binder was developed
Development of Advanced Combustions using Cylinder Pressure Signal
Get PDFZero-carbon powertrains development has become one of the main challenges for automotive industries around the world. Following this guideline, several approaches such as powertrain electrification, advanced combustions, and hydrogen internal combustion engines have been aimed to achieve the goal. Low Temperature Combustions, characterized by a simultaneous reduction of fuel consumption and emissions, represent one of the most studied solutions moving towards a sustainable mobility.
Previous research demonstrate that Gasoline partially premixed Compression Ignition combustion is one of the most promising LTC. Mainly characterized by the high-pressure direct-injection of gasoline and the spontaneous ignition of the premixed air-fuel mixture, GCI combustion has shown a good potential to achieve the high thermal efficiency and low pollutants in compression ignited engines required by future emission regulations. Despite its potential, GCI combustion might suffer from low combustion controllability and stability, because gasoline spontaneous ignition is significantly affected by slight variations of the local in-cylinder thermal conditions. Therefore, to properly control GCI combustion assuring the maximum performance, a deep knowledge of the combustion process, i.e., gasoline auto-ignition and the effect of the control parameters on the combustion and pollutants, is mandatory.
This PhD dissertation focuses on the study of GCI combustion in a light-duty compression ignited engine. Starting from a standard 1.3L diesel engine, this work describes the activities made moving toward the full conversion of the engine. A preliminary study of the GCI combustion was conducted in a “Single-Cylinder” engine configuration highlighting combustion characteristics and dependencies on the control parameters. Then, the full engine conversion was performed, and a wide experimental campaign allowed to confirm the benefits of this advanced combustion methodologies in terms of pollutants and thermal efficiency. The analysis of the in-cylinder pressure signal allowed to study in depth the GCI combustion and develop control-oriented models aimed to improve the combustion stability
Adaptive Neural Translation for Enterprises (ANTE). La traduzione automatica neurale a sostegno delle imprese emiliano-romagnole
Get PDFIl progetto ANTE riguarda i nuovi sistemi di traduzione automatica (TA) e la loro applicazione nel mondo delle imprese. Lo studio prende spunto dai recenti sviluppi legati all’intelligenza artificiale e ai Big Data che negli ultimi anni hanno permesso alla TA di raggiungere livelli qualitativi molto elevati, al punto tale da essere impiegata da grandi multinazionali per raggiungere nuove quote di mercato.
La TA può rispondere positivamente anche ai bisogni delle imprese di piccole dimensioni e a basso tenore tecnologico, migliorando la qualità delle comunicazioni multilingue attraverso delle traduzioni in tempi brevi e a costi contenuti. Lo studio si propone quindi di contribuire al rafforzamento della competitività internazionale delle piccole e medie imprese (PMI) emiliano- romagnole, migliorando la loro capacità di comunicazione in una o più lingue straniere attraverso l’introduzione e l’utilizzo efficace e consapevole di soluzioni ICT di ultima generazione e fornire, così, nuove opportunità di internazionalizzazione.The ANTE project focuses on new machine translation (MT) systems and their application in the business world. The study starts from the recent developments related to artificial intelligence and Big Data, which have enabled MT systems to reach very high levels of quality. For this reason, MT is nowadays employed by large multinational companies to achieve new market shares.
MT systems can also positively address the needs of small, low-tech firms by improving the quality of multilingual communications through cost-effective and time-efficient translations. The study aims to contribute to the strengthening of the international competitiveness of small and medium-sized enterprises (SMEs) in the Emilia-Romagna region, by improving their ability to communicate in one or more foreign languages through the introduction of the latest ICT solutions and thus provide new opportunities for internationalization
Photoactive (supra)molecular devices in double layer membranes
Get PDFBiological systems are complex and highly organized architectures governed by non-covalent interactions responsible for the regulation of essential tasks in all living organisms. These systems are a constant source of inspiration for supramolecular chemists aiming to design multicomponent molecular assemblies able to perform elaborated tasks, thanks to the role and action of the components that constitute them. Artificial supramolecular systems exploit non-covalent interactions to mimic naturally occurring events. In this context, stimuli-responsive supramolecular systems have attracted attention due to the possibility to control macroscopic effects through modifications at the nanoscale.
This thesis is divided in three experimental chapters, characterized by a progressive increase in molecular complexity.
Initially, the preparation and studies of liposomes functionalized with a photoactive guest such as azobenzene in the bilayer were tackled, in order to evaluate the effect of such photochrome on the vesicle properties.
Subsequently, the synthesis and studies of thread-like molecules comprising an azobenzene functionality was reported. Such molecules were conceived to be intercalated in the bilayer membrane of liposomes with the aim to be used as components for photoresponsive transmembrane molecular pumps.
Finally, a [3]rotaxane was developed and studied in solution. This system is composed of two crown ether rings interlocked with an axle containing three recognition sites for the macrocycles, i.e. two pH-switchable ammonium stations and a permanent triazolium station. Such molecule was designed to achieve a change in the ratio between the recognition sites and the crown ethers as a consequence of acid-base inputs. This leads to the formation of rotaxanes containing a number of recognition sites respectively larger, equal or lower than the number of interlocked rings and connected by a network of acid-base reactions
From educational continuity to transition: a action-research-training in the Integrates System of ECEC services
Get PDFIl progetto di ricerca relativo a questa tesi prende le mosse dalla più recente normativa italiana (l. 107/15; d.l. 65/2017) ed europea (EU Council Recommendation on high quality ECEC systems, 2019) e dalla riflessione teorica ad essa collegata in relazione all’istituzione e al riconoscimento del Sistema Integrato 0-6. La ricerca, metodologicamente impostata come ricerca-formazione, si è posta come obiettivo la definizione di categorie di analisi connesse a temi educativi e didattici emergenti nelle sperimentazioni di percorsi 0-6, e alla loro declinazione per fini formativi.
La cornice teorica di riferimento è stata identificata nella riflessione sul concetto di continuità, con particolare riferimento alle declinazioni di curricolo verticale (Venturelli & Cigala, 2017; Cerini et al., 2019) e curricolo implicito (Gariboldi, 2007; Prott & Pressing, 2007). Si è giunti, grazie ai risultati di ricerca, a proporre una riflessione rispetto all’operalizzazione del costrutto di continuità nell’ambito del sistema integrato 0-6, fino ad arrivare a definire il suo progressivo superamento all’interno di percorsi di progettazione che caratterizzano le sperimentazioni in corso di attuazione all’interno di Poli 0-6, attraverso la definizione del tema delle transizioni. Tale tema, emerso durante la ricerca, come cornice di riferimento tra i temi caratteristici lo 0-6 potrebbe, infatti, andare ad affiancare la riflessione sul tema della continuità, portando a risignificare la declinazione pratica dello stesso.
Dentro un approccio qualitativo più ampio, la ricerca-formazione è stata eletta come cornice metodologica di riferimento per questa ricerca, coniugando alcuni strumenti propri della stessa (identificazione degli obiettivi specifici, co-costruzione dei dati e analisi congiunta insieme ai soggetti coinvolti, focus group sul materiale raccolto) con alcuni strumenti di raccolta dati della ricerca etnografica (osservazioni, interviste semi-strutturate). La scelta di queste strategie metodologiche ha avuto sempre come obiettivo quello di sostenere la riflessività del gruppo di lavoro, rendendo continuamente espliciti i nessi tra teorie e prassi.The research project presented in this thesis focuses on the intersection between recent ECEC developments taking place both in national (l. 107/15; d.l. 65/2017) and European legislation (EU Council Recommendation on high quality ECEC systems, 2019) and the pedagogical reflections on the 0-6 integrated system in its constitutive phase in Italy. The research aims to identify relevant conceptual categories for interpreting 0-6 educational continuity within the integrated system, starting from the analysis of existing educational practice carried out in the ECEC services selected for the purpose of this study.
Through this research process, an original criticism was posed about the practical declination of educational continuity within the integrated system of ECEC to finally reach the progressive overcoming of such construct in the field of the experimental 0-6 paths, characterized instead by the theme of transition. Transitions emerged in the empirical work of this doctoral thesis as crucial elements to shape the analytical framework for the study the integrated system: they appear to be useful to critically integrate the notion of educational continuity and to decline it in practical terms.
The theoretical framework is based on the concept of educational continuity, with particular reference to the possible articulation of the vertical curriculum (Venturelli & Cigala, 2017; Cerini et al., 2019) and the implicit curriculum (Gariboldi, 2007; Prott & Pressing, 2007).
From a methodological point of view this study is positioned at the intersection between educational ethnography (i.e. tools adopted for data collection, such as participant observations, video-recordings and semi-structured interviews) and action-research-training methodology (i.e. involvement of participants as co-researchers ). In this sense one of the expected result of the project is to reinforce collective reflexivity among 0-3 and 3-6 professionals by adopting research procedures which increase their agency - by connecting theory and praxis
Responsible Innovation processes and practices: the role of Advanced Design in the collaborative transformation of territories
Get PDFLa ricerca indaga il rapporto tra Design e Innovazione Responsabile calandolo all’interno della relazione tra territorio e pratiche collaborative guidate dal design, ma anche legate al patrimonio culturale immateriale e a un sistema di conoscenza a quintupla elica. La necessità emergente di cura del futuro porta a rivedere il contesto del territorio come campo strumentale per la trasformazione degli individui e della comunità e a domandarsi in che modo il design possa supportare questo cambiamento, abilitando la produzione di conoscenza collaborativa.
La ricerca parte dal dimostrare come il modello di innovazione recentemente proposto dalla Comunità Europea attraverso il concetto di Responsible Research Innovation (RRI), poi ripreso nella nozione di Responsible Innovation (RI), sia un campo aperto e responsivo: se integrato con altre discipline, in particolare con il design, può supportare lo sviluppo di processi, politiche, prodotti, servizi e comportamenti che rispettino la relazione tra società, ambiente, identità individuale e collettiva e i ritmi ad essi connessi.
Partendo dal contesto sopra descritto, ci si chiede come il design e il designer possano integrare le dimensioni RI nei processi di progettazione, per innovare in modo collaborativo i territori. Si individua quindi nell’Advanced Design la metodologia che, grazie alla sua natura anticipatrice, collaborativa, trasformativa, riesce a coniugarsi virtuosamente con l’approccio RI e supportare il cambiamento in atto.
L’intersezione di questi elementi porta alla creazione del Modello Advanced Design per/con l’Innovazione Responsabile (ADIR): un sistema multidimensionale per gruppi di innovazione (quintupla elica) che hanno l’obiettivo di rigenerare in modo collaborativo e inclusivo i territori.
L’esperienza sul campo ha confermato come la struttura del modello, formata da un corpus di semi-lavorati, permetta di creare un proprio ritmo, una compenetrazione tra azioni e forme progettuali volti a mantenere il senso di comunità e il coinvolgimento degli attori, a creare relazioni, a sviluppare una trasformazione continua.This research investigates the relationship between Design and Responsible Innovation, within the relationship between territory and design-led collaborative practices, linking them to intangible cultural heritage and to a quintuple-helix knowledge system.
The research starts by showing how the model of innovation recently proposed by the European Commission through the concept of Responsible Research and Innovation (RRI), later taken up in the notion of Responsible Innovation (RI), is an open and responsive field: when integrated with other disciplines, in particular design, it can support the development of processes, policies, products, services and behaviors that respect the relationship between society, environment, individual and collective identities and the associated rhythms.
Starting from the context described above, the question arises as to how design and designers can integrate the dimensions and principles of RI into the design processes, in order to collaboratively innovate territories. Therefore, Advanced Design is identified as the methodology that, thanks to its anticipatory, collaborative and transformative nature, can virtuously integrate with the RI approach and support the ongoing change.
The intersection of these elements leads to the creation of the Advanced Design for/with Responsible Innovation (ADIR) model: a multidimensional system for innovation groups (quintuple helix) that aims to collaboratively and inclusively regenerate territories.
Field experience has confirmed how the structure of the model, made up of a set of formats, makes it possible to create its own rhythm, intensity and interpenetration between design actions, aimed at maintaining a sense of community and the involvement of the actors, creating relationships and developing a transformation of both individuals and the community
Economic constitution interpretations: constitutional framework and relationships between public powers, competition and inequalities
Get PDFLa tesi affronta la questione controversa di cosa si intenda per costituzione economica e di quali possano essere le sue interpretazioni. Il concetto è stato elaborato nel contesto del dibattito dottrinario, contemporaneo e successivo, all’Assemblea Costituente della Repubblica di Weimar. Questo dibattito ha influenzato, sotto molteplici profili, la stesura della Costituzione italiana, nonché le successive interpretazioni della costituzione economica che sono state prospettate dalla dottrina e dalla giurisprudenza.
Nel corso dei decenni, sono state proposte diverse interpretazioni dell’idea di costituzione economica, ognuna delle quali particolarmente caratterizzata dal punto di vista ideologico, in grado di aprire una diversa prospettiva sull’interazione fra poteri pubblici, mercato e disuguaglianze.
A partire dagli anni Ottanta, si è registrato un progressivo indebolimento dei vincoli posti dalla costituzione economica alle dinamiche dell’economia e alle forze incontrollate dei mercati. L’emergenza pandemica ha, tuttavia, determinato un cambiamento di paradigma, con l’inizio di un nuovo protagonismo dei poteri pubblici nel contesto europeo.
Occorre chiedersi quali siano attualmente le linee essenziali dell’idea di costituzione economica, nel contesto europeo e nazionale, quale interpretazione possa essere sposata e quali ricadute concrete possa comportare, in termini di politiche dei poteri pubblici in ambito economico.The thesis is about the controversial question of what is meant by economic constitution and what its interpretations may be. The concept was developed in the context of the doctrinal debate at the Constituent Assembly of the Weimar Republic. This debate has influenced, in many ways, the drafting of the Italian Constitution, as well as the interpretations of the economic constitution that have been proposed by doctrine and jurisprudence.
Over the decades, different interpretations of economic constitution have been proposed. Each one is characterized from an ideological point of view, capable of opening a different perspective on the interaction between public powers, competition and inequalities.
Since the 1980s, there has been a progressive weakening of the constraints fixed by the economic constitution on the dynamics of the economy. The pandemic emergency has, however, determined a paradigm shift, with the beginning of a new role of public powers in the European context. It is necessary to answer what is the economic constitution, in the European and national context, what interpretation can be married and what concrete consequences there are, in terms of public power policies in the economic sphere