Diet Effects on Activation and Maturation of Feed Control over the Gastrointestinal Defence Barrier in Piglets

Weaning is an important and complex step involving many stresses that interfere deeply with feed intake, gastro-intestinal tract (GIT) development and adaptation to the weaning diet in young pigs. The health of the pig at weaning, its nutrition in the immediate post-weaning period, and the physical, microbiological and psychological environment are all factors that interact to determine food intake and subsequent growth. GIT disorders, infections and diarrhoea increase at the time of weaning, in fact pathogens such as enterotoxigenic Escherichia coli (ETEC) are major causes of mucosal damage in post-weaning disease contributing to diarrhoea in suckling and post-weaned pigs. The European ban in 2006 put on antibiotic growth promoters (AGP) has stimulated research on the mechanisms of GIT disorders and on nutritional approaches for preventing or reducing such disturbances avoiding AGPs. Concerning these aspects here are presented five studies based on the interplay among nutrition, genomic, immunity and physiology with the aim to clarify some of these problematic issues around weaning period in piglets. The first three evaluate the effects of diets threonine or tryptophan enriched on gut defence and health as possible alternatives to AGP in the gut. The fourth is focused on the possible immunological function related with the development of the stomach. The fifth is a pilot study on the gastric sensing and orexygenic signal given by fasting or re-feeding conditions. Although some results are controversial, it appears that both tryptophan and threonine supplementation in weaning diets have a preventive role in E.coli PWD and favorable effects in the gut especially in relation to ETEC susceptible genotype. While the stomach is believed as almost aseptic organ, it shows an immune activity related with the mucosal maturation. Moreover it shows an orexygenic role of both oxyntic mucosa and pyloric mucosa, and its possible relation with nutrient sensing stimuli.

Multiscale fabrication of functional materials for life sciences

Regenerative medicine claims for a better understanding of the cause-effect relation between cell behaviour and environment signals. The latter encompasses topographical, chemical and mechanical stimuli, electromagnetic fields, gradients of chemo-attractants and haptotaxis. In this perspective, a spatial control of the structures composing the environment is required. In this thesis I describe a novel approach for the multiscale patterning of biocompatible functional materials in order to provide systems able to accurately control cell adhesion and proliferation. The behaviour of different neural cell lines in response to several stimuli, specifically chemical, topographical and electrical gradients is presented. For each of the three kind of signals, I chose properly tailored materials and fabrication and characterization techniques. After a brief introduction on the state of art of nanotechnology, nanofabrication techniques and regenerative medicine in Chapter 1 and a detailed description of the main fabrication and characterization techniques employed in this work in Chapter 2, in Chapter 3 an easy route to obtain accurate control over cell proliferation close to 100% is described (chemical control). In Chapter 4 (topographical control) it is shown how the multiscale patterning of a well-established biocompatible material as titanium dioxide provides a versatile and robust method to study the effect of local topography on cell adhesion and growth. The third signal, viz. electric field, is investigated in Chapter 5 (electrical control), where the very early stages of neural cell adhesion are studied in the presence of modest steady electric fields. In Chapter 6 (appendix) a new patterning technique, called Lithographically Controlled Etching (LCE), is proposed. It is shown how LCE can provide at the same time the micro/nanostructuring and functionalization of a surface with nanosized objects, thus being suitable for applications both in regenerative medicine in biosensing.

Interactions between normative systems and software cognitive agents. A formalization in temporal modal defeasible logic and its implementation

Sustainable computer systems require some flexibility to adapt to environmental unpredictable changes. A solution lies in autonomous software agents which can adapt autonomously to their environments. Though autonomy allows agents to decide which behavior to adopt, a disadvantage is a lack of control, and as a side effect even untrustworthiness: we want to keep some control over such autonomous agents. How to control autonomous agents while respecting their autonomy? A solution is to regulate agents’ behavior by norms. The normative paradigm makes it possible to control autonomous agents while respecting their autonomy, limiting untrustworthiness and augmenting system compliance. It can also facilitate the design of the system, for example, by regulating the coordination among agents. However, an autonomous agent will follow norms or violate them in some conditions. What are the conditions in which a norm is binding upon an agent? While autonomy is regarded as the driving force behind the normative paradigm, cognitive agents provide a basis for modeling the bindingness of norms. In order to cope with the complexity of the modeling of cognitive agents and normative bindingness, we adopt an intentional stance. Since agents are embedded into a dynamic environment, things may not pass at the same instant. Accordingly, our cognitive model is extended to account for some temporal aspects. Special attention is given to the temporal peculiarities of the legal domain such as, among others, the time in force and the time in efficacy of provisions. Some types of normative modifications are also discussed in the framework. It is noteworthy that our temporal account of legal reasoning is integrated to our commonsense temporal account of cognition. As our intention is to build sustainable reasoning systems running unpredictable environment, we adopt a declarative representation of knowledge. A declarative representation of norms will make it easier to update their system representation, thus facilitating system maintenance; and to improve system transparency, thus easing system governance. Since agents are bounded and are embedded into unpredictable environments, and since conflicts may appear amongst mental states and norms, agent reasoning has to be defeasible, i.e. new pieces of information can invalidate formerly derivable conclusions. In this dissertation, our model is formalized into a non-monotonic logic, namely into a temporal modal defeasible logic, in order to account for the interactions between normative systems and software cognitive agents.

Sviluppo di algoritmi avanzati di analisi e diagnosi combustione in tempo reale per motori endotermici alternativi

Increasingly stringent exhaust emission limits and higher fuel economy are the main drivers of the engine development process. As a consequence, the complexity of the propulsion units and its subsystems increase, due to the extensive use of sensors and actuators needed to obtain a precise control over the combustion phase. Since engine calibration process consumes most of the development time, new tools and methodologies are needed to shorten the development time and increase the performance attainable. Real time combustion analysis, based on the in-cylinder pressure signal, can significantly improve the calibration of the engine control strategies and the development of new algorithms, giving instantaneous feedback on the engine behavior. A complete combustion analysis and diagnosis system has been developed, capable of evaluating the most important indicators about the combustion process, such as indicated mean effective pressure, heat release, mass fraction burned and knock indexes. Such a tool is built on top of a flexible, modular and affordable hardware platform, capable of satisfying the requirements needed for accuracy and precision, but also enabling the use directly on-board the vehicle, due to its small form factor.

Supramolecular functional assemblies with photo or chemical addressability

Supramolecular self-assembly represents a key technology for the spontaneous construction of nanoarchitectures and for the fabrication of materials with enhanced physical and chemical properties. In addition, a significant asset of supramolecular self-assemblies rests on their reversible formation, thanks to the kinetic lability of their non-covalent interactions. This dynamic nature can be exploited for the development of “self-healing” and “smart” materials towards the tuning of their functional properties upon various external factors. One particular intriguing objective in the field is to reach a high level of control over the shape and size of the supramolecular architectures, in order to produce well-defined functional nanostructures by rational design. In this direction, many investigations have been pursued toward the construction of self-assembled objects from numerous low-molecular weight scaffolds, for instance by exploiting multiple directional hydrogen-bonding interactions. In particular, nucleobases have been used as supramolecular synthons as a result of their efficiency to code for non-covalent interaction motifs. Among nucleobases, guanine represents the most versatile one, because of its different H-bond donor and acceptor sites which display self-complementary patterns of interactions. Interestingly, and depending on the environmental conditions, guanosine derivatives can form various types of structures. Most of the supramolecular architectures reported in this Thesis from guanosine derivatives require the presence of a cation which stabilizes, via dipole-ion interactions, the macrocyclic G-quartet that can, in turn, stack in columnar G-quadruplex arrangements. In addition, in absence of cations, guanosine can polymerize via hydrogen bonding to give a variety of supramolecular networks including linear ribbons. This complex supramolecular behavior confers to the guanine-guanine interactions their upper interest among all the homonucleobases studied. They have been subjected to intense investigations in various areas ranging from structural biology and medicinal chemistry – guanine-rich sequences are abundant in telomeric ends of chromosomes and promoter regions of DNA, and are capable of forming G-quartet based structures– to material science and nanotechnology. This Thesis, organized into five Chapters, describes mainly some recent advances in the form and function provided by self-assembly of guanine based systems. More generally, Chapter 4 will focus on the construction of supramolecular self-assemblies whose self-assembling process and self-assembled architectures can be controlled by light as external stimulus. Chapter 1 will describe some of the many recent studies of G-quartets in the general area of nanoscience. Natural G- quadruplexes can be useful motifs to build new structures and biomaterials such as self-assembled nanomachines, biosensors, therapeutic aptamer and catalysts. In Chapters 2-4 it is pointed out the core concept held in this PhD Thesis, i.e. the supramolecular organization of lipophilic guanosine derivatives with photo or chemical addressability. Chapter 2 will mainly focus on the use of cation-templated guanosine derivatives as a potential scaffold for designing functional materials with tailored physical properties, showing a new way to control the bottom-up realization of well-defined nanoarchitectures. In section 2.6.7, the self-assembly properties of compound 28a may be considered an example of open-shell moieties ordered by a supramolecular guanosine architecture showing a new (magnetic) property. Chapter 3 will report on ribbon-like structures, supramolecular architectures formed by guanosine derivatives that may be of interest for the fabrication of molecular nanowires within the framework of future molecular electronic applications. In section 3.4 we investigate the supramolecular polymerizations of derivatives dG 1 and G 30 by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties. Chapter 4 will describe photoresponsive self-assembling systems. Numerous research examples have demonstrated that the use of photochromic molecules in supramolecular self-assemblies is the most reasonable method to noninvasively manipulate their degree of aggregation and supramolecular architectures. In section 4.4 we report on the photocontrolled self-assembly of modified guanosine nucleobase E-42: by the introduction of a photoactive moiety at C8 it is possible to operate a photocontrol over the self-assembly of the molecule, where the existence of G-quartets can be alternately switched on and off. In section 4.5 we focus on the use of cyclodextrins as photoresponsive host-guest assemblies: αCD–azobenzene conjugates 47-48 (section 4.5.3) are synthesized in order to obtain a photoresponsive system exhibiting a fine photocontrollable degree of aggregation and self-assembled architecture. Finally, Chapter 5 contains the experimental protocols used for the research described in Chapters 2-4.

Liquid crystal polymers: macromolecular design for enhanced performances

During this work, done mainly in the laboratories of the department of Industrial Chemistry and Materials of the University of Bologna but also in the laboratories of the Carnegie Mellon University in collaboration with prof. K. Matyjaszewski and at the university of Zaragoza in collaboration with prof. J. Barberá, was focused mainly on the synthesis and characterization of new functional polymeric materials. In the past years our group gained a deep knowledge about the photomodulation of azobenzene containing polymers. The aim of this thesis is to push forward the performances of these materials by the synthesis of well defined materials, in which, by a precise control over the macromolecular structures, better or even new functionality can be delivered to the synthesized material. For this purpose, besides the rich photochemistry of azoaromatic polymers that brings to the application, the control offered from the recent techniques of controlled radical polymerization, ATRP over all, gives an enormous range of opportunity for the developing of a new generation of functional materials whose properties are determinate not only by the chemical nature of the functional center (e.g. azoaromatic chromophore) but are tuned and even amplified by a synergy with the whole macromolecular structure. Old materials in new structures. In this contest the work of this thesis was focused mainly on the synthesis and characterization of well defined azoaromatic polymers in order to establish, for the first time, precise structure-properties correlation. In fact a series of well defined different azopolymers, chiral and achiral, with different molecular weight and highly monodisperse were synthesized and their properties were studied, in terms of photoexpansion and photomodulation of chirality. We were then able to study the influence of the macromolecular structure in terms of molecular weight and ramification on the studied properties. The huge amount of possibility offered by the tailoring of the macromolecular structure were exploited for the synthesis of new cholesteric photochromic polymers that can be used as a smart label for the certification of the thermal history of any thermosensitive product. Finally the ATRP synthesis allowed us to synthesize a total new class of material, named molecular brushes: a flat surface covered with an ultra thin layer of polymeric chain covalently bond onto the surface from one end. This new class of materials is of extreme interest as they offer the possibility to tune and manage the interaction of the surface with the environment. In this contest we synthesized both azoaromatic surfaces, growing directly the polymer from the surface, and mixed brushes: surfaces covered with incompatible macromolecules. Both type of surfaces acts as “smart” surfaces: the first it is able to move the orientation of a LC cell by simply photomodulation and, thanks to the robustness of the covalent bond, can be used as a command surface overcoming all the limitation due to the dewetting of the active layer. The second type of surface, functionalized by a grafting-to method, can self assemble the topmost layer responding to changed environmental conditions, exposing different functionality according to different environment.

Corporate Governance and Dividend Policy in European Banking

This dissertation investigates corporate governance and dividend policy in banking. This topic has recently attracted the attention of numerous scholars all over the world and currently remains one of the most discussed topics in Banking. The core of the dissertation is constituted by three papers. The first paper generalizes the main achievements in the field of relevant study using the approach of meta-analysis. The second paper provides an empirical analysis of the effect of banking corporate governance on dividend payout. Finally, the third paper investigates empirically the effect of government bailout during 2007-2010 on corporate governance and dividend policy of banks. The dissertation uses a new hand-collected data set with information on corporate governance, ownership structure and compensation structure for a sample of listed banks from 15 European countries for the period 2005-2010. The empirical papers employ such econometric approaches as Within-Group model, difference-in-difference technique, and propensity score matching method based on the Nearest Neighbor Matching estimator. The main empirical results may be summarized as follows. First, we provide evidence that CEO power and connection to government are associated with lower dividend payout ratios. This result supports the view that banking regulators are prevalently concerned about the safety of the bank, and powerful bank CEOs can afford to distribute low payout ratios, at the expense of minority shareholders. Next, we find that government bailout during 2007-2010 changes the banks’ ownership structure and helps to keep lending by bailed bank at the pre-crisis level. Finally, we provide robust evidence for increased control over the banks that receive government money. These findings show the important role of government when overcoming the consequences of the banking crisis, and high quality of governance of public bailouts in European countries.

Project Financing nelle Infrastrutture del Trasporto

L’elaborato ha avuto ad oggetto l’analisi delle sofisticate soluzioni normative proposte dall’ordinamento nazionale in relazione all’evoluzione della finanza di progetto. In particolare, è stata condotto un dettagliato studio delle fasi che compongono il project financing, nonché dei soggetti che, a diverso titolo e ragione, vi partecipano. L’elaborato contiene, poi, recenti esempi concreti di project financing nelle infrastrutture primarie (autostrade) tra cui il progetto di costruzione e la successiva gestione dell’autostrada regionale Medio Padana veneta, dell’autostrada regionale Cispadana, e dell’autostrada “Nogara-mare”. L’ultimo parte della tesi è stata infine incentrata sull’analisi delle più recenti pronunce giurisprudenziali in materia di project financing. In particolare, si ha avuto modo di analizzare il fenomeno dello jus poenitendi dell’amministrazione aggiudicatrice, nonché, più in generale gli eventi che possono negativamente incidere sulla finanza di progetto (mancata aggiudicazione, risoluzione del contratto di gestione, ecc.).

Synthetic strategies of new spin-labelled supramolecular systems

Molecular recognition and self-assembly represent fundamental issues for the construction of supramolecular systems, structures in which the components are held together through non-covalent interactions. The study of host-guest complexes and mechanical interlocked molecules, important examples in this field, is necessary in order to characterize self-assembly processes, achieve more control over the molecular organization and develop sophisticated structures by using properly designed building blocks. The introduction of paramagnetic species, or spin labelling, represents an attractive opportunity that allows their detection and characterization by the Electron Spin Resonance spectroscopy, a valuable technique that provides additional information to those obtained by traditional methods. In this Thesis, recent progresses in the design and the synthesis of new paramagnetic host-guest complexes and rotaxanes characterized by the presence of nitroxide radicals and their investigation by ESR spectroscopy are reported. In Chapter 1 a brief overview of the principal concepts of supramolecular chemistry, the spin labelling approach and the development of ESR methods applied to paramagnetic systems are described. Chapter 2 and 3 are focused on the introduction of radicals in macrocycles as Cucurbiturils and Pillar[n]arenes, due to the interesting binding properties and the potential employment in rotaxanes, in order to investigate their structures and recognition properties. Chapter 4 deals with one of the most studied mechanical interlocked molecules, the bistable [2]rotaxane reported by Stoddart and Heath based on the ciclobis (paraquat-p-phenylene) CBPQT4+, that represents a well known example of molecular switch driven by external stimuli. The spin labelling of analogous architectures allows the monitoring by ESR spectroscopy of the switch mechanism involving the ring compound by tuning the spin exchange interaction. Finally, Chapter 5 contains the experimental procedures used for the synthesis of some of the compounds described in Chapter 2-4.