958 resultados para Goût
Resumo:
This thesis gathers the work carried out by the author in the last three years of research and it concerns the study and implementation of algorithms to coordinate and control a swarm of mobile robots moving in unknown environments. In particular, the author's attention is focused on two different approaches in order to solve two different problems. The first algorithm considered in this work deals with the possibility of decomposing a main complex task in many simple subtasks by exploiting the decentralized implementation of the so called \emph{Null Space Behavioral} paradigm. This approach to the problem of merging different subtasks with assigned priority is slightly modified in order to handle critical situations that can be detected when robots are moving through an unknown environment. In fact, issues can occur when one or more robots got stuck in local minima: a smart strategy to avoid deadlock situations is provided by the author and the algorithm is validated by simulative analysis. The second problem deals with the use of concepts borrowed from \emph{graph theory} to control a group differential wheel robots by exploiting the Laplacian solution of the consensus problem. Constraints on the swarm communication topology have been introduced by the use of a range and bearing platform developed at the Distributed Intelligent Systems and Algorithms Laboratory (DISAL), EPFL (Lausanne, CH) where part of author's work has been carried out. The control algorithm is validated by demonstration and simulation analysis and, later, is performed by a team of four robots engaged in a formation mission. To conclude, the capabilities of the algorithm based on the local solution of the consensus problem for differential wheel robots are demonstrated with an application scenario, where nine robots are engaged in a hunting task.
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Until recently the debate on the ontology of spacetime had only a philosophical significance, since, from a physical point of view, General Relativity has been made "immune" to the consequences of the "Hole Argument" simply by reducing the subject to the assertion that solutions of Einstein equations which are mathematically different and related by an active diffeomorfism are physically equivalent. From a technical point of view, the natural reading of the consequences of the "Hole Argument” has always been to go further and say that the mathematical representation of spacetime in General Relativity inevitably contains a “superfluous structure” brought to light by the gauge freedom of the theory. This position of apparent split between the philosophical outcome and the physical one has been corrected thanks to a meticulous and complicated formal analysis of the theory in a fundamental and recent (2006) work by Luca Lusanna and Massimo Pauri entitled “Explaining Leibniz equivalence as difference of non-inertial appearances: dis-solution of the Hole Argument and physical individuation of point-events”. The main result of this article is that of having shown how, from a physical point of view, point-events of Einstein empty spacetime, in a particular class of models considered by them, are literally identifiable with the autonomous degrees of freedom of the gravitational field (the Dirac observables, DO). In the light of philosophical considerations based on realism assumptions of the theories and entities, the two authors then conclude by saying that spacetime point-events have a degree of "weak objectivity", since they, depending on a NIF (non-inertial frame), unlike the points of the homogeneous newtonian space, are plunged in a rich and complex non-local holistic structure provided by the “ontic part” of the metric field. Therefore according to the complex structure of spacetime that General Relativity highlights and within the declared limits of a methodology based on a Galilean scientific representation, we can certainly assert that spacetime has got "elements of reality", but the inevitably relational elements that are in the physical detection of point-events in the vacuum of matter (highlighted by the “ontic part” of the metric field, the DO) are closely dependent on the choice of the global spatiotemporal laboratory where the dynamics is expressed (NIF). According to the two authors, a peculiar kind of structuralism takes shape: the point structuralism, with common features both of the absolutist and substantival tradition and of the relationalist one. The intention of this thesis is that of proposing a method of approaching the problem that is, at least at the beginning, independent from the previous ones, that is to propose an approach based on the possibility of describing the gravitational field at three distinct levels. In other words, keeping the results achieved by the work of Lusanna and Pauri in mind and following their underlying philosophical assumptions, we intend to partially converge to their structuralist approach, but starting from what we believe is the "foundational peculiarity" of General Relativity, which is that characteristic inherent in the elements that constitute its formal structure: its essentially geometric nature as a theory considered regardless of the empirical necessity of the measure theory. Observing the theory of General Relativity from this perspective, we can find a "triple modality" for describing the gravitational field that is essentially based on a geometric interpretation of the spacetime structure. The gravitational field is now "visible" no longer in terms of its autonomous degrees of freedom (the DO), which, in fact, do not have a tensorial and, therefore, nor geometric nature, but it is analyzable through three levels: a first one, called the potential level (which the theory identifies with the components of the metric tensor), a second one, known as the connections level (which in the theory determine the forces acting on the mass and, as such, offer a level of description related to the one that the newtonian gravitation provides in terms of components of the gravitational field) and, finally, a third level, that of the Riemann tensor, which is peculiar to General Relativity only. Focusing from the beginning on what is called the "third level" seems to present immediately a first advantage: to lead directly to a description of spacetime properties in terms of gauge-invariant quantites, which allows to "short circuit" the long path that, in the treatises analyzed, leads to identify the "ontic part” of the metric field. It is then shown how to this last level it is possible to establish a “primitive level of objectivity” of spacetime in terms of the effects that matter exercises in extended domains of spacetime geometrical structure; these effects are described by invariants of the Riemann tensor, in particular of its irreducible part: the Weyl tensor. The convergence towards the affirmation by Lusanna and Pauri that the existence of a holistic, non-local and relational structure from which the properties quantitatively identified of point-events depend (in addition to their own intrinsic detection), even if it is obtained from different considerations, is realized, in our opinion, in the assignment of a crucial role to the degree of curvature of spacetime that is defined by the Weyl tensor even in the case of empty spacetimes (as in the analysis conducted by Lusanna and Pauri). In the end, matter, regarded as the physical counterpart of spacetime curvature, whose expression is the Weyl tensor, changes the value of this tensor even in spacetimes without matter. In this way, going back to the approach of Lusanna and Pauri, it affects the DOs evolution and, consequently, the physical identification of point-events (as our authors claim). In conclusion, we think that it is possible to see the holistic, relational, and non-local structure of spacetime also through the "behavior" of the Weyl tensor in terms of the Riemann tensor. This "behavior" that leads to geometrical effects of curvature is characterized from the beginning by the fact that it concerns extensive domains of the manifold (although it should be pointed out that the values of the Weyl tensor change from point to point) by virtue of the fact that the action of matter elsewhere indefinitely acts. Finally, we think that the characteristic relationality of spacetime structure should be identified in this "primitive level of organization" of spacetime.
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In this PhD-thesis new synthetic approaches towards new azetidinone derivatives are described. In particular, 4-alkyliden-β-lactams were used as starting materials for the preparation of new biologically active compounds. The carbapenem Thienamycin has got a broad spectrum of activity as antibiotic. It has got 3 stereocenters and apart of one epimer, all isomers have been synthesized. Using the 4-alkyliden-β-lactam benzilyc ester as precursor, we developed a synthesis for this missing epimer, which is described in chapter II. Biological tests in order to establish its biological activity are under way. The Hunsdiecker-Borodine reaction was extensively studied for the preparation of the mono halogenated and – surprisingly – the dihalogenated derivative from the 4-alkyliden-azetidinone carboxylic acid. The herein described synthetic procedures allowed the preparation of chloro-, bromo- and iodo derivatives in good to excellent yield. Furthermore, the reaction mechanism was investigated by NMR-experiments and is described in detail in chapter III. In chapter IV, synthetic approaches towards new β-lactam derivatives for inhibition of the histone deacetylase enzymes (HDACs) are reported. In collaboration with the company Sigma-Tau (Rome), 14 new β-lactams were synthesized. The new β-lactams were evaluated for the activity showing a promising activityparticulary, 10 of the β-lactams synthesized were evaluated for the in vitro inhibitory activity against the 11 human HDACs isoforms and they showed a selective inhibition of HDAC6 or HDAC8 in micromolar range. Finally, preliminary studies were conducted for the employment of 4-alkyliden-β-lactams as precursors for the synthesis of chiral β-amino acids by an opening of the β-lactam ring. In chapter V is described the ring opening reaction catalyzed by the enzyme lipase Cal-B. Preliminary results have shown that the enzyme not only catalyzes the ring opening of the β-lactam precursor, moreover, it leads to the formation of a cyclic dimer by the reaction of two molecules of β-amino acid obtained.
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ZUSAMMENFASSUNGZiel der vorliegenden Arbeit war es, zunächst möglichst viele Kalluskulturen mit reduziertem Arbeitsaufwand aus zufällig ausgewählten Pflanzen anzulegen. Dies wurde an 140 verschiedenen Samenpflanzen versucht, was bei 45 (32 %) der eingesetzten Arten gelang. Hatte sich ausreichend Kallusgewebe gebildet, wurden Suspensionskulturen angelegt. Dies gelang für alle 21 eingesetzten Kalluskulturen. Aus 14 Zellsuspensionskulturen wurden Extrakte hergestellt, und aus ihnen mit Hilfe semipräparativer HPLC die Inhaltsstoffe isoliert. Insgesamt konnte die Struktur von 29 isolierten Substanzen mit Hilfe von LC-MS-Spektrometrie und NMR-Spektroskopie aufgeklärt werden.Bei den meisten Substanzen handelte es sich um Verbindungen, die bereits in vielen Pflanzen nachgewiesen werden konnten,.Die neben Rosmarinsäure aus Rosmarinus officinalis isolierte 3-Deoxy-rosmarinsäure und das Anthrachinonderivat aus der Zellkultur von Galium odoratum sind Beispiel für Verbindungen, die zuvor noch nicht in Pflanzen nachgewiesen wurden. Besonders auffällige Verbindungen sind die isolierten Isopropanolderivate, von denen sich Vertreter in fast allen Pflanzenzellkulturen finden ließen. Sie sind wahrscheinlich Metabolisierungsprodukte des beim Überimpfen der Zellkulturen eingebrachten Isopropanols. Eine besondere Eignung der Zellkulturen als Quelle neuer pharmakologisch einsetzbarer Substanzen konnte nicht nachgewiesen werden. Aber erst die Identifizierung, der in geringerer Menge gebildeten Substanzen ermöglicht es, das Inhaltsstoffspektrum der Zellkulturen im Vergleich zu denen der differenzierten Pflanze abschließend zu bewerten.
Resumo:
Zusammenfassung Im Rahmen dieser Arbeit wurde der PAC1-Rezeptor (Pituitary Adenylate Cyclase Activating-Polypeptide-Rezeptor), ein Mitglied der VIP-Glucagon-Rezeptorfamilie, aus Sf21-Insektenzellen angereichert. Zur Überexpression wurde das Baculovirussystem genutzt. Die Expression konnte um das 20fache gegenüber natürlichem Gewebe gesteigert werden (40 pmol/mg). Das Drosophila-Expressionssystem und die Expression in suspensionsadaptierten HEK-Zellen erwiesen sich dagegen als weniger effizient für die Überexpression des PAC1-Rezeptors. Der PAC1-Rezeptor wurde mit Digitonin aus den Sf21-Zellmembranen solubilisiert und mittels eines Rhodopsin-Epitops über Antikörperaffinitätschromatographie funktionell angereichert. Der funktionell angereicherte Rezeptor wurde mit einem photoreaktiven und radioaktiven PACAP-Liganden markiert. Anschließend erfolgte der proteolytische Verdau mit Kallikrein. Aufgrund der Zuordnung der radioaktiven Spaltfragmente konnte die Ligandenbindungsstelle im PAC1-Rezeptor auf den N-Terminus und den ersten extrazellulären Loop beschränkt werden. Dieses Ergebnis bestätigt Resultate, die für andere Mitglieder dieser Rezeptorfamilie vorliegen.Alternativ wurde der PAC1-Rezeptor unfunktionell in E.colis überexprimiert und in hohen Maße über ein C-terminales His6-Tag aus Inclusion bodies angereichert. Zudem wurde in dieser Arbeit erstmals ein Einfluss des PAC1-Rezeptors auf die APP-Prozessierung festgestellt. Dies äußerte sich in einem Anstieg der APPsa-Sekretion. Obwohl weitere Untersuchungen über genauere Mechanismen und Wechselwirkungen noch ausstehen, konnte hier gezeigt werden, dass der PAC1-Rezeptor einen positiv regulatorischen Einfluss auf die APPsa-Sekretion besaß. Der PAC1-Rezeptor ist wahrscheinlich ein Stimulator der a-Sekretasen und erstmals in direkten Zusammenhang mit der Alzheimerschen Erkrankung diskutierbar.
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Questa ricerca mostra l’evoluzione della letteratura mitologica per ragazzi in Italia. Il primo libro italiano di mitologia per bambini è stato pubblicato nel 1911 (lo stesso anno di un’importante e violenta guerra coloniale tra l’Italia e la Libia): la scrittrice italiana Laura Orvieto pubblicò allora “Storie della storia del mondo”, in cui riunì antichi racconti greci per giovani lettori. Queste storie erano ispirate al libro mitologico per bambini “Il libro delle meraviglie” di Hawthorne (titolo originale “A Wonder Book for Girls and Boys”). In seguito molti scrittori italiani scrissero libri mitologici per giovani lettori: serie importanti di libri di mitologia per bambini furono pubblicate durante il regime mussoliniano – talvolta per diffondere l’ideologia fascista della superiorità romana. Durante questo periodo, i libri mitologici spesso mostravano uno stile letterario solenne. Dopo la seconda guerra mondiale, la letteratura mitologica per bambini cambiò lentamente prospettiva: gli scrittori italiani cominciarono ad usare il mito per parlare di problemi sociali (p.e. Gianni Rodari descriveva re Mida come un capitalista) e per spiegare le diverse condizioni umane (p.e. Beatrice Masini fa riferimento alle dee e alle eroine greche per descrivere la condizione femminile). La ricerca analizza anche la relazione tra mito e scuola in Italia: i racconti mitologici hanno sempre fatto parte dei programmi scolastici italiani per bambini dagli 8 agli 11 anni. Le riforme scolastiche – deliberate negli anni ’20 e ’40 – fissarono pratiche didattiche sui miti ancora oggi in uso. I racconti mitologici erano soprattutto un supporto per gli studi storici e letterari. Tuttavia, negli ultimi decenni, i miti sono divenuti un importante aiuto per gli insegnamenti scientifici e artistici.
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Plakate begleiten den Film auch in Deutschland schon seit seinen Anfängen 1895/96. Filmplakate sollen Filminhalte in einem grafischen Kürzel zusammenfassen. Aufraggeber ist zumeist der Filmverleih bzw. die Filmgesellschaft, seltener einzelne Kinos. Filmplakate sind im wesentlichen bildlich-figürlich bestimmt, viele illustrieren auf naive Art eine Szene des Films, verbunden mit der Darstellung der Schauspieler. Die Grafiker können sich oft lediglich anhand von Inhaltsangaben und Fotos einen Eindruck von der zu bewerbenden Sache verschaffen. Zunächst werben sie für Programme, weniger für einzelne Filme. Das ändert sich mit der zunehmenden Länge der Produktionen. Neben zahlreichen anonymen Zeichnern werden schon bald auch namhafte Plakatkünstler mit Filmplakaten beschäftigt, wie Klinger, Deutsch, Kainer, Hohlwein, Erdt, die jeweils verschiedene Plakatauffassungen vertreten. Plakate für Asta Nielsen oder Henny Porten dokumentieren frühe Stardarstellungen, diejenigen für frühe Detektivfilme stehen für ein Genre. Mit dem Namen Fenneker steht das expressionistische Filmplakat um 1920 in Verbindung. Grafiker wie Matejko; Leonard, oder Kupfer-Sachs arbeiten eher naturalistisch. Konstruktivistische Plakate entwirf Tschichold. 1927 für den Münchener Phoebus-Palast. Zwischen 1930 und 1945 ist der Plakatstil des Ufa-Werbedienstes maßgebend. Abweichend davon kann Pewas Fotomontageplakate gestalten.. Sehr früh beginnt die Zensur sich der Filmplakate anzunehmen. Zunächst in unterschiedlichen Rechtstiteln enthalten, wird die Plakatzensur 1920 im Reichslichtspielgesetz verankert.
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In der vorliegenden Arbeit wurde die Rolle von Interleukin-18 (IL-18) in der Leber untersucht. IL-18 wurde eine Bedeutung bei verschiedenen Lebererkrankungen zugeschrieben, die genauen Mechanismen sind jedoch nicht geklärt. IL-18 kann ein wesentlicher Faktor bei der Regulierung des Th1/Th2-Gleichgewichts in der Leber sein. Es wurden transgene Mäuse mit konstitutiver Überexpression der inaktiven Form von IL-18 (proIL-18) sowie transgene Mäuse mit Expression der aktiven Form von IL-18 ohne Signalpeptid (FLAG-IL-18) und mit Signalpeptid (SP-IL-18) in Hepatozyten unter der transkriptionellen Kontrolle des murinen Albumin-Promoters etabliert. In eigenen Vorarbeiten wurde eine konstitutive Expression von proIL-18 in Wildtyp-Hepatozyten festgestellt. Bei der Überexpression von proIL-18 in Hepatozyten zeigte sich eine Akkumulierung des Proteins in der Zelle und eine spontane entzündliche und fibrotische Aktivität in der Leber. Die Expression der aktiven Form von IL-18 ohne Signalpeptid (FLAG-IL-18) in Hepatozyten führte zu einer Speicherkrankheit in der Leber. Das Fusionieren des aktiven Teils von IL-18 mit IgG-k-Leadersequenz (SP-IL-18) ermöglichte die Sezernierung von IL-18 aus der Zelle ohne Einfluß auf die Produktion von IFN-g, TNF-a, IL-4 sowie Transaminasen. Die Rolle von IL-18 bei einem LPS-abhängigen Leberschaden mit und ohne Präkonditionierung mit CpG-Oligonukleotiden in vivo wurde untersucht. Die Behandlung proIL-18-transgener Mäuse mit LPS führte zur Sezernierung von biologisch aktivem IL-18 aus Hepatozyten. IL-18 hatte bei proIL-18- sowie bei SP-IL-18-transgenen Mäusen nach der LPS-Gabe keinen Einfluß auf die Leberschädigung und Produktion von IFN-g, TNF-a, IL-4. Nach sequenzieller Behandlung mit CpG und LPS fand sich bei SP-IL-18-transgenen Tieren im Gegensatz zu proIL-18-transgenen Mäusen eine stärkere Produktion von GOT, IFN-g und TNF-a im Vergleich zu Wildtyptieren. In dieser Arbeit konnte gezeigt werden, daß IL-18 alleine keine hepatotoxische Wirkung und keinen Einfluß auf die Produktion von IFN-g, TNF-a, IL-4 hat, wofür ein zusätzlicher Stimulus notwendig ist. Die in der vorliegenden Arbeit etablierten proIL-18- und SP-IL-18-transgenen Mausmodelle liefern die Grundlage zu weiteren Untersuchungen der Rolle von IL-18 in der Leber bei der Immunmodulation.
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Diese Arbeit charakterisiert die Funktion und das Expressionmuster der beiden Zinkfinger-Homöodomänentranskriptionsfaktoren zfh1 und zfh2 von Drosophila melanogaster. Das zfh2 Gen wurde hierbei vor allem molekular charakterisiert. Es wurden eine Vielzahl möglicher Spleißformen identifiziert, welche das regulatorische Potential von Zfh2 enorm erweitern. Für Überexpressionsexperimente wurde zudem erstmalig die cDNA des längsten zfh2-Transkriptes kloniert. Durch Analysen an zfh1 Mutanten konnte gezeigt werden, dass zfh1 sowohl notwendig ist für die embryonale Entwicklung von Motoneuronen, als auch das larvale Wachstum motoneuronaler Endplatten reguliert. Wegen weit reichender pleiotroper Effekte, die zfh1 Funktionsverlustmutanten haben, war es notwendig, neben dem Einsatz hypomorpher Allele auf die Analyse genetischer Mosaike auszuweichen. Die als MARCM-Technik (Lee und Luo, 1999) bezeichnete Methode zur Erzeugung genetischer Mosaike wurde modifiziert um in dieser Arbeit erstmals für die Analyse mutanter larvaler Motoneurone eingesetzt werden zu können. Weitergehend konnte gezeigt werden, dass Zfh1 notwendig ist für die larvale Expression des Neuropeptides FMRFamid. Anhand von Sequenzvergleichen und durch Verwendung eines fmrfamid-Promoterkonstruktes (Benveniste et al., 1998) konnten Hinweise dafür gesammelt werden, dass die Zfh1-abhängige Regulation sehr wahrscheinlich direkter Natur ist. Bei fmrfamid handelt es sich somit um das erste identifizierte neurale Zielgen von Zfh1, an dem sich zudem modellhaft der molekulare Wirkmechanismus von Zfh1 erforschen lässt.
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Il territorio italiano presenta una grandissima ricchezza nel campo dei Beni Culturali, sia mobili che immobili; si tratta di un patrimonio di grande importanza che va gestito e tutelato nel migliore dei modi e con strumenti adeguati, anche in relazione ai problemi ad esso legati in termini di manutenzione e di salvaguardia dai fattori di rischio a cui può essere esposto. Per una buona conoscenza del Patrimonio Culturale, è fondamentale un’acquisizione preliminare di informazioni condotte in modo sistematico e unitario, che siano diffuse ed organiche, ma anche utili ad una valutazione preventiva e ad una successiva programmazione degli interventi di restauro di tipo conservativo. In questo ambito, l'impiego delle tecniche e tecnologie geomatiche nel campo dei Beni Culturali, può fornire un valido contributo, che va dalla catalogazione e documentazione del bene culturale al suo controllo e monitoraggio. Oggigiorno il crescente sviluppo di nuove tecnologie digitali, accompagnato dai notevoli passi avanti compiuti dalle discipline della geomatica (in primo luogo topografiche e fotogrammetriche), rende possibile una efficace integrazione tra varie tecniche, favorita anche dalla diffusione di soluzioni per l’interscambio dati e per la comunicazione tra differenti dispositivi. Lo studio oggetto della presente tesi si propone, di approfondire gli aspetti legati all’uso delle tecniche e tecnologie della Geomatica, per mettere in risalto le condizioni di un bene ed il suo stato di degrado. Per la gestione e la salvaguardia di un bene culturale , si presenta il SIT Carta del Rischio che evidenzia le pericolosità legate al patrimonio, e come esse sommate alla vulnerabilità di un singolo bene, contribuiscano all’individuazione del grado di rischio. di approfondire gli aspetti legati all’uso delle tecniche e tecnologie delle Geomatica, per mettere in risalto le condizioni di un bene ed il suo stato di degrado.
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Data Distribution Management (DDM) is a core part of High Level Architecture standard, as its goal is to optimize the resources used by simulation environments to exchange data. It has to filter and match the set of information generated during a simulation, so that each federate, that is a simulation entity, only receives the information it needs. It is important that this is done quickly and to the best in order to get better performances and avoiding the transmission of irrelevant data, otherwise network resources may saturate quickly. The main topic of this thesis is the implementation of a super partes DDM testbed. It evaluates the goodness of DDM approaches, of all kinds. In fact it supports both region and grid based approaches, and it may support other different methods still unknown too. It uses three factors to rank them: execution time, memory and distance from the optimal solution. A prearranged set of instances is already available, but we also allow the creation of instances with user-provided parameters. This is how this thesis is structured. We start introducing what DDM and HLA are and what do they do in details. Then in the first chapter we describe the state of the art, providing an overview of the most well known resolution approaches and the pseudocode of the most interesting ones. The third chapter describes how the testbed we implemented is structured. In the fourth chapter we expose and compare the results we got from the execution of four approaches we have implemented. The result of the work described in this thesis can be downloaded on sourceforge using the following link: https://sourceforge.net/projects/ddmtestbed/. It is licensed under the GNU General Public License version 3.0 (GPLv3).
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In recent years, the use of Reverse Engineering systems has got a considerable interest for a wide number of applications. Therefore, many research activities are focused on accuracy and precision of the acquired data and post processing phase improvements. In this context, this PhD Thesis deals with the definition of two novel methods for data post processing and data fusion between physical and geometrical information. In particular a technique has been defined for error definition in 3D points’ coordinates acquired by an optical triangulation laser scanner, with the aim to identify adequate correction arrays to apply under different acquisition parameters and operative conditions. Systematic error in data acquired is thus compensated, in order to increase accuracy value. Moreover, the definition of a 3D thermogram is examined. Object geometrical information and its thermal properties, coming from a thermographic inspection, are combined in order to have a temperature value for each recognizable point. Data acquired by an optical triangulation laser scanner are also used to normalize temperature values and make thermal data independent from thermal-camera point of view.
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The market’s challenges bring firms to collaborate with other organizations in order to create Joint Ventures, Alliances and Consortia that are defined as “Interorganizational Networks” (IONs) (Provan, Fish and Sydow; 2007). Some of these IONs are managed through a shared partecipant governance (Provan and Kenis, 2008): a team composed by entrepreneurs and/or directors of each firm of an ION. The research is focused on these kind of management teams and it is based on an input-process-output model: some input variables (work group’s diversity, intra-team's friendship network density) have a direct influence on the process (team identification, shared leadership, interorganizational trust, team trust and intra-team's communication network density), which influence some team outputs, individual innovation behaviors and team effectiveness (team performance, work group satisfaction and ION affective commitment). Data was collected on a sample of 101 entrepreneurs grouped in 28 ION’s government teams and the research hypotheses are tested trough the path analysis and the multilevel models. As expected trust in team and shared leadership are positively and directly related to team effectiveness while team identification and interorganizational trust are indirectly related to the team outputs. The friendship network density among the team’s members has got positive effects on the trust in team and on the communication network density, and also, through the communication network density it improves the level of the teammates ION affective commitment. The shared leadership and its effects on the team effectiveness are fostered from higher level of team identification and weakened from higher level of work group diversity, specifically gender diversity. Finally, the communication network density and shared leadership at the individual level are related to the frequency of individual innovative behaviors. The dissertation’s results give a wider and more precise indication about the management of interfirm network through “shared” form of governance.
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Over the years the Differential Quadrature (DQ) method has distinguished because of its high accuracy, straightforward implementation and general ap- plication to a variety of problems. There has been an increase in this topic by several researchers who experienced significant development in the last years. DQ is essentially a generalization of the popular Gaussian Quadrature (GQ) used for numerical integration functions. GQ approximates a finite in- tegral as a weighted sum of integrand values at selected points in a problem domain whereas DQ approximate the derivatives of a smooth function at a point as a weighted sum of function values at selected nodes. A direct appli- cation of this elegant methodology is to solve ordinary and partial differential equations. Furthermore in recent years the DQ formulation has been gener- alized in the weighting coefficients computations to let the approach to be more flexible and accurate. As a result it has been indicated as Generalized Differential Quadrature (GDQ) method. However the applicability of GDQ in its original form is still limited. It has been proven to fail for problems with strong material discontinuities as well as problems involving singularities and irregularities. On the other hand the very well-known Finite Element (FE) method could overcome these issues because it subdivides the computational domain into a certain number of elements in which the solution is calculated. Recently, some researchers have been studying a numerical technique which could use the advantages of the GDQ method and the advantages of FE method. This methodology has got different names among each research group, it will be indicated here as Generalized Differential Quadrature Finite Element Method (GDQFEM).
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Intense research is being done in the field of organic photovoltaics in order to synthesize low band-gap organic molecules. These molecules are electron donors which feature in combination with acceptor molecules, typically fullerene derivarntives, forming an active blend. This active blend has phase separated bicontinuous morphology on a nanometer scale. The highest recorded power conversionrnefficiencies for such cells have been 10.6%. Organic semiconductors differ from inorganic ones due to the presence of tightly bonded excitons (electron-hole pairs)resulting from their low dielectric constant (εr ≈2-4). An additional driving force is required to separate such Frenkel excitons since their binding energy (0.3-1 eV) is too large to be dissociated by an electric field alone. This additional driving force arises from the energy difference between the lowest unoccupied molecular orbital (LUMO) of the donor and the acceptor materials. Moreover, the efficiency of the cells also depends on the difference between the highest occupied molecular orbital (HOMO) of the donor and LUMO of the acceptor. Therefore, a precise control and estimation of these energy levels are required. Furthermore any external influences that change the energy levels will cause a degradation of the power conversion efficiency of organic solar cell materials. In particular, the role of photo-induced degradation on the morphology and electrical performance is a major contribution to degradation and needs to be understood on a nanometer scale. Scanning Probe Microscopy (SPM) offers the resolution to image the nanometer scale bicontinuous morphology. In addition SPM can be operated to measure the local contact potential difference (CPD) of materials from which energy levels in the materials can be derived. Thus SPM is an unique method for the characterization of surface morphology, potential changes and conductivity changes under operating conditions. In the present work, I describe investigations of organic photovoltaic materials upon photo-oxidation which is one of the major causes of degradation of these solar cell materials. SPM, Nuclear Magnetic Resonance (NMR) and UV-Vis spectroscopy studies allowed me to identify the chemical reactions occurring inside the active layer upon photo-oxidation. From the measured data, it was possible to deduce the energy levels and explain the various shifts which gave a better understanding of the physics of the device. In addition, I was able to quantify the degradation by correlating the local changes in the CPD and conductivity to the device characteristics, i.e., open circuit voltage and short circuit current. Furthermore, time-resolved electrostatic force microscopy (tr-EFM) allowed us to probe dynamic processes like the charging rate of the individual donor and acceptor domains within the active blend. Upon photo-oxidation, it was observed, that the acceptor molecules got oxidized first preventing the donor polymer from degrading. Work functions of electrodes can be tailored by modifying the interface with monomolecular thin layers of molecules which are made by a chemical reaction in liquids. These modifications in the work function are particularly attractive for opto-electronic devices whose performance depends on the band alignment between the electrodes and the active material. In order to measure the shift in work function on a nanometer scale, I used KPFM in situ, which means in liquids, to follow changes in the work function of Au upon hexadecanethiol adsorption from decane. All the above investigations give us a better understanding of the photo-degradation processes of the active material at the nanoscale. Also, a method to compare various new materials used for organic solar cells for stability is proposed which eliminates the requirement to make fully functional devices saving time and additional engineering efforts.