957 resultados para Chimie de coordination


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La tesi si propone di sviluppare un modello, l'architettura e la tecnologia per il sistema di denominazione del Middleware Coordinato TuCSoN, compresi gli agenti, i nodi e le risorse. Identità universali che rappresentano queste entità, sia per la mobilità fisica sia per quella virtuale, per un Management System (AMS, NMS, RMS) distribuito; tale modulo si occupa anche di ACC e trasduttori, prevedendo questioni come la tolleranza ai guasti, la persistenza, la coerenza, insieme con il coordinamento disincarnata in rete, come accade con le tecnologie Cloud. All’interno dell’elaborato, per prima cosa si è fatta una introduzione andando a descrivere tutto ciò che è contenuto nell’elaborato in modo da dare una visione iniziale globale del lavoro eseguito. Di seguito (1° capitolo) si è descritta tutta la parte relativa alle conoscenze di base che bisogna avere per la comprensione dell’elaborato; tali conoscenze sono relative a TuCSoN (il middleware coordinato con cui il modulo progettato dovrà interfacciarsi) e Cassandra (sistema server distribuito su cui si appoggia la parte di mantenimento e salvataggio dati del modulo). In seguito (2° capitolo) si è descritto JADE, un middleware da cui si è partiti con lo studio per la progettazione del modello e dell’architettura del modulo. Successivamente (3° capitolo) si è andati a spiegare la struttura e il modello del modulo considerato andando ad esaminare tutti i dettagli relativi alle entità interne e di tutti i legami fra esse. In questa parte si è anche dettagliata tutta la parte relativa alla distribuzione sulla rete del modulo e dei suoi componenti. In seguito (4° capitolo) è stata dettagliata e spiegata tutta la parte relativa al sistema di denominazione del modulo, quindi la sintassi e l’insieme di procedure che l’entità consumatrice esterna deve effettuare per ottenere un “nome universale” e quindi anche tutti i passaggi interni del modulo per fornire l’identificatore all’entità consumatrice. Nel capitolo successivo (5° capitolo) si sono descritti tutti i casi di studio relativi alle interazioni con le entità esterne, alle entità interne in caso in cui il modulo sia o meno distribuito sulla rete, e i casi di studio relativi alle politiche, paradigmi e procedure per la tolleranza ai guasti ed agli errori in modo da dettagliare i metodi di riparazione ad essi. Successivamente (6° capitolo) sono stati descritti i possibili sviluppi futuri relativi a nuove forme di interazione fra le entità che utilizzano questo modulo ed alle possibili migliorie e sviluppi tecnologici di questo modulo. Infine sono state descritte le conclusioni relative al modulo progettato con tutti i dettagli in modo da fornire una visione globale di quanto inserito e descritto nell’elaborato.

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This thesis work has been carried out during the Erasmus exchange period at the “Université Paris 6 – Pierre et Marie Curie”, in the “Edifices PolyMétalliques – EPOM” team, leaded by Prof. Anna Proust, belonging to the “Institut Parisien de Chimie Moléculaire”, under the supervision of Dr. Guillaume Izzet and Dr. Geoffroy Guillemot. The redox properties of functionalized Keggin and Dawson POMs have been exploited in photochemical, catalytic and reactivity tests. For the photochemical purposes, the selected POMs have been functionalized with different photoactive FGs, and the resulting products have been characterized by CV analyses, luminescence tests and UV-Vis analyses. In future, these materials will be tested for hydrogen photoproduction and polymerization of photoactive films. For the catalytic purposes, POMs have been firstly functionalized with silanol moieties, to obtain original coordination sites, and then post-functionalized with TMs such as V, Ti and Zr in their highest oxidation states. In this way, the catalytic properties of TMs were coupled to the redox properties of POM frameworks. The redox behavior of some of these hybrids has been studied by spectro-electrochemical and EPR methods. Catalytic epoxidation tests have been carried out on allylic alcohols and n-olefins, employing different catalysts and variable amounts of them. The performances of POM-V hybrids have been compared to those of VO(iPrO)3. Finally, reactivity of POM-VIII hybrids has been studied, using styrene oxide and ethyl-2-diazoacetate as substrates. All the obtained products have been analyzed via NMR techniques. Cyclovoltammetric analyses have been carried out in order to determine the redox behavior of selected hybrids.

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L'elasticità è un concetto fondamentale nell'ambito del cloud computing, ma propone problemi di coordinazione che, se non compresi nella loro natura, rischiano di renderla inefficiente. Tramite il concetto di “elasticità consapevole della coordinazione” (coordination-aware elasticity), in questa tesi si discute come si possa espandere il linguaggio per l’elasticità cloud SYBL in modo che possa eseguire alcune funzioni elastiche tramite il linguaggio di coordinazione ReSpecT.

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We have developed a haptic-based approach for retraining of interjoint coordination following stroke called time-independent functional training (TIFT) and implemented this mode in the ARMin III robotic exoskeleton. The ARMin III robot was developed by Drs. Robert Riener and Tobias Nef at the Swiss Federal Institute of Technology Zurich (Eidgenossische Technische Hochschule Zurich, or ETH Zurich), in Zurich, Switzerland. In the TIFT mode, the robot maintains arm movements within the proper kinematic trajectory via haptic walls at each joint. These arm movements focus training of interjoint coordination with highly intuitive real-time feedback of performance; arm movements advance within the trajectory only if their movement coordination is correct. In initial testing, 37 nondisabled subjects received a single session of learning of a complex pattern. Subjects were randomized to TIFT or visual demonstration or moved along with the robot as it moved though the pattern (time-dependent [TD] training). We examined visual demonstration to separate the effects of action observation on motor learning from the effects of the two haptic guidance methods. During these training trials, TIFT subjects reduced error and interaction forces between the robot and arm, while TD subject performance did not change. All groups showed significant learning of the trajectory during unassisted recall trials, but we observed no difference in learning between groups, possibly because this learning task is dominated by vision. Further testing in stroke populations is warranted.

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Coordinating organizational activity across different sectors is crucial in disaster management. We analysed the response of 291 aid workers to the Haiti earthquake in 2010 and found that common incentives and a high degree of equality among aid organizations positively affected perceived network coordination. Large and public organizations were more likely to take leadership roles and high numbers of public organizations involved in the disaster response network led to improved network coordination. These results indicate the need for mechanisms that enable smaller and non-profit organizations to participate in network coordination and leadership.

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Cross-sectoral interorganizational relationships in post-conflict situations occur regularly. Whether formal task forces, advisory groups or other ad hoc arrangements, these relations take place in chaotic and dangerous situations with urgent and turbulent political, economic and social environments. Furthermore, they typically involve a large number of players from many different nations, operating across sectors, and between multiple layers of bureaucracy and diplomacy. The organizational complexity staggers many participants and observers, as do the tasks they are charged with completing. Reform efforts in Bosnia and Herzegovina starting in 1995 may serve as the archetype model of conflict, transition and development for the 21st century. It wins this honor due not to its particular programmatic successes and failures, rather to the interorganizational complexity of the International Community. From the massive response to the crisis, to the modern nation-building policies it spawned, and the development assistance practices and institutional arrangements it created, the Bosnian development experience has much to offer by way of lessons learned. This manuscript frames the unique Bosnian development situation, and provides lessons learned from the experience of nation building given local realities. Pettigrew (1992) called this "contextualizing." While network and/or organizational structure, strategy and process explain many interorganizational relationship issues, the development variables identified in this manuscript prove equally important, yet elusive and difficult to measure despite their very real and overt presence.

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Schizophrenia has been postulated to involve impaired neuronal cooperation in large-scale neural networks, including cortico-cortical circuitry. Alterations in gamma band oscillations have attracted a great deal of interest as they appear to represent a pathophysiological process of cortical dysfunction in schizophrenia. Gamma band oscillations reflect local cortical activities, and the synchronization of these activities among spatially distributed cortical areas has been suggested to play a central role in the formation of networks. To assess global coordination across spatially distributed brain regions, Omega complexity (OC) in multichannel EEG was proposed. Using OC, we investigated global coordination of resting-state EEG activities in both gamma (30–50 Hz) and below-gamma (1.5–30 Hz) bands in drug-naïve patients with schizophrenia and investigated the effects of neuroleptic treatment. We found that gamma band OC was significantly higher in drug-naïve patients with schizophrenia compared to control subjects and that a right frontal electrode (F3) contributed significantly to the higher OC. After neuroleptic treatment, reductions in the contribution of frontal electrodes to global OC in both bands correlated with the improvement of schizophrenia symptomatology. The present study suggests that frontal brain processes in schizophrenia were less coordinated with activity in the remaining brain. In addition, beneficial effects of neuroleptic treatment were accompanied by improvement of brain coordination predominantly due to changes in frontal regions. Our study provides new evidence of improper intrinsic brain integration in schizophrenia by investigating the resting-state gamma band activity.

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The explorative coordination chemistry of the bridging ligand TTF-PPB is presented. Its strong binding ability to Co(II) and then to Ni(II) or Cu(II) in the presence of hexafluoroacetylacetonate (hfac(-)), forming new mono-and dinuclear complexes 1-3, is described. X-ray crystallographic studies have been conducted in the case of the free ligand TTF-PPB as well as its complexes [Co(TTF-PPB)(hfac)(2)] (1) and [Co(hfac)(2)(mu-TTF-PPB)Ni(hfac)(2)] (2). Each metal ion is bonded to two bidentate hfac-anions through their oxygen atoms and two nitrogen atoms of the PPB moiety with a distorted octahedral coordination geometry. Specifically, nitrogen donor atoms of TTF-PPB adopt a cis-coordination but not in the equatorial plane, which is quite rare. Electronic absorption, photoinduced intraligand charge transfer ((1)ILCT), and electrochemical behaviour of 1-3 have been investigated. UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred pi-pi* transitions and an intense broad band in the visible region corresponding to a spin-allowed pi-pi* (1)ILCT transition. Upon coordination, the (1)ILCT band is bathochromically shifted by 3100, 6100 and 5900 cm(-1) on going from 1 to 3. The electrochemical studies reveal that all of them undergo two reversible oxidation and one reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the PPB unit, respectively.

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Benzodifuran-functionalised pyrene and anthracene fluorophores 1 and 2 were obtained in reasonable yields. Their single crystal structures, electrochemical, optical absorption, and fluorescence characteristics have been described. They show strong luminescence with high quantum yields of 0.53 for 1 and 0.48 for 2. Magnetic measurements for the 2D coordination polymer [Mn(Pht(Pyz(H2O)2]n (1), in which metal centres are linked together by pyrazine (Pyz) and 1,6-bridging o-phthalate ligand (Pht2-), revealed antiferromagnetic interactions between Mn(II) ions.