986 resultados para Carbonyl groups


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The thin alumina film-supported metallic molybdenum model catalyst was prepared by thermal decomposition of MO(CO)6, and CO chemisorption on the catalyst was investigated in-situ by thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). The results showed that a molybdenum-carbonyl-like species was formed on the alumina surface at low temperature by high coordination of CO with the surface metallic molybdenum nanoparticles, indicating a reversible regeneration of molybdenum carbonyl on the alumina surface. CO chemisorption on the model catalyst surface caused the Mo 3d XPS peak to shift toward higher binding energy. The formed molybdenum carbonyl species appeared at about 240 K in the TDS. The supported metallic molybdenum nanoparticles were quite different from the bulk molybdenum in chemical properties, which indicated a prominent particle-size effect of the clusters.

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This thesis presents a framework for aggregated congestion management for TCP flows and shows how to integrate such an approach in an existing TCP protocol stack. The thesis presents an initial implementation of this congestion management scheme in Linux, with performance evaluation in ns as well.

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Although cooperation generally increases the amount of resources available to a community of nodes, thus improving individual and collective performance, it also allows for the appearance of potential mistreatment problems through the exposition of one node’s resources to others. We study such concerns by considering a group of independent, rational, self-aware nodes that cooperate using on-line caching algorithms, where the exposed resource is the storage of each node. Motivated by content networking applications – including web caching, CDNs, and P2P – this paper extends our previous work on the off-line version of the problem, which was limited to object replication and was conducted under a game-theoretic framework. We identify and investigate two causes of mistreatment: (1) cache state interactions (due to the cooperative servicing of requests) and (2) the adoption of a common scheme for cache replacement/redirection/admission policies. Using analytic models, numerical solutions of these models, as well as simulation experiments, we show that online cooperation schemes using caching are fairly robust to mistreatment caused by state interactions. When this becomes possible, the interaction through the exchange of miss-streams has to be very intense, making it feasible for the mistreated nodes to detect and react to the exploitation. This robustness ceases to exist when nodes fetch and store objects in response to remote requests, i.e., when they operate as Level-2 caches (or proxies) for other nodes. Regarding mistreatment due to a common scheme, we show that this can easily take place when the “outlier” characteristics of some of the nodes get overlooked. This finding underscores the importance of allowing cooperative caching nodes the flexibility of choosing from a diverse set of schemes to fit the peculiarities of individual nodes. To that end, we outline an emulation-based framework for the development of mistreatment-resilient distributed selfish caching schemes.

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In this report, we extend our study of the intensity of mistreatment in distributed caching groups due to state interaction. In our earlier work (published as BUCS-TR-2006-003), we analytically showed how this type of mistreatment may appear under homogeneous demand distributions. We provided a simple setting where mistreatment due to state interaction may occur. According to this setting, one or more "overactive" nodes generate disproportionately more requests than the other nodes. In this report, we extend our experimental evaluation of the intensity of mistreatment to which non-overactive nodes are subjected, when the demand distributions are not homogeneous.

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Aims and objectives: This study represents the first sustained quantitative and qualitative attempt to involve both Republicans and Loyalists in an investigation of the impact of imprisonment and the role of politically motivated former prisoners in the process of conflict transformation in Northern Ireland. The overall aim of the project is to examine the ways in which groups of former prisoners are involved in peace-building and conflict transformation work and to evaluate the constraints and impediments placed upon their activities by the effects of the imprisonment process, politically motivated release and residual criminalisation. In pursuing the evaluation of the role of politically motivated former prisoners working within and without their own communities, the research has six specific objectives: To trace the evolution and development of former prisoner groups; To evaluate the impacts of imprisonment and release on the personal lives of former prisoners; To assess the constraints imposed on former prisoners as agents of change by the residual criminalisation arising from their status; To determine the potential of the former prisoner community in challenging intra-community tensions and evaluate their potential and actual contribution to conflict transformation at the inter-community level; To compare and contrast the effectiveness of Loyalist and Republican former prisoners as agents of change within their own communities; To explore the notion of former prisoners as agents of social and communal transformation within broader political processes through grounding the knowledge and practical experience of the former prisoner community within the broader conceptual context of conflict transformation.

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The research described in this thesis involved the chemistry of borane-species which contain one or more halide or pseudohalide groups. Both monoboron species e.g. [BH3X]- and "cluster" borane species e.g. [B10H9X]2- and I-Se B11H10 were studied. The first chapter is a review of the syntheses, properties and reactions of halide and pseudohalide species containing from one to ten boron atoms. Chapter Two is a theoretical investigation of' the electronic and molecular structures of two series of boranes i. e. [BH3X]- and [B10H9X]2- where X = H, CI, CN, NCS, SCN and N3. The calculational method used was the Modified Neglect of Differential Overlap (MNDO) method of Dewar et al. The results were compared where possible with experimental results such as the X-ray crystallographically determined structures of [BH3CI]- and [B10H10]2-. Chapter Three concerns halogenated selenaborane clusters and reports an improved synthesis of 12-Br-SeB11H10 and the first structural data for a simple non-metal containing selenaborane cage with the X-ray crystallographically determined structure of 12-1-SeB11H10. Finally, an indepth n.m.r. study of Se2B9H9 is also reported together with attempts to halogenate this compound. The last two chapters are based on single boron systems. Chapter Four concerns the synthetic routes to amine-boranes and -cyanoboranes from [BH4]- and [BH3CN]- substrates. This chapter discusses some difficulties encountered when polyamines were used in these reactions. The characterisation of an unusual ketone isolated from some of these reactions, the X-ray crystallographically determined structure of 4-dimethylamino-pyridine-cyanoborane and a new route to pyrazabole dimeric species are also discussed. The final chapter reports on work carried out at producing BH2X (X = H, CN) adducts of aminophosphines. Three routes were attempted to generate P-B and N-B bonded species with varying degrees of success. Some unusual products of these reactions are discussed including [Ph2(O) PPPh2 ] [Ph2NH]2, the structure of which was determined by X-ray crystallography.

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Terrorist attacks by transnational armed groups cause on average 15,000 deaths every year worldwide, with the law enforcement agencies of some states facing many challenges in bringing those responsible to justice. Despite various attempts to codify the law on transnational terrorism since the 1930s, a crime of transnational terrorism under International Law remains contested, reflecting concerns regarding the relative importance of prosecuting members of transnational armed groups before the International Criminal Court. However, a study of the emerging jurisprudence of the International Criminal Court suggests that terrorist attacks cannot be classified as a war crime or a crime against humanity. Therefore, using organisational network theory, this thesis will probe the limits of international criminal law in bringing members of transnational armed groups to justice in the context of changing methods of warfare. Determining the organisational structure of transnational armed groups, provides a powerful analytical framework for examining the challenges in holding members of transnational armed groups accountable before the International Criminal Court, in the context of the relationship between the commanders and the subordinate members of the group.

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Using novel data on European firms, this paper investigates the relationship between business groups and innovation. Controlling for various firm characteristics, we find that group affiliates are more innovative than standalones. We examine several hypotheses to explain this finding, focusing on group internal capital markets and knowledge spillovers. We find that group affiliation is particularly important for innovation in industries that rely more on external funding and in groups with more diversified capital sources, consistent with the internal capital markets hypothesis. Our results suggest that knowledge spillovers are not the main driver of innovation in business groups because firms affiliated with the same group do not have a common research focus and are unlikely to cite each other's patents. © 2010 INFORMS.