It is ideal to theoretically predict the activity of a catalyst. It has been recognized that not only the type of metal, but also its atomic size plays an important role in catalysis. In the past, atomic clusters have been created by sputtering from a sacrificial metal plate and then using a mass selector to choose cluster sizes from 1-233 atoms of gold. This approach has practical limitations. In this thesis, I describe a procedure by which atomic clusters of gold containing 1-8 atoms are deposited in polyaniline as an isolation matrix. My atomic deposition follows a cyclic pathway. Atomic clusters of palladium and atomic alloys of gold and palladium are also deposited in polyaniline using the same process. It is to show that this method will also work for other metals. These composite materials are characterized, and the catalytic activity for alcohol oxidation is evaluated. This thesis is divided into seven chapters. The first chapter discusses the chemistry of polyaniline for using gold and palladium as catalysts. The technique developed to deposit the atomic clusters is discussed in the second chapter. This technique deposits one atom of metal per imine site on polyaniline, per cycle. The cycle is repeated n-times until a cluster of specified size, Mn, and composition has been synthesized. It is known that polyaniline plays an important role in stabilization of the formed clusters which prevents their aggregation. The optimization of this technique is the topic of the third chapter along with the description of how these composite films are produced. To end this chapter, the composite films are characterized by cyclic voltammetry, Kelvin probe, and X-ray photoelectron spectroscopy. In chapters 4 and 5, the catalytic activity of the polyaniline/gold composites for the oxidation of alcohols in alkaline media using cyclic voltammetry is evaluated. In chapter 4, the correlation of the electrochemical activity for the oxidation of n-PrOH with the odd-even pattern from the calculated HOMO-LUMO gap energies for the same size clusters is shown. It is shown that the infrared spectrum of polyaniline with different sizes of atomic gold clusters also follows the odd-even pattern. Chapter 5 expands on the discussion of the catalytic oxidation of alcohols. The oxidation of methanol, ethanol, propanol, and butanol is surveyed. The peak currents are again dominated by the odd-even pattern. In chapter 6, the versatility of the atomic deposition cycle is shown by depositing atomic palladium clusters. The peak currents for the oxidation of n-PrOH by these palladium composite films again follows the predicted pattern of the calculated HOMO-LUMO gap energies for atomic palladium clusters. This chapter also explores bimetallic atomic clusters of gold and palladium. The results indicate that the catalytic activity depends on the orientation of the cluster in the polyaniline matrix. Chapter 7 discusses the oxidation of methanol, ethanol, and isopropanol on AunPd1 bimetallic atomic clusters. The addition of palladium in the cluster increases the peak current densities for the oxidation of both alcohols except for the most stable of the atomic gold clusters, while it inactivated the electrodes for isopropanol. The possible future work for this project is discussed in chapter 8. Overall, this thesis has developed a novel and unique technique for depositing atomic metal clusters into a polyaniline matrix. The technique is versatile enough to deposit atomic metal clusters other than gold, as shown by creating atomic palladium clusters and atomic bimetallic clusters of gold and palladium. This is extremely useful, since this single technique can produce many different types of atomic catalysts. The composite materials have been shown to be catalytically active for the oxidation of alcohols in alkaline media. This indicates a significant improvement to conserve precious metals while still retaining a high catalytic activity.

We study the galaxy populations in 74 Sunyaev-Zeldovich effect selected clusters from the South Pole Telescope survey, which have been imaged in the science verification phase of the Dark Energy Survey. The sample extends up to z similar to 1.1 with 4 x 10(14)M(circle dot) <= M-200 <= 3 x 10(15)M(circle dot). Using the band containing the 4000 angstrom break and its redward neighbour, we study the colour-magnitude distributions of cluster galaxies to similar to m(*) + 2, finding that: (1) The intrinsic rest frame g - r colour width of the red sequence (RS) population is similar to 0.03 out to z similar to 0.85 with a preference for an increase to similar to 0.07 at z = 1, and (2) the prominence of the RS declines beyond z similar to 0.6. The spatial distribution of cluster galaxies is well described by the NFW profile out to 4R(200) with a concentration of c(g) = 3.59(-0.18)(+0.20), 5.37(-0.24)(+0.27) and 1.38(-0.19)(+0.21) for the full, the RS and the blue non-RS populations, respectively, but with similar to 40 per cent to 55 per cent cluster to cluster variation and no statistically significant redshift or mass trends. The number of galaxies within the virial region N-200 exhibits a mass trend indicating that the number of galaxies per unit total mass is lower in the most massive clusters, and shows no significant redshift trend. The RS fraction within R-200 is (68 +/- 3) per cent at z = 0.46, varies from similar to 55 per cent at z = 1 to similar to 80 per cent at z = 0.1 and exhibits intrinsic variation among

Recent observations have shown that a growing number of the most massive Galactic globular clusters contain multiple populations of stars with different [Fe/H] and neutron-capture element abundances. NGC 6273 has only recently been recognized as a member of this "iron-complex" cluster class, and we provide here a chemical and kinematic analysis of > 300 red giant branch and asymptotic giant branch member stars using high-resolution spectra obtained with the Magellan-M2FS and VLT-FLAMES instruments. Multiple lines of evidence indicate that NGC 6273 possesses an intrinsic metallicity spread that ranges from about [Fe/H] = -2 to -1 dex, and may include at least three populations with different [Fe/H] values. The three populations identified here contain separate first (Na/Al-poor) and second (Na/Al-rich) generation stars, but a Mg-Al anti-correlation may only be present in stars with [Fe/H] greater than or similar to -1.65. The strong correlation between [La/Eu] and [Fe/H] suggests that the sprocess must have dominated the heavy element enrichment at higher metallicities. A small group of stars with low [alpha/Fe] is identified and may have been accreted from a former surrounding field star population. The cluster's large abundance variations are coupled with a complex, extended, and multimodal blue horizontal branch (HB). The HB morphology and chemical abundances suggest that NGC 6273 may have an origin that is similar to omega Cen and M54.

Measurement of the gas velocity distribution in galaxy clusters provides insight into the physics of mergers, through which large scale structures form in the Universe. Velocity estimates within the intracluster medium (ICM) can be obtained via the Sunyaev-Zel'dovich (SZ) effect, but its observation is challenging both in term of sensitivity requirement and control of systematic effects, including the removal of contaminants. In this paper we report resolved observations, at 150 and 260 GHz, of the SZ effect toward the triple merger MACS J0717.5 + 3745 (z = 0.55), using data obtained with the NIKA camera at the IRAM 30 m telescope. Assuming that the SZ signal is the sum of a thermal (tSZ) and a kinetic (kSZ) component and by combining the two NIKA bands, we extract for the first time a resolved map of the kSZ signal in a cluster. The kSZ signal is dominated by a dipolar structure that peaks at -5.1 and + 3.4 sigma, corresponding to two subclusters moving respectively away and toward us and coincident with the cold dense X-ray core and a hot region undergoing a major merging event. We model the gas electron density and line-of-sight velocity of MACS J0717.5 + 3745 as four subclusters. Combining NIKA data with X-ray observations from XMM-Newton and Chandra, we fit this model to constrain the gas line-of-sight velocity of each component, and we also derive, for the first time, a velocity map from kSZ data (i. e. that is model-dependent). Our results are consistent with previous constraints on the merger velocities, and thanks to the high angular resolution of our data, we are able to resolve the structure of the gas velocity. Finally, we investigate possible contamination and systematic effects with a special care given to radio and submillimeter galaxies. Among the sources that we detect with NIKA, we find one which is likely to be a high redshift lensed submillimeter galaxy.

We present VIMOS-Very Large Telescope (VLT) spectroscopy of the Frontier Fields cluster MACS. J0416.1-2403 (z = 0.397). Taken as part of the CLASH-VLT survey, the large spectroscopic campaign provided more than 4000 reliable redshifts over similar to 600 arcmin(2), including similar to 800 cluster member galaxies. The unprecedented sample of cluster members at this redshift allows us to perform a highly detailed dynamical and structural analysis of the cluster out to similar to 2.2 r(200) (similar to 4Mpc). Our analysis of substructures reveals a complex system composed of a main massive cluster (M-200 similar to 0.9 x 10(15) M-circle dot and sigma(V r200) similar to 1000 km s(-1)) presenting two major features: (i) a bimodal velocity distribution, showing two central peaks separated by Delta V-rf similar to 1100 km s(-1) with comparable galaxy content and velocity dispersion, and (ii) a projected elongation of the main substructures along the NE-SW direction, with a prominent sub-clump similar to 600 kpc SW of the center and an isolated BCG approximately halfway between the center and the SW clump. We also detect a low-mass structure at z similar to 0.390, similar to 10' south of the cluster center, projected at similar to 3Mpc, with a relative line-of-sight velocity of Delta V-rf similar to 1700 km s(-1). The cluster mass profile that we obtain through our dynamical analysis deviates significantly from the "universal" NFW, being best fit by a Softened Isothermal Sphere model instead. The mass profile measured from the galaxy dynamics is found to be in relatively good agreement with those obtained from strong and weak lensing, as well as with that from the X-rays, despite the clearly unrelaxed nature of the cluster. Our results reveal an overall complex dynamical state of this massive cluster and support the hypothesis that the two main subclusters are being observed in a pre-collisional phase, in agreement with recent findings from radio and deep X-ray data. In this article, we also release the entire redshift catalog of 4386 sources in the field of this cluster, which includes 60 identified Chandra X-ray sources and 105 JVLA radio sources.

Le point de départ de cette thèse a été constitué par la création, en France, des Pôles de Compétitivité pour fonder une nouvelle économie nationale basée sur la science. Ces structures s’inscrivent dans la perspective théorique qui s’est construite sur l’importance de l’action partenariale, dans l’émergence, la diffusion et le développement de l’innovation technologique des petites entreprises. Toute l’organisation actuelle des pôles repose en effet sur un courant théorique qui stipule que le principe fondateur de l’innovation au sein des petites entreprises est la proximité. Ce courant a connu un considérable essor, notamment avec les écrits de M. Porter sur la notion du « Cluster ». Cependant, l’innovation technologique est un défi d'envergure pour les petites entreprises innovantes, car celles-ci sont confrontées à des situations de risques qui freinent leur développement. Au même temps, pour faire face à ces risques, bon nombre de chercheurs ont mis en évidence le lien étroit entre la nature du financement et le développement de l’innovation technologique des petites entreprises ainsi que l’ensemble d’un cluster. C’est notamment le cas dans la co-location de la science, l’industrie, et la finance par capital-risque au sein de la Silicon Valley. Au sein de ce cluster, il existe un lien intime entre le financement par capital-risque et son évolution économique. Ainsi, comme pour les pôles de compétitivité (Dupuy et Granier, 2010), le financement par capital-risque est alors présenté comme l’ultime alternative pour le financement et le développement de l’innovation entrepreneuriale (Gompers et al., (2005), Klagge et Martin (2005), Ferrary (2006, 2007, 2009)). Ces sociétés sont alors considérées comme les « encastreurs » ; le relais entre les ressources locales d’un cluster et les besoins des petites entreprises. Non seulement elles financent le projet entrepreneurial, mais elles soutiennent également l’innovation des petites entreprises à travers des actions concertées avec les acteurs locaux d’un cluster, comme les centres de recherche, de formation, et les grandes entreprises. Notre recherche vise, par conséquent, répondre à la problématique suivante: « Comment les sociétés de capital-risque assurent-elles le management des entreprises innovantes dans le cadre d’un pôle de compétitivité? ». Il faut dire que la littérature est riche en ce qui concerne le lien entre le financement de l’innovation par capital-risque et le développement des réseaux d’innovation (Gompers et al., 2005 ; Ferrary, 2006, 2007), néanmoins, cette question demeure sans explication complète et définitive dans le cas des pôles de compétitivité. Ainsi, afin d’apporter de nouveaux éléments qui expliquent ce paradoxe, nous allons essayer, à travers cette thèse, d’élaborer un cadre explicatif du comportement des sociétés du capital-risque au sein d’un pôle de compétitivité. / The starting point of this thesis was formed by the creation in France of the “Pôle de Competitive” as Clusters to found a new economy based on science. These structures are part of the theoretical perspective that has been built on the importance of partnership action, in the emergence, dissemination and development of technological innovation of small businesses. All the current organization of the poles is indeed based on a theoretical current which states that the founding principle of innovation in small firms is proximity. This trend has seen a considerable growth, particularly with the writings of Michael Porter about the notion of "Cluster". However, technological innovation is a major challenge for small innovative companies, as they face situations of risk which hamper their development. At the same time, to address these risks, many researchers have highlighted the close link between the nature of the financing and development of technological innovation of small businesses as well as an entire cluster. This is the case in the co-location of science, industry, finance and venture capital in Silicon Valley. Within this cluster, there is a close link between funding by venture capital and its economic development. Thus, as for Pôles de Compétitivité (Dupuy and Granier, 2010), the venture capital financing is then presented as the ultimate alternative for the financing and development of entrepreneurial innovation (Gompers et al., (2005) , Klagges and Martin (2005), Ferrary (2006, 2007, 2009)). These companies are then considered as the link between local resources in a cluster and the needs of small businesses. They not only fund the entrepreneurial project, but they also support small business innovation through joint actions with local actors in a cluster, such as research, training, and large enterprises. Our research is, therefore, answer the following question: "How do venture capital companies they provide the management of innovative companies as part of a pôle de compétitivité? ". It must be said that literature is rich regarding the link between the financing of innovation through venture capital and development of innovation networks (Gompers et al. 2005; Ferrary, 2006, 2007), however, this remains unexplained in the case of these clusters. Thus, in order to bring new elements that explain this paradox, we will try, through this thesis, to develop a framework explaining the behavior of venture capital firms in a pôle de compétitivité.

Depuis les années 2000, des clusters culturels, ou grappes d'entreprises du secteur culturel,se développent sur les territoires des métropoles et grandes villes françaises. Parallèlement,ces territoires urbains se transforment, s'aménagent, se construisent, tant dans le cadre depolitiques de renouvellement urbain que de projets de quartiers culturels créatifs. Cette thèsepose l'hypothèse que la rencontre de ces deux types de phénomènes, notamment si elle faitl'objet d'un pilotage dominé par les institutions locales, constitue majoritairement uneressource pour le développement territorial et la valorisation des espaces urbains, au dépensde la structuration des acteurs culturels. Sur la base de données de terrain issues d'entretienset d'un corpus de publications et supports de communication, huit clusters musicaux françaisont été observés dans leur contexte territorial et politique local. Les pratiques, stratégies etmodes d'organisation des acteurs mis en situation d'inter-dépendance via ces clustersconstituent un faisceau d'hétérogénéités que les équipes des clusters ne parviennent quedifficilement à mettre en concordance.Trois idéaux-types des conditions d'émergence de ces clusters culturels sont proposés. Ilsposent les différentes représentations de ces dispositifs que développent les entrepreneurs,les acteurs publics et les acteurs locaux. / Since the 2000's, many cultural clusters have emerged and have been developped in Frenchcities and urban areas. At the same time, these local territories have been physically andsymbolically re-shaped, re-configured, through social development or creative cities policies.The statement of this thesis is that the encounter of these two phenomena, especially whenthey are dominated by local institutions, mostly enhances territorial development andvalorization, at the expense of cultural workers' economic structuration. Eight Frenchmusical clusters have been studied in relation with their own local political context. Practices,strategies and modalities of the organization of the inter-dependent actors of these clustersare constitutive of a range of material and symbolic heterogeneities that clusters' teamshardly manage to match.We propose three ideal types related to the emergence of such cultural clusters. Each of themspecifies the representations of the cluster that cultural entrepreneurs, politics and localsconjure up.

Os Clusters de acetato de rutênio de fórmula geral [Ru3O(AcO)6L3]n proporcionam blocos de montagem interessantes para sistemas supramoleculares, exibindo características eletrocrômicas e redox reversível, cobrindo uma ampla faixa de potenciais em solventes aquosos e orgânicos. Nesta Tese, estas espécies foram combinadas com o ligante tridentado, 4\'-piridil-2,2\':6\',2\"-terpiridina (pytpy), produzindo complexos do tipo [Ru3O(AcO)6(pytpy)3]n e [Ru3O(AcO)6(py)2(pytpy)]n, que foram totalmente caracterizados em estado sólido e solução. Nestes complexos a terpiridina permanece disponível para ligar-se a íons metálicos como o Fe(II), gerando um complexo binuclear de baixo spin muito estável, do tipo {Fe[Ru3O(AcO)6(py)2(pytpy)]2}n. Este processo pode ser monitorado eletroquimicamente, partindo de íons Fe(III), que exibem uma baixa afinidade pela terpiridina central, e ciclando o potencial para gerar íons de Fe(II). Desta forma, pode-se executar um procedimento típico de click chemistry, que leva a uma estrutura estendida, Fe-cluster-pytpy na superfície do eletrodo. Este filme conserva a funcionalidade dos blocos de montagem, permitindo aplicações interessantes em dispositivos moleculares, tais como sensores e smart Windows. / Ruthenium acetate clusters of general formula [Ru3O(AcO)6L3]n provide interesting building blocks for assembling supramolecular systems, displaying reversible redox and electrochromic characteristics, over a wide range of potentials in aqueous and organic solvents. In this thesis, such species has been combined with the tritopic, 4\'-pyridil-2,2\':6\',2\"-terpiridine (pytpy) ligand, yielding complexes of the type [Ru3O(AcO)6(pytpy)3]n and [Ru3O(AcO)6(py)2(pytpy)]n, which have been fully characterized in solid state and solution. In these complexes, the terpyridine moiety remains available for binding metals ions, such as Fe(II), generating very stable, low spin binuclear complexes, of the type n. This process can be monitored electrochemically, starting from Fe(III) ions, which exhibits a much lower affinity for the terpyridine center, and cycling the potentials in order to generate Fe(II) ions. In this way, one can start a click chemistry, ending up with an extended structure of Fe-cluster-pytpy film at the electrode surface. This film preserves the functionality of the building block complexes, a llowing many possible applications in molecular devices, such as sensors and smart windows.

O complexo R2TP está presente em eucariotos, de leveduras a humanos, e está envolvido no correto dobramento de outras proteínas e montagem de complexos multiproteicos. R2TP é formado pelas proteínas Rvb1, Rvb2, Tah1 e Pih1/Nop17 em levedura, e direciona as chaperonas à proteínas alvo durante a montagem dos complexos. Os clusters Fe/S são sintetizados nas mitocôndrias e posteriormente transferidos para o citoplasma. Dre2 é uma proteína que contém cluster Fe/S, e está envolvida na transferência desses clusterspara outras proteínas citoplasmáticas. Nosso laboratório identificou a interação entre a subunidade Nop17 do complexo R2TP e Dre2 pelo método de duplo-híbrido, mas o papel desta interação ainda não foi elucidado. O objetivo deste trabalho foi o de estudar o papel funcional da interação entre Dre2 e Nop17 e identificar seus domínios de interação. Nossos resultados mostram que a porção N-terminal de Nop17 interage com a porção C-terminal de Dre2 e esta interação é necessária para a manutenção dos níveis de Dre2 na célula, indicando que o complexo R2TP atue na montagem do complexo CIA, de proteínas citosólicas Fe/S, do qual Dre2 faz parte. Dre2 também afeta a estabilidade de Nop17, sugerindo que Dre2 possa transferir um clusterFe/S para Nop17. Os dados mostrados aqui, portanto, indicam que a interação Nop17-Dre2 seja mutuamente importante para a estabilidade das duas proteínas / The R2TP protein complex is present in eukaryotes from yeast to humans, and is involved in the correct assembly of other protein or ribonucleoprotein complexes. R2TP is formed by proteins Rvb1, Rvb2, Tah1 and Pih1/Nop17 in yeast, and directs chaperones to target proteins during complexes assembly. Fe/S clusters are synthesized in mitochondria and later transferred to the cytoplasm. Dre2 is a Fe/S cluster protein, involved in transferring of Fe/S clusters to cytoplasmic proteins. Our laboratory has identified the interaction between the R2TP subunit Nop17 and Dre2 in the two-hybrid system. The aim of this work was to study the functional role of the interaction between Dre2 and Nop17, and to identify their domains of interaction. The results show that the N-terminal portion of Nop17 interacts with the C-terminal region of Dre2, and that this interaction is necessary for maintaining the levels of Dre2 in the cell, which suggests that the R2TP complex affects the cytosolic iron-sulfur protein assembly complex (CIA), of which Dre2 is a subunit. Dre2 also affects Nop17 stability, suggesting that Dre2 may transfer a Fe/S cluster to Nop17. The data here indicate that the interaction Nop17-Dre2 is mutually important for these proteins stabilities.

Este trabalho analisa a competitividade das empresas de bens de capital para calçados a partir das interações usuário-produtor nos dois principais sistemas locais de produção de calçados no Brasil, o Vale dos Sinos (RS) e Franca (SP). Desse modo são caracterizadas as formas de aprendizado a partir das relações entre as empresas de máquinas e os seus usuários da cadeia de calçados e os efeitos dessas interações para a organização e o desenvolvimento das empresas de bens de capital. Para realizar esse levantamento, a pesquisa contou com duas estratégias complementares, a análise de informações secundárias e a realização de uma pesquisa empírica junto aos produtores de máquinas. As empresas de bens de capital para calçados são caracterizadas pela variedade tecnológica de produtos fabricados sob encomenda e pela flexibilidade no atendimento de diferentes tipos de usuários com distintas especializações produtivas. Adicionalmente, os fluxos de informação com os usuários, produtores de calçados, têm contribuído para o desenvolvimento tecnológico das máquinas. Todavia, percebe-se que os segmentos fabricantes de máquinas customizadas apresentam uma tendência a acumular, relativamente, mais competências tecnológicas que as empresas de máquinas commoditizadas. O resultado mostra que o processo de aprendizado resultante das interações entre produtores de máquinas e seus usuários pode variar em função das características competitivas dos segmentos de máquinas, das estruturas de oferta e das flutuações no ambiente macroeconômico. Além disso, fica claro que os sistemas locais de produção exercem importante papel ao acentuar as formas de articulação local e a integração entre os sistemas de produção e de conhecimento, contribuindo para o desenvolvimento de capacitações internas às empresas de máquinas. / This master dissertation focuses on the competitiveness of the capital goods producers, by looking at the user-producer interaction in the two main Local Productive Systems of footwear in Brazil, the Sinos Valley (RS) and Franca (SP). By this way, it is characterized the modes of learning generated by the interaction between machinery firms and its users of the footwear chain and its effects for the capital goods producers. To do this, there were two different research strategies, the analysis of secondary data, and a empirical survey with capital goods producers. The footwear capital goods producers present a great technological diversity of outputs manufactured under order and flexibility in the attendance of different types of users, with different productive specialization. Additionally, the information flows with their users, the footwear producers, have contributed to the technological development of the capital goods. However, it could be seen that the segment of customized manufacturers of machines presents a trend to accumulate relatively more capabilities. The main results show that the learning process that comes from the interaction between machinery producers and their users can vary in function of the competitive characteristics of the capital goods segments, of the supply structure and the macroeconomic fluctuations. So, it\'s clear that the Local Production Systems plays an important role in fostering the local linkages among manufacturing and knowledge systems, in order to improve of the technological capabilities of Brazilian machinery producers.