Les études détaillées d'amas de galaxies confirmés à grands redshifts sont peu nombreuses. L’objectif de cette Thèse est d’établir le premier catalogue d'amas confirmés spectroscopiquement à grand redshift et, pour la première fois à ces redshifts, d’étudier de manière statistique les propriétés des galaxies membres des amas. Dans cette Thèse, nous caractérisons et étudions 20 candidats amas à redshifts 1.4 < z < 2.8 parmi les candidats les plus prometteurs de l’échantillon CARLA. Nous réduisons et analysons des données spectroscopiques grism sans fente et imagerie proche-infrarouge des amas candidats, obtenues avec le télescope spatial Hubble. Nous mesurons plus de 700 redshifts au sein des champs observés, et confirmons spectroscopiquement 16 amas CARLA dans l’intervalle 1.4 < z < 2.8; ces amas sont associés à des noyaux galactiques actifs à fortes émissions radios (RLAGN) en leur centre, par sélection. Cet effort fait plus que doubler le nombre d’amas confirmés à ces redshifts. Nous étudions également le taux de formation stellaire des galaxies membres des amas en fonction de leur masses stellaires, et de la distance aux RLAGN. Nous trouvons que les galaxies membres massives sont situées sous la séquence principale jusqu’à z=2, ce qui suggère déjà à ces redshifts une évolution accélérée des galaxies massives au sein des amas. Nous trouvons également une concentration plus importante de membres actifs à plus petits rayons des RLAGN, jusqu’à z=2. Ceci est en accord avec un renversement de la relation densité vs. taux de formation stellaire pour nos amas CARLA à 1.4 < z < 2.0, ce qui suggère que les amas CARLA représentent une phase de transition de l’évolution des galaxies au sein des amas. Nous étudions également les populations stellaires de deux de nos amas confirmés à redshift z=2.0. Nous analysons les relations couleurs-couleurs et couleurs-magnitudes de ces deux amas et montrons que l’une des structures à z=2 possède une séquence rouge de galaxies passives. Globalement, nos résultats démontrent que les amas CARLA représentent des structures riches comprenant des populations mixtes de galaxies évoluées et massives sans formation stellaire, et des galaxies actives formant des étoiles. Cet échantillon sans précédent de 16 amas confirmés spectroscopiquement dans l’intervalle de redshift 1.4 < z < 2.8 constitue un échantillon idéal pour étudier statistiquement la phase de transition des amas de galaxies, ainsi que les mécanismes de suppression de la formation stellaire. (Abrégé) / Detailed studies of high-redshift confirmed galaxy clusters are based on a few individual objects. In this Thesis, we therefore aim at building the first sample of spectroscopically confirmed clusters at high-redshifts and, for the first time at these redshifts, statistically infer cluster member galaxy properties. In this Thesis, we study and characterize 20 cluster candidates at redshifts 1.4 < z < 2.8, which represent the most promising cluster candidates from the CARLA sample. We reduce and analyze slitless grism spectroscopic and near-infrared imaging data of the fields, obtained with the Hubble Space Telescope. We measure redshifts for over 700 star-forming sources in the 20 fields, and we spectroscopically confirm 16 CARLA clusters in the range 1.4 < z < 2.8; by selection, these clusters are associated with powerful radio-loud active galactic nuclei (RLAGN) at their center. This effort alone more than doubles the number of confirmed clusters at these redshifts. We study cluster member star-formation rates (SFRs) as a function of their stellar masses and distances from the RLAGN. We find that massive members are located below their star-forming main-sequence up to z=2. This implies that the massive star-forming end of the cluster population already followed an accelerated evolution at these high redshifts. We also find an increasing concentration of star-forming members with smaller radii relative to the RLAGN, at all redshifts up to z=2. Our 1.4 < z < 2.0 cluster members are therefore consistent with a reversal of the SFR-density relation. This is a first evidence showing that CARLA clusters represent a transition phase for cluster galaxy evolution. We also study stellar populations of two of our confirmed CARLA clusters at z=2.0. We study their color-color and color-magnitude relations and show that one of the two structures is comprised of a z=2 red sequence of passive candidate members. Together, these results provide clear evidence that our confirmed CARLA clusters represent rich structures comprised of mixed populations, including both evolved, passive, massive galaxies, and galaxies with ongoing star formation. Together, this unprecedented sample of 16 confirmed clusters at 1.4 < z < 2.8 constitutes an ideal sample for further statistical investigation of the cluster transition phase, including study of quenching mechanisms. (Abridged)

Le développement d'une nouvelle classe de composés inorganiques par combinaison chimique entre deux types de clusters "Hydroborates" HYD et "polyoxométalates" POM a été étudiée. La fonctionnalisation des polyoxométalates par des closo-décaborates pourrait créer une synergie entre ces différents types de clusters et optimiser leurs propriétés, en particulier vers des applications biologiques.Le lien direct entre POM et HYD a échoué en raison de leurs caractères anioniques, des problèmes de solubilité et de la dépendance de la stabilité du POM en fonction du pH. Une autre méthode a ensuite été utilisée basée sur le greffage de ligands espaceurs entre les entités POM et HYB. L'hydroborate [B10H10]2- a été transformé en son dérivé carbonyle [B10H9CO]- pour réagir avec différentes familles hybrides de POM fonctionnalisées par des ligands amine tris- (hydroxyméthyl) méthylamine dans le cas des POMs de type Anderson "MMo6" (avec M: Al, Mn ) ou par des groupements aminopropyltri (éthoxy) silane dans le cas des dérivés vacants de type Keggin et Dawson, tels que "SiW10" et "P2W17" respectivement . Après avoir établi les conditions expérimentales permettant de synthétiser les adduits covalents POM-Bore, ces derniers ont été entièrement caractérisés à l'état solide et en solution. L’analyse élémentaire supportée par l’analyse thermogravimétrique, les spectroscopies FT-IR UV-Visible, MALDI-TOF et ESI-MS et diverses techniques RMN ont mis en évidence la formation de composés mono ou di-adduits qui ont été étudiés en électrochimie pour démontrer l'influence des clusters de bore greffés sur les fragments POM. Enfin les calculs DFT réalisés pour ces systèmes ont donné des modèles structuraux et des profils énergétiques permettant de comprendre la complexité de la synthèse de tels systèmes. Une autre approche méthodologique a également été étudiée en utilisant le concept supramoléculaire en prolongeant les interactions connues CD / POM de cyclodextrine et CD / closo-borate pour synthétiser des systèmes ternaires associant [B10H10]2-, CD et POMs ou clusters métalliques. Des études en solution ont été réalisées par ESI-MS et RMN qui ont mis en évidence la formation de complexes d'inclusion 1: 1 entre [B10H10]2- et CD alors que seule la structure des rayons X a été obtenue avec α-CD et caractérisée à l'état solide. Les mesures RMN DOSY nous ont permis d'accéder aux constantes d'association qui apparaissent relativement faibles avec une constante optimale obtenue avec -CD. Les mesures ITC ont confirmé ces constantes et ont donné les paramètres thermodynamiques associés à la formation des complexes d'inclusion qui mettent notamment en évidence le caractère chaotrope du cluster [B10H10]2-. Encore une fois, les calculs de DFT ont apporté un élément important prouvant que les composés d'inclusion issus de -CD sont les plus stables en raison de la bonne adéquation entre la taille de l'amas de bore et la taille de la cavité de la -CD. Les résultats du système ternaire sont préliminaires, et ils nécessitent d'autres développements et investigations. Les détails de la synthèse et de la caractérisation seront présentés dans ce manuscrit. / Development of a novel class of inorganic compounds by chemical combination between two types of clusters "Hydroborates" HYD and "polyoxometalates” POM has been investigated. Functionalization of polyoxometalates by closo-decaborates could create a synergy between these different types of clusters and optimize their properties, especially towards biological applications.The direct link between POM and HYD was unsuccessful due to their anionic characters, to solubility problems and to the stability dependence of POM according to pH. Another method was then used based on the grafting of linkers on POM and HYB. Hydroborate [B10H10]2-; was transformed to its carbonyl derivative [B10H9CO]- to react with differents families of POMs functionalized by tris-(hydroxymethyl)methylamine ligands in the case of the "MMo6" (with M: Al, Mn) Anderson-type POMs or by aminopropyltri(ethoxy)silane groups in the case of the vacant Keggin and Dawson-type derivatives"SiW10"and "P2W17", respectively. After establishing the experimental conditions allowing to synthestise the targeted covalently linked POM-Boron adducts, the later were fully characterized in the solid state and in solution. Elemental analysis supported by TGA, FT-IR spectroscopy, UV-VIS, MALDI-TOF, ESI-MS and various NMR technqiues evidenced the formation of mono or di-adducts compounds which were studied in electrochemistry to demonstrate the influence of the boron clusters grafted on the POM moieties. Finally DFT calculations performed for these systems gave structural models and energetic profiles allowing to understand the complexity of the synthesis of such systems.Another approach was also studied using supramolecular concept by extending the known cyclodextrin CD/POM and CD/closo-Borate interactions to synthesize ternary systems associating [B10H10]2- ,CD and POMs or metallic clusters. Solution studies were performed by ESI-MS and NMR which evidence the formation of 1:1 inclusion complexes between [B10H10]2- and CDs while only X-ray structure was obtained with α-CD and characterized in the solid state. DOSY NMR allowed us to access the association constants which appear relatively low with an optimal constant obtained with α-CD. ITC measurements confirmed these constants and gave the thermodynamic parameters associated to the formation of the inclusion complexes which notably evidence the chaotrope character of the [B10H10]2- cluster. Once again, DFT calculations brought important element proving that the inclusion compounds fomed with -CD is the most stable because of the good matching between the size of the boron cluster and the size of the cavity of the -CD. The results of ternary system are preliminary, and require further development and investigations. Details of synthesis and characterization will be presented in this manuscript.

Understanding the formation and evolution of galaxies is one of the most active areas of research in astrophysics. Hierarchical merging of proto-galactic fragments to build more massive galaxies is the current preferred model. A key prediction of this theory is that haloes of nearby galaxies should contain remnants of this assembly process in the form of tidal debris. Found in all but the smallest of dwarf galaxies, globular clusters (GC) are excellent probes of galaxy haloes. Having high luminosities, they are favourable targets in the outer regions of galaxies where the associated stellar surface brightness is low. GCs are thought to be amongst the oldest stellar systems in the Universe, and are likely born in the most significant phases of galaxy formation. Their metallicities, ages, spatial distributions and kinematics can be used to constrain the assembly history of their host galaxy. In this thesis, I explore the photometric and kinematic properties of several GC systems in our cosmological backyard, the Local Group of galaxies. The work is based on a major spectroscopic campaign, follow-up to the photometric Pan- Andromeda Archaeological Survey (PAndAS), as well as additional optical and near-IR data sets. Radial velocities are obtained for 78 GCs in the halo ofM31, 63 of which had no previous spectroscopic information. The GCs have projected radii between ∼ 20 and 140 kpc, thus sampling the true outer halo of this galaxy. In addition, GCs in the dwarf galaxies NGC 147, NGC 185 and NGC 6822 are also spectroscopically observed. By conducting a detailed kinematic analysis, I find that GCs in the outer halo of M31 exhibit coherent rotation around the minor optical axis, in the same direction as their more centrally located counterparts, but with a smaller amplitude of 86 ± 17 km s−1. There is also evidence that the velocity dispersion of the outer halo GC system decreases as a function of projected radius from theM31 centre, and this relation can be well described by a power lawof index ≈ −0.5. I detect and discuss various velocity correlations amongst GCs that lie on stellar streams in the M31 halo. Simple Monte Carlo tests show that such configurations are unlikely to form by chance, implying that significant fraction of the GCs in the M31 halo have been accreted alongside their parent dwarf galaxies. I also estimate the dynamical mass of M31 within 200 kpc to be (1.2 − 1.6) ± 0.2 × 1012 M⊙. I also characterize the GC systems of three dwarf galaxies in the Local Group: the dwarf elliptical satellites of M31, NGC 147 and NGC 185, and the isolated dwarf irregular NGC 6822. Using uniform optical and near-IR photometry, I constrain the ages and metallicities of their constituent GCs. The metallicities of the GCs around NGC 147 and NGC 185 are found to be metal-poor ([Fe/H]. −1.25 dex), while their ages are more difficult to constrain. The GCs hosted by NGC 6822 are found to be old (>9 Gyr) and to have a spread of metallicities (−1.6 . [Fe/H] . −0.4). I find close similarity between the mean optical (V − I)0 colours of the GCs hosted by these three dwarf galaxies to those located in the M31 outer halo, consistent with the idea that dwarf galaxies akin to them might have contributed toward the assembly of the M31 outer halo GC population. Analysing their kinematics, I find no evidence for systemic rotation in either of these three GC systems. Finally, I use the available GC kinematic data to calculate the dynamical masses of NGC 147, NGC 185 and NGC 6822.

No description available.

Strong trust based relationships are one of the pillars of the communitarian model of industrial districts. District literature calls upon trust in order to explain several elements of the model. The existence of trust may explain how a highly fragmented and essentially local value chain reduces transaction costs compared with an integrated firm. It may also allow for closer ties where up to date pertinent information and innovative ideas are transferred between firms. Trusting, long term relationships and district networks are also evoked in the literature as being, in themselves, sources of competitive advantage. Yet despite large sections of district literature calling upon trust to explain the existence and efficiency of industrial districts, few scholars have investigated empirically the sources of trust in local ties. In depth semi-directive interviews with small firm managers in the Arve Valley industrial district near Geneva were analysed in order to examine the context and quality of intra-district relationships (mainly supplier and peers) which were then ompared with extra-district links with clients. The sources of trust are analysed by applying Möllering’s (2006) model of trust based on reason, routine and reflexivity. Findings indicate that managers rely more on a rational calculation of partner’s motives than ‘blind’ adherence to local, historical norms of behaviour. This finding contributes to the view that districts are organizational fields where agents possess large amounts of information about markets, technologies and partners. Managers also demonstrate a willingness to maintain local links over the long term, thus ensuring a crucial element of their firms’ competitive advantage and will adjust their behaviour accordingly. This thesis contributes to district literature by examining detailing the existence and foundations of close intra-district ties created between managers mobilising resources based on cognitive, organisational and geographical proximities. A major contribution to trust literature is the 5 analysis and discussion of the complex interplay between the three antecedents outlined in Möllering’s model in the creation of local trust and proposes that while trust decisions in information rich districts are based more on rational calculation than on local norms and institutions, other trust decisions (with external clients), in the absence of sufficient information are founded on very different bases. This comparison of the foundations of trust in two different contexts highlights the role of identity and routine in the ‘leap of faith’ or suspension of doubt that is trust.

published_or_final_version / Business / Doctoral / Doctor of Philosophy

This thesis describes the preparation and study of a wide range of supported gold catalysts based on atomically-precise triphenyl phosphine stabilised gold clusters. This selected range of ligand-stabilised gold clusters were prepared in attempt to study the effect of increasing cluster nuclearity on the electronic and catalytic properties of these materials. A novel far-infrared study was conducted on the pure cluster materials in attempt to understand the metal-metal and the metal–ligand vibrations, which was also compared to the simulated spectra for each cluster. The design and activation of these novel catalysts based on gold clusters was discussed and the factors that influence activity were described. A comprehensive photoelectron study of the catalysts was conducted in an attempt to understand the electronic structure of the supported gold clusters and the effect of various activation conditions have on the electronic structure of the gold clusters. A selection of the prepared supported gold catalysts were tested for their catalytic activity for the partial oxidation of styrene and the influence of the several activation conditions on the reactivity of the catalyst is also examined. In collaboration, the application of a selection of ligand-stabilised gold clusters as hydrogen sensors and as catalysts for the photocatalytic generation of hydrogen from ethanol is also investigated.

This thesis contains two main parts: the first part focusses on an electron diffraction study on unsupported antimony (Sb) clusters, while in the second part the design and development of a time-of-flight mass spectrometer (TOFMS) is discussed. Electron diffraction is an ideal tool to study the structure of clusters entrained in a beam. The main advantage of this technique is the ability to study the clusters in situ and in an interaction-free environment. It is therefore not necessary to remove the particles from the vacuum system which would lead to oxidation. Since the particles do not have to be deposited on a sample for further investigation, there is also no substrate which could influence the cluster structure. An additional advantage is the short exposure to the electron beam, thereby minimising the likelihood of damaging the particles. Sb clusters were produced using an inert-gas aggregation source. To control the cluster properties the source temperature, pressure and type of cooling gas can be adjusted. In the range of source parameters tested, Sb clusters with three different structures were observed: a crystalline structure corresponding to the rhombohedral structure of bulk Sb, an amorphous structure equivalent to the structure of amorphous Sb thin films, and a structure with the same diffraction signature as Sb4 (Sb evaporates mainly as Sb4). This last structure was found to belong to large particles consisting of randomly oriented Sb4 units. In order to study the size distributions and morphologies of the Sb clusters, the clusters were deposited onto substrates and studied under an electron microscope. The crystalline particles showed a wide variety of strongly faceted shapes. Depending on source conditions, the average cluster diameters ranged from 15 to 130 nm. There was a considerable disagreement between these values and the size estimates from the diffraction results with the latter being smaller by an order of magnitude. This might be due to the existence of domains inside the clusters. The amorphous particles were all found to be spherical with mean sizes between 27 and 45 nm. The Sb4 particles showed a liquid-like morphology and tended to coalesce easily. Their sizes ranged from 18 to 35 nm. To obtain an independent method for determining the cluster size, a TOFMS was designed and developed in collaboration with Dr Bernhard Kaiser. However, the TOFMS failed to detect a cluster signal in the original set-up which is most likely due to a defective ioniser and underestimated cluster energies. Further tests were performed in a new vacuum system and mass spectra for palladium clusters were successfully recorded.

A thorough understanding of nucleosynthesis and element formation in stars of all evolutionary phases is of vital importance in stellar astrophysics. It provides information about internal structure, conditions and nuclear processes occurring in the stellar interior. The heavy elements formed in a star throughout its life are returned to the interstellar medium through mass loss processes. New populations of stars are then formed from this previously enriched material. This continues the cycle of element recycling in the Universe and has great consequence for galactic chemical evolution. As both modelling and observing techniques advance, more surveys are required to ensure there is agreement between the two. It is hoped that when a thorough understanding of the internal processes in giant stars is reached, the evolutionary models will reproduce the observed elemental yields. This work provides an internally self-consistent analysis of the element abundances produced via nucleosynthesis and s-process element formation occurring in giant stars in different stellar environments. High resolution spectroscopic observations have been taken of Asymptotic Giant Branch (AGB) and Red Giant Branch (RGB) stars in three different stellar environments. Spectrum synthesis has been used to determine s-process element abundances for RGB stars in the Hyades open cluster, RGB and AGB stars in the globular cluster, 47 Tucanae, and AGB stars in the galactic field. It was found that the two Hyades giant studied showed solar, or near-solar, abundances of s-process elements. Enhancements in the light s-process elements, Y and Zr, of +0.02 to +0.11 were observed, while enhancements in the heavy s-process elements, La, Pr and Nd, ranged from +0.06 to +0.16. These results are consistent with previous findings of enhancements in Y of ~+0.12, and of ~+0.15 for the heavy s-process elements. The results from 47 Tucanae suggest a genuine star-to-star scatter in the s-process element abundances in the giant stars of this globular cluster. This is unexpected due to the fact that stars in a globular cluster are thought to have the same formation and chemical history. However, spreads in s-process element abundances of as much as +-0.7 dex are observed between this study and three other studies of similar stars in the same cluster. A range of field stars along the AGB phase, ranging from M to MS to S to SC, have been analysed for s-process enrichment. The observed element abundances are compared with those predicted by recent modelling of the AGB phase of evolution. Enhancements in s-process element abundances range from [s/Fe]~0.00 for M stars, to ~+0.50 for MS stars, through to ~+0.95 for S stars. The comparison of these enhancements with those predicted by modelling provides an indication of the success of these models and will enable theoreticians to further refine their understanding of the internal nucleosynthetic processes present in giant stars.

No description available.