La radioimmunothérapie (RIT) est une stratégie théranostique associant la spécificité de reconnaissance d’anticorps monoclonaux (AcMs) (ou de formes dérivées) vis-à-vis des antigènes tumoraux et les propriétés des radionucléides (imagerie/thérapie). L’efficacité de la RIT est cependant limitée sur les tumeurs solides à cause de la lente diffusion des AcMs et de leur longue demi-vie plasmatique. Les approches de radioimmunothérapie préciblée (PRIT), qui dissocient l’injection des AcMs de celle des radioligands constituent des alternatives pertinentes envisagées pour diminuer l’hématotoxicité et améliorer l’efficacité thérapeutique de la RIT classique. Nous avons ainsi travaillé sur une stratégie de PRIT utilisant la chimie bioorthogonale par interaction entre un trans-cyclooctène (TCO) et une tétrazine (TZ), à la fois pour l’imagerie et pour la thérapie de la carcinose péritonéale (CP) d’origine colorectale (modèle A431-CEA-Luc/ AcM 35A7). Dans un premier temps nous avons évalué à la fois in vitro et in vivo dans le modèle de CP ainsi que dans un modèle sous-cutané de cancer colorectal (modèle HT29/ AcM Ts29.2) l’effet des modifications apportées aux AcMs. Nous avons ainsi montré que les modifications d’AcMs influencent l’interaction entre les TCO et la TZ, sans pour autant altérer leur immunoréactivité. L’ajout d’espaceurs PEGylés (polyéthylène glycol) entre les AcMs et les TCO induit une diminution significative de l’interaction TCO/TZ. De plus, nous avons montré que les TCO sont sujets à l’isomérisation en cis-cyclooctènes, inactifs vis-à-vis de la TZ, et que la PEGylation aggrave ce phénomène. Ces études ont ainsi montré à la fois que les AcMs-TCO ne contenant pas d’espaceur PEGylé étaient les plus favorables pour le préciblage mais également, qu’il était primordial de contrôler le taux d’isomérisation des TCO avant greffage aux AcMs pour ne pas altérer l’interaction vis-à-vis des TZ. Dans un second temps nous avons effectué avec succès la preuve de concept de l’imagerie SPECT de la CP par préciblage entre l’AcM 35A7-TCO et la TZ-PEG4-DOTA-177Lu (i.e. TZ-1). Un ciblage spécifique des tumeurs péritonéales a ainsi été obtenu, avec un très bon contraste. L’étude de PRIT effectuée avec cette même sonde TZ-1 a cependant échoué à mettre en évidence une amélioration des médianes de survie ou un ralentissement de la croissance tumorale, nous amenant ainsi à reconsidérer la structure de la TZ-1. Trois autres TZ (i.e. TZ-2-4) ont donc été évaluées par la suite, en biodistribution, afin de déterminer la meilleure pour la PRIT de la CP. Ainsi, la TZ-3, qui comporte un espaceur PEGylé plus long que la TZ-1, s’est avérée être la plus favorable dans ce type de stratégie et sera prochainement utilisée pour une nouvelle étude de thérapie. En conclusion, ces travaux de thèse ont permis de démontrer la faisabilité du concept de préciblage par chimie bioorthogonale utilisant l’interaction TCO/TZ pour l’imagerie de tumeurs disséminées dans la cavité péritonéale. Cette stratégie reste néanmoins compliquée à mettre en place du fait de l’instabilité des TCO et des problèmes de réactivité de certaines sondes TZ et nécessite encore de nombreuses optimisations avant de pouvoir envisager une application thérapeutique. / Radioimmunotherapy (RIT) consists to combine the specificity of monoclonal antibodies (mAbs), or mAbs derived structures, towards tumor antigens with the imaging/therapy properties of radionuclides, representing thus a theranostic strategy. RIT efficiency in solid tumors is limited due to both mAbs slow diffusion and long blood clearance. Pretargeted radioimmunotherapy (PRIT) appears as an alternative to circumvent hematotoxicity and improve therapeutic efficacy. We have thus worked on PRIT based on bioorthogonal click chemistry relying on the interaction between trans-cyclooctene (TCO) and tetrazine (TZ). Application of this strategy was made for imaging and therapy of peritoneal carcinomatosis (PC) from colorectal origin (A431-CEA-Luc model/ 35A7 mAb). We have first assessed the influence of mAbs modifications, in vitro and in vivo experiments made on both PC model and subcutaneous colorectal cancer (HT29 model/ Ts29.2 mAb). We thus demonstrated that mAbs modifications influence the interaction between TCO and TZ without decreasing their antigen binding capacities. Indeed, addition of PEGylated (polyethylene glycol) linkers between mAbs and TCO induced a significant decrease of TCO/TZ interaction. In addition, we also demonstrated that TCO moieties undergo severe isomerization to cis-cyclooctene (CCO) moieties which are unreactive towards TZ. Addition of PEG linkers also increased the isomerization rate of TCO to CCO. Our results highlighted that a non PEGylated mAb should represent the best structure for PRIT to avoid isomerization and consequently to control the ratio of CCO before mAbs coupling to maximize TCO/TZ interaction. In disseminated PC, we have made for the first time the proof of concept of SPECT imaging between 35A7-TCO and TZ-PEG4-DOTA-177Lu (i.e. TZ-1). We indeed obtained a specific signal corresponding to PC tumors with a very good contrast. However, a PRIT experiment using TZ-1 did not allow observing neither improvement of median survivals nor tumor growth slow down. Those disappointing results led to reconsider the TZ-1 structure and evaluate three new TZ (i.e. TZ-2-4). The TZ-3, bearing a longer PEG linker than TZ-1, appears as the most appropriate for PRIT studies and will soon be considered for a new therapy experiment. In conclusion, we demonstrated the possibility to do pretargeted imaging of peritoneal disseminated tumors using bioorthogonal click chemistry with TCO/TZ interaction. Nevertheless, this strategy is quite complicated to do due to both TCO isomerization and reactivity of radiolabelled TZ probes. Further optimizations will be mandatory before therapy can be transferred to clinic.

Oxide materials exhibit a wide variety of structures and properties. In particular, transition metal oxides tend to be highly stable while exhibiting a wide range of properties that can be used for numerous applications. This work focuses on investigating how the structures��� of 4d and 5d transition metal oxides influences their properties. Specifically oxides of Ru, Rh and Ir were investigated. A complete solid solution was found between isostructural Pb���Mn���O������ and Pb���Rh���O������. Pb���Rh���O������ shows a Verwey-type transition at 185 K. This transition remains with a 3 % substitution of Mn for Rh but disappears with a 4 % substitution of Mn for Rh. The structure was found to expand in the direction perpendicular to the layers of the structure, which is the c-axis, despite a contracting unit cell. Bi for Pb substitution in Pb���Mn���O������ was found to be limited as compared to in Pb���Rh���O������. Alkali metal substitution on the A-site of the orthorhombic perovskite SrRuO��� showed only low substitution levels were possible. Nonetheless, the substituted phases showed decreased ferromagnetic Curie temperatures, increased electrical resisitivity and relatively unchanged Seebeck coefficients. Thermoelectric studies of Sr[subscript 2-x]La[subscript x]CoRuO��� perovskite phases showed Sr���.���La���.���CoRuO��� with the best thermoelectric performance. This system showed possible correlations between cation ordering on the B-site and the charge carrier transport. A similar thermoelectric study of (RhV)[subscript 1+x]Ti[subscript 1-2x]O��� phases crystallizing in a disordered trirutile structure was done. Electron carriers were found to be dominant and dependent on Ti content. The electron carriers appear to become diminished at higher temperatures. Sr���IrO��� crystallizes in a K���NiF���-type structure. Effects of Ti, Fe and Co substitution for Ir were investigated. A complete Sr���Ir[subscript 1-x]Ti[subscript x]O��� solid solution was synthesized and characterized while limited solubility was found for Fe and Co substitutions. All substitutions showed a decrease in the c-cell parameter coupled with a decrease in octahedral tilting. All substitutions also showed a decrease in magnetic susceptibility and an increase in the paramagnetic effective moment was observed for Co and Fe doped samples. An incomplete solid solution was formed for Sr���Ti[subscript 1-x]Rh[subscript x]O��� phases; however effects of increased octahedral tilting with higher Rh content were observed. / Graduation date: 2013

The present study focuses on the characterization of solid-liquid extraction techniques for the separation and preconcentration of rare-earth elements and precious metals. We developed an impregnated resin with di (2-ethylhexyl)phosphoric acid (D2EHPA) in order to separate rare-earth elements / Els treballs realitzats es centren en la caracterització de sistemes d’extracció sòlid-líquid per a la separació i preconcentració de terres rares i metalls preciosos. Amb aquest objectiu es varen avaluar diferents resines quelants, majoritàriament disponibles comercialment, per a la separació i recuperació de metalls preciosos, així com la seva aplicació a processos en columna utilitzant llits de resina fixos. També s’inclou la caracterització del procés de separació d’itri i neodimi mitjançant una resina impregnada amb dissolvent

In this thesis the relationship between Brent oil prices, LME copper prices, Turkish gold and silver spot prices, XU100 index, interest rate and exchange rate is examined. Their long run Granger causality relationship is investigated by looking at Wald statistics. The short run relationship between them is examined by using generalized impulse responses. The data range is from January 2, 2002 to February 24, 2011. Due to the oil crisis in 2008, we divide the data into three periods: January 2, 2002 to December 31 as first period, 2007, from January 1, 2008 to December 31 as second period, 2008 and January 1, 2009 and February 24, 2011 as third period. We conduct each test separately for these periods but in third period we use Toda-Yamamoto procedure since maximum order of integration is 1.

Noble metal nanostructures possess unique properties including large near-field enhancement and strong light scattering and absorption due to their plasmon resonance - the collective coherent oscillation of the metal free electrons in resonance with the electromagnetic field of light. The effect of nanostructure size, shape, composition, and environment on the plasmon resonance frequency and plasmonic enhancement is well known. In this thesis, we describe the effect of inter-particle coupling in assembled plasmonic nanostructures on their radiative and non-radiative properties. When metal nanoparticles assemble, plasmon oscillations of neighboring particles couple, resulting in a shift in the plasmon resonance frequency. Our investigation of plasmon coupling in gold nanorods shows that the coupling between the plasmons is "bonding" in nature when the plasmon oscillations are polarized along the inter-particle axis, whereas an "anti-bonding" interaction results when the polarization is perpendicular. We studied the distance-dependence of plasmon coupling using electrodynamic simulations and experimental plasmon resonances of lithographically fabricated gold nanoparticle pairs with systematically varying inter-particle separations. The strength of plasmon bonding, reflected by the fractional plasmon shift, decays near-exponentially with the inter-particle separation (in units of particle size) according to a universal trend independent of the nanoparticle size, shape, metal type, or medium. From the universal scaling model, we obtain a "plasmon ruler equation" which calculates (in good agreement with the experiments of Alivisatos and Liphardt) the inter-particle separation in a gold nanosphere pair from its plasmon resonance shift, making it applicable to the determination of inter-site distances in biological systems. Universal size-scaling is valid also in the metal nanoshell structure, a nanosphere trimer, and pairs of elongated nanoparticles, thus making it a generalized fundamental model, which is useful in optimizing plasmon coupling for achieving tunable plasmon resonances, enhanced plasmonic sensitivities, and large SERS cross-sections. Ultrafast laser pump-probe studies of non-radiative electronic relaxation in coupled metal nanospheres in aggregates and in gold nanospheres conjugated to thiol SAMs are also reported. We also show that the relative contribution of scattering (radiative) to absorption (non-radiative) part of the plasmon relaxation, respectively useful in optical and photothermal applications, can be increased by increasing the nanostructure size.

In the first section, the electrical conductivity of rhodium phenylene-diisocyanide polymer is reported to be 3.4E-11 S/cm. However, the conductivity also exhibits an inverse exponential decay in air with t = 8 days. This change is attributed to the oxidation of the isocyanide functional group to an isocyanate, leading to degradation in the long-range metal-metal bonding, the dominant conductivity mechanism. Using a more stable carboxylate ligand, the Cu terephthalate (TPA) system is studied and compared against the Mg, Co, Ni, and Zn terephthalates. A synthesis in N,N-dimethylformamide (DMF) is developed and large quantities of the Cu(TPA)DMF can be synthesized in air. The crystal structure of the Cu(TPA) DMF is shown to be in the C2/m spacegroup. Upon desolvation, the Cu(TPA) is shown to have a large surface area of 625 m2/g. The magnetic susceptibility of the Cu(TPA) indicates anti-ferromagnetic coupling between adjacent Cu centers in the same dimer. The thermal stability of the Zn, Ni, Co, and Mg terephthalates is shown to increase with decreasing symmetric carboxylate stretch in the IR. The magnetic susceptibilities of the Co and Ni terephthalates have paramagnetic behavior, with a Weiss temperature of T = -12.9 K and T = 8.8 for Co(TPA) DMF and Ni(TPA)DMF respectively. A heterometallic Zn-Cu terephthalate is synthesized with Cu concentrations ranging from 0 to 100%. Upon the addition of Cu, Zn-rich frameworks increase in surface area, change in thermal stability, and increase their solvent retention from 16% to 25%. Zn is shown to couple with Cu in the same dimer at a high rate, changing the behavior of the dimer from anti-ferromagnetic to paramagnetic. The Weiss temperature suggests weak ferromagnetic interaction.

À ce jour, la récupération de métaux précieux contenus dans les déchets d’équipements électriques et électroniques (DEEE) se fait par des procédés présentant un niveau de dangerosité certain du fait de l’utilisation de cyanure ou d’eau régale qui impactent l’environnement avec une toxicité notoire pour l’homme dans le cas des cyanures. C’est dans la perspective de répondre à ces enjeux environnementaux que le projet PEPITE a été construit en associant un industriel (RECUPYL®) le LEPMI avec le soutien de L’ADEME. L’objet du projet vise à récupérer les métaux précieux contenus dans les DEEE par un procédé utilisant des liquides ioniques (LIs). Les travaux ont permis de compiler une base de connaissance très utile sur les propriétés physicochimiques des liquides ioniques retenus. Nous avons également pu bâtir un schéma de traitement aussi efficace mais sans rejet de gaz toxiques ou d’effluents. Les résultats de nos travaux ont conduit à l’émergence d’une nouvelle voie de recyclage par chimie verte grâce à l’application des liquides ioniques. Enfin, cet avantage environnemental s’accompagne d’une viabilité économique en regard des procédés actuels. / To date, the recovery of precious metals contained in waste electrical and electronic equipment (WEEE) reported a significant level of danger due to the use of cyanide or aqua regia extremely harmful and dangerous to the humans and the environment. This is in view to respond to environmental and economic issues that RECUPYL® society, LEPMI laboratory and the French Environment and Energy Management Agency (ADEME) developed the PEPITE project. It aims to recover the precious metals contained in WEEE by a hydrometallurgical process using ionic liquid electrolytes (ILs). This work led us to establish a knowledge base and to make measurements on the physico-chemical properties of LIs. We were able to develop a process flow sheet without release neither toxic gases nor effluents. The research work undertaken has led to significant results and demonstrated that there is a real solution for the recovery of precious metals in ionic liquid electrolyte.

This dissertation assesses the significance of luxury dining ware within Roman society by analyzing the economic and socio-cultural value of these objects. Specifically, I focus on silver and gold tableware from the Roman Republic through the third century CE. Precious metal vessels are particularly well-suited to a study of socio-economical value because they are somewhere between an art object and a commodity. Because these objects are made from silver and gold, they have material value, but they are also valuable for their functionality within the dining context, particularly for hosting guests at the convivium. Their utility is, therefore, expressly social in nature. In the Roman world, silver and gold vessels were also highly decorative and as such served as display pieces and objects of attention. Their ability to communicate was not limited only to their material or their functionality; they were neither mere utilitarian commodities, nor simple stores of wealth. Scholars often note that precious metal vessels were status symbols and stores of wealth, but they rarely analyze the way that these objects functioned within those roles. I seek to address this issue by considering the different forms of attention and the processes of valuation which were applied to luxury products in the Roman period. I will ask how social and cultural contexts affected the value of precious metal tableware and how the monetary value of these items determined the social contexts in which they were used. Additionally, this dissertation includes a study of the epigraphic habits on surviving silver and gold tableware in order to better understand how these vessels were used and exchanged. The inscriptions give a sense of the kinds of attention that was given to these objects and the way in which owners or makers might use them to communicate. I will approach these questions through an analysis of four primary types of value: economic, cultural, social, and aesthetic value. Value can be an economic measure achieved by quantifying the significance of an object and expressing this as price. But value can also be applied through cognitive processes via the attention paid to objects and the attitudes of people towards them. By looking at the significance of tableware as a luxury product, utility object, and display piece, I take account of the different ways in which these vessels could be used to communicate within social contexts. I will show that the value of precious metal tableware, in both an economic and cultural sense, provided its owners with opportunities to convey particular messages aimed at navigating the fraught networks of status that existed in Roman society. Gold and silver dining ware could be a store of wealth, but not one which produced financial returns like other assets. Rather, the benefits of storing wealth as luxury dining products were social in nature. The use of precious metal dining ware at communal dinners, or for display, could project an image of wealth, taste, and, most of all, generosity. The return on assets of silver and gold dining ware was social rather than financial capital. Luxury commodities like silver and gold plate were enmeshed in the social interactions and behaviors of elite Romans and so become agents in defining the social personas of their owners.

No description available.

This dissertation explores a crucial period in the monetary geography of the Atlantic economy by examining the market for gold and silver coins (specie) in New Orleans between the Panic of 1839 and the U.S. naval blockade of the Confederate port in 1861. Situated at the intersection of global financial history and U.S. economic and business history, the dissertation reconstructs New Orleans’ supply chain of precious metals, shedding light on the port’s strategic role linking mining regions to specie-scarce nations under international bimetallism, and reveals how commission merchants, cotton factors, and merchant banks’ agents relied on metallic liquidity to engage in international trade and financial intermediation during a crucial era for nation-building and economic development in the Americas. The dissertation employs three main research strategies: (1) statistical and geographic analyses of a novel specie imports dataset (the first of its kind in the scholarly literature on specie in the early U.S. economy), extracted from the New Orleans Price-Current, a semi-weekly business newspaper, (2) group profiles and social network analysis of specie importers, leveraging multi-archival research and case studies of individuals, families, and banking and financial entities, (3) historical statistics on U.S. specie imports and Mexican specie production and exports. Chapter 1 reveals New Orleans’ centrality in the antebellum U.S. specie market and its strategic position in securing and shipping specie for the Atlantic economy under international bimetallism. Chapter 2 examines the demand side of the New Orleans specie market by focusing on the port’s cosmopolitan community of specie importers. Foreign residents received more specie than U.S. importers and New Orleans banks combined. The Louisiana Creole commission merchant and cotton factor Edmond Jean Forstall was the market’s key arbitrageur. Importers sorted into “silver barons” and “gold princes:” foreign residents handled mostly Mexican silver, while English residents, Anglo-Americans, and New Orleans banks obtained primarily gold. Chapter 3 focuses on the production and exports of Mexican specie to New Orleans. The port’s commission merchants exported British, Western European, and U.S. goods to Mexico in exchange for pesos (dollars); they reshipped U.S. cotton and Mexican pesos to European markets demanding specie for currency arbitrage operations in Europe and trade with China. Although New Orleans rapidly obtained metallic liquidity amid episodes of financial distress such as the Panic of 1857, its specie supply chain was highly vulnerable to disruptions from geopolitical shocks such as the Mexican-American War (1846-1848) and the U.S. Civil War.