Le développement de cancer entraîne une dérégulation du métabolisme du cuivre (Cu) qui a notamment été étudiée par analyse de la composition isotopique naturelle du Cu. Les cellules tumorales hépatiques sont enrichies en isotopes lourds du Cu par rapport aux cellules péri-tumorales. Le but de cette thèse est d'identifier les mécanismes responsables de cette différence, en utilisant la levure Saccharomyces cerevisiae dont les mécanismes de réduction et d'import du Cu sont proches de ceux de l'Homme. En mutant les gènes codants pour les importateurs ou les réductases du Cu, j’ai montré que son import protéique génère un enrichissement intracellulaire en isotopes légers du Cu, qui est modulé par l'activité des réductases. Une modélisation numérique m’a permis de montrer que le flux de Cu par les importateurs haute-affinité Ctr est linéairement et négativement corrélé à la composition isotopique du Cu. Ce flux étant modulé par la capacité de réduction membranaire du Cu, j’ai pu lier l'enrichissement en isotopes lourds du Cu des cellules hépatiques tumorales à une diminution de l'activité des réductases membranaires. Par ailleurs, pour un même fond génétique, j'ai mis en évidence une corrélation entre un moindre enrichissement en isotopes légers du Cu et une résistance accrue à un médicament anticancéreux, le cisplatine. De plus, le traitement au cisplatine entraîne un enrichissement des cellules en isotopes lourds du Cu d'autant plus petit que la souche est résistante au cisplatine. Ainsi, ces résultats montrent que la mesure de la composition isotopique du Cu avant et après traitement au cisplatine pourrait permettre de suivre l'apparition d’une chimiorésistance chez les malades, caractérisée par un enrichissement en isotopes lourds du Cu dans les tumeurs, ce qui ouvre la voie au développement d'un nouveau biomarqueur non-invasif de l'apparition d'une résistance au cisplatine. / Cancer development leads to Cu metabolism disregulation which were especially studied by the natural copper (Cu) isotopic composition. Hepatocellular carcinoma (hCC) are enriched in heavy Cu isotopes compared to peri-tumoral cells. The goal of this thesis is to identify the mechanism responsible for this difference. I used the yeast Saccharomyces cerevisiae where Cu reduction and Cu import mechanism are close to the human. By mutating the genes coding for Cu reductases or Cu importers, I showed that protein Cu import generate an intracellular light Cu enrichment which is modulated by Cu reductases activity. With a numerical modelisation I calculated that the Cu flux through high-affinity Cu importers is linearly and negatively correlated to the natural Cu isotopic composition. This flux is modulated by the cell reduction ability. Therefore, I have linked the heavy Cu isotopes enrichment in hCC to a lower reductases activity. Besides, for a same genetic background, I observed a correlation between a lower light Cu enrichment and an higher resistance to a anti-tumoral drug, the cisplatin. Moreover, I observed that cisplatin treatment leads to an enrichment in heavy Cu isotopes which is lower for resistant to cisplatin strains. Those results shown that the Cu isotopes measurement in tumors before and after the cisplatin treatment might be used to trace the chemoresistance apparition in patient with cancer which is characaterize by a tumoral heavy Cu isotopes enrichment. This results might pave the way to the development of a new prognosis biomarker of the cisplatin resistance apparition.

The recognition of the negative impact of NOx resulted in increasingly tighter automotive emission regulations. Companies are under pressure to develop methods, which can meet the legislative demands. After treatment solutions, and especially Selective Catalytic Reduction, became the focus of research and have shown so far promising results. However, more in depth understanding of the SCR process under different conditions is needed. This thesis describes an investigation of the SCR performance using gas and urea injections under steady state and transient conditions undertaken on a light duty diesel engine using a 1D exhaust system designed for uniform flow across the catalyst. Under steady state conditions, the SCR performance was examined for low and high temperature conditions. Ammonia was supplied either as 5% ammonia gas or in form of urea injection. The engine was operating at 1500 rpm and 6 and 8 bar BMEP to provide an exhaust gas temperature of 210 °C and 265 °C respectively. Also, the effect of SCR brick length on the NOx conversion was investigated using SCR catalysts of length 30, 45 and 75 mm. To measure the influence of NO2:NOx ratio on the SCR performance, different sizes of standard DOC were used. NH3:NOx dosage levels included; α~0.5 - deficient ammonia, α~1.0 - stoichiometric ammonia, α~1.25 - excess ammonia. Gas emissions were measured before and after the SCR catalysts with a Horiba FTIR analyser during steady state and long transient tests. It was found that conditions such as temperature and NO2:NOx had the biggest impact on the SCR performance. During the steady state engine conditions, at α~1.0 ammonia dosing and NO2:NOx ratio of 0, only 17% of NO was converted in the first 30 mm of the SCR brick length. The conversion was improved at high temperature (263 °C) to 31%. A fast response CLD analyser was used during short transient testing to sample emissions with a high resolution. The short transient test with standard 0.5 and 1 DOC, and fixed ammonia dosing, showed that NOx conversion was reduced during the ramp event due to deficient ammonia and a drop in the supplied NO2:NOx ratio. During urea injection experiments, urea was injected either through an oblique pipe arrangement with a mixer device placed downstream or directly into a mixing can. In this case the mixer device was replaced with a straight pipe. A 75mm SCR was fitted and to ensure that supplied NO2:NOx ratio was zero, a palladium only DOC was used post a DPF. It was found that a large proportion of urea decomposition and hydrolysis was occurring on the surface of the SCR catalyst. Comparing NOx performance between urea injection and ammonia gas dosing experiment, more NO was converted for a given NH3:NOx ratio when ammonia was supplied in the form of gas. That was true for low and high temperature tests. For most studies, a long 10 degree diffuser was used in front of the SCR to provide uniform gas distribution across the catalyst. In addition SCR performance was investigated with a 180 degree sudden expansion diffuser in order to measure the influence of temperature and velocity profiles. During this study, a 45 mm SCR catalyst was used to provide a moderate amount of NO conversion and ammonia slip. The results showed that the flow and temperature distribution upstream of the SCR catalyst will have an effect on the NOx conversion, and that gas velocity has bigger impact on NOx conversion than gas temperature.

Utilisés pour leur bon compromis entre propriétés mécaniques, thermiques et électriques, les alliages Cu-Ni-Si à durcissement structural par précipitation sont notamment employés pour la maintenance ferroviaire. Ils sont donc soumis aux passages des trains et aux effets d’environnement. C’est pourquoi la résistance d’un alliage CuNi2Si a été étudiée en fatigue oligocyclique, en corrosion aqueuse et en fatigue-corrosion. Le but est de relier les propriétés macroscopiques aux mécanismes microstructuraux. Les essais de fatigue ont montré un durcissement initial de l’alliage, suivi d’un adoucissement continu jusqu’à la rupture. À l’aide des microscopies électroniques en transmission (MET) et à balayage (MEB), notamment en ECCI (Electron Channeling Contrast Imaging) et en EBSD (Electron BackScattered Diffraction), une formation initiale de cellules de dislocations a été identifiée, ces dernières disparaissant au profil de la formation de bandes dénuées de précipités suite à la dissolution mécanique des précipités δ-Ni2Si. Ceci constitue le mécanisme d’accommodation de la déformation cyclique. L’avancée de la formation de ces bandes explique les différents régimes observés sur le diagramme de Manson-Coffin. L’alliage présente en milieu NaCl à 50 g.L1 un mécanisme de corrosion intergranulaire. La spectroscopie d’impédance électrochimique (SIE) semble indiquer la présente d’un film passif compact en surface de l’alliage. Enfin, une sensibilité à la fatigue-corrosion apparaît, notamment aux plus hauts niveaux de déformation où la durée de vie est réduite d’un tiers. De plus, un faciès de rupture semblable à ceux observés en corrosion sous contrainte est constaté. / Employed for their good balance between mechanical, thermal and electrical properties, precipitation hardened Cu-Ni-Si alloys are used for various purposes, including railway maintenance. In the latter case, they are submitted to train traffic and environmental effects. This is why the low cycle fatigue (LCF), the wet corrosion and the fatigue-corrosion behaviours of a CuNi2Si alloy have been studied. The aim of the present work is to relate the macroscopic properties to the microstructural behaviour. The fatigue life of the alloy is composed of an initial hardening step, followed by a continuous softening until fracture. Thanks to the combination of transmission and scanning electron microscopies (respectively TEM and SEM), including ECCI (Electron Channeling Contrast Imaging) in addition to EBSD (Electron BackScattered Diffraction), the formation of dislocation cells has been identified, which ones are then consumed by the formation of precipitate free bands after the mechanical dissolution of the δ-Ni2Si precipitates. This sequence describes the cyclic strain accommodation mechanism. The progress in the formation of these bands explains the different regimes observed into the Manson-Coffin diagram. The alloy exhibits intergranular corrosion in 50 g.L-1 NaCl solution. The electrochemical impedance spectroscopy (EIS) indicates the formation of a compact passive film at the surface of the alloy. Finally, the alloy seems to be sensible to fatigue-corrosion, especially at high strain range where the number of cycle to failure is reduced by a third. Moreover, a fracture surface similar to a stress corrosion cracking surface is also observed.

Organic semiconductor interfaces are promising materials for use in next-generation electronic and optoelectronic devices. Current models for metal-organic interfacial electronic structure and dynamics are inadequate for strongly hybridized systems. This work aims to address this issue by identifying the factors most important for understanding chemisorbed interfaces with an eye towards tuning the interfacial properties. Here, I present the results of my research on chemisorbed interfaces formed between thin-films of phthalocyanine molecules grown on monocrystalline Cu(110). Using atomically-resolved nanoscale imaging in combination with surface-sensitive photoemission techniques, I show that single-molecule level interactions control the structural and electronic properties of the interface. I then demonstrate that surface modifications aimed at controlling interfacial interactions are an effective way to tailor the physical and electronic structure of the interface. This dissertation details a systematic investigation of the effect of molecular and surface functionalization on interfacial interactions. To understand the role of molecular structure, two types of phthalocyanine (Pc) molecules are studied: non-planar, dipolar molecules (TiOPc), and planar, non-polar molecules (H2Pc and CuPc). Multiple adsorption configurations for TiOPc lead to configuration-dependent self-assembly, Kondo screening, and electronic energy-level alignment. To understand the role of surface structure, the Cu(110) surface is textured and passivated by oxygen chemisorption prior to molecular deposition, which gives control over thin-film growth and interfacial electronic structure in H2Pc and CuPc films. Overall, the work presented here demonstrates a method for understanding interfacial electronic structure of strongly hybridized interfaces, an important first step towards developing more robust models for metal-organic interfaces, and reliable, predictive tuning of interfacial properties.

In this work, the possibility of Cu electrodeposition on Ru-Ta alloy thin films is explored. Ru and Ta were sputter deposited on Si substrate with different composition verified by RBS. Four point probe, XRD, TEM and AFM were used to study the properties of Ru-Ta thin films such as sheet resistance, crystallinity, grain size, etc. Cyclic voltammetry is used to study the Cu electrodeposition characteristics on Ru-Ta after various surface pretreatments. The results provide insights on the removal of Ta oxide such that it enables better Cu nucleation and adhesion. Bimetallic corrosion of Cu on modified Ru-Ta surface was studied in CMP related chemicals. In Cu interconnect fabrication process, the making of trenches and vias on low-k dielectric films involves the application of fluorocarbon plasma etch gases. Cu microdots deposited on Ru and Ta substrate were treated by fluorocarbon plasma etch gases such as CF4, CF4+O2, CH2F2, C4F8 and SF6 and investigated by using x-ray photoelectron spectroscopy, contact angle measurement and electrochemical techniques. Micropattern corrosion screening technique was used to measure the corrosion rate of plasma treated Cu. XPS results revealed different surface chemistry on Cu after treating with plasma etching. The fluorine/carbon ratio of the etching gases results in different extent of fluorocarbon polymer residues and affects the cleaning efficiency and Cu corrosion trends.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23029号 / 理博第4706号 / 新制||理||1675(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 加納 太一, 教授 依光 英樹, 教授 時任 宣博 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The Cassenha Hill copper-gold prospect is situated in the Catabola area, Huambo Province, southwestern Angola. Geologically, the prospect is part of the Angolan Central Eburnean Zone (CEZ) and consists of Paleoproterozoic metasedimentary rock sequences which have been intruded by Eburnean granitoids at ± 2.1 Ga. The prospect itself comprises an area of 180 Km2 and has been intermittently explored since 2005 by Rift Valley Resources (RVR) and its associates. The Cassenha Hill prospect is characterized by the occurrence of partially altered and highly oxidized metasedimentary rocks (meta-mudstone, meta-siltstone, carbonate-rich rock, meta-sandstone, breccia, and quartzite), and altered isolated granitoids. This study represents the first detailed study of the prospect and aims to shed light on the characteristics of the various rock types (i.e., host and barren rocks), their source/provenance, styles of alteration, and the origin and/or type of the fluid responsible for the mineralization. Techniques applied include borehole core logging, petrography, whole-rock geochemistry (XRF and ICP-MS), and stable isotope geochemistry on samples collected on the surface and from exploration boreholes drilled as part of RVR exploration program. Overall, the petrographic and geochemical studies undertaken in the rocks of the Cassenha Hill prospect indicate the following: (1) The rocks are moderately to strongly fractured; (2) The rocks have experienced weak to moderate chemical weathering; (3) The rocks are compositionally immature and originated from felsic provenance; (4) The rocks are sulfur-poor, and lacking in sulfide minerals (5) The rocks are enriched in LREE and LILE elements and depleted in HREE and HFSE elements; (6) The mineralization is associated with chloritization alteration and predominantly occurs within and/or at the edges of quartz/chlorite-rich veins/fractures and is not restricted to any rock type. Two ore stages could be identified, namely, hypogene ore (stage I) consisting of pyrite ± chalcopyrite ± other copper sulfides, and supergene ore (stage II) consisting of malachite ± azurite ± chrysocolla, which represents the prevalent mineralization at the prospect. The δ 18O value of quartz veins range from +12.81 to +13.53‰, while the δD of chlorite minerals range from -51 to -45‰. Therefore, assuming fluid-rock interaction took place at ≈ 350oC, due to the presence of quartz, the fluid had δ 18OH20 values of about +8‰, which are typical of magmatic waters. On the other hand, at a temperature of ≈ 350oC, and with the difference between chlorite and water being -33.5‰, such fluids would have had δDH20 values of about -20‰ (δ 18OH20= -4‰), which are typical of meteoric waters. Although the various mineral phases have yielded different isotopic signatures, this study suggests that water is ultimately of meteoric origin but exchanged with hydrogen-poor magmatic rock, thus maintaining the meteoric signature. The continuous influx of meteoric waters within the fracture system led to the development of copper oxides such as malachite, azurite and chrysocolla, which possibly originated from the insitu oxidation of the hypogene sulfides. This signature, together with other field, petrographic and geochemical observations allows one to, tentatively, suggest that the Cassenha Hill prospect represents an extension of a polymetallic vein-type of porphyry Cu deposit that has been subjected to supergene processes at the weathering profile.

Title: Electronics and adsorption properties of model catalytic systems contains cerium Author: Miloš Cabala Department: Department of Surface and Plasma Science, Supervisor: RNDr. Kateřina Veltruská, Department of Surface and Plasma Science, Abstract: The doctoral thesis contains the study of model catalyst systems based on cerium and ceria. The thesis deals with model systems of CeAg, CeO2/Cu(111), Ni- CeO2/Cu(111) a Ni-Sn-CeO2/Cu(111). We have studied these systems using photoelectron spectroscopy, ion scattering spectroscopy and low energy electron diffraction. Model systems were prepared under strictly defined conditions. The strong bimetallic interaction was observed on the CeAg layers. Molecular adsorption of carbon monoxide on CeAg was demonstrated. We also observed intensive reaction of these layers with oxygen. By measurements in different directions of surface Brillouin zone, we managed to reconstruct the band structure of the prepared CeO2/Cu(111) layer. We have shown that the Cu substrate interacts weakly with deposited CeO2 layer. This interaction results in a charge transfer from Cu into CeO2. Overall, in the valence spectrum we have identified three main electron bands corresponding to O 2p state bound in CeO2. It has been proven that the deposition of Ni on CeO2 layers leads to partial...

Die Cu – Ag - Mikroverbund – Werkstoffe besitzen das Potenzial die gegensätzlichen Anforderungen an das Leitermaterial für den Einsatz in einem Hochfeldmagneten, wie hohe Festigkeit bei gleichzeitig hoher elektrischen Leitfähigkeit und ausreichender Verformbarkeit, zu erfüllen. Außerdem bieten diese Werkstoffe gegenüber den anderen, die dafür in Frage kommen können, den großen technologischen Vorteil einer konventionellen schmelzmetallurgischen Herstellung. Jedoch wurde bisher dafür eine sehr aufwändige Technologie verwendet, die die Herstellung des Leitermaterials nur im Labormaßstab ermöglicht. Die vorliegende Arbeit befasst sich mit einer Technologie der Herstellung von Leitern, die den Anforderungen für den Einsatz in einem Hochfeldmagneten genügen können und in einem großtechnischen Maßstab verfügbar sind. Der Schwerpunkt der Leiterherstellung aus Cu – Ag - Legierung lag in der Einstellung der geeigneten Mikrostruktur über metallkundliche Mechanismen vor der Drahterzeugung. Hierfür wurden während der einzelnen Prozessschritten die Gefügeentwicklung und für die Anwendung relevante Eigenschaften der Legierungen in binären Cu – Ag – Legierungen und in ternären Cu – Ag -X –Legierungen untersucht. Darüber hinaus wurde der Einfluss der Mikrostruktur und der Zusammensetzung auf die mechanischen und elektrischen Eigenschaften der Drähte ermittelt sowie eine Korrelation zwischen Mikrostruktur und elektrischen Eigenschaften aufgestellt.

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