Norint ištirti vario (Cu) ir kadmio (Cd) įtaką augalams, augintiems skirtingose terpėse, buvo vertinamas diferencijuotas ir kompleksinis sunkiųjų metalų poveikis jų morfologiniams ir fiziologiniams rodikliams. Varis reikalingas mažais kiekiais kaip mitybos elementas, bet tampa toksišku esant didesnėms jo koncentracijoms aplinkoje. Kadmis neturi biologinės funkcijos ir gali būti toksiškas esant mažoms koncentracijoms, priklausomai nuo aplinkos sąlygų, jo cheminio būvio ir t.t. Tyrimo objektais buvo pasirinkti vasariniai miežiai (Hordeum vulgare L.) ir mažosios plūdenos (Lemna minor). Šio darbo tikslas yra įvertinti ir palyginti Cd ir Cu poveikį esant skirtingam biologiniam prieinamumui iš vandeninės terpės ir dirvožemio. Tiriamas darbas buvo atliekamas dviem etapais. Visų pirma buvo tiriamas pavienis metalų poveikis Lemna minor. Savaitę jos buvo auginamos 0,1 µM; 0,5 µM; 1 µM; 10 µM; 50 µM ir 100 µM koncentracijos kadmio bei 1 µM; 5 µM; 10 µM; 50 µM ir 100 µM koncentracijos vario tirpaluose. Metalų mišinių koncentracijos, kuriomis buvo veikiamos Lemna minor, pasirinktos pagal diferencituotas, kuriose augalai išgyveno daugiau kaip pusę tiriamojo laikotarpio. Nustačius EC50 koncentracijas pagal tiriamojo parametro, lyginant su kontrole, sumažėjimą, apskaičiuota EC50 mišinio. Mišinio koncentracijos išreikštos kaip TU. Įvertinti Lemna minor biomasės prieaugio, augimo inhibicijos pokyčiai. Kompleksinio poveikio atveju augimo greičiui (EC50 mišinio = 2,5 TU) ir biomasės... [toliau žr. visą tekstą] / The aim of this study was to investigate the influence of cadmium (Cd) and copper (Cu) to plants froms diferent growing medium and evaluate the single and combined effect to their morphologic and physiologic parameters. Cu is known as micronutrient. It is necessary for plants but becames toxic at higher concentrations. Cd doesn‘t have any biological function and can be toxic even at small concentrations. It‘s toxicity depends on environmental conditions, chemical state and etc. The subject of this research is agricultural plants summer barley (Hordeum vulgare L.) and water plants duckweed (Lemna minor). The purpose of study is to value and to compare Cd and Cu effects to plants from water and soil medium. The research was done in two stages. At first, the single heavy metal effect to Lemna minor was investigated. Plants were treated one week by 0,1 µM; 0,5 µM; 1 µM; 10 µM; 50 µM; 100 µM Cd and 1 µM; 5 µM; 10 µM; 50 µM; 100 µM Cu concentrations. Considered to single concentrations, combained concentrations were chosen. Concentrations in the mixtures was expressed as TU, as fraction of their median affective concentration (EC50). Biomass and growing inhibition were measured. Antagonistic responses to biomass (EC50 mix = 2 TU) and growth inhibition (EC50 mix = 2,5 TU) occurred with Cd+Cu mixture. The experiment was also done with summer barley (Hordeum vulgare L.). Two weeks they were grown in soil and water solutions affected by the same heavy metal concentrations like Lemna... [to full text]

Ce travail a pour but l’acquisition de connaissances fondamentales dans les équilibres de phases et les transformations de phases des alliages ternaires contenant du fer, du nickel et du cuivre.Cette étude est composée de trois parties : la première est consacrée aux équilibres de phase entre600°C et 1000°C dans le coin riche en fer du système ternaire Cu-Fe-Ni, la seconde concerne l’analyse des transformations de phases dans des alliages modèles suivant deux vitesses de refroidissement et la troisième étudie les alliages industriels.Cette approche expérimentale est appuyée par des calculs thermodynamiques. Une comparaison est effectuée avec les données issues de la littérature. Les sections isothermes à 600°C, 800°C et1000°C ont été reconfirmées. Les domaines triphasés αFe/γFe/γCu ont été déterminés à 600°C et800°C et semblent décalés vers de plus fortes teneurs en Ni. La lacune de miscibilité est moins étendue que celle calculée et ce particulièrement du côté du binaire Cu-Ni.Les transformations de phase γ→α apparaissant lors du refroidissement d’alliages Fe-xCu-10Ni et Fe-10Cu-xNi (0<x<15 % en masse) ont été étudiées. Elles sont observées dans tous les alliages refroidis lentement par dilatométrie sauf dans l’alliage binaire Fe-Cu. Les températures de transformation sont systématiquement inférieures aux températures d’équilibre et cet écart augmente lorsque les teneurs en Ni et Cu augmentent. La formation de la ferrite bainitique est favorisée par l’addition de Cu dans les alliages trempés Fe-xCu-10Ni et par l’addition de Ni dans les alliages Fe-10Cu-xNi tandis que la ferrite massive se forme préférentiellement lors du refroidissement lent. Une diminution des températures de transformation se produit lorsque la taille de grains est affinée et est reliée au processus d’accommodation plastique liée à la transformation.La composition et la vitesse de refroidissement jouent un rôle sur la dureté de ces alliages via la présence de Ni en solution solide ainsi que le nombre et la taille des précipités de Cu. / This work aims in getting fundamental knowledge of phase equilibria and microstructures of ternary alloys containing copper, nickel and iron. The thesis is composed of three parts: a first part is devoted to phase equilibria in the Fe-rich corner of the ternary Cu-Fe-Ni system between 600°C and 1000°C, a second part is devoted to the microstructures in these materials for model alloys, for two cooling rates and a third part is devoted to industrial alloys.Phase equilibria of the system are investigated in the range 600-1000°C using diffusion multiples in conjunction with selected equilibrated alloys. This experimental approach is supplemented by thermodynamic calculations. A comparison is drawn with data reported in the literature. The isothermal sections at 600°C, 800°C and 1000°C have been reconfirmed. The three-phase regions αFe/γFe/γCu are determined at 600°C and 800°C and appear shifted to a higher Ni content. The miscibility gap is narrower than the calculated, particularly on the Cu-Ni binary sides.Austenite/ferrite phase transformations occurring on cooling in Fe-xCu-10Ni and Fe-10Cu-xNi alloys,0<x<15 (mass%), have been studied. The influence of copper and nickel additions and of the cooling rate on the microstructure is discussed. Metastable transformations in slowly cooled alloys have been detected by dilatometry in all alloys except in the binary Fe-10Cu alloy: all the cooling transformation temperatures are systematically lower than the equilibrium temperature and the Ni and Cu addition decrease this transformation temperature. The formation of bainitic ferrite is favoured by copper additions in quenched Fe-xCu-10Ni alloys and by Ni addition in Fe-10Cu-xNi alloys while massive ferrite form preferentially during slow cooling. A decrease of the transformation temperatures is recorded when the alloys have a finer grain size likely related to plastic accommodation processes.The composition and cooling rate influence the hardness of the alloys mostly dependant on the amount of Ni in solid solution and on the rate and size of Cu precipitates.

Através do processo de evaporação térmica é possível produzir filmes de KCl e KBr altamente dopados com íons Cu+. Investigamos o efeito de altas concentrações de Cu+ (1020 - 1021 cm -3) nestes filmes policristalinos, onde, associado com o efeito fora de centro do Cu+, origina uma forte banda de absorção propícia para aplicação ótica destes filmes como filtros passa banda na região do UV. Os filmes estudados, de 1 UM, foram preparados por coevaporação resistiva de KCl (Br), como hospedeiro, com 1 a 10% de CuCl(Br), como dopante, sobre diferentes substratos. Diversas técnicas foram usadas para obter as propriedades estrutural e ótica, tais como: microscopia eletrônica de varredura (MEV), difração de raios-X, elipsometria, absorção ótica e transmitância. Do estudo da morfologia é observado um aumento na densidade dos grãos com a concentração nominal de Cu+ de até 1021 átomos/cm-3. Este comportamento também resulta em um aumento na transmitância na região do visível. A banda de absorção em 266 nm (278 nm) para KCl ()KBr): Cu+ é atribuída à transição eletrônica parcialmente permitida de 3d10 3d94s e sua área integrada em função da temperatura mostra o comportamento da força do oscilador com a temperatura, que é propriedade do efeito fora de centro. A este efeito fora de centro está associado um dipolo elétrico devido ao deslocamento da carga da posição substitucional. Para verificar a existência de um sistema de relaxação dipolar elétrica, usamos o método de Corrente de Despolarização Termicamente Estimulada (CDTE). As medidas de CDTE mostram uma fraca e alargada banda em 49K, com energia de ativação média de 147 meV e um fator pré-exponencial de 2x10-14 seg, para amostras de KCl + 1% CuCl, com 3 UM de espessura. Nossos resultados são discutidos e comparados com outros observados em monocristais do mesmo material / Through the thermal evaporation procedure it is possible to obtain highly Cu+ doped KCl and KBr films. We have investigated the effect of 1020 - 1021 cm-3 Cu<sup+ concentration in these polycristalline films, where beside the Cu+ off-center effect it is detected a strong absorption band suitable for UV band pass optical filter application. The studied films are APROXIMADAMENTE 1 UM thick and are prepared from coevaporated KCl (KBr), as host, jointly with 1 to 10% of CuCl (CuBr) nominal doping value. Several techniques were used to obtain the optical and structural properties, such as optical absorption and transmittance, scanning electronic microscopy (SEM), X-ray diffraction and ellipsometry. From the morphology study it is observed that the grain density increases as the Cu+ concentration increase. This behavior results in an increasing transmittance in the visible region tôo. The absorption banda t 266 nm (276 nm) for KCl (KBr):Cu+ is attributed to the Cu+ partially allowed electronic transition 3d10 3d94s and its integrated área shows a temperature independent oscillator strenght behavior which is a property of the off-center effect. To this off-center effect it is associated a electric dipole due to the íon charge displaced from the substitutional position. To verify the existence of a relaxing electric dipole system, we use the thermally stimulated depolarization current (TSDC) method to find out for the Cu+ off-center electric dipole system. The TSDC measurements show a very weak result for our KCl + 1% CuCl samples, resulting in a meanactivation energy of 147 meVwith a peak position at 49K and a pré-exponential Arrhenius time of 2x10-14 sec. We compare and discuss the present results with others found in the same single crystal materials

nicialmente descreve-se o Sistema Cu-A1 e as fases que ocorrem do lado rico em cobre; em seguida faz-se uma revisão sobre as reações de decomposição da fase ? de alta temperatura no resfriamento e sobre as reações de decomposição da martensita ?\'? no revenido. Faz-se também a revisão de alguns conceitos teóricos sobre interfaces e estabilidade das microestruturas. Estudou-se, na parte experimental, a decomposição isotérmica (revenido) da martensita ?\'? de duas ligas hipoeutetóides em temperaturas que correspondem aos campos ? + ?? (520 ºC) e ? + ? (650 ºC) do diagrama Cu-A1. Realizaram-se ainda experiências de solubilização no campo ? + ? a 576 ºC da estrutura ? + ?? obtida pelo revenido por 90 minutos a 520 ºC. No revenido a 520 ºC da martensita ?\'? de ambas as ligas observou-se inicialmente a precipitação de alotriomorfos de fase ? em contornos de grão, a reversão parcial da martensita para fase ?? , e transformação in situ da martensita em fase ? supersaturada, que gradualmente passa a fase ? de equilíbrio. Com tempos maiores, observou-se a decomposição da fase ?? em ?? e? . A fase ? tem a forma de plaquetas que mantém planos de hábito herdados da martensita. A fase ?? precipita como glóbulos que coalescem sem formar contornos de grão, formando lamelas de interface lisas entre as plaquetas de ? . A estrutura ? + ?? não coalesce nem esferoidiza para os tempos estudados, o que pode ser explicado pela existência de interfaces ? / ?? , e ? / ?? de baixa energia. Para se estudar a existência de interfaces de baixa energia entre a fase ? da transformação in situ e a fase ? da reversão da martensita, realizou-se a decomposição da martensita no campo ? + ? .Observou-se que a fase ? resultante de transformação in situ mantém os planos de hábito da martensita; as plaquetas de fase ? coalescem sem esferoidizar, mantendo interfaces retas com a fase ? e os mesmos planos de hábito que a martensita obtida pelo resfriamento da fase ? de reversão. Cada grão de ? original dá origem a apenas um grão de ? , com a mesma orientação cristalográfica. Para estudar a existência de interfaces de baixa energia entre as fases ?? e ?? e de ambas com fase ? , realizou-se a solubilização no campo ? + ? da estrutura ? + ?? obtida por revenido. Verificou-se que a fase ? precipita no interior da fase ?? na forma de glóbulos, que depois crescem dissolvendo parcialmente a fase ? . As interfaces ? / ? mantém-se planas e as plaquetas de ? mantém os planos de hábito herdados da martensita. Cada antigo grão de ? dá origem a um grão de ? com a mesma orientação. Discutiu-se os resultados sob o ponto de vista da relação entre morfologia e a natureza das interfaces. Concluiu-se que os resultados podem ser explicados pela existência de interfaces ? / ?? , ? / ?? e ? / ? de baixa energia em algumas direções e interfaces ?? / ?? e ?? / ? em todas as direções. Discutiu-se ainda a origem de relações de orientação entre os reticulados que correspondem a interfaces de baixa energia. / The Cu-Al system, in the copper-rich side, is described. The reactions that occur during decomposition of the high temperature ? phase, as well as the decomposition of the ?\'? martensite during tempering, are reviewed. Some theoretical concepts about interfaces and microstructural stability are also reviewed. In the experimental part of this dissertation, the isothermal decomposition (tempering) of the ?\'? martensite is studied in two hipoeutectoid alloys, at temperature in the ? + ?? field (520 ºC) and in the ? + ? field (650 ºC) of the Cu-Al equilibrium diagram. Experiments on the solubilization of the ? + ?? structure obtained by tempering, in the ? + ? field of the equilibrium diagram at 576 ºC, are also made. During tempering at 520 ºC of the ?\'? martensite, for both alloys, it was initially observed the precipitation of ? phase alotriomorphs in grain boundaries, the partial reversion of the martensite ?? phase, and the transformation \"in situ\" of the martensite to supersaturated ? phase, which gradually becomes equilibrium ? phase. Later it was observed the decomposition of the ?? phase to ?? and ? phases. The \"in situ\" formed ? phase is plate-like, and maintain the habit plane of the martensite. The ?? phase precipitates as globules, which coalesce without leaving grain boundaries, forming lamellas between ? plates, with smoth inbterfaces. The ? + ?? structure neither coarsen nor spheroidizes for the studied periods of times. The results can be explained by the existence of low energy ? / ?? and ? / ?? interfaces. Experiments on the decomposition of the martensite in the ? + ? field were made to check the existence of low energy interfaces between the \"in situ\" transformed ? phase and the ? phase from the martensite reversion. It was observed that ? phase plates maintain the martensite habit planes. The plates coarsen without spheroidizing, but maintaining straight interfaces with the ? phase, and with the same habit plane of the martensite that results from the quenching of the ? phase from the reversion. Each ? grain originates only one new ? grain, with the same crystallographic orientation. Experiments on the solubilization in the ? + ? field of the ? + ?? structures obtained by tempering were made in order to study the existence of low energy interfaces between the ?? and ?? phases, and between both and the ? phase. It was observed that the ? phase precipitates inside the ?? as globules which later grow, dissolving partially the ? phase. The ? / ? interfaces stay straight and the ? plates maintain their habit planes. Each original ? grain originates one new ? grain with the same orientation. The results were discussed by relating the morphologies to the nature of the interfaces. It was concluded that the results could be explained by the existence of low energy ? / ?? , ? / ?? and ? / ? interfaces on some directions, and ?? / ?? and ?? / ? interfaces in all directions. The origins of the lattices orientation relationships that gives low energy interfaces are discussed.

Com base em trabalhos tanto teóricos como experimentais, tem-se concluído que o Cu+ fica em posição fora de centro em alguns halogenetos alcalinos. Neste, trabalho apresentamos resultados obtidos por técnicas de correntes termoestimuladas(ITC), para, verificar propriedades de dipolos elétricos devido a Íons de Cu+ em posição fora da centro em cristais de KCl. Ampliou-se o estudo do comportamento do Cu+ em cristais de KBr e KI. As bandas de ITC observadas nestes cristais, apresentam máximos em 62, 70 e 83 &#176K, e as energias de ativação são de 0.177, 0.196 e 0.232 eV em KCl, KBr e KI, respectivamente. A partir da integração das bandas de ITC e as concentrações de Cu+ achados por absorção ótica, o momento, dipolar elétrico é determinado, conduzindo a valores de 1.5, 1.9 e 2.6 e &#197 no KCl, KBr e KI, respectivamente. Dada a forma da banda de ITC, comprova-se que a reorientação dos dipo1os segue o modelo clássico com um tempo de relaxação simples, e que o Cu+ fica congelado em posição fora de centro abaixo daquelas temperaturas em que ocorre o máximo da banda de ITC. / Theoretical and experimental investigations have concluded that Cu+ occupies an off-canter position in several alkali halides. In this work we report results obtained by ionic thermal-currents technique (ITC) to verify the electric dipole properties due to Cu+ ions in off-center position in KC1 crystals. This was developed to study the Cu+ ion behaviour in KBr and KI crystals. The ITC band observed in these crystals geve maxima at 62, 70 and 83 &#176K, and the activation energies were 0.177, 0.196 end 0.232 eV in KCI, KBr and KI, respectively. From the integration of the ITC bands and the concentration of Cu+ obtained by optical absorption, the dipole moment is determined, giving values of 1.5, 1.9 and 2.6 e &#197 in KC1, KBr and KI, respectively. Due to the shape of the ITC band, we conclude that the dipole reorientation follows the classical model with a single relaxation time, and that the Cu+ freeze in off-center position below those temperatures where maximum occur at the ITC band.

Ressonância Paramagnética Eletrônica (RPE) e Absorção Ótica Eletrônica foram utilizadas para estudar-se os complexos de Cobre (II) com tris-hidroximetil aminometano em solução. A análise dos parâmetros de RPE e óticos medidos na solução a diversos pHs foi feita tendo-se à mão as curvas de formação dos complexos. Estas curvas foram construídas em função do pH da solução, usando os dados de equilíbrio químico publicado por K. S. Bai e Martell (J. Inorg. Nucl. Chem. 31 (1969) 1697-1707), numa faixa de concentração de tris na qual este reagente é usando como tampão em estudos biológicos e químicos. Determinou-se cinco conjunto de parâmetros de RPE (go, ao, a11 e A11, correspondentes a diferentes complexos de íon metálico. Cada um desses espectros é encontrado em determinados intervalos de pH, sendo possível associá-los aos complexos previstos nas curvas de formação. A maior estabilidade dos complexos que se formam a pHs mais altos segundo as constantes de equilíbrio é evidenciada pelos valores e go isotrópico (RPE) menores pelos desdobramentos hiperfino isotrópico ao (RPE) e de campo cristalino (ótica) maiores do que os encontrados nas soluções menos alcalinas. A formação do complexo quelato neutro a pH alcalino foi observada, e obteve-se seu tensor g, das medidas do cristal simples. Este tensor encontra-se em bom acordo com o valor de g isotrópico determinado em solução (go=1/3(gxx+gyy+gzz)). Existe evidência de que este complexo seja pentacoordenado). Observou-se similaridade entre os parâmetros para os complexos coordenados por: 2N e 1N+1 0&#8254; 3N e 2N+1 0&#8254 ; 4N e 2N+2 0&#8254. Isto leva à conclusão de que do ponto de vista energético a coordenação de nitrogênio Cu2+ e a coordenação do oxigênio negativo ao Cu2+ nestes complexos são equivalentes, pelo menos dentro de nossa resolução experimental. / Electron Paramagnetic Ressonance (EPR) and optical visible spectroscopies were used to study the complexes of Cu (II) íon with tris-hydroxymethylamino methane (tris) in solution. Analyses of EPR and optical parameters measured in solution were made using the calculated formation curvesof the complexes. These formation curves were calculated as function of the solution pH, on the basis of the equilibrium constants published by K.S. Bai and Martell (J. Inorg.Nucl. Chem. 31 (1969)-1967-1707), for a concentration of this normally employed in a buffer in biochemical studies. Five sets of EPR parameters ((go, ao, a11 e A11) were determined corresponding to different metal complexes. Each det is found in a characteristic pH range and it was possible to make a correlation of these complexes with the appear in the formation curve plot. The greater stability of the complexes in the high pH range is indicated by the values of go, wich are smaller and the values of the hyperfine splittings ao and the crystal field splittings (from optical measurements) which are greater tahn at the less alcaline solutions. The formation of the neural chelate complexa t alcaline pH was observed, and its g-factors were obtained from measurements with the single crystal. These g-factors agree very well with the solution value (go=1/3(gxx+gyy+gzz)) and the orthorombic symmetriy is obtained. Evidence is present that this complex is penta-coordinated. It was observed a similarity between the EPR parameters for the complexes coordinated by: : 2N e 1N+1 0&#8254; 3N e 2N+1 0&#8254 ; 4N e 2N+2 0&#8254. This lead us the conclusion that from the energetical point of view the coordination of Cu2+ to nitrogen or to negative oxigen in these cases are equivalent, at or our resolution is not sufficent to differentiate between them.

L’émergence de nouveaux matériaux structurés à l’échelle nanométrique, aux propriétés contrôlées, a ouvert de nouvelles perspectives vis-à-vis des matériaux qui nous entourent. C’est notamment le cas des métaux et de leurs alliages et il est crucial d’établir le lien entre leurs propriétés structurales et leurs propriétés chimique et physique pour en permettre une utilisation optimale. Cette thèse s’inscrit dans ce contexte et porte sur la synthèse et la caractérisation en microscopie électronique en transmission de nanoparticules d’alliage bimétallique Au-Cu. En s’appuyant sur le diagramme de phase décrit à l’échelle macroscopique, nous nous sommes particulièrement intéressés aux nanoparticules de compositions nominales Au3Cu, AuCu et AuCu3. Le premier axe de ce travail consiste en l’élaboration de nanoparticules d’alliage Au-Cu. Deux voies de synthèse sont explorées : la voie chimique reposant sur le procédé polyol et la voie physique par ablation par laser pulsé. Le premier mode d’élaboration permet l’obtention de nanoparticules parfaitement cubiques dont la composition est systématiquement riche en Au. Les nanoparticules produites par voie physique présentent en revanche une composition maitrisée et modifiable. D’un point de vue structural, un recuit de ces dernières particules mène à leur mise en ordre chimique et à l’observation de structures L10 et L12. Cependant, nous montrons que cette transition de phase est bloquée dans les nanostructures présentant des défauts structuraux. Enfin, l’évolution du paramètre de maille des nanoparticules synthétisées selon ces deux voies de synthèse, en fonction de leur composition, a été établie et suit exactement la loi de Vegard décrite pour le matériau massif.Dans un second temps, nous avons observé des nanoparticules obtenues par voie physique en microscopie électronique en transmission environnementale, c’est-à-dire dans des conditions proches des environnements d’utilisation habituellement appliqués en catalyse. Les expériences menées en température révèlent que le mécanisme de dissolution de nanoparticules d’Au et d’alliage Au-Cu portées à haute température se fait en deux étapes : il y a fusion des nanoparticules suivi de leur évaporation pour des tailles de nanoparticules centrées autour de 10 nm. Les expériences réalisées en couplant le chauffage des nanoparticules au passage d’un gaz (H2 ou O2), en flux et dans des conditions de pression bien supérieures à celles accessibles jusqu’à maintenant, ont permis d’étudier leur comportement thermodynamique en condition oxydantes et réductrices. Nous avons notamment montré que des cycles d’oxydo-réduction de nanoparticules de taille moyenne supérieure à 20 nm conduisent à un effet Kirkendall menant, de manière réversible, à la formation de nanoparticules creuses (doughnut). Cette thèse interdisciplinaire constitue travail pionnier dans la compréhension du système d’alliage bimétallique Au-Cu à l’échelle nanoscopique / The emergence of new materials, structured at the nanoscale, with controlled properties, has opened new prospects regarding materials around us. In particular for metals and alloys, it seems crucial to connect their structural properties to their chemical and physical properties in order to optimise their use.Within this context, this thesis is focused on the synthesis and the characterisation of Au-Cu bimetallic alloy nanoparticles by transmission electron microscopy. On the basis of the bulk phase diagram, we especially studied particles with nominal compositions Au3Cu, AuCu et AuCu3.The first part of this work is dedicated to the synthesis of nanoparticles in two different ways. The chemical way is based on the polyol process and leads to nanoparticles exhibiting a cubic shape, and a systematically rich Au content. On the other hand, nanoparticles obtained by Pulsed Laser Deposition (PLD), a physical method of synthesis, display a well-controlled and tuneable composition. From a structural point of view, the annealing of the particles leads to chemical order and the stabilisation of L10 and L12 structures. However, we reveal that this phase transition is blocked in nanostructures with crystal defects. Moreover, we establish the evolution of the lattice parameter of the particles as a function of the composition and we demonstrate that, as in the bulk case, it is in agreement with Vegard’s law.In the second part, the nanoparticles synthesised via the physical method are studied using environmental transmission electron microscopy, i.e. in conditions close to those usually applied in catalytic reactors. Experiments performed at high temperature highlight that the dissolution of Au and Au-Cu nanoparticles occurs in a two-step process: fusion occurs first and is followed by evaporation for nanoparticles with a mean diameter of 10 nm.Coupling heating with gas flow (H2 or O2) in higher pressure condition than those usually reached allows us to study the thermodynamic behaviour of the nanoparticles in oxidative or reductive conditions. Most Notably, we show that oxidation-reduction cycles performed on nanoparticles with a diameter larger than 20 nm leads to a Kirkendall effect and the reversible formation of hollow particles (doughnuts).This cross-disciplinary thesis is a pioneering work towards understanding the bimetallic Au-Cu alloy system at atomic scale

Des populations tolérante (métallicole: M) et sensible (non-métallicole: NM) d’Agrostis capillaris L. ont été exposées à des doses croissantes de Cu (1-50 μM) pour étudier la tolérance au Cu par une approche pluridisciplinaire. Selon les paramètres phénotypiques (biomasse, longueur des feuilles et symptômes visuels), les plantes M ont une meilleure croissance aux expositions supérieures à 10 μM Cu. Les concentrations en Cu des tissus reflètent une rétention racinaire (phénotype d’exclusion) et une réduction de la translocation vers les feuilles quand le stress augmente. En excès de Cu, le protéome soluble racinaire présente des altérations du métabolisme énergétique chez M et NM, plus marquées chez NM (glycolyse, cycle de Krebs /phosphorylation oxydative). Le protéome foliaire indique des impacts sur les phases claires et obscures de la photosynthèse chez M et NM, et un besoin plus important en acides aminés soufrés (augmentation des cystéine et méthionine synthases). Chez NM, l’augmentation d’enzymes de la glycolyse, de la voie des pentoses phosphates et du cycle de Calvin indiquent un besoin énergétique accru, tandis que la stimulation des chaperonnes et des processus de synthèse protéique suggère des impacts sur le métabolisme des protéines et celle des enzymes redox un stress oxydatif plus fort. Plusieurs protéines, surexprimées ou accumulées, interviendraient dans la tolérance au Cu chez M, en protégeant le métabolisme des protéines (HSP70, racines et feuilles) et en augmentant les mécanismes anti-oxydants (ascorbate péroxydases), de détoxification (GST et aldéhyde déshydrogénase) et de protéolyse (peptidase et protéasomes, racines). / Cu-tolerant (metallicolous: M) and sensitive (non-metallicolous: NM) populations of Agrostis capillaris L. were exposed to increasing Cu concentrations (1-50 μM) to investigate Cu tolerance by a pluridisciplinary approach. Phenotypic parameters (biomass production, shoot length, and visual symptoms) indicated a higher growth and a better fitness of M plants over 10 μM Cu. Plant Cu concentrations indicated root Cu retention (‘excluder’ phenotype) and a reduced root-to-shoot translocation with increasing Cu stress. Based on root soluble proteome energy metabolism was altered by Cu excess in both populations with stronger impacts in NM (glycolysis, Krebs cycle/oxidative phosphorylation). Changes in shoot proteome showed impacts on both light dependent and independent photosynthesis phases in both populations, and an enhanced need in S-containing amino-acids (up-regulation of cysteine/methionine synthases). In NM leaves, increase of enzymes involved in glycolysis, pentose phosphate pathway and Calvin cycle indicated a stimulation of energy metabolism, while enhanced protein synthesis processes and protein chaperones suggested impacts on protein metabolism and increase of redox enzymes indicated a higher oxidative stress. Several over-expressed or accumulated proteins may be pivotal for Cu tolerance in M plants, for protecting protein metabolism (Heat shock protein 70kDa, roots and leaves), increasing anti-oxidative (ascorbate peroxidases, roots) – detoxification (Glutathione S-transferase and aldehyde dehydrogenase, roots) and proteolysis (peptidase and proteasome subunits) processes.

Verbindungen mit einer Vielzahl von Oberflächeneinheiten (Multimere) sind im Hinblick auf eine nuklearmedizinische Anwendung von besonderem Interesse, da durch definierte Strukturmodifizierung das Bindungsverhalten an bestimmte Zielstrukturen, die Löslichkeit und damit die Bioverteilung und Pharmakokinetik beeinflusst werden können. Baut man eine Verbindung so auf, dass sich im Inneren ein metallbindendes Zentrum befindet, ergibt sich einerseits die Möglichkeit, das Radiometall chemisch stabil zu binden, andererseits durch genannte Oberflächenfunktionalisierung eine spezifische Bindung im Zielgewebe zu erreichen. Im Rahmen dieser Arbeit wurden neuartige mehrfunktionale Verbindungen mit einer Cyclam-Kerneinheit synthetisiert. Cyclam bildet mit Cu(II)-Ionen äußerst stabile Komplexe, was im Hinblick auf eine radiopharmazeutische Anwendung der Radiometallkomplexe von 64Cu oder 67Cu für diagnostische und therapeutische Zwecke äußerst interessant ist. Für eine symmetrische Mehrfachfunktionalisierung wurde auf ein Tetraamin mit Cyclamkern zurückgegriffen. Die Kupplung von vier Dansylchlorid-Einheiten war erfolgreich. Über geschützte Glucosyl-Isothiocyanate wurden Derivate mit vier Zuckereinheiten gewonnen. Nach der Entfernung der Schutzgruppen wurde die Bindung an das kohlenhydratbindende Lektin Concanavalin A mittels isothermer Kalorimetrie bestimmt. Es war ein deutlicher Anstieg der Stabilitätskonstante K im Vergleich zu den monomeren Zuckern zu beobachten. Die Kinetik der Cu(II)-Komplexierung wurde UV/Vis-spektroskopisch bestimmt. Wegen der langsamen Cu-Komplexierungskinetik der Thioharnstoff-verbrückten Glycodendrimere wurde der Schwerpunkt bei den nachfolgenden Untersuchungen zur Kupplung von Peptiden über Amidbindungen gelegt. Nach zahlreichen erfolglosen Kupplungsversuchen von Peptiden mit einer freien Aminogruppe an Cyclamtetrapropionsäure im organischen Medium wurden im wässrigen Milieu Cyclamderivate mit ein bis zu drei Peptideinheiten durch Peptidkupplung erzeugt. Die Synthese kupplungsfähiger Peptidisothiocyanate blieb erfolglos. Schließlich führte eine Michael-Addition von Acrylamid-Arg-Tyr-OH und Acrylamid-Neurotensin(8-13)-OH an Cyclam zu den gewünschten tetrameren Verbindungen. Das Neurotensintetramer mit vier zielsuchenden Einheiten wurde für weiterführende radiochemische und radiopharmakologische Untersuchungen eingesetzt. Es kann unter milden Bedingungen sehr effizient mit 64Cu radiomarkiert werden, wobei eine spezifische Aktivität von 12 GBq pro µmol und Markierungsausbeuten von durchschnittlich 95-98% erzielt werden können. Erwartungsgemäß werden die Neurotensineinheiten unter diesen Bedingungen abgebaut, wobei im Vergleich zu freiem H-Neurotensin(8-13)-OH, welches innerhalb von zwei Minuten abgebaut wird, die In-vivo-Halbwertszeit des Tetramers 34 Minuten beträgt. Es konnte keine Transmetallierung beziehungsweise Transchelatisierung beobachtet werden, was die Stabilität des Komplexes zeigt. PET-Untersuchungen nach Applikation des 64Cu-markierten Neurotensin-Tetramers wiesen eine erhöhte Anreicherung von radioaktiver Substanz in Tumoren von LoVo- und HT29-Mäusen nach. Um zu unsymmetrischen Cyclamderivaten mit dem Ziel der gleichzeitigen Einführung zielsuchender, löslichkeitsvermittelnder und fluoreszierender Einheiten zu gelangen, wurden unterschiedliche Schutzgruppen eingesetzt. Die Blockierung primärer Aminogruppen eines Cyclam-Derivates mit MMTr-, Boc- und Z-Schutzgruppen lieferte Produkte, die sauber isoliert, aber nicht selektiv entschützt werden konnten. Daher wurden die Aminstickstoffatome des Cyclams direkt geschützt. Ausgehend von Cyclam-Boc3 konnten über Kupplungsreaktionen Aminosäure- und Dipeptidmethylester als unsymmetrische Cyclamderivate gewonnen werden. Damit ist ein Syntheseweg entwickelt worden, der die Darstellung unsymmetrischer Cyclamderivate mit einer definierten Anzahl von gewünschten biologisch aktiven Molekülen beziehungsweise löslichkeitsvermittelnder oder fluoreszierender Einheiten gestattet.

Cathodic processes occurring in the solutions containing Cu(II) tartaric complexes have been investigated. The equations accounting for the material balance have been constructed and used for the estimation of distribution of complexes and ligands in the bulk of solution. It was established that dominating particles in acidic media (pH < 3) are: Cu2+ and tartaric complex CuL, tartaric acid LH2 and its anion LH-. Potentials of non-polarized copper electrodes were found to be reversible and to follow Nernst equation. According to the analysis performed, surface oxide Cu2O is not able to form in acidic (pH < 3) media. Cathodic voltammograms obtained for the solutions of different acidity exhibit two characteristic current peaks arising from Cu(II) reduction and hydrogen evaluation. An analysis of voltammetric extrema shows that both processes are irreversible. Based on the regularities of the mass transport of chemically interacting substances, surface distribution of components has been simulated. These date were used for the transformation of experimental voltammograms into normalized Tafel plots. According to their analysis, the rate-controlling step of Cu(II) reduction is the transfer of the first electron onto Cu2+ aqua-complex. The values of kinetic parameters were found to be as follows: the cathodic charge transfer coefficient is equal to 0.33 and the exchange current density is equal to 50 mA cm-2. An analysis of the second current peak leads to the conclusion... [to full text]