Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / The structural and thermal decomposition properties of Mg-Fe and Co-Cu-Fe hy- drotalcites (HT) have been studied through thermogravimetric analysis, X ray powder difraction (XRD), Fourier transform infrared spectroscopy and 57Fe MÃssbauer spec- troscopy. In the Mg-Fe system, the destruction of the layered structure took place at about 300 oC. The broad peaks observed in the X ray difractograms suggests that the resultant oxides constitute a solid solution. For samples treated at temperatures higher than 500 oC the formation of the MgO and MgFe2O4 formation of the MgO and MgFe2O4 spinel phases is observed. 57Fe MÃssbauer spectroscopy was employed to monitor the Fe chemical environment for the samples annealed at diferent temperatures (100-900 oC). In situ XRD experiments revealed that the HTs start an interlayer contraction at about 180 oC. This phenomenon is identified as being due to a grafting process for which the interlamellar anions attach to the layers through a covalent bond. The reconstruction of the Mg-Fe HTs was also investigated and its eficiency depends on the thermal anneal- ing temperature and on the Mg/Fe ratio. The structure of the reconstructed samples was found to be exactly the same as the parent structure. The in situ 57Fe MÃssbauer experiments were performed in the 100-500 oC temperature range confirm an increasing structural disorder in this temperature range. The quadrupolar splitting indicates that the maximum disorder occurs at 300 oC. Regarding the Co-Cu-Fe ternary system we have observed that due to the strong Jahn-Teller effect the Cu-Fe layered system is stabilized only in the presence of Co2+. At low Co2+ contents, additional phases are segregated in the solids. X ray patterns diffraction show the presence of Cu(OH)2 and CuO. The decomposition process was investigated by in situ X ray, in situ MÃssbauer and FTIR experiments. By increasing the temperature from 25 oC up to 180 oC we observed that the structural disorder increases. This effect has been likely attributed to the Co2+ to Co3+ oxidation since thermal decomposition was carried out under static air atmosphere. Part of the Co3+ cations could migrate to the interlayer region, thus forming a metastable compound that still has a layered structure. Collapse of the layered structure was ob- served at about 200 oC. By further increasing the temperature the system becomes more crystalline and the formation of Co3O4 is observed in the X ray patterns. In Cu-rich HT, some of the carbonate anions are released at temperatures higher than 550 oC and this phenomenon is attributed to the formation of a carbonate-rich phase. The specific surface area data present its highest values in the temperature range where the collapse of the layered structure takes place. / As propriedades estruturais e de decomposiÃÃo tÃrmica das hidrotalcitas Mg-Fe e Co-Cu-Fe foram estudadas atravÃs de espectroscopia MÃssbauer de 57Fe, anÃlise termo- gravimÃtrica, difraÃÃo de raios X, e espectroscopia de absorÃÃo no infravermelho (FTIR). No sistema Mg-Fe a destruiÃÃo da estrutura lamelar ocorre em torno de 300 oC. O alargamento dos picos de difraÃÃo de raios X observados nos difratogramas sugerem que os Ãxidos resultantes constituem uma soluÃÃo sÃlida. Para as amostras tratadas em temperaturas maiores do que 500 oC a formaÃÃo de fases do tipo MgO e MgFe2O4 à observada. A espectroscopia MÃssbauer de 57Fe foi empregada para monitorar o ambiente quÃmico do Fe na faixa 100-900 oC de temperatura. As medidas in situ de difraÃÃo de raios X revelam que em 180 oC inicia-se uma contraÃÃo interlamelar. Este fenÃmeno à atribuÃdo ao processo de âgrafting" no qual os Ãnions interlamelares ligam-se nas camadas atravÃs de uma ligaÃÃo covalente. A reconstruÃÃo estrutural da hidrotalcita Mg-Fe tambÃm foi investigada. A eficiÃncia da reconstruÃÃo estrutural depende da temperatura de tratamento e da razÃo molar Mg/Fe. A estrutura das amostras reconstruÃdas sÃo as mesmas da amostra inicial. As medidas in situ de espectroscopia MÃssbauer de 57Fe foram realizadas na faixa 100-500 oC confirmaram uma desordem estrutural crescente nesta regiÃo de temperaturas. Os valores do desdobramento quadrupolar indicam que o mÃximo de desordem ocorre em 300 oC. Com relaÃÃo ao sistema ternÃrio Co-Cu-Fe observamos que devido ao efeito Jahn-Teller o sistema Cu-Fe somente à estabilizado na presenÃa de Co2+. Para baixas concentraÃÃes Co2+ fases adicionais segregadas sÃo observadas nos sÃlidos. Os padrÃes de difraÃÃo de raios X indicam a presenÃa de Cu(OH)2 e CuO. O processo de decomposiÃÃo tÃrmica foi investigado atravÃs de difraÃÃo de raios X, espectroscopia MÃssbauer de 57Fe in situ e de espectroscopia de absorÃÃo no infravermelho (FTIR). Aumentando a temperatura de tratamento tÃrmico das amostras de 25 oC a 180 oC observamos um aumento da desordem estrutural. Este efeito tem sido atribuÃdo a oxidaÃÃo Co2+ para Co3+ uma vez que a decomposiÃÃo foi realizada ao ar. Parte dos cÃtions Co3+ migram para a regiÃo interlamelar formando um composto metastÃvel que ainda possui uma estrutura lamelar. O colapso da estrutura lamelar à observado a 300 oC. Com o aumento posterior da temperatura o sistema torna-se mais cristalino e a formaÃÃo de Co3O4 à observada atravÃs do ensaio de raios X. Nas hidrotalcitas com maior teor de Cu, alguns dos Ãnions carbonato sÃo liberados somente acima de 550 oC sendo este fenÃmeno atribuÃdo a formaÃÃo de uma fase rica em carbonato. Os valores de Ãrea superficial especÃfica apresentam um mÃximo na faixa de temperatura onde ocorre o colapso da estrutura lamelar.

O excesso de Fe no organismo gera espécies reativas de oxigênio (ERO) que são potencialmente tóxicas. Entretanto, a magnitude dos efeitos da exposição à moderada sobrecarga de Fe e da sua interação com facilitadores e/ou inibidores da absorção mineral não é conhecida. O objetivo deste trabalho foi avaliar esses efeitos e a sua interação com fruta nos e/ou fitato (facilitadores e inibidores da absorção de Fe, respectivamente) nos índices séricos do estado nutricional em Fe, no perfil dos lipídeos séricos e em parâmetros do metabolismo hepático e ósseo. Para o experimento foram utilizados 34 ratos machos Wistar, pesando inicialmente 49,3 ± 3,9g, alojados individualmente em gaiolas de aço semimetabólicas por 92 dias. Uma dieta AIN-93G (Dieta 1: Grupo Controle) e quatro dietas AIN93G modificadas foram usadas para o estudo, com as seguintes características: Dieta 2: sobrecarga moderada de ferro com 550mgFe/kg de ração (Grupo SBC); Dieta 3: sobrecarga moderada de ferro + 18% de farinha de yacon (Grupo SBC+FY); Dieta 4: sobrecarga moderada de ferro + 0,6% de fitato (Grupo SBC+FIT); Dieta 5: sobrecarga moderada de ferro + 18% de farinha de yacon + 0,6 % de fitato (Grupo SBC+FY+FIT). Os resultados demonstraram que a moderada sobrecarga de Fe ou a sua interação com farinha de yacon e/ou fitato não alterou os índices séricos do estado nutricional em Fe. Ocorreu aumento na atividade sérica da AST apenas no grupo SBC (p=0,055). Nos grupos SBC e SBC+FY houve diminuição na concentração do colesterol sérico (p=0,002) e, apenas no grupo SBC+FY+FIT, diminuição da concentração sérica do VLDL. No fígado, houve aumento significativo (p=0,002) da concentração de Fe não-heme nos grupos IO (+83%) e SBC+FIT (+117%) e, em todos os grupos SBC, na atividade da enzima GPx (p=0,000). A atividade da CAT foi menor (p=0,036) apenas para o grupo SBC+FY+FIT. Em todos os grupos SBC ocorreu significativo aumento nos depósitos de hemossiderina em torno das células de Kupffer (p=0,000). Houve aumento na apoptose em todos os grupos SBC, com os grupos SBC+FY e SBC+FY +FIT apresentando o maior número de corpúsculos apoptóticos/área (+405% e +342%, respectivamente) (p=0,000). Não houve alteração nos parâmetros relacionados ao metabolismo ósseo. No grupo SBC+FY houve significativo aumento na absorção aparente de Ca (p<0,05). Conclusões: A moderada sobrecarga de Fe não alterou os índices séricos do estado nutricional em Fe, mas resultou em alterações no tecido hepático e no perfil dos lipídeos séricos. Com exceção do perfil de lipídeos séricos, no qual apenas o fitato pareceu exercer efeito protetor, nos demais parâmetros avaliados a interação com farinha de yacon rica em fruta nos e/ou fitato reverteu parcial ou totalmente as alterações induzidas pela moderada sobrecarga de Fe. / Excess Fe in the organism generates potentially toxic reactive oxygen species (ROS). However, the magnitude of the effects of a moderate Fe overload and its interaction with factors which inhibit or facilitate mineral absorption is not known. The aim of the present work was to evaluate such effects and their interaction with fructans and/or phytate (compounds which facilitate and inhibit Fe absorption, respectively) on serum iron status indices, on the profile of serum lipids and on hepatic and bone metabolism parameters. In the experiment, thirty-four male Wistar rats initially weighing 49,3 ± 3,9g were used. The rats were housed in individual stainless-steel wire-mesh cages for 92 days. An AIN-93G diet (Diet 1: Control Group) and four modified AIN-93G diets were used in the study. The modified diets presented the following formulations: Diet 2: moderate Fe overload with 550mgFe/kg diet (IO Group); Diet 3: moderate Fe overload + 18% yacon flour (IO-YF Group); Diet 4: moderate Fe verload + 0.6% phytate (IO-Phy Group); Diet 5: moderate Fe overload + 18% yacon flour + 0.6% phytate (IO-YF-Phy Group). The results demonstrated that a moderate Fe overload or its interaction with yacon flour and/or phytate did not alter the serum iron status indices. An increase in the serum AST activity was observed only in the IO group (p=0,055). In the IO and IO-YF groups, there was a reduction in the serum cholesterol concentration (p=0,002) and a reduction in the serum VLDL concentration was observed only in the IO-YF-Phy group. In the liver, there was a significant increase (p=0,002) in non-heme Fe concentration in the IO (+83%) and IO-Phy (+117%) groups. Also, GPx activity was significantly increased (p=0,000) in all IO groups. CAT activity was lower (p=0,036) only in the IO-YF-Phy group. A significant increase in hemosiderin deposition around Kupffer cells was observed in all IO groups (p=0,000). Apoptosis was increased in all IO groups, whereas the IO-YF and IO-YF-Phy groups showed the largest number of apoptotic bodies/area (+405% and +342%, respectively) (p=0,000). There was no alteration in the parameters related to bone metabolism. In the IO-YF group, there was a significant increase in Ca apparent absorption (p<0,05).Conclusions: The moderate Fe overload did not alter the serum iron status índices, but led to alterations in the hepatic tissue and in the profile of serum lipids. Except for the profile of serum lipids where only phytate seemed to have a protective effect, in the other evaluated parameters the interaction with yacon flour rich in fructans and/or phytate partially or totally reversed the alterations induced by the moderate Fe overload.

Chez les plantes, les protéines à centre fer-soufre (Fe-S) sont impliquées dans de nombreux processus cellulaires (e.g. photosynthèse, respiration). La maturation de ces protéines nécessite la synthèse de novo des centres Fe-S à l’aide de machineries d’assemblage spécifiques. Les plantes possèdent trois machineries d’assemblage nommées SUF, ISC et CIA, dédiées à la maturation des protéines plastidiales, mitochondriales et nucléaires ou cytosoliques, respectivement. Lors de la maturation des protéines mitochondriales, un centre [2Fe-2S] est initialement assemblé sur la protéine d’échafaudage ISU puis transféré vers les apoprotéines cibles à l’aide de chaperons et de diverses protéines de transfert. Si ces étapes semblent suffisantes pour la maturation de protéines incorporant des centres [2Fe-2S], un couplage réductif de deux centres [2Fe-2S] est nécessaire pour la maturation des protéines de type [4Fe-4S]. Cette conversion nécessite des protéines de transfert et un donneur d’électrons, potentiellement la même ferrédoxine que celle qui agit déjà lors des étapes précoces pour la réduction du soufre. En combinant des approches moléculaires, biochimiques et génétiques, l’implication des protéines de transfert NFU et ISCA et des ferrédoxines mitochondriales (mFDX) dans les étapes tardives de transfert et de conversion a été explorée au cours de cette thèse chez la plante modèle Arabidopsis thaliana. Des expériences de complémentation en levure ont démontré que les protéines NFU et ISCA de plantes peuvent assurer les mêmes fonctions que leurs orthologues respectifs, suggérant que ces étapes tardives ont été conservées. Cependant, contrairement à la levure, l’analyse de lignées n’exprimant pas les deux protéines NFU indiquent qu’elles sont essentielles pour le développement de l’embryon. Au niveau moléculaire, les analyses effectuées à l’aide d’approches in vivo et/ou in vitro ont permis d’identifier une interaction entre ISCA1a ou ISCA1b et ISCA2, NFU4 et NFU5 mais aucune interaction avec les deux mFDX dont le rôle dans les dernières étapes d’assemblage des centres Fe-S reste donc incertain. La formation d’holo-hétérocomplexes entre ISCA1 et ISCA2 a été confirmée par co-expression chez E. coli et purification des protéines recombinantes. Globalement, en associant la littérature à propos de la machinerie ISC et les résultats obtenus, le modèle qui ressort est que des hétérocomplexes ISCA1/2 agiraient immédiatement en amont des protéines NFU qui permettraient a minima la maturation des centres [4Fe-4S] de la lipoate synthase. Ce seul partenaire pourrait expliquer en grande partie la létalité d’un mutant nfu4 x nfu5 car l’activité de plusieurs protéines centrales pour le métabolisme mitochondrial dépend de l’acide lipoïque / In plants, iron-sulfur (Fe-S) proteins are involved in crucial processes such as photosynthesis and respiration. The maturation of these proteins requires the de novo synthesis of their Fe-S clusters through dedicated assembly machineries. Plants have three Fe-S cluster assembly machineries, namely SUF, ISC and CIA, devoted to the maturation of plastidial, mitochondrial and nuclear or cytosolic proteins, respectively. During the mitochondrial Fe-S protein maturation, a [2Fe-2S] cluster is first assembled on the ISU scaffold protein then transferred to target proteins with the help of chaperones and various transfer proteins. If these steps are sufficient for the maturation of [2Fe-2S] proteins, a reductive coupling process of two [2Fe-2S] clusters is required for the maturation of [4Fe-4S] proteins. This conversion needs transfer proteins and an electrons donor, potentially the same ferredoxin which acts during the first step of the Fe-S cluster biogenesis for sulfur reduction. By combining molecular, biochemical and genetic approaches, the involvement of NFU and ISCA transfer protein and mitochondrial ferredoxin (mFDX) in the late transfer and conversion steps has been explored during this PhD project by using the Arabidopsis thaliana plant model. Yeast complementation experiments have demonstrated that plant NFU and ISCA proteins have functions similar to their respective orthologs, suggesting that these late steps are conserved. However, unlike yeast, the characterization of nfu mutant lines indicates that both proteins are essential for early embryonic development. At the molecular level, in vivo and in vitro approaches have shown an interaction between ISCA1a or ISCA1b and ISCA2, NFU4 and NFU5 but no interaction with the two mFDX whose participation in the late steps remains uncertain. The formation of ISCA1-ISCA2 holo-heterocomplexes has been confirmed by co-expression in E. coli and purification of recombinant proteins. Overall, the literature and results obtained here highlight a model where ISCA1/2 heterocomplexes would act immediately downstream of NFU proteins which would a minima allow [4Fe-4S] cluster maturation of the lipoate synthase. This sole partner could primarily explain the lethality of a nfu4 x nfu5 double mutant because the activity of several proteins central for the mitochondrial metabolism depends on lipoic acid

No description available.

Au cours de la dernière décennie, le procédé de fabrication additive par fusion sélective d'un lit de poudre SLM a attiré une grande attention dans le domaine de l'industrie, car il permet de produire rapidement des pièces de formes complexes. Le but de ce travail est d'étendre les performances des procédés SLM en étudiant la possibilité d'élaborer des pièces en atmosphère raréfiée. Pour atteindre cet objectif, une approche théorique et expérimentale a été développée, avec la mise en place d'une machine de fusion sélective par laser capable de travailler dans le domaine de pression de 1 à 10-2 mbar.Le travail sous vide permet d'éviter la formation du "bouclier" de plasma généré à partir de l'atmosphère de gaz ionisé par l'énergie du laser. Ceci permet d'une part d'éviter la contamination chimique du matériau (oxydation, nitruration,...) au cours des processus de fusion et d'autre part de réduire le taux de porosité. L'effet des paramètres du laser et des variables d'environnement sur la qualité de pièces a été étudié en considérant le cas du fer pur, de l'acier Inox 316L et du titane.Par ailleurs nous avons étudié la possibilité d'obtenir des alliages in-situ au cours de la fabrication par la technique SLM à partir de mélanges de poudres.Des essais ont été conduits à partir de mélanges Mg/Al, Fe/Ni et Ti/Ni. Dans tous les cas nous avons pu obtenir des alliages in-situ pour les domaines de composition visés qui correspondent à des applications pratiques (structures légères, alliage magnétique à faible coercivité, alliage à mémoire de forme). Les propriétés des matériaux obtenus, d'après les premières caractérisations effectuées, se comparent de façon favorable par rapport aux techniques classiques d'élaboration et de mise en œuvre. / During the last decade, selective laser melting attracted attention in industry because it could allow producing parts with complex shapes rapidly and accurately. The aim of this work is to obtain parts with desired properties by SLM technology. To achieve this point, a theoretical and experimental approach was developed concerning a new process which carries out the selective laser melting process at pressures in the range 1 to 1×10-2 mbar.Vacuum operating under allows avoiding the plasma shield generated from the gas atmosphere ionized by the high laser energy, which on the one hand avoids the chemical contamination (oxidizing, nitriding…) during the melting process and on the other hand reduces the porosity rate. The effect of laser parameters and environment variables on the quality of parts was studied by considering the case of pure iron, stainless steel 316L and titanium.Moreover, we studied the possibility of obtaining in-situ alloys during the SLM manufacturing technique from mixtures of powders.Tests were conducted from mixtures Mg/Al, Fe/Ni and Ti/Ni. In all cases we were able to obtain in-situ alloys for areas covered composition corresponding to practical applications (lightweight structures, low coercivity magnetic alloy, shape memory alloy). The properties of material obtained from the characterizations performed, which are comparable with the conventional development and implementation.

Les jonctions tunnel magnétiques épitaxiées sont des systèmes modèles permettant de confronter l'expérience à la théorie de l'effet tunnel polarisé en spin. Celles à barrière de MgO(001) font à ce titre l'objet de nombreuses études, dont certaines ont permis d'établir expérimentalement l'existence de phénomènes tunnel cohérents dépendant de la symétrie des états de Bloch. Les expériences réalisées au cours de cette thèse visent à identifier et contrôler plusieurs propriétés des interfaces, de la barrière et des électrodes qui s'expriment dans le transport tunnel. Nous étudions les conséquences d'un excès d'oxygène à l'interface Fe/MgO dans les jonctions Fe/MgO/Fe(001). La réalisation d'un empilement modèle Fe/p(1×1) O/MgO/Fe(001) nous permet de confirmer certains effets attendus, notamment la formation d'une barrière additionnelle à l'interface pour les états de symétrie Δ1. Cependant, et contre toute attente, la magnétorésistance dépend peu de la présence d'oxygène. Elle est en revanche très sensible à la qualité cristallographique des interfaces. Nous démontrons ainsi les influences néfastes du désordre et du désaccord paramétrique entre la barrière de MgO et l'électrode sous-jacente. L'emploi d'alliages Fe V de composition variable permet de réduire le désaccord paramétrique et de diminuer la densité de dislocations, ce qui conduit à une forte augmentation de la magnétorésistance. Nous étudions enfin comment les structures électroniques des alliages Fe Co et Fe V se manifestent dans le transport tunnel. Des mesures de photoémission résolue en spin nous permettent de sonder directement les bandes Δ et les états de résonnance interfaciale des surfaces (001) libres ou recouvertes de MgO.

Les mécanismes de formation de phases dans des films minces du système ternaire Al-Cu-Fe et des systèmes binaires Al-Cu, Al-Fe et Cu-Fe ont été étudiés. Dans chacun des systèmes, plusieurs échantillons avec des compositions distinctes ont été préparés par pulvérisation cathodique. Des couches d'aluminium, de cuivre et de fer ont été déposées séquentiellement sur des substrats de silicium oxydé et ont été traités thermiquement par différentes méthodes puis caractérisés. Des mesures de diffraction de rayons X et de résistivité in-situ ont été effectuées pour suivre la formation des phases. Des recuits thermiques suivis de trempe ont été réalisés et les échantillons ont été caractérisés par diffraction des rayons X. L'analyse enthalpique différentielle a également été utilisée ainsi que des mesures simultanées in-situ de résistivité et de diffraction des rayons X. L'ensemble des résultats obtenus nous a permis de proposer des mécanismes de formation de phases pour chacun des échantillons étudiés et en utilisant des modèles théoriques de croissance de phases nous avons pu déterminer des données cinétiques sur la formation de phases dans ces films.

West Anatolien, welches die östliche laterale Verlängerung der ägäischen Domäne darstellt, besteht aus mehreren tektono-metamorphen Einheiten, die Hochdruck/Niedrigtemperatur (HP/LT) Gesteine aufweisen. Einige dieser metamorphen Gesteine Zeugen der panafrikanischen oder der kimmerischen Orogenese sind, entstanden andere während die jüngere Alpine Orogenese. <br /> <br /> Das Menderes Massiv, in der SW Türkei, wird im N von Decken der Izmir-Ankara Suturzone, im E von der Afyon Zone sowie im S von den Lykischen Decken tektonisch überlagert. In den Metasedimenten der Lykischen Decken und dem darunterliegenden Menderes Massiv treten weitverbreitete Vorkommen von Fe-Mg-Carpholith-führenden Gesteinen auf. Diese neue Entdeckung belegt, dass beide Deckenkomplexe während der alpinen Orogenese unter HP/LT Bedingungen überprägt wurden. Die P-T Bedingungen für die HP-Phase liegen bei 10-12 kbar/400&#176;C in den Lykischen Decken und 12-14 kbar/470-500&#176;C im südlichen Menderes Massiv, was eine Versenkung von min. 30 km während der Subduktion und Deckenstapelung dokumentiert.<br /> <br /> Die Analyse der duktilen Deformation sowie thermobarometrische Berechnungen zeigen, dass die Lykischen Metasedimente unterschiedliche Exhumierungspfade nach der gemeinsamen HP-Phase durchliefen. In Gesteinen, die weiter entfernt vom Kontakt der Lykischen Decken mit dem Menderes Massiv liegen, lässt sich lediglich ein Hochdruck-Abkühlungspfad belegen, der mit einer &bdquo;top-NNE&ldquo; Bewegung an die Akçakaya Scherzone gebunden ist. Diese Scherzone ist ein Intra-Deckenkontakt, der in den frühen Stadien, innerhalb des Stabilitätsfeldes von Fe-Mg-Carpholith, der Exhumierung aktiv war. Die nahe am Kontakt mit dem Menderes Massiv gelegenen Gesteine weisen wärmere Exhumierungspfade auf, die mit einer &bdquo;top-E&ldquo; Scherung assoziiert sind. Diese Deformation erfolgte nach dem S-Transport der Lykischen Decken und somit zeitgleich mit der Reaktivierung des Kontakts der Lykischen Decken/Menderes Massiv als Hauptscherzone (der Gerit Scherzone), die eine späte Exhumierung der HP-Gesteine unter wärmeren Bedingungen erlaubte. Die Hochdruckgesteine des südlichen Menderes Massiv weisen eine einfache isothermale Dekompression bei etwa 450&#176;C während der Exhumierung nach. Die begleitende Deformation während der Hochdruckphase und der Exhumierung ist durch eine starke N-S bis NE-SW&ndash;Dehnung charakterisiert.<br /> <br /> Das Alter der Hochdruckmetamorphose in den Lykischen Decken kann zwischen oberster Kreide (jüngste Sedimente in der Lykischen allochthonen Einheit) und Eozän (Kykladische Blauschiefer) festgelegt werden. Ein mögliches Paläozänes Alter kann somit angenommen werden. Das Alter der Hochdruckmetamorphose in den Deckschichten des Menderes Massiv liegt demnach zwischen mittlerem Paläozän (oberste Metaolistostrome der Menderes &bdquo;Cover&ldquo;-Einheit) und dem mittleren Eozän (HP-Metamorphose in der Dilek-Selçuk Region des Kykladenkomplex). Apatit-Spaltspur-Daten von beiden Seiten des Kontakts der Lykischen Decken/Menderes Massiv lassen darauf schließen, daß diese Gesteine im späten Oligozän/frühen Miozän sehr nahe der Paläo-Oberfläche waren. <br /> <br /> Die hier dargestellten Arbeiten in den Lykischen Decken und im Menderes Massiv lassen auf die Existenz eines ausgedehnten alpinen HP-Metamorphose-Gürtels im SW der Türkei schließen. Die Hochdruckgesteine wurden im Akkretionskomplex einer N-wärtigen Subduktion des Neo-Tethys Ozeans gebildet, der spät-Kretazisch obduziert und dann in die früh-Tertiäre Kontinentalkollision des passiven Randes (Anatolid-Taurid Block) mit der nördlichen Platte (Sakarya Mikrokontinent) miteinbezogen war. Im Eozän bestand der Akkretionskomplex aus drei gestapelten Hochdruckeinheiten. Die Unterste entspricht dem eingeschuppten Kern und Hochdruck-&bdquo;Cover&ldquo; des Menderes Massivs. Die Mittlere besteht aus dem Kykladischen Blauschiefer-Komplex (Dilek-Selçuk Einheit) und die oberste Einheit wird von den Hochdruck Lykischen Decken gebildet. <br /> <br /> Während die Basiseinheiten der ägäischen und anatolischen Region tektonisch unterschiedliche Prä-mesozoische Geschichten durchliefen, wurden sie wahrscheinlich am Ende des Paläozikums zusammengeführt und durchliefen dann ein gemeinsame mesozoische Geschichte. Dann wurden die Basis und ihre Deckschichten, ebenso wie die Kykladischen Blauschiefer und Lykischen Decken, in ähnlich entstandene akkretionäre Komplexe während des Eozäns und Oligozäns involviert. / Western Anatolia that represents the eastward lateral continuation of the Aegean domain is composed of several tectono-metamorphic units showing occurrences of high-pressure/low-temperature (HP-LT) rocks. While some of these metamorphic rocks are vestiges of the Pan-African or Cimmerian orogenies, others are the result of the more recent Alpine orogenesis. <br /> <br /> In southwest Turkey, the Menderes Massif occupies an extensive area tectonically overlain by nappe units of the Izmir-Ankara Suture Zone in the north, the Afyon Zone in the east, and the Lycian Nappes in the south. In the present study, investigations in the metasediments of the Lycian Nappes and underlying southern Menderes Massif revealed widespread occurrences of Fe-Mg-carpholite-bearing rocks. This discovery leads to the very first consideration that both nappe complexes recorded HP-LT metamorphic conditions during the Alpine orogenesis. P-T conditions for the HP metamorphic peak are about 10-12 kbar/400&#176;C in the Lycian Nappes, and 12-14 kbar/470-500&#176;C in the southern Menderes Massif, documenting a burial of at least 30 km during subduction and nappe stacking. <br /> <br /> Ductile deformation analysis in concert with multi-equilibrium thermobarometric calculations reveals that metasediments from the Lycian Nappes recorded distinct exhumation patterns after a common HP metamorphic peak. The rocks located far from the contact separating the Lycian Nappes and the Menderes Massif, where HP parageneses are well preserved, retained a single HP cooling path associated with top-to-the-NNE shearing related to the Akçakaya shear zone. This zone of strain localization is an intra-nappe contact that was active in the early stages of exhumation of HP rocks, within the stability field of Fe-Mg-carpholite. The rocks located close to the contact with the Menderes Massif, where HP parageneses are completely retrogressed into chlorite and mica, recorded warmer exhumation paths associated with top-to-the-E intense shearing. This deformation occurred after the southward emplacement of Lycian Nappes, and is contemporaneous with the reactivation of the &rsquo;Lycian Nappes-Menderes Massif&prime; contact as a major shear zone (the Gerit shear zone) that allowed late exhumation of HP parageneses under warmer conditions. The HP rocks from the southern Menderes Massif recorded a simple isothermal decompression at about 450&#176;C during exhumation, and deformation during HP event and its exhumation is characterized by a severe N-S to NE-SW stretching.<br /> <br /> The age of the HP metamorphism recorded in the Lycian Nappes is assumed to range between the Latest Cretaceous (age of the youngest sediments in the Lycian allochthonous unit) and the Eocene (age of the Cycladic Blueschists). A probable Palaeocene age is suggested. The age of the HP metamorphism that affected the cover series of the Menderes Massif is constrained between the Middle Palaeocene (age of the uppermost metaolistostrome of the Menderes &rsquo;cover&prime;) and the Middle Eocene (age of the HP metamorphism in the Dilek-Selçuk region that belongs to the Cycladic Complex). Apatite fission track data for the rocks on both sides of the &rsquo;Lycian Nappes/Menderes Massif&rsquo; contact suggest that these rocks were very close to the paleo-Earth surface in the Late Oligocene-Early Miocene time.<br /> <br /> This study in the Lycian Nappes and in the Menderes Massif establishes the existence of an extensive Alpine HP metamorphic belt in southwest Turkey. HP rocks were involved in the accretionary complex related to northward-verging subduction of the Neo-Tethys Ocean, Late Cretaceous obduction and subsequent Early Tertiary continental collision of the passive margin (Anatolide-Tauride block) beneath the active margin of the northern plate (Sakarya micro-continent). During the Eocene, the accretionary complex was made of three stacked HP units. The lowermost corresponds to the imbricated &rsquo;core&prime; and HP &rsquo;cover&prime; of the Menderes Massif, the intermediate one consists of the Cycladic Blueschist Complex (Dilek-Selçuk unit), and the uppermost unit is made of the HP Lycian Nappes.<br /> <br /> Whereas the basement units of both Aegean and Anatolian regions underwent a different pre-Mesozoic tectonic history, they were probably juxtaposed by the end of the Paleozoic and underwent a common Mesozoic history. Then, the basements and their cover, as well as the Cycladic Blueschists and the Lycian Nappes were involved in similar evolutional accretionary complexes during the Eocene and Oligocene times.

Studies of ribosomal reading frame maintenance are often based on frameshift mutation suppression experiments. In this thesis, suppression of a frameshift mutation in Salmonella enterica serovar Typhimurium by a tRNA and a ribosomal protein are described. The +1 frameshift mutation hisC3072 (that contains an extra G in a run of Gs) is corrected by mutations in the argU gene coding for the minor tRNAArgmnm5UCU. The altered tRNAArgmnm5UCU has a decreased stability and reduced aminoacylation due to changed secondary and/or tertiary structure. Protein sequencing revealed that during the translation of the GAA-AGA frameshifting site the altered tRNAArgmnm5UCU reads the AGA codon inefficiently. This induces a ribosomal pause, allowing the tRNAGlumnm5s2UUC residing in the ribosomal P-site to slip forward one nucleotide. The same frameshift mutation (hisC3072) was also suppressed by defects in the large ribosomal subunit protein L9. Single base substitutions, truncations, and absence of this protein induced ribosome slippage. Mutated ribosome could shift to the overlapping codon in the +1 frame, or bypass to a codon further downstream in the +1 frame. The signal for stimulation of slippage and function of L9 needs to be investigated. During the search for suppressors of the hisD3749 frameshift mutation, a spontaneous mutant was isolated in the iscU gene that contained greatly decreased levels of the thiolated tRNA modifications ms2io6A and s2C. The iscU gene belongs to the iscR-iscSUA-hscBA-fdx operon coding for proteins involved in the assembly of [Fe-S] clusters. As has been shown earlier, IscS influences the synthesis of all thiolated nucleosides in tRNA by mobilizing sulfur from cysteine. In this thesis, it is demonstrated that IscU, HscA, and Fdx proteins are required for the synthesis of the tRNA modifications ms2io6A and s2C but are dispensable for the synthesis of s4U and (c)mnm5s2U. Based on these results it is proposed that two distinct pathways exist in the formation of thiolated nucleosides in tRNA: one is an [Fe-S] cluster-dependent pathway for the synthesis of ms2io6A and s2C and the other is an [Fe-S] cluster-independent pathway for the synthesis of s4U and (c)mnm5s2U. MiaB is a [Fe-S] protein required for the introduction of sulfur in ms2io6A. TtcA is proposed to be involved in the synthesis of s2C. This protein contains a CXXC conserved motif essential for cytidine thiolation that, together with an additional CXXC motif in the C-terminus may serve as an [Fe-S] cluster ligation site.

Ferritisch/martensitische Cr-Stähle und deren oxiddispersionsverfestigte Varianten gehören zu den potenziellen Konstruktionswerkstoffen für Komponenten zukünftiger kerntechnischer Einrichtungen, wie z. B. Fusionsreaktoren und Spaltreaktoren der IV. Generation, die Strahlungsfeldern mit hohem Neutronenfluss ausgesetzt sind. Ein Hauptproblem dieser Materialgruppen ist das Auftreten des Spröd-duktil-Übergangs und dessen maßgeblich durch die Strahlenhärtung verursachte Verschiebung zu höheren Temperaturen. In der vorliegenden Arbeit wird das Bestrahlungsverhalten von binären Fe-Cr-Modelllegierungen untersucht, die ein vereinfachtes Modell für ferritisch/martensitische Cr-Stähle darstellen. Dabei werden Bestrahlungen mit Eisenionen zur Simulation der durch Neutronen hervorgerufenen Schädigung verwendet. Die auf wenige Mikrometer begrenzte Eindringtiefe der Ionen macht es erforderlich, dass für dünne Schichten geeignete Charakterisierungsmethoden eingesetzt werden. Im Rahmen dieser Arbeit sind das Nanohärtemessungen und Transmissionselektronenmikroskopie (TEM). Im Ergebnis liegen die bestrahlungsinduzierte Härteänderung der Schicht in Abhängigkeit von Chromgehalt, Bestrahlungsfluenz und –temperatur sowie, für ausgewählte Zustände, quantitative TEM-Analysen vor. Zusammen mit begleitenden Ergebnissen von Neutronenkleinwinkelstreuexperimenten an neutronenbestrahlten Proben der gleichen Werkstoffe ermöglichen sie die Identifizierung von bestrahlungsinduzierten Versetzungsringen und nm-großen α’-Ausscheidungen als Quellen der Strahlenhärtung. Im Rahmen eines vereinfachten Modells, das auf Orowan zurückgeht, werden die Hindernisstärken dieser Gitterbaufehler für das Gleiten von Versetzungen abgeschätzt. Darauf aufbauend erfolgt ausblickartig eine Erweiterung des Untersuchungsgegenstands auf komplexere Situationen hinsichtlich der Bestrahlungsbedingungen und des Werkstoffs. Durch das Einbeziehen simultaner und sequentieller Bestrahlungen mit Eisen- und Heliumionen kann gezeigt werden, dass der Effekt von Helium auf die Strahlenhärtung von der Bestrahlungsreihenfolge abhängt und dass der simultane Eintrag fusionsrelevanter Mengen von Helium zu einer Verstärkung der Strahlenhärtung führt, die auf einem synergistischen Effekt beruht. Für Cr-Stähle mit 9 % Cr und deren oxiddispersionsverfestigte Varianten wird kein grundlegend anderes Bestrahlungsverhalten beobachtet als für binäres Fe-9at%Cr. Es gibt jedoch Hinweise, dass Oxid-dispersionsverfestigung die Strahlenhärtung unter bestimmten Bedingungen reduzieren kann. Im Ergebnis der Arbeit zeigt sich, dass Ionenbestrahlungen in Kombination mit Nanohärtemessungen zu einem vertiefenden Verständnis der Strahlenhärtung in Werkstoffen auf Fe-Cr-Basis sowie zu einer effektiven Materialvorauswahl beitragen können. Voraussetzung ist, dass der Eindruckgrößeneffekt und der Substrateffekt auf geeignete Weise in Rechnung gestellt werden.