Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-08-24T15:50:11Z No. of bitstreams: 1 thamismalenamarcianocaria.pdf: 4769123 bytes, checksum: c70cfcf0f0b7af79a988b07929beeac2 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-08-25T11:51:55Z (GMT) No. of bitstreams: 1 thamismalenamarcianocaria.pdf: 4769123 bytes, checksum: c70cfcf0f0b7af79a988b07929beeac2 (MD5) / Made available in DSpace on 2017-08-25T11:51:55Z (GMT). No. of bitstreams: 1 thamismalenamarcianocaria.pdf: 4769123 bytes, checksum: c70cfcf0f0b7af79a988b07929beeac2 (MD5) Previous issue date: 2016-09-30 / Nosso objetivo nesta dissertação é verificar a trajetória da obra Cleópatra que pertenceu a Coleção Le Gros até 1859, passando para Academia Imperial de Belas Artes em 1860, por compra ou doação, integrando a coleção do Museu Nacional de Belas Artes e finalmente sendo destinada ao acervo do Museu D. João VI tendo como data de incorporação o ano de 1979. Trataremos da possibilidade desta obra ser uma cópia utilizando como modelo de uma pintura do artista genovês Bartolomeo Biscaino (1632-1657) a partir da comparação de algumas de suas pinturas com a obra em questão. Aqui também será discutido como a arte Italiana do século XVII representava e idealizava a personagem Cleópatra, e do mesmo modo será analisada a possível função da obra Cleópatra dentro da Antiga Academia Imperial de Belas Artes (AIBA) do Rio de Janeiro. Por ter pertencido, a obra, à coleção privada do colecionador J. G. Le Gros (João Guilherme Le Gros ou Legros) e integrado os catálogos das Exposições Gerais de Belas Artes (EGBA) de 1859, 1860, 1863, 1866, 1889, 1890, 1891 e o Pequeno Catálogo de Bens da ENBA de 1957, nos aprofundaremos na história deste colecionador, sobre a prática do colecionismo no Rio de Janeiro do século XIX e faremos uma análise da sua coleção, a fim de compreender o seu gosto pela arte. / Our intention in this dissertation is to research the trajectory of the painting Cleopatra that belonged to Le Gros Collection until 1859; moving to Academia Imperial de Belas Artes (Imperial Academy of Fine Arts) in 1860, by purchase or donation, integrating the Museu Nacional de Belas Artes and finally being destined to the collection Museum D. João VI, having as incorporation date of the year 1979. We argue the possibility of this work being a copy using a model based on Genoese artist Bartolomeo Biscaino (1632-1657) from the comparison of some of his paintings with the work in question. Here it will also be discussed how the Italian art of the seventeenth century represented and idealized character Cleopatra. Likewise it will be analyzed the possible function of the Cleopatra painting within the Academia Imperial de Belas Arters (AIBA) in Rio de Janeiro. By having the canvas belonged to the private collection of the J.G. Le Gros (João Guilherme Le Gros or Legros), and integrated the catalog of Exposições Gerais de Belas Artes (EGBA) from 1859, 1860, 1863, 1866, 1889, 1890, 1891 and the Pequeno Catálogo de Bens da ENBA de 1957, we will research the history of this collector and the practice of collecting in Rio de Janeiro in nineteenth century. We will also do an analysis of his collection in order to understand his taste for art.

Master's thesis Transformations of the Church at the Time of the Incoming Enlightenment discusses the ongoing contradictions between faiths. Catholic confession, which initially imposed on all subjects and nobilities in the Roman Empire has been slowly losing its previous power. Its power has been decreasing in inverse proportion by the time Enlightenment spreaded to the Czech lands throughout Germany and Italy. It changed everything, what was perceived in some way, and in turn created a lot of new knowledge. Enlightenment appeared under the rule of Emperor Charles VI., although not as much as of his daughter Marie Terezie and of his grandson Emperor Joseph II. at all. Joseph II. transformed his entire empire based on his Enlightenment ideas. By the time of reforms the "liberation" of non-Catholics and the abolition of serfdom is gradually coming. The Church at this time was very fragmented and was creating new spiritual insights on the Catholic Church and Christianity itself.

Abstract Background and aims: Stage and grade are the most widely used prognostic parameters for renal cell carcinoma (RCC). The clinical course of this disease is not, however, always predictable by traditional prognostic factors. In the era of new molecular targeted therapies a more accurate prognostication of RCC patient survival is important for the individualization of treatment and follow-up of patients. Despite exhaustive research there are still no prognostic biomarkers for RCC in clinical practice. In order to find novel prognostic tissue markers for RCC, we examined the expression of 14 biomarkers involved in carcinogenesis and clarified their prognostic significance in RCC. Material and methods: Out of 189 consecutive patients who underwent surgery for kidney cancer at Oulu University Hospital in the 1990s, 152 patients with histologically verified RCC were included in this study. The stage distribution was 70 (46%), 12 (8%), 51 (34%) and 19 (12%) patients with stages I-IV, respectively. The majority of the tumours (83 tumours, 55%) were nuclear grade II and 5 (3%), 40 (27%) and 22 (15%) of the tumours were grades I, III and IV, respectively. Clinical and follow-up data were obtained from patient records, the Finnish Cancer Registry and on demand from the Population Register Centre of Finland. The biomarkers studied included markers of the oxidative and neuroendocrine systems as well as proteins related to cell adhesion and migration, invasion, metastasis, inflammation and immune responses. The expression of various biomarkers was characterized via immunohistochemical tests of archival tumour material. The staining intensity was compared to clinicopathological parameters and patient RCC-specific survival. Results: The 5-year RCC-specific survival was 77%. The expression of Toll-like receptor 9 (TLR9) was an independent marker of favourable RCC-specific survival whereas cytoplasmic myosin VI expression was found to be an independent prognostic factor of poor RCC-specific survival. Cell culture experiments showed how cyclooxygenase-2 (COX-2) expression is regulated by HuR in RCC. HuR and COX-2 immunoexpression were also related to decreased RCC-specific survival. Immunostaining of Keap1 was associated with advanced RCC and a marker of a poorer RCC-specific prognosis. The expression of different neuroendocrine markers was evaluated but we could not establish any prognostic value for them. Conclusions: In particular, TLR9, HuR and myosin VI can be regarded as promising novel prognostic biomarkers in RCC. Stage, however, is the most important single prognostic factor for RCC. / Tiivistelmä Munuaissyöpä on vuosikymmenten ajan jatkuvasti yleistynyt. Vaikka se diagnosoidaan nykyisin useimmiten sattumalöydöksenä vatsan alueen kuvantamistutkimuksissa ja hoitomenetelmät ovat viime vuosikymmenten aikana kehittyneet, munuaissyöpäkuolleisuus ei ole laskenut. Munuaissyövän ennusteen määrittäminen voi olla haasteellista. Perinteiset ennustetekijät, levinneisyys ja erilaistumisaste, eivät riitä selittämään kaikkien potilaiden taudinkulkua, eikä munuaissyövälle vielä ole kliinisessä käytössä ennusteellista merkkiainetta. Munuaissyöpähoitojen kehittyessä taudinkulun ennustaminen on yhä tärkeämpää, jotta potilaiden hoito ja seuranta voidaan yksilöidä. Tämän väitöskirjatyön tarkoituksena oli etsiä uusia ennusteellisia kudosmerkkiaineita munuaissyöpäkasvaimille. Väitöskirjatutkimus perustuu 1990-luvulla Oulun yliopistollisessa sairaalassa leikatun 152 munuaissyöpäpotilaan aineistoon. Lähes puolet aineiston kasvaimista edusti levinneisyysluokkaa I, ja yli puolet munuaissyöpäkasvaimista oli hyvin erilaistuneita (tumagradus I ja II). Tutkimuspotilaista kerättiin kattavat seurantatiedot. Leikkauksessa poistettujen munuaissyöpäkasvainten arkistomateriaalista tutkittiin eri merkkiaineiden ilmenemistä. Tutkitut merkkiaineet käsittivät oksidatiivisen ja neuroendokriinisen järjestelmän merkkiaineita sekä valkuaisaineita, jotka liittyvät keskeisiin syövän ominaisuuksiin, kuten solujen välisiin liitoksiin ja solujen liikkumiseen sekä etäpesäkkeiden syntymiseen. Lisäksi tutkittiin merkkiaineita, jotka liittyvät tulehdusreaktioihin ja immuunipuolustukseen. Väitöskirjatutkimus paljasti useita uusia kudosmerkkiaineita, joiden ilmeneminen munuaissyöpäkasvaimessa on yhteydessä potilaan ennusteeseen. Näistä merkittävimpiä ovat myosiini VI, joka liittyy syöpäkasvainten metastasointiin, sekä immuunipuolustuksessa vaikuttava Tollin kaltainen reseptori 9 (Toll-like receptor 9, TLR9). Molemmat merkkiaineet osoittautuivat itsenäisiksi ennustetekijöiksi munuaissyövässä. Muita ennusteeseen vaikuttavia merkkiaineita ovat tutkimuksen mukaan oksidatiivista stressiä aistiva Keap1 sekä immunologisiin reaktioihin liittyvä syklo-oksigenaasi 2 (COX-2) ja sen ilmenemistä säätelevä HuR.

L'arsenic est un élément toxique présent naturellement dans l'environnement. Parfois en fortes concentrations dans les eaux souterraines, utilisées comme eaux de boisson, il est responsable d'une des plus grandes mortalités au monde. Il est donc important de mieux comprendre les interactions de l'As avec l'environnement et son mode de transfert jusqu'aux aquifères. Cette thèse a pour objectif de comprendre les mécanismes de complexation direct et indirect de l'As(III) par la matière organique (MO) en milieu anoxique, notamment via les groupements thiols de la MO et sous forme de complexes ternaires faisant intervenir le Fe ionique. La première partie de ce travail a été consacrée à la complexation de l'As(III) par les groupements thiols de la MO. Des expériences de complexation d'As(III) par un acide humique (AH) naturel greffé ou non en sites thiols ont été réalisées. L'As(III) se complexe à la MO directement mais les concentrations complexées sont faibles et dépendantes de la densité en site thiol. La modélisation à l'aide de PHREEQC-Model VI modifié afin de tenir compte des sites thiols, a mis en évidence que l'As était complexé à la MO sous forme de complexes monodentates. Il existe, un autre mécanisme qui propose une complexation indirecte via la formation d'un pont cationique. Nous nous sommes intéressés ici, en conditions anoxiques, à la possibilité que ce pont soit un pont de Fe(II). Il n'existe cependant que très peu d'information sur la complexation du Fe(II) par la MO. Des expériences de complexation du Fe(II) par des substances humiques (SH) ont donc été réalisées. Les résultats expérimentaux ont montré que le Fe(II) est faiblement complexé aux SH lorsque le pH était acide et les groupements fonctionnels protonés. Au contraire à pH neutre à basique, 100% du Fe(II) est complexé aux SH. La modélisation a montré que le Fe(II) forme majoritairement des complexes bidentates carboxyliques à pH acides et des complexes bidentates carboxy-phénoliques et phénoliques à pH basiques. Dans la dernière partie, la complexation de l'As(III) par des complexes ternaires As(III)-Fe(II, III) ionique-MO a été testée. Les résultats expérimentaux ont montré que des complexes ternaires As(III)-Fe(II)-MO pouvaient se former en milieu anoxique. La modélisation a permis de tester différentes conformations structurales de complexes ternaires. Le complexe le plus probable est un complexe bidentate mononucléaire d'As(III) sur un complexe bidentate de Fe(II)-AH. Cependant, PHREEQC-Model VI doit être amélioré car la distribution des sites bidentate n'est pas réaliste en comparaison des données spectroscopiques. Au contraire pour de faibles concentrations en Fe(III), l'As(III) ne forme pas de complexes ternaires As(III)-Fe(III) ionique-MO. La spéciation de l'As et du Fe est particulièrement importante dans l'étude du transfert de l'As. Si l'As(III) est complexée à la MO, son transfert dépendra totalement des mécanismes de transfert de la MO. / Arsenic occurs naturally in groundwater used as drinking water. It is thus responsible of a great mortality in the world. Understand the As interactions with its environment and its transfer mode to the aquifers is therefore crucial. This work was focused on the direct and indirect binding mechanisms of As(III) by organic matter (OM) in anoxic environments, in particular via OM thiol groups and as ternary complexes involving ionic Fe. The first part of this work was dedicated to the complexation of As(III) by the OM thiol. Binding experiments of As(III) by a humic acid (HA) grafted or not by thiol were thus performed. Grafted or not OM were able to bind As(III) but bound As(III) concentrations were low and dependant on the thiol site density. Modeling with PHREEQC-Model VI modified to take into account thiol site demonstrated that As(III) was bound as monodentate complexes to OM thiol sites. Another indirect binding mechanism involving ternary complex via cationic bridge was however described to explain larger binding of As(III, V) to natural OM. Here under anoxic conditions, we speculated that this bridge was an ionic Fe(II) bridge. However, little information exists about the binding of Fe(II) by OM. Complexation experiments of Fe(II) by humic substances (HS) were thus conducted. The experimental results showed that Fe(II) was weakly complexed to HS at acidic pH, when the functional groups were protonated. By contrast, at basic pH, 100% of Fe(II) were complexed to HS. Modeling calculations demonstrated that Fe(II) formed mainly carboxylic bidentate at acidic pH and carboxy-phenolic and phenolic bidentate at basic pH. In the last part, the complexation of As(III) as As(III)-ionic Fe(II, III)-OM ternary complexes was tested. Experimental results showed that As(III)-Fe(II)-OM ternary complexes could form in anoxic environments. Modeling allowed to test several ternary complexes conformations. The most potential was the binding of As(III) as mononuclear bidentate complex onto a bidentate Fe(II)-AH complex. However, another definition of the model that should be constrained by XAS data is required. By contrast, at low concentrations of Fe (III), when the oxidizing and reduced species coexist, As(III) does not form As(III)-ionic Fe(III)-OM ternary complexes. Speciation of As and Fe is particularly important in the study of the As(III) transfer. When As(III) is bound to OM as ternary complexes, its transfer is entirely controlled by the own OM transfer mechanisms. Here, we calculated, however, that much of As(III) remains as labile species and can therefore reach underlying aquifers as long as anoxic conditions exist.

Les gisements d’U de type discordance sont associés à des circulations de saumures chlorurées acides et caractérisés par des tonnages et concentrations exceptionnels ce qui amènent à s’interroger sur les processus de transport et de dépôt de l’U contribuant à leur genèse. Cette thèse est donc dédiée à des études expérimentales de la spéciation de l’U6+ et sa précipitation en UO2 par réduction en U4+ en condition hydrothermale. Concernant le transport de l’U, l’étude de la spéciation de l’U6+ dans ces fluides chlorurés (T ≤ 350°C) est réalisée par spectroscopie Raman et XAS. Les résultats montrant la coexistence de plusieurs complexes d’uranyle chlorurés UO2Cln2-n (n=0-5) dont certaines constantes de complexation sont proposées. Ainsi, la complexation de l’uranyle par les chlorures explique la forte capacité de transport en U6+ par les saumures chlorurées acides, condition nécessaire à la formation de gisements de fort tonnage. Pour le dépôt de l’U, les cinétiques de réduction de l’U6+ en U4+ par H2, CH4, Fe2+ et C-graphite sont mesurées et paramétrées en fonction de la température, de la chlorinité, du pH et de la concentration en réducteur. H2, CH4 et le C-graphite sont être très efficaces, contrairement au Fe2+. Le caractère mobile des gaz réducteurs explique en partie les minéralisations massives et focalisées observées dans ces gisements. Enfin des coefficients de partage UO2/fluide d’éléments en traces, dont certaines ETR, sont mesurés, ouvrant de nouvelles perspectives quant à (i) la compréhension de la signature des ETR caractéristiques de chaque type de gisement d’U, et (ii) la composition des fluides à l’origine des minéralisations uranifères / Circulations of acidic chloride brines are associated with unconformity-related uranium (URU) deposits. The spectacular high grade combined with the large tonnage of these deposits is at the origin of the key questions concerning the geological processes responsible for U transport and precipitation. The aim of this work is to performed experimental studies of U6+ speciation and its reduction to U4+ subsequently precipitation to UO2 under hydrothermal condition. About U transport, the study of U6+ speciation in acidic brines at high temperature is performed by Raman spectroscopy and XAS, showing the coexistence of several uranyl chloride complexes UO2Cln2-n (n=0-5). From this study, complexation constants are proposed. The strong capability of chloride to complex uranyl is at the origin of the transport of U6+ at high concentration in acidic chloride brines. Concerning U precipitation, the reactivity of four potential reductants under conditions relevant for URU deposits genesis is investigated: H2, CH4, Fe2+ and the C-graphite. The kinetics of reduction reaction is measured as a function of temperature, salinity, pH and concentration of reductant. H2, CH4, and the C-graphite are very efficient while Fe2+ is not able to reduce U6+ in same conditions. These mobile and efficient gaseous reductant could be at the origin of the extremely focus and massive character of ore in URU deposits. Finally, first partition coefficients UO2/fluid of trace elements are obtained. This last part opens-up new perspectives on (i) REE signatures interpretation for a given type of U deposit (ii) and reconstruction of mineralizing fluids composition

Purpose: The purpose of this study is to compare the legal requirements for Euro VI and CARB regarding OBD certification in order to identify the challenges that may come for a manufacturer’s move from Euro VI classified heavy-duty engines to engines that meet the requirements of CARB. Furthermore, the study also aims to identify the effects that these challenges will have on the organisation. Research question: What type of challenges arise for a manufacturing company when developing an OBD certification process according to the requirements from CARB compared to Euro VI and how do these challenges affect the organisation? Method: The nature of this study was qualitative with a deductive method as an approach, where theories and empirical findings interacts. The theoretical framework is divided into two parts, in which the first part is obtained from scientific articles and books and the second part from legislations. The empirical data was gathered from interviews at a case study company and the information was thematically analysed. Conclusion: This study concludes that the movement from Euro VI to CARB standards will result in comprehensive changes for a company’s OBD process itself as well as organisational changes within the company. There will be a need to establish new processes and new ways of working within the organisation which can lead to comprehensive coordination difficulties that should be taken into consideration. In conclusion, it is as important to consider the effects of the changes that this movement will bring on the company and the actors within, as it is with the implementation of the process itself. / Syfte: Syftet med denna studie är att jämföra lagkraven för Euro VI och CARB angående OBD certifieringen och därmed identifiera de utmaningar som kan uppstå i och med övergången från Euro VI klassificerade motorer till motorer som uppfyller kraven från CARB. Vidare syftar studien även till att undersöka hur dessa utmaningar påverkar organisationen. Forskningsfråga: Vilka utmaningar uppstår för ett tillverkande företag vid utveckling av en OBD certifieringsprocess enligt lagkrav från CARB i jämförelse med Euro VI och hur påverkar dessa utmaningar organisationen? Metod: Denna studie är av en kvalitativ karaktär som är baserad på en deduktiv forskningsmetod. Den teoretiska referensramen är uppdelat i två sektioner, vari den första är baserad på vetenskapliga artiklar och böcker och den andra från lagkrav. Empiriska data har samlats från intervjuer på fallstudieföretaget och metoden som har använts för att analysera materialet är tematisk analys. Slutsats: Denna studie konkluderar att övergången från Euro VI till CARB lagkrav resulterar i omfattande förändringar för företagets OBD process och bringar organisationsförändringar inom företaget. Det kommer att finnas ett behov av att etablera nya processer och nya arbetssätt inom organisationen som kan leda till omfattande samordningsproblem som bör has i åtanke. Sammanfattningsvis är det av yttersta vikt att ta hänsyn till de organisationsförändringarna som förväntas uppstå i och med denna förändring och inte enbart fokusera på att implementera en ny process.

Im Mittelpunkt der in dieser Arbeit durchgeführten Untersuchungen steht die Aufklärung der Strukturen der Komplexe von Uran mit aliphatischen (Hydroxy-)Carbonsäuren als Liganden sowie die Strukturen, die bei Sorption von Uran an dem Eisenmineral Hämatit in An- und Abwesenheit organischer Säuren gebildet werden. Das ternäre System aus Hämatit, Uran(VI) und organischem Ligand ist sehr komplex. Daher ist es notwendig eine Aufspaltung in einfachere binäre Systeme vorzunehmen und die Ergebnisse dieser Teilsysteme heranzuziehen, um das komplexere ternäre System zu verstehen. Anhand der umfangreichen durchgeführten Arbeiten zu den wässrigen Uran(VI)-Komplexen können nun Rückschlüsse von der Struktur einer Carbonsäure auf die Struktur der gebildeten Uran(VI)-Komplexe in Abhängigkeit vom pH getroffen werden. Zuerst sollte festgehalten werden, dass Uran(VI) üblicherweise pentagonal-bipyramidale Komplexe ergibt. Das Pentaaquauranylion zeigt beispielsweise zwei axiale Sauerstoffatome (Oax) bei einem Abstand von 1,76 Å und fünf äquatoriale Sauerstoffatome (Oeq) bei einem Abstand von 2,40 Å, die von koordinierten Wassermolekülen stammen. Im Zuge der Komplexierung mit organischen Liganden werden die Wassermoleküle durch organische Liganden ersetzt, was zu messbaren Veränderungen der Bindungsabstände führt. Monocarbonsäuren bilden mit Ausnahme der Ameisensäure nacheinander mit steigendem pH 1:1-, 1:2- und 1:3-Komplexe. Die teilweise in der Literatur postulierten 1:4-Komplexe beschränken sich wahrscheinlich auf extrem hohe Ligandkonzentration (>>1 M) oder nicht-wässrige Lösungen (z. B. 1:4-U-ac-Komplex [Ryan 1967]). Anhand der Verringerung der spektralen Aufspaltung Δν der symmetrischen und antisymmetrischen Valenzschwingung der Carboxygruppe konnte für diese Komplexe eine bidentate Koordination nachgewiesen werden. Mittels EXAFS konnte die bidentate Struktur anhand einer Verlängerung des Oeq-Abstandes auf 2,47 Å im Falle der 1:3-Komplexe in den Systemen U-ac und U-prop bestätigt werden. Die Ameisensäure hingegen bildet monodentate Komplexe. Dies konnte durch eine Erhöhung von Δν und eine Verkürzung des Oeq-Abstandes gezeigt werden. Ursache für dieses Verhalten ist der fehlende +I-Effekt durch den organischen Rest, der unter anderem eine deutliche Erhöhung der Säurestärke im Falle der Ameisensäure nach sich zieht. Bei Bi- und Tricarbonsäuren bestimmt der Abstand der Carboxygruppen zueinander, welche Art der Koordinierung auftritt. Werden die Carboxygruppen durch maximal ein Kohlenstoffatom voneinander getrennt (Oxal- und Malonsäure) oder wird durch eine cis-Doppelbindung eine cis-Konfiguration der Carboxygruppen zueinander erzwungen (Maleinsäure), treten 1:1- und 1:2 , sowie für Oxalsäure auch 1:3-Komplexe mit chelatartiger Koordinierung auf. Dies wird durch eine Erhöhung von Δν und eine Verringerung von r(U-Oeq) auf 2,36 Å (1:2-Komplexe) untermauert. Liegen mindestens zwei Kohlenstoffatome zwischen den Carboxygruppen (Bernsteinsäure, Tricarballylsäure), so bilden sich überwiegend bidentate Komplexe aus. Der 1:3-Komplex im System U-suc ist allerdings gemischt bidentat/monodentat und erreicht deshalb auch einen gegenüber dem 1:3 U-ac Komplex etwas verkürzten Oeq-Abstand von 2,45 Å. Eine weitere wichtige Gruppe von Liganden sind die α- und β-Hydroxycarbonsäuren. Die α-Hydroxycarbonsäuren bilden 1:1-, 1:2-, 2:2- und 3:3-Komplexe aus. Der Ligand koordiniert dabei als 5-Ring-Chelat an Uran(VI). Die Bildung polynuklearer Spezies wird belegt mit einem stufenweisen und sehr starken Ansteigen der Absorption im UV/VIS-Bereich, der durch eine Deformation der linearen O=U=O-Bindung hervorgerufen wird. Außerdem zeigt die EXAFS-Spektroskopie, dass bei pH ~ 2–4 eine U-U-Wechselwirkung bei r(U-U) ~ 3,92 Å auftritt, wodurch die Bildung eines µ2-O verbrückten Dimers nachgewiesen ist. Im nahneutralen pH-Bereich (pH 6–7) ist eine sehr starke U-U-Wechselwirkung bei r(U-U) ~ 3,83 Å er-kennbar. Diese kann durch Ausbildung einer µ3-O verbrückten dreikernigen Struktur erklärt werden. Zwischen den α-Hydroxymonocarbonsäuren und den α-Hydroxydi- und -tricarbon-säuren, die als substituierte Äpfelsäure aufgefasst werden können, besteht der wesentliche Unterschied, dass die Homologen der Äpfelsäure das Dimer im oben genannten pH-Bereich als dominierende Spezies aufweisen, während es bei den Monocarbonsäuren erst bei höheren pH-Werten (pH ~ 4–5) und lediglich zu ~50 % (lac) auftritt. Die β-Hydroxycarbonsäuren bilden hingegen bidentat koordinierende 1:1-, 1:2- und 1:3-Komplexe. Die 1:3-Komplexe sind isostrukturell zum 1:3-U-ac-Komplex. Die Hydroxygruppe in β-Position beteiligt sich folglich nicht an der Komplexierung. Bei der Sorption von Uran(VI) an Hämatit in An- und Abwesenheit organischer Liganden ergibt sich ein breit gefächertes Spektrum an Möglichkeiten. Allgemein lässt sich feststellen, dass die Sorption etwa bei pH 3–4 einsetzt und im nahneutralen pH-Bereich (pH 6–7) maximal wird. Die Anwesenheit organischer Liganden bewirkt im Allgemeinen eine Verschiebung der Sorptionskante zu höheren pH-Werten, wobei folgende Reihenfolge der pH-Werte bei 50 %iger Sorption zu beobachten war: ohne Ligand ~ Protocatechusäure < Essigsäure < Bernsteinsäure < Weinsäure. Weiterhin kann festgestellt werden, dass die Sorptionskomplexe in der Nähe der Sorptionskante monomer sind und in oligomere Urankomplexe im nahneutralen pH-Bereich übergehen. Ohne Zugabe eines Liganden bildet sich mit steigendem pH zuerst ein über Kante verknüpfter, monomerer Sorptionskomplex (ES-Monomer) aus, der sich durch einen Fe-Abstand von ~3,45 Å und einen Oeq-Abstand von ~2,40 Å auszeichnet. Im neutralen pH-Bereich sorbiert Uran als oligomerer (wahrscheinlich dreikerniger) Sorptionskomplex (ES-Trimer) mit r(U-U) = 3,82–3,88 Å und r(U-Oeq) = 2,33–2,37 Å. Im Übergangsbereich kann sich zu geringen Teilen ein einfach oder doppelt über Ecke verknüpfter Sorptionskomplex (SCS- oder DCS-Monomer), wobei das SCS-Monomer einen Fe-Abstand von ~3,70–3,75 Å und einen Oeq-Abstand von ~2,40 Å aufweist, bilden. In Gegenwart von Essigsäure ändern sich lediglich die Strukturparameter minimal. In Gegenwart von Bernstein- und Weinsäure bilden sich im Gegensatz dazu über den Liganden verknüpfte Sorptionskomplexe aus, die also keine U-Fe-Wechselwirkung zeigen und sich besonders durch ihren sehr niedrigen DW(Oeq) von den anderen Sorptionskomplexen unter-scheiden. Im neutralen pH-Bereich liegen wiederum dreikernige Sorptionskomplexe vor, wo-bei es im Falle der Weinsäure auch möglich wäre, dass das aus dem aquatischen System be-kannte Trimer über die Weinsäure an die Oberfläche bindet. Im Unterschied dazu sorbiert Uran(VI) in Gegenwart der Protocatechusäure nahe der Sorptionskante als Gemisch eines monomeren ES- und DCS-Komplexes. Bei weiterer Erhöhung des pH dominiert der DCS-Komplex, der eine starke U-Fe-Wechselwirkung bei r(U-Fe) = 4,19 Å zeigt. Eine Oligomerisierung bleibt in diesem Falle aus. Die im Rahmen dieser Arbeit gewonnenen Ergebnisse tragen zu einem besseren Verständnis der Wechselwirkung von Uran(VI) mit organischen Säuren, sowie von Uran(VI) mit Hämatit in Gegenwart organischer Säuren, bei und liefern die Strukturen für die gebildeten wässrigen Komplexe und die Sorptionskomplexe. Damit unterstützen sie den Aufklärungsprozess des Transports radioaktiver Stoffe und können somit zuverlässigere Risikobewertungen für Endlager nuklearer Abfälle und für Rückstände des Uranerzbergbaus ermöglichen. / This study is focussed on throwing light on the structures of uranium(VI) complexes with aliphatic (hydroxy-) carboxylic acids and on the structures of the sorption complexes on the iron mineral hematite in presence and absence of organic acids. The ternary system of hematite, uranium(VI), and organic ligand is very complicated, thus it is necessary to decompose it in binary systems. The results within these binary systems are used to better understand the complicated ternary system. Based on the comprehensive investigations on the aqueous uranium(VI) complexes, it is now possible to draw inferences from the structure of the carboxylic acid about the structure of the formed uranium(VI) complex in dependence of the pH. At first it has to be mentioned that uranium(VI) commonly gives pentagonal bipyramidal complexes. The pentaaquauranylion is formed by two axial oxygen atoms (Oax) at a distance of 1.76 Å and five equatorial oxygen atoms (Oeq) at 2.40 Å stemming from coordinated water molecules. Due to complexation with organic ligands water is replaced by the ligand, thus the interatomic distances change. Monocarboxylic acids, except for formic acid, form with rising pH 1:1, 1:2, and 1:3 complex-es, successively. 1:4-complexes that were sometimes postulated in literature are probably restricted to very high ligand concentrations (>>1 M) or to non-aqueous solutions. On the basis of the decrease of the spectral splitting Δν of the symmetric and antisymmetric vibration mode of the carboxylic group bidentate coordination is verified. By using EXAFS spectros-copy the structure of the 1:3 complexes with acetic and propionic acid shows an elongation of the U-Oeq distance (r(U-Oeq)) to 2.47 Å and a six fold coordination in the equatorial plane. This distance is characteristic for bidentate coordination of the carboxylic group. In contrast, formic acid gives monodentate complexes. This is proved by an increase of Δν and a shortening of r(U-Oeq). The reason for this behaviour is the missing +I effect from the organic chain that accounts for a dramatically stronger acidity of formic acid. Among the bi- and tricarboxylic acids, the distance between the carboxylic groups is decisive for the prevailing mode of coordination. If the carboxylic groups are only separated by no more than one carbon atom (oxalic and malonic acid) or if the cis-configuration of the carboxylic groups is enforced by a cis-configuration of the ligand (maleic acid), 1:1 and 1:2 complexes with chelating coordination will be formed. This is evidenced by an increase of Δν and a decrease of r(U-Oeq) to 2.36 Å (1:2-complexes). If at least two carbon atoms separate the carboxylic groups from each other (succinic acid), the coordination will be mainly bidentate. However, the 1:3 complex in the U-suc system gives a mixed bidentate/monodentate coordination, thus r(U-Oeq) is only increased to 2.45 Å. Another important group of ligands are the α- and β-Hydroxy acids. α-Hydroxy acids form 1:1, 1:2, 2:2, and 3:3 complexes with rising pH. In all cases the ligand gives 5-membered ring chelates. The formation of polynuclear species is evidenced by a stepwise and very strong increase of the absorption in the UV-Vis range that is caused by a deformation of the linear O=U=O moiety. Moreover, EXAFS spectroscopy shows a uranium-uranium interaction at r(U-U) ~ 3.92 Å in the pH range of 2–4. This distance gives evidence for the formation of a µ2-O bridged dimer. In the near neutral pH range (pH 6–7) a very strong U-U interaction is visible at r(U-U) ~ 3,83 Å. This feature can be explained by the formation of a µ3-O bridged trimeric structure. The main difference between the α-Hydroxy diacids that can be understood as homologues of malic acid and the α-Hydroxy monoacids (glycolic acid, lactic acid, etc.) is the strength of the dimeric complex. Among the homologues of malic acid the complex sta-bility constant of the dimer is so high that the formation of a 1:2 complex is suppressed and the relative concentration of the dimer is at least 90 % in the pH range of 2–4. Among the α-Hydroxy monoacids the occurrence of the dimer is shifted to higher pH values and the relative concentration is limited (e.g. ~50 % in the U-lac system). On the contrary, β-Hydroxy acids form bidentate coordinated 1:1, 1:2, and 1:3 complexes. The 1:3 complexes are isostructural to the 1:3 complex in the U-ac system. Hence, the β-Hydoxy group does not participate in the coordination. For the sorption of uranium(VI) on hematite in absence and presence of organic ligands a widespread array of opportunities exists. In general, sorption starts at pH 3–4 and reaches its maximum in the near neutral pH range (pH 6–7). The presence of organic ligands leads to a shift of the sorption edge to higher pH. The following sequence of the pH where 50 % sorp-tion is reached were found: without ligand ~ protocatechuic acid < acetic acid < succinic acid < tartaric acid. Moreover, it can be stated that the complexes near to the sorption edge are monomeric and merge into oligomeric uranium(VI) complexes in the near neutral pH range. In the absence of organic ligands a monomeric edge-sharing complex (ES monomer) is formed at low pH which is characterized by an U-Fe distance of ~3.45 Å and an Oeq distance of ~2.40 Å. In the near neutral pH range an oligomeric edge-sharing complex (ES trimer) is formed with r(U-U) = 3.82–3.88 Å and r(U-Oeq) = 2.33–2.37 Å. It is possible that in the intermediate pH range a small fraction of single or double corner-sharing (SCS or DCS) complexes occur. The SCS monomer is characterized by r(U-Fe) ~3,70–3,75 Å and r(U-Oeq) ~2,40 Å. The presence of acetic acid has only small effects on the structural parameters. In presence of succinic and tartaric acid and at low pH the sorption complexes are of the type hematite-ligand-uranium, thus no uranium-iron interaction can be found and the DW(Oeq) is very small in contrast to all the other investigated sorption complexes. In the neutral pH range trimeric sorption complexes are formed again. In case of tartaric acid it is conceivable that the trimeric complex known from the aqueous U-tar system is sorbed to the hematite surface. In contrast, the presence of protocatechuic acid results in the formation of a mixture of ES and DCS monomeric complexes at low pH. With ongoing increase of pH the fraction of the DCS monomer rises. This DCS complex shows a strong uranium-iron interaction at r(U-Fe) = 4,19 Å. A formation of oligomeric complexes at neutral pH does not appear. The results gained during all these investigations can help to better understand the interaction of uranium(VI) and carboxylic acids, and beyond that the sorption of uranium(VI) on hematite in the presence of carboxylic acids. Structures of the aqueous and sorption complexes are proposed. All these findings support the ongoing research on the transport behaviour of radioactive matter and may lead to more reliable risk assessment in connection with the permanent disposal of nuclear waste and the residues of uranium mining.

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À partir de 1422 l’Anglais Jean de Lancastre (1389-1435), duc de Bedford, fut le régent du royaume français de son jeune neveu Henri VI. Le traité de Troyes (1420) prévoyant une présence anglaise pérenne en France, le régent dut mettre en place une structure de domination sociale consentie plutôt qu’entretenue par la coercition. C’est dans cette optique que le duc de Bedford instaura une politique culturelle et linguistique, fortement inspirée de celle des grands Valois, lui permettant de cultiver l’assentiment à son régime et de légitimer sa propre autorité. Cette politique est l’objet principal de notre recherche. Nous proposons en un premier temps d’analyser dans le détail les éléments constitutifs de la politique culturelle du régent Bedford, dont les somptueuses résidences, les riches manuscrits et le généreux patronage étaient autant de manifestations de la puissance anglaise en France. Ces dernières lui permettaient de s’insérer dans une société courtoise continentale, notamment auprès de son beau-frère et plus important allié, Philippe de Bourgogne. Parallèlement sa politique lui permettait aussi, notamment à travers l’imitation des rois de France, le déploiement de ce qu’on pourrait appeler des éléments de propagande. L’analyse de ces divers éléments révèle cependant qu’ils étaient peut-être moins destinés à convaincre les gouvernés qu’à consolider les convictions des gouvernants. Nous consacrons ensuite un chapitre dédié à l’exercice du pouvoir par l’écriture. Nous y analysons la production d’actes du duc de Bedford, autant en France qu’en Angleterre, sous le prisme de sa conformité ou de sa divergence d’avec les normes françaises. Le respect des traditions diplomatiques locales et de la langue des actes constituait, en soi, une affirmation des principes du traité de Troyes et un symbole de la continuité du pouvoir entre Valois et Lancastre. Parallèlement, la présence de certains éléments typiquement anglais dans l’administration militaire de la France de Bedford trahit une intégration imparfaite des pratiques locales. Nous y soulignons également l’importance du rôle des secrétaires français dans la coordination avec le royaume anglais d’Henri VI, certains se trouvant même à en intégrer l’appareil étatique. Si au final l’administration anglaise s’avère avoir été peu encline à l’adoption de pratiques étrangères, elle fut le théâtre d’importants changements linguistiques qui n’étaient pas étrangers à l’expérience de la France lancastrienne. En troisième lieu, nous soulignons la contribution d’autres figures importantes de la vie culturelle en France anglo-bourguignonne. La participation de personnages comme Richard Beauchamp et John Talbot à la vie de cour instaurée par le régent témoigne de l’intégration, par les Anglais en séjour sur le continent, de nombreux éléments de culture française. Une telle activité culturelle persista d’ailleurs longtemps après la mort de Jean de Lancastre. Le patronage, la circulation des idées, des artistes et, surtout, l’intériorisation du récit lancastrien en France y résulta en une certaine acculturation des élites, entraînant subséquemment une transformation de la culture anglaise outre-Manche. Cette appropriation culturelle participa à la pérennité de la langue et de la littérature française dans l’Angleterre du XVe siècle, tout en contribuant paradoxalement à la promotion d’une identité proprement anglaise. / From 1422 the Englishman John of Lancaster (1389-1435), duke of Bedford, was regent of his young nephew’s French kingdom. Because the treaty of Troyes (1420) provided for a long-lasting English presence in France, the regent had to put in place a social domination structure based on consent rather than coercion. In this context, the duke of Bedford devised a cultural and language policy inspired by the attitudes of the most prominent members of the Valois family. It allowed him to bolster support for his regime and legitimize his power. This policy is the main object of our research. We first propose to examine each element of Bedford’s cultural policy. His magnificent households, precious manuscripts and generous patronage were outward symbols of the might and stability of English rule in France. These possessions also allowed their owner to present himself as a legitimate member of continental courtly society. As such, they were a mean to strengthen the bond with his most important ally, his brother-in-law Philip, duke of Burgundy. At the same time the regent depicted himself, and by extension Henry VI, as the legitimate ruler of France by actively imitating past French kings. Some of his cultural enterprises can be conceived as propaganda. However under careful scrutiny these representations of power appear to have been intended not only for the conquered, but also for the conquerors themselves. We devote a second chapter to the exercise of power through writing. We analyze the duke’s production of written documents, both sides of the Channel, in light of its compliance to or defiance of French diplomatic tradition. In itself, the adoption of local practices and language was both respectful of the spirit of the treaty of Troyes and a convenient way to conceal the dynastic rift between Valois and Lancaster. On the other hand, the continued use of typical English documents in Bedford’s organization of the military reveals the limited extent of his acculturation. We also consider the important role of the French secretaries in the coordination between the two kingdoms, which in theory were supposed to be kept separate. Some of them were so involved in English affairs that they moved to England to serve Henry VI. In the end however the English bureaucracy remained mostly unaffected by extraneous innovations. Nonetheless, the very significant linguistic shift it underwent was contemporary, and linked, to the demise of Lancastrian France. The last chapter examines the contribution of other important figures of the anglo-burgundian cultural environment. The continental activity of magnates like Richard Beauchamp and soldiers like John Talbot exemplifies the relative vitality of courtly life in Lancastrian France and highlights the adoption of some elements of French culture by the English there. The subsequent patronage, circulation of texts and artists and, ultimately, the internalization of the Lancastrian French narrative, led to the transformation of English culture. This cultural appropriation contributed to the perpetuation of French language and literature in fifteenth-century England. Paradoxically, it also reinforced a properly English identity.

Работа посвящена участию маршала Жана II Ле Менгра, прозванного Бусико, во французской политике в Средиземноморье на рубеже XIV–XV в. Для достижения целей исследования был установлен ход и результаты французской внешней политики, а также личность самого маршала Бусико. В результате было установлено, что Жан II Ле Менгр участвовал в военных экспедициях французской короны на Балканы (1396 г.) и в Малую Азию (1399), а также управлял Генуей (1401–1409) от имени французского короля Карла VI Валуа. Военный опыт и дипломатические связи позволили Бусико обеспечить локальные тактические успехи на каждом направлении проводимой внешней политики в Средиземноморье, однако его ресурсов и навыков не хватило для того, чтобы Франция добилась стратегического успеха в Средиземноморском регионе на рубеже XIV–XV в. / The work is devoted to the participation of Marshal Jean II Le Meingres, called Boucicaut, in French politics in the Mediterranean at the turn of the 14th–15th centuries. To achieve the goals of the study, the course and results of French foreign policy, as well as the personality of Marshal Boucicaut himself, were established. As a result, it was established that Jean II Le Meingres participated in the military expeditions of the French crown to the Balkans (1396) and Asia Minor (1399), and also ruled Genoa (1401–1409) on behalf of the French king Charles VI of Valois. Military experience and diplomatic connections allowed Boucicaut to ensure local tactical successes in each direction of foreign policy in the Mediterranean, but his resources and skills were not enough for France to achieve strategic success in the Mediterranean region at the turn of the 14th–15th centuries.