Dans ce travail, nous nous concentrons sur la caractérisation de l'environnement physico-chimique des éléments présents dans des multicouches à base de cobalt qui travaillent dans les domaines des rayons X mous et extrême ultra-violet (EUV). L'observation des modifications des interface des deux systèmes Co/Mo2C et Co/Mo2C/Y lors du recuit est important pour l'amélioration de leurs performance optique. Ils ont été étudiés en combinant des méthodes non destructives, spectroscopie d'émission des rayons X, résonance magnétique nucléaire, réflectométrie de rayons X et des méthodes destructrices, spectrrométrie de masse d'ions secondaires par temps de vol et la Microscopie électronique en transmission pour étudier leurs propriétés interfaciales. Ce travail vise non seulement à la conception et la fabrication de nouveaux éléments optiques pour faire face au développement des sources et des applications dans les demaines des rayons X mous et l'EUV, mais aussi à développer une méthodologie combinant des simulations et des expérimentations consacrée à l'analyse des interfaces dans structures multicouches afin d'améliorer leur propriétés optiques. / In this work, we focus on the characterization of physico-chemical environment of the element present in Co-based multilayers working in the soft x-ray and EUV ranges. The observation of interface changes of both systems Co/Mo2C and Co/Mo2C/Y upon annealing is important for improving their optical performance. They were studied by combining non-destructive methods, x-ray emission spectroscopy, nuclear magnetic resonance spectroscopy, x-ray reflectometry and destructive methods, time-of-flight secondary ions mass spectroscopy and transmission electron microscopy to investigate their interface properties. This work aims not only at designing and fabricating new optical elements to face the development of sources and applications in the EUV and soft x-ray ranges, but also at developing a methodology combining simulations and experiments devoted to the interface analysis in these multilayer structures in order to improve their optical properties.

Dans cette thèse, nous avons étudié plusieurs combinaisons de matériaux et quelques méthodes d’ingénierie des interfaces : introduction de barrières de Zr dans les multicouches Co/Mg ; pulvérisation réactive des multicouches Co/Ti ; incorporation de B et C dans les multicouches Cr/Ti and remplacement de Mo par Mo2C dans le système Mo/B4C. Les propriétés des interfaces enterrées ont pu être étudiées en combinant XRR, XPS, TEM, etc. De plus, un modèle pour analyser les empilements a été développé en se basant sur la fluorescence X induite par ondes stationnaires. Pour les multicouches à base de Co, nous avons effectué des mesures RMN pour comprendre le comportement des atomes de cobalt dans les empilements. Ces méthodes se révèle des outils puissants pour analyser les multicouches sans dommages. / In this thesis, we study several material combinations and some interface engineering methods...

Abstract During DNA replication cells accurately copy their DNA to transfer the genetic information to daughter cells. DNA polymerases synthesise the new DNA strand using the old strand as a template. Other functions of DNA polymerases are recombination linked and DNA iamage repair linked DNA synthesis, regulation of replication complex formation and regulation of transcription – a process in which the genetic information is transformed into an RNA sequence needed to guide protein synthesis. In this study, the TopBP1 protein was shown to associate with DNA polymerase epsilon. TopBP1 contains eight BRCT domains mediating interactions between phosphorylated proteins and is a human homolog of bakers yeast Dpb11 and fission yeast Cut5. These yeast proteins act on DNA replication and cell cycle arrest after DNA damage. TopBP1 was found to be phosphorylated and expressed in elevated amounts during S phase suggesting an involvement in DNA replication. This was directly demonstrated by DNA synthesis inhibition by a competing TopBP1 fragment and by an antibody targeted to block TopBP1. Ultraviolet irradiation damages DNA and decreases the amount of TopBP1 in the nucleus. The transcription factor Miz-1 was found to associate with TopBP1 and was released from this interaction after UV damage. Free Miz-1 activated the expression of the cell cycle arresting proteins p15 and p21 cooperatively with other transcription factors and allowed extra time for DNA damage repair. TopBP1 was also found to interact with the breast cancer susceptibility protein 1 and both proteins localised together to arrested DNA synthesis apparatuses. The interaction of TopBP1 with the damage recognition and processing protein Rad9 is still further evidence of a link between TopBP1 and DNA damage. DNA polymerase epsilon forms a complex with Cdc45, a protein involved in DNA replication initiation and elongation. This complex does not interact with Cdc45 complexed with DNA polymerase delta, suggesting that these complexes synthesise DNA independently of each other. Our results are in agreement with the view that polymerase epsilon synthesises the first strand of DNA and polymerase delta the other. Finally,DNA polymerase epsilon binds to the RNA synthesising form of RNA polymerase II and nascent transcripts. The physiological meaning of this interaction needs to be determined.

Masters of Science / Fumonisins, carcinogenic mycotoxins produced by various Fusarium species, occur naturally in maize and maize-based food products. They are hazards for animal and human health as they cause cancer in rodents and have been associated with oesophageal cancer and neural tube defects in humans. The most abundant naturally occurring fumonisins analogues in maize are fumonisin B1, B2 and B3 (FB1, FB2 and FB3). For analytical determination, they mostly require suitable extraction, clean-up and pre or post-column derivatization together with reversed-phase HPLC separation. o- Phthaldialdehyde (OPA) had been adopted as the most widely used derivatization reagent for fumonisins as they lack useful chromophores or fluorophores. Alternative derivatization reagents, naphthalene-2,3- dicarboxaldehyde (NDA) and dansyl chloride (DnS-Cl), were investigated in this study. / South Africa

No description available.

Aminoácidos tipo micosporinas (MAAs) são compostos responsáveis pela fotoproteção no ultravioleta de diversos organismos aquáticos. São sintetizados pela via do ácido chiquímico por algas, bactérias e fungos, de maneira similar à síntese de flavonóides em plantas superiores. Neste trabalho foram conduzidos estudos relacionados a estes compostos em algas. Protocolos de extração de diferentes algas foram testados alterando-se parâmetros como solventes, temperatura e condições de incubação. Os resultados mostraram que dependendo da alga estudada, diferentes condições podem mudar a concentração de MAAs extraída, ressaltando a importância de se testar diversos parâmetros na extração, evitando assim valores sub- ou superestimados de concentrações. O desenvolvimento de um método por HPLC permitiu a separação de 6 MAAs com boa resolução. A caracterização estrutural foi realizada majoritariamente por espectrometria de massas utilizando diferentes tipos de analisadores. Estas análises permitiram a proposição de mecanismos de fragmentação descritos pela primeira vez para esta classe de compostos e possibilitaram a identificação de diferentes MAAs em algumas micro e macroalgas. Ensaios in vitro foram realizados com o extrato obtido da macroalga Gracilaria domingensis no intuito de avaliar seu potencial uso em formulações cosméticas direcionadas à fotoproteção. Os testes de estabilidade quanto ao pH, temperatura e exposição à radiação ultravioleta bem como os ensaios de citotoxicidade, fototoxicidade e avaliação do fator de proteção solar sugeriram que este extrato pode ser promissor quando incorporado em formulações direcionadas para a fotoproteção. Este extrato não apresentou atividade antioxidante significativa. Os estudos com o dinoflagelado Prorocentrum minimum isolado de duas regiões diferentes, quando exposto às radiações ultravioleta, mostraram que houve uma indução das MAAs em ambas linhagens em todos os tratamentos realizados no período de 72 h. A indução foi mais rápida e pronunciada na linhagem oriunda de Lisboa, em Portugal do que na linhagem proveniente de Kattegat, na Dinamarca. Estes dados estão de acordo com as características do local de origem das linhagens, uma vez que os dinoflagelados originários de Portugal em seu meio natural estavam sujeitos a maiores irradiações. Medidas do rendimento quântico do fotossistema II indicaram que a síntese e acúmulo de MAAs em P. minimum isolada de Lisboa ofereceu vantagens na proteção do sistema fotossintético e na supressão de espécies reativas de oxigênio desta microalga quando comparada aos indivíduos da mesma espécie de regiões com menores irradiações. / Mycosporine-like amino acids (MAAs) are chemically related water soluble compounds responsible for UV photoprotection in many aquatic organisms. They are biosynthesized via the shikimate pathway by algae, bacteria and fungi in a similar manner to the biosynthesis of UV-screening flavonoids in terrestrial plants. In this work, studies related to this class of compounds were performed with algae. Extraction protocols of some algae were tested using diverse solvents at different temperature. The results showed that depending on the organism examined, both solvent concentration and temperature affected extraction efficiency and final MAA concentration. The improvement of a HPLC method separated a mix of 6 MAAs with good resolution. The structural characterization was made by mass spectrometry using different analyzers. The analysis by mass spectrometry allowed the proposition of new mechanisms of fragmentation and identification of different MAAs in some micro and macroalgae. In vitro preliminary assays were performed to evaluate the potential use of Gracilaria domingensis extract in suncare products. The extract showed no antioxidant activity, however the pH, temperature and UV exposure stability, as well the citotoxicity, phototoxicity and sun protection factor showed a potential commercial utilization for the extracts. The UV exposure experiments with the dinoflagellate Prorocentrum minimum isolated from Lisbon, Portugal and Kattegat, Denmark, showed that MAAs were induced in all treatments during 72 h. The induction was faster in the species from Lisbon than the ones from Kattegat. These data are in agreement with local isolation place, since the dinoflagellates from Portugal are submitted to high irradiance regime in their natural enviroment. The quantum yield of photosystem II suggested that the over production of MAAs by P. Minimum from Lisbon protects the photosynthetic apparatus, indicating that MAAs act as spectrally specific UV sunscreens in phytoplankton.

Les expériences de laboratoire ont montré que la photo-irradiation ultraviolette d'analogues de glaces astrophysiques suivie de leur réchauffement à température ambiante mène à la formation de résidus organiques réfractaires. Ces résidus, solubles dans l'eau, consistent en un riche mélange de composés organiques incluant entre autres des acides aminés, molécules potentiellement importantes pour la chimie prébiotique. Ces résidus sont considérés comme des analogues de la matière organique réfractaire que l'on pense être synthétisée sur les grains de poussière dans les nuages moléculaires et/ou dans les disques protoplanétaires, produit de l'évolution des glaces, et qui pourra être accrétée plus tard en comètes ou en astéroïdes et finalement délivrée sur la Terre primitive. Ainsi, l'étude de ces analogues, produits dans des conditions astrophysiques pertinentes, représente un outil efficace pour explorer les processus à l'origine de la formation des molécules organiques complexes dans le Système Solaire et en particulier la possible introduction d'excès énantiomériques dans les molécules chirales.Ce travail de thèse est consacré à l'étude de ces résidus organiques, leur caractérisation et les applications astrophysiques de ces résultats. Nous avons utilisé différentes techniques d'analyse comme la chromatographie en phase gazeuse couplée à la spectrométrie de masse (GC MS, classique et multidimensionnelle), la spectrométrie de masse par résonnance cyclotronique ionique à transformée de Fourier (FT ICR MS) ou encore la spectroscopie infrarouge. Nous avons mesuré les excès énantiomériques induits dans cinq acides aminés par irradiation de nos analogues avec de la lumière UV polarisée circulairement (UV CPL) et insérons nos résultats dans le cadre d'un scénario astrophysique cohérent pour expliquer l'origine des excès énantiomériques observés dans les acides aminés météoritiques. Nous avons étudié le contenu en acides aminés de la météorite de "Paris" et montré des similarités avec la distribution en acides aminés de nos résidus organiques. Nous avons également produit des analogues plus réalistes de grains interstellaires en incluant une surface silicatée, afin de tester l’effet potentiel de cette surface sur la formation et la nature des résidus organiques. Enfin, nous effectuons une discussion générale à propos de la pertinence de ces résultats dans le contexte astrophysique et soulignons le possible lien entre astrochimie et chimie prébiotique. / Laboratory experiments have shown that ultraviolet photo-irradiation of astrophysical ice analogs and their following warm-up until room temperature lead to the formation of refractory organic residues. These residues consist of rich mixtures of organic compounds, including amino acids, which have a potential importance for prebiotic chemistry. They are considered as analogs of the organic refractory materials that are thought to be synthesized on dust grains in molecular clouds and/or in protoplanetary disks, as a product of ices evolution, and that could be later accreted into comets and asteroids and eventually be delivered to the early Earth. Hence, the study of these analogs, produced under astrophysically relevant conditions, represents a valid tool to investigate the processes at work for the origin of complex organic molecules in the Solar System and in particular the possible introduction of enantiomeric excesses in chiral molecules. This PhD work is devoted to the study of these laboratory organic residues, their characterization and the astrophysical applications of the results. We used different analytical techniques such as gas chromatography mass spectrometry (GC MS, classical and multidimensional), Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), and infrared spectroscopy. We measured the enantiomeric excesses induced in five chiral amino acids by UV circularly polarized light (UV CPL) irradiation of our analogs and insert our result in a coherent astrophysical scenario for the origin of the enantiomeric excesses observed in meteoritic amino acids. We studied the amino acid content of the Paris meteorite and evidence some similarities with the distribution of the amino acids in our organic residues. We also produced more realistic analogs of interstellar grains, including a silicate surface, to test the potential effect of such a surface on the formation and nature of organic residues. Finally, we discuss the significance of these results in the astrophysical context and the possible relationship between astrochemistry and prebiotic chemistry.

Tato diplomová práce je zaměřena na analýzu lehkých prvků (tj. uhlík, sýra a fosfor) v železných slitinách pomocí metody laserem indukovaného plazmatu (LIBS). Hlavním cílem je vyvinout a implementovat nový modul, který bude umožňovat analýzu v hluboké ultrafialové oblasti (VUV), což je nezbytné jak pro stanovení chemického složení lehkých prvků v ocelích tak pro mnoho dalších aplikací metody LIBS. V první části je vytvořen přehled moderních přístupů optické emisní spektroskopie (OES) a rovněž jsou shrnuty tradiční techniky používané v metalurgii pro analýzu ocelí. Teorie absorpce ultrafialového záření vzduchem a optickými skly byla důkladně studována a shrnuta k získání potřebného teoretického základu k vývoji modulu. Před návrhem finální verze modulu byl navržen experimentální modul s cílem otestovat navržený koncept analýzy ve VUV oblasti metodou LIBS. Na základě testování byla navrhnuta finální verze založená na unikátním klínovém mechanismu. Funkční vzorek byl vyroben ve spolupráci s extérním výrobcem a vlastnosti modulu byly následně demonstrovány naměřením pěti certifikovaných ocelových standardů. Experiment určil limity detekce pro uhlík jako 0.028 hm.%. Nicméně, síra ani fosfor nebyly detekovány v žádném ze vzorků. Tato práce vytvořila modul nezbytný pro budoucí zkoumání metody LIBS v oblasti VUV v Laboratoři laserové spektroskopie v Brně.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22775号 / 工博第4774号 / 新制||工||1747(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 邑瀬 邦明, 教授 杉村 博之, 教授 宇田 哲也 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The bachelor thesis submitted deals with properties of electro-insulating lacquer hardenable by ultraviolent radiation and temperature. Within the theoretical part a summary of electro-insulating lacquers used in electrotechnics has been elaborated. Chemical changes that take place in this material group have been described during hardening process. A method of dielectric relaxation spectroscopy specifically focused on mathematic and physical description of polarisation and conductive mechanisms taking place in the structure of the given material has been closely studied. In the experimental part a workplace for hardening and long-term exposition of lacquered samples during simultaneous effect of various climatic elements has been designed and built. The selected electric and mechanical properties have been monitored on three sets of experimental samples prepared by means of different methodical procedures. The results gained have been mathematically evaluated and physically interpreted in term of methodical procedure of hardening and different temperature of measurement.