Les travaux de recherche de cette thèse concernent sur la préparation et l’étude des propriétés physiques de nanocristaux commutables basés sur des matériaux de type transition de spin et photomagnétiques potentiellement candidats en tant que nanocapteurs. Les nanocristaux à transition de spin appartiennent à la famille des réseaux de coordination basés sur les chlatrates de Hoffman [Fe(pyrazine)] [Pt(CN)4]. L’étude se concentre sur le contrôle de la taille des nano-bâtonnets et sur l’étude de leur bistabilité thermique en relation avec leur environnement et de leur interaction avec les molécules invitées. Nous montrons que la croissance des nanocristaux en forme de bâtonnets est obtenue en présence de nanoparticules préformées de 2 à 3 nm de l’analogue du bleu de Prusse CsNiCr(CN)6, censées diriger la croissance anisotrope des objets. Les nano-bâtonnets formés sont stables pendant une longue période en solution en raison de leurs charges négatives. Ils possèdent une hystérèse thermique assez large centrée sur la température ambiante. La largeur et la position en température de l’hystérèse thermique dépendent de la nature de l'environnement des nanocristaux. Avec des sels d'ammonium à longue chaîne (tels que le bromure de dodécyltrimentylammonium ou le bromure de dexhyl triméthyl ammonium), l’hystérèse thermique se rétrécit et se décale vers les basses températures. Avec des chaînes alkyles plus courtes, le décalage de l’hystérèse est plus petit sans que sa largeur ne change beaucoup. Lorsque les tiges sont noyées dans une matrice de silice rigide, la transition est déplacée à très basse température et l'hystérésis thermique disparaît. L'insertion de molécules de I2 conduit à une hystérèse thermique plus large centrée sur une température plus élevée que la température ambiante. Les nanoparticules photomagnétiques appartiennent à la famille des réseaux bimétalliques d’analogues du bleu de Prusse (PBA) basés sur le CoFe. Ce type de matériaux peut subir une transition thermique de l'état paramagnétique CoIIFeIII à l'état diamagnétique CoIIIFeII. L'état de haute température peut ensuite être rétabli par un éclairage lumineux à basse température. Nous nous sommes concentrés sur trois types de nanoparticules de CoFe contenant les ions alcalins CsI (11 nm) et RbI avec deux tailles différentes : 30 et 80 nm pour ces dernières. La taille des objets était contrôlée par différents paramètres tels que la nature de l'ion alcalin, la concentration des précurseurs et leur stœchiométrie. La combinaison de différentes techniques, telles que les spectroscopies électronique et infrarouge, associée à la spectroscopie par résonance paramagnétique électronique et à la diffraction des rayons X sur poudre permet de suivre l’évolution de la composition des nanoparticules avec le temps en solution à la température ambiante. L’étude de l’évolution conduit à la conclusion générale que le phénomène de transfert d’électrons de CoII à FeIII se produit en solution pendant plusieurs jours avant que les objets n’atteignent leur état thermodynamique stable qui dépendait de la nature de l’ion alcalin et de la taille des objets. Le comportement (photo)magnétique a ensuite été étudié à l’état solide pour différents temps d’évolution des trois types de particules, ce qui a permis de proposer un mécanisme qualitatif de leur formation en solution. / The research work in this thesis is focused on the preparation and the study of the physical properties of switchable nanocrystals based on spin crossover and photomagnetic materials that are potential candidates as nanosensors. The spin crossover nanocrystals belong to the coordination network family based on the Fe(II) Hoffman chlatrates [Fe(pyrazine)][Pt(CN)4]. The study is focused on controlling the size of self-standing nanorods and on the investigation of their thermal bistability in relation with their environment and their interaction with guest molecules. We show that the growth of the rod-shaped nanocrystals is obtained in the presence of preformed 2-3 nm nanoparticles of the Prussian Blue Analogue CsNiCr(CN)¬6 that is thought to direct to anisotropic growth of the objects. The formed rods can be stable for a long time due to their negative charge. They possess a rather wide thermal hysteresis centered around room temperature. The width and position in temperature of the thermal hysteresis depends on the nature of the environment of the nanocrystals. With very long ammonium salt (such as dodecyl trimetylammonium bromide or dexhyl trimethyl ammonium bromide), the thermal hysteresis becomes narrower and shifts to low temperature. While with shorter alkyl chains, the shift of the hysteresis is smaller without much change in its width. When the rods are embedded in a rigid silica matrix, the transition is shifted to very low temperature and the thermal hysteresis vanishes. The insertion of I2 molecules leads to a wider thermal hysteresis centered at a higher temperature.The photomagnetic nanoparticles belong to the bimetallic Prussian Blue Analogues (PBAs) family based on CoFe. This type of materials may undergo a thermal transition from the paramagnetic CoIIFeIII state to the diamagnetic CoIIIFeII one. The high temperature state can then be restored at low temperature by light illumination. We focused on three types of CoFe PBAs nanoparticles containing the CsI (11 nm) and the RbI alkali ions with two different sizes 30 and 80 nm for the latter. The size of the objects was controlled by different parameters such as the nature of the alkali ion, the concentration of the precursors and their stoichiometry. The combination of different techniques such as electronic and infra spectroscopies together with Electron Spin Resonance Spectroscopy and X-ray powder diffraction allows following the evolution of the nanoparticles’ composition with time in solution at room temperature. The evolution study leads to the general conclusion that the electron transfer phenomenon from CoII to FeIII occurs in solution during several days before the objects reach their thermodynamic stable state that was found to depend on the nature of the alkali ion and on the size of the objects. The (photo)magnetic behavior was then investigated in the solid state for different evolution time of the three types of particles, which allowed proposing a qualitative mechanism of their formation in solution.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19992号 / 工博第4236号 / 新制||工||1655(附属図書館) / 33088 / 京都大学大学院工学研究科マイクロエンジニアリング専攻 / (主査)教授 田畑 修, 教授 北條 正樹, 教授 山田 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20166号 / 理博第4251号 / 新制||理||1611(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 松田 祐司, 教授 川上 則雄, 教授 前野 悦輝 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21247号 / 理博第4417号 / 新制||理||1634(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 石田 憲二, 教授 前野 悦輝, 教授 松田 祐司 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

While not accounting for a significant proportion of overall crashes, median crossover crashes in the state of Utah do account for a significant proportion of interstate fatalities. Due to the seriousness of median crossover crashes in the state of Utah, the need exists to evaluate the impact of median crossover crashes in the state, to identify locations where median crossover crashes may be occurring at particularly high rates, and to identify methods to help mitigate these crashes. Previous research has noted that median crossover crash rates appear to increase in the vicinity of interchanges. The purpose of this research, therefore, is to develop a strategy to mitigate median crossover crashes statewide and determine the role that the interchanges play in contributing to median crossover crashes. Fourteen years of crash data spanning the years 1992 through 2005 on Interstates 15, 70, 80, 84, and 215 were used to determine overall characteristics of median crossover crashes in Utah and determine the relationship between median crossover crashes and other types of crashes. Using a chi-square goodness of fit test, the distributions of median crossover crashes and all types of interstate crashes in the vicinity of interchanges were compared. Three-year median crossover crash rates spanning the years 2003 through 2005 for rural and urban areas were then used to identify which sections of Utah interstates are most prone to median crossover crashes. Finally, recommendations were made concerning appropriate median barrier installation for the 37 critical sections as identified by the three-year analysis.

Acutumine is a tetracyclic alkaloid isolated from the Asian vine Menispermum dauricum with selective T-cell cytotoxicity and antiamnestic properties. We have developed a total synthetic route to this congested alkaloid, during which we also found a novel, stereoselective radical-crossover reaction that combines an intramolecular radical conjugate addition with a subsequent enolate hydroxylation. Key features of this synthesis also include a reagent-controlled diastereoselective ketone allylation, an anionic oxy-Cope rearrangement to form a congested quaternary sterocenter, a pyridine-mediated selective ozonolysis, and a Lewis acid promoted Michael-type cyclization.

No description available.

Meiosis is the specialized process of cell division utilized during gametogenesis in all sexually reproducing eukaryotes, which consists of one round of DNA replication followed by two rounds of chromosome segregation and results in four haploid cells. Crossovers between homologous chromosomes promote proper alignment and segregation of chromosomes during meiosis. Crossover interference is a genetic phenomenon in which crossovers are non-randomly placed along chromosomes. Crossover assurance ensures that every homologous chromosome pair obtains at least one crossover during Prophase I. Crossovers physically connect homologous pairs, allowing spindle fibers to attach and separate homologs properly. However, some organisms have shown an ability to segregate chromosomes that fail to receive at least one crossover, a phenomenon termed distributive disjunction. In Saccharomyces cerevisiae, mutation of either Tid1 or Ndj1 results in a similar defect in crossover interference. The overall number of crossovers is not substantially different from the wild type, however they are distributed more randomly with respect to each other. In this thesis, the roles of Tid1 and Ndj1 on crossover assurance and distributive disjunction have been further elucidated through use of knock-out mutants and tetrad dissection. To analyze meiotic chromosome segregation in isogenic tid1 and ndj1 strains, the spore viability of dissected tetrads was utilized as an indirect measure of nondisjunction events. An elevated number of 2- and 0- spore viable tetrads were seen in ndj1, but not tid1 yeast, confirming previous results. Elevated 2- and 0- spore viable tetrads are an indication of meiosis I (MI) nondisjunction, commonly resulting from failure of crossover formation. These results suggest crossover assurance is disrupted in njd1, but not tid1 mutants. However, MI chromosome segregation is an indirect readout of crossover formation; distributive disjunction, for example, can lead to proper segregation of achiasmate chromosomes. To determine if distributive disjunction is functional in yeast, wild type, tid1 and ndj1 versions of diploid yeast carrying a single homeologous pair of chromosomes were constructed. These strains have one chromosome (chr. III or V) replaced with one from a closely related species of yeast. The homeologous chromosome functionally replaces the homolog, however crossovers are significantly reduced between homeologs. A spore viability pattern typical of MI nondisjunction was detected in ndj1 mutants, but not in tid1 mutants. In the context of these homeologs, this pattern is suggestive of a role for Ndj1, but not Tid1, in distributive disjunction. Further, these results suggest that tid1 and ndj1 mutant yeast may not be different in their competence for crossover assurance. To directly assay competence for crossover assurance in native mutants, the incidence of E0 chromosome pairs (those lacking crossovers) was determined. To do this we assayed crossover formation along the length of chromosome III of isogenic wild type, ndj1 and tid1 mutant strains. The incidence of E0 chromosomes was comparably elevated in both tid1 and ndj1 mutant yeast, suggesting that crossover assurance is nonfunctional in both strains. We find evidence that supports the idea that interference and assurance are genetically linked. Our data also suggests that distributive disjunction may be genetically separable from some meiotic genes.

Hybridization of two or more DNA or RNA strands is well documented for the process taking place with all strands free in solution or when one strand is immobilized on a substrate. This study contributes to the investigation of the hybridization process when two single DNA strands (ssDNA) are in close proximity. We took advantage of an X sensor in which hybridization of four DNA strands enables the formation of a DNA four-way junction (crossover or X) structure. We immobilized multiple layers of crossover structures to study its hybridization being triggered by short ssDNA coming from solution and further investigate how many layers of these structures can hybridize by the addition of only one ssDNA (called input). Using a molecular beacon as reporter, we combined crossover DNA strands that recognize the reporter sequence at one side and at the other, the sequence of its input or downward crossover layer. Fluorescent signal was detected by separation of the molecular beacon’s fluorophore and quencher, as it hybridizes with the system of layers. Immobilization of the X structures into the scaffold proved to increase their communication, in comparison to being free in solution. This evidence gives us significant information for the communication of hybridized layers in a localized system, showing a promising standard for development of multilayered logic gates. The potential of these crossover DNA strands using X structure include applications in the future of biological systems, nanotechnology, and target DNA recognition for its ability to quickly recognize a signal and propagate it through extended DNA nanostructure in a controlled manner.

No description available.