Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14634号 / 工博第3102号 / 新制||工||1461(附属図書館) / 26986 / UT51-2009-D346 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 大塚 浩二, 教授 木村 俊作, 教授 松原 誠二郎 / 学位規則第4条第1項該当

This thesis reports the design, synthesis, optical resolution of polypyridyl metal complexes and their molecular recognition of DNA. These metal complexes have been synthesised to bind DNA intercalation in a sequence selective manner. Modifications have manipulated the intercalative segments to bind to DNA in a rigid fashion by appending chemical groups directly to the aromatic extensions of the fragment. Also the ancillary non-intercalative ligands comprised of either bidentates or tetradentates, have been specifically chosen to deliver appended groups along the DNA sugar phosphate backbone, for hydrogen bonding and van der Waals interactions. Classical and chromatographic separation methods were investigated to separate the optical isomers of these ruthenium (II) complexes. A liquid recycling chromatography system was most successfully employed. Stereoselective synthesis was also investigated. Ultimately, it has been shown that the systematic modification of simple metal complexes is a useful method in determining the interactions of simple metal for nucleic acids. / Doctor of Philosophy (PhD)

L’énantiomère R (énantiomère cible) d’un mélange racémique d’une molécule organique est isolé par cristallisation du sel diastéréoisomère qu’il forme préférentiellement en s’associant à l’acide énantiomériquement pur R-acétyl(L)valine. Cependant l’énantiomère S (contre-énantiomère) peut aussi cristalliser sous forme d’un sel de R-acétyl(L)valine. Les solubilités des deux sels sont déterminées par des cristallisations par refroidissement en réacteur fermé. La modélisation de ces données expérimentales permet de maximiser la quantité d’énantiomère R cristallisé en sel pur en réacteur fermé à une température choisie. Cette température est ensuite augmentée : la durée de filtration des cristaux, systématiquement obtenus sous forme d’aiguilles, est avantageusement réduite. Une réduction est encore obtenue en appliquant un profil de refroidissement favorisant la croissance des cristaux : au final, l’amélioration de la filtrabilité des cristaux est corrélée aux augmentations conjointes du facteur d’élongation et de la longueur des cristaux. La cristallisation est ensuite transposée à un mode de fonctionnement continu en injectant les réactifs séparément dans un réacteur ouvert. Afin d’atteindre des performances égales à celles du réacteur fermé, le temps de passage et la concentration de la solution de R-acétyl(L)valine sont ajustés : il en résulte une productivité accrue de la cristallisation. La filtrabilité des cristaux obtenus en réacteur continu reste cependant médiocre. Bien que toujours inférieur à celui atteint en réacteur fermé optimal, le facteur d’élongation des cristaux est tout de même augmenté en optant pour une configuration de cascade de deux réacteurs continus / The R enantiomer (target enantiomer) of the racemic mixture of an organic molecule is isolated by a preferential crystallization of the salt it forms by association with the enantiomerically pur acid R-acetyl(L)valine. The S enantiomer (counter enantiomer) may somehow also crystallize under the form a R-acetyl(L)valinate salt. Solubilities of the two salts are measured by cooling crystallizations in a batch reactor, carried out for various stoechiometric conditions. The interpretation and the modelisation of the experimental data gathered lead to the maximisation of the quantity of R enantiomer crystallized as a pur salt in a batch reactor by cooling crystallization to a given temperature. This temperature is then increased : the filtration duration of the crystals, always exhibiting the shape of needles, is thus advantageously decreased. A further decrease is made possible by applying a temperature cooling profile that promotes the growth of crystals. Finally, the enhancement of the filterability of crystals is correlated to an increase of the elongation factor of crystals. The crystallization is then transposed to a continuous operating mode : reactants are injected separately in a continuous stirred tank reactor. With a view to match the results of the optimized batch reactor, the residence time and the R-acetyl(L)valine concentration are adjusted : a better productivity is then obtained, though filterability remains lower. The elongation factor is slightly increased by implementing two continous stirred tank in serie. The complete range of possible enhancements of crystals morphology by such cascades could be further studied for such needle-like crystals

Inom materialforskning och en stor del av den mekaniska och mekatroniska industrin finns ett intresse av att utnyttja blixtröntgen för att studera dynamiska händelseförlopp i inneslutna system, ej synbara med konventionella kameror. I och med att många rörelser inom de benämna områdena även sker i hyperhastighet så tillåter blixtröntgen statisk bildtagning  av rörelser i flera km/s, med minimal rörelseoskärpa. Detta examensarbete har grundats i att utveckla och utvärdera koncept för en komplett systemuppställning inklusive höghastighetskamera för denna tillämpning.  Syftet med arbetet har således varit att både identifiera och definiera produktens ingående produktkrav, för att spegla den funktion och syftet som önskas uppfyllas, och utifrån detta generera koncept för uppställningen på systemnivå, samt för separata  komponenter. Slutligen har de utvalda koncepten utvärderats genom praktiska prestandatester för att kontrollera dess uppfyllelse av produktkraven. Datainsamlingen för arbetet skedde i form av flertalet praktiska experiment för insamling av kvantitativ data, samt återkommande uppföljningsmöten med involverade medarbetare för insamling av kvalitativ data.  Undersökningen resulterade i ett koncept för en slutprodukt, benämnt funktionsprototyp som motsvarade och uppfyllde de definierade produktkraven vad gäller funktionalitet och prestanda. En diskussion fördes även för den kommande vidareutvecklingen av slutprodukten, inklusive färdigställandet av samtliga koncept och den följande designfasen. / In materials research and a large part of the mechanical and mechatronic industry, there is an interest in using flash X-rays to study dynamic events in enclosed systems, not visible with conventional cameras. Since many movements within the named areas also take place at hyper-speed, flash X-rays allow to capture static images of movements in several km / s, with minimal distortion. This thesis has been based on developing and evaluating concepts for a complete system setup including a high speed camera for this application. The purpose of the work has thus been to both identify and define the product's included product requirements, to reflect the function and purpose that is desired to be fulfilled, and based on this generate concepts for the set-up at system level, as well as for separate components. Finally, the selected concepts have been evaluated through practical performance tests to check its compliance with the product requirements. The data collection for the work took place in the form of two practical experiments for the collection of quantitative data, as well as recurring follow-up meetings with involved employees for the collection of qualitative data. The study resulted in a concept for an end product, called an end concept that corresponded to, and met the defined product requirements in terms of functionality and performance. A discussion was also held for the further development of the end product, including the completion of all concepts and the subsequent design phase.