京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22494号 / 農博第2398号 / 新制||農||1076(附属図書館) / 学位論文||R2||N5274(農学部図書室) / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 小川 順, 教授 栗原 達夫, 教授 加納 健司 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Submitted by MATHEUS ANTONIO DA SILVA null (0118999881999119725i@gmail.com) on 2016-08-12T01:55:42Z No. of bitstreams: 1 Corrigida dissertação2.pdf: 2484322 bytes, checksum: 10738553dadaaf9fdbd738efd3bb2d48 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-08-12T13:34:14Z (GMT) No. of bitstreams: 1 silva_ma_me_sjrp.pdf: 2484322 bytes, checksum: 10738553dadaaf9fdbd738efd3bb2d48 (MD5) / Made available in DSpace on 2016-08-12T13:34:14Z (GMT). No. of bitstreams: 1 silva_ma_me_sjrp.pdf: 2484322 bytes, checksum: 10738553dadaaf9fdbd738efd3bb2d48 (MD5) Previous issue date: 2016-07-08 / Tratou-se e modificou-se o argisolo caulinítico da região amazônica, a fim de se obter novos materiais para remoção de contaminantes da fase aquosa. As modificações fora realizadas por dois métodos: tratamento térmico em presença de fibra de cana de açúcar e modificação com surfactantes em solução; com posterior utilização dos materiais modificados na adsorção do corante Azul de Metileno (AM), usado como sonda espectrofotométrica. Tratou-se o argisolo com ataque ácido e troca de cátions e posterior calcinação a 400 0C com e sem fibra, e a 800 0C sem fibra. Os sólidos foram caracterizados por difratometria de raios X, espectrofotometria na região do infravermelho e análise térmica. Procedeu-se também a adsorção do AM em argisolo em presença de surfactante catiônico, Brometo de Cetiltrimetilamônio, e aniônico, Dodecil Sulfato de sódio. O argisolo sem calcinação apresentou apenas argila caulinita e quartzo como constituintes com cristalinidade. As amostras calcinadas a 400 0C com fibra e a 800 0C sofreram o processo de desidroxilação, ocasionando a mudança de fase da caulinita presente no argisolo; com a amostra calcinada a 400 0C sem fibra mantendo a estrutura característica da caulinita e do quartzo. Por meio da análise térmica, foi possível notar que a energia liberada pela fibra é suficiente para promover a mudança de fase da caulinita em temperaturas mais baixas em relação à mesma sem fibra, promovendo o processo de desidroxilação do material em condições ambientais mais brandas. Os estudos de variação no tempo de calcinação e de razão fibra:solo indicaram que ambos influenciam na desidroxilação do material e razões fibra:solo maiores que 1:2 e o tempo de três horas são as condições mais indicadas para a formação da metacaulinita. As isotermas de adsorção de AM evidenciam uma mudança na forma da isoterma de adsorção, onde o argisolo calcinado a 400 0C sem fibra e sem calcinação possuem isotermas do tipo L e maior correlação ao modelo de Freundlich, característicos de adsorção favorável e em multicamadas; enquanto os materiais calcinados a 800 0C e a 400 0C com fibra exibem isotermas do tipo C e correlação com o modelo de Langmuir, comuns a materiais de superfície microporosa e em monocamada. Os estudos de adsorção na presença de surfactantes evidenciaram que a interação do surfactante catiônico com o argisolo e do corante aniônico com o AM desfavoreceram a adsorção e resultaram em menor remoção do corante da fase aquosa. / Kaolinitic clay soil of Amazon region was treated and modified,in order to obtain new materials for removal of contaminants from aqueous phase. The modification was performed by two methods: thermal treatment in presence of sugar cane fiber and modification with surfactants; using the new materials in adsorption of Methylene Blue (AM), used as spectrophotometric probe. The clay soil was treated with acid attack, cation change and after calcination at 400 0C with and without sugar cane fiber, and at 800 0C. All material was characterized by X-ray Diffraction, Infrared spectrophotometry and thermal analysis. Adsorption of AM was proceed in presence of cationic (Cetyltrimethylammonium Bromide) and anionic (Sodium Dodecyl Sufate) surfactants. Samples of clay soil without calcination presents only kaolinite and quartz as compounds with cristallinity. Clay soil calcined at 400 0C with fiber and 800 0C were dehydroxyled, causing a phase change form kaolinite to metakaolin; when the kaolinite structure was maintained in clay soil calcined at 400 0C without fiber. In thermal analysis, the energy released by the fiber is sufficient to cause the phase change of kaolinite at lower temperatures relative to the same without fiber, promoting the process of dehydroxylation of the material in softer environmental conditions. The variation in time of calcination studies and ratio fiber:clay evidence that both influence the dehydroxylation and rates fiber:clay larger than 1:2 and the time of three hours are the best conditions for formation of metakaolin. Adsorption isotherms of AM exhibit changes in isotherms format, clay soil calcined at 400 0C without fiber and clay soil without calcination shows L-type isotherms and best correlation with Freundlich model, typical for favourable multiple layered adsorption; when the materials calcined at 400 0C with fiber and 800 0C shows C-type and correlation with Langmuir isotherms, typical monolayered adsorption in materials with microporous surface. The study of adsorption in presence of surfactants indicated that interactions among cationic surfactant with claysoil and anionic surfactant with AM prejudicing the adsorption of AM and results in less dye remotion of aqueous phase.

The first part of the thesis discuss general characterization of heterogeneous processes in silicates. This part is focused on kinetics of heterogeneous processes and mathematical description of reactions time behavior. The other part describes important technologies in silicate industry such as sintering, solid matter decomposition, transition modification, etc. Another chapter deals mineralogy, structure and properties of eminent silicate raw materials. Emphases is given to characterization of clay minerals and their utilising. The experimental part handle the analytic techniques used for investigation of thermal decompostion, dehydroxylation, crystalization of Al-Si spinel phase and sintering process of washed kaolin Sedlec Ia from the region Carlsbad (Czech Republic). Concluding chapter reports on results of experimental work.

La multivalence est reconnue en tant qu’outil permettant d’augmenter le pouvoir d’inhibition d’un inhibiteur. La mise en évidence, en 2010, d’un effet multivalent puissant sur l’inhibition des glycosidases par un iminosucre multivalent a ouvert la voie vers la synthèse de clusters toujours plus puissants. En 2016, un composé multivalent a permis d’atteindre une inhibition 173000 fois meilleure que le composé monovalent correspondant, ce qui équivaut à une augmentation record du pouvoir d’inhibition par iminosucre de 4800. La synthèse d’une nouvelle génération d’iminosucres multivalents à ligand affin pour sa cible, pour parvenir à augmenter encore l’effet multivalent, était mon objectif de thèse. Au cours de ce travail, de nouveaux iminosucres multivalents à motif gluco- ou mannoimidazole, très affin des mannosidases, ont été synthétisés. Ces composés multivalents ont permis de travailler sur deux projets parallèles : un projet fondamental et un projet appliqué. Le premier a consisté en l’étude de l’influence de l’affinité du ligand sur l’effet multivalent par mesure du pouvoir d’inhibition sur l’enzyme commerciale répondant le mieux à l’effet multivalent, l’α-mannosidase de Jack-bean. Les résultats montrent l’existence d’un effet multivalent notable mais sa valeur n’est pas aussi importante comparée aux études précédentes. Les iminosucres multivalents pouvant également cibler les glycosidases d’intérêt thérapeutique, nous nous sommes intéressés, dans le cadre du projet appliqué, au traitement de la mucoviscidose. L’idée était de viser les mannosidases I et II du réticulum endoplasmique pour permettre de secourir la protéine CFTR déficiente impliquée dans cette maladie. Malheureusement, aucun effet correcteur ni potentiateur n’a pu être observé pour nos composés. En marge de ces axes principaux, une méthode de déshydroxylation sélective a été optimisée et développée en élargissant son champ d’application et en apportant des preuves mécanistiques. / Multivalency is known to be a tool to drive inhibitors more potent. The multivalent effect, evidenced in 2010 with multivalent iminosugar on glycosidase inhibition, paved the way to the synthesis of multimeric inhibitors even more powerful. In 2016, an iminosugar cluster was reported to be 173 000 times more potent inhibitor compared to the monovalent reference. This is equal to an inhibitory potency enhancement of 4800 per iminosugar. The goal of my PhD was the synthesis of a new generation of multivalent iminosugars very potent towards their target, to keep increasing multivalent effect. New multivalent iminosugars with glycoimidazole motifs, with high affinity towards mannosidases, were synthetised. Those multivalent compounds allowed us to work on two parallel projects: a fundamental and an applied one. The first one focused on the influence of ligand affinity on multivalent effect by measuring the inhibition potency on the most sensitive to multivalent effect commercially available enzyme: the Jack-bean α-mannosidase. Results showed that multivalent effect was maintained but at a lower level than those reported previously. Multivalent iminosugars being also able to target glycosidases of therapeutic interest, we were interested in the treatment of cystic fibrosis. Targeting endoplasmic reticulum mannosidases I and II could restore the CFTR protein whose deficiency is the root cause of the disease. Unfortunately, no corrective or potentiation effect were observed. Aside those principal lines, a selective dehydroxylation method was optimized and developed widening the scope and providing mechanistic proofs.

This thesis focuses on the synthesis and characterisation of organoclays. X-ray diffraction has been used to study the changes in the basal spacings of montmorillonite clay and surfactant-intercalated organoclays. Variation in the d-spacing was found to be a step function of the surfactant concentration. Three different molecular environments for surfactant octadecyltrimethylammonium bromide (ODTMA) within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. High-resolution thermogravimetric analysis (HRTG) shows that the thermal decomposition of montmorillonite modified with ODTMA takes place in four steps attributing to dehydration of adsorbed water, dehydration of water hydrating metal cations, loss of surfactant and the loss of OH units respectively. In addition, it has shown that the decomposition procedure of DODMA and TOMA modified clays are very different from that of ODTMA modified ones. The surfactant decomposition takes place in several steps in the DODMA and TOMA modified clays while for ODTMA modified clays, it shows only one step for the decomposition of surfactant. Also TG was proved to be a useful tool to estimate the amount of surfactant within the organoclays. A model is proposed in which, up to 0.4 CEC, a surfactant monolayer is formed between the montmorillonite clay layers; up to 0.8 CEC, a lateral-bilayer arrangement is formed; and above 1.5 CEC, a pseudotrimolecular layer is formed, with excess surfactant adsorbed on the clay surface. While for dimethyldioctadecylammonium bromide (DODMA) and trioctadecylmethylammonium bromide (TOMA) modified clays, since the larger sizes of the surfactants, some layers of montmorillonite are kept unaltered because of steric effects. The configurations of surfactant within these organoclays usually take paraffin type layers. Thermal analysis also provides an indication of the thermal stability of the organoclay as shown by different starting decomposition temperatures. FTIR was used as a guide to determine the phase state of the organoclay interlayers as determined from the CH asymmetric stretching vibration of the surfactants to provide more information on surfactant configurations. It was used to study the changes in the spectra of the surfactant ODTMA upon intercalation into a sodium montmorillonite. Surfaces of montmorillonites were modified using ultrasonic and hydrothermal methods through the intercalation and adsorption of the cationic surfactant ODTMA. Changes in the surfaces and structure were characterized using electron microscopy. The ultrasonic preparation method results in a higher surfactant concentration within the montmorillonite interlayer when compared with that from the hydrothermal method. Both XRD patterns and TEM images demonstrate that SWy-2-Namontmorillonite contains superlayers. TEM images of organoclays prepared at high surfactant concentrations show alternate basal spacings between neighboring layers. SEM images show that modification with surfactant will reduce the clay particle aggregation. Organoclays prepared at low surfactant concentration display curved flakes, whereas they become flat with increasing intercalated surfactant. Fundamentally this thesis has increased the knowledge base of the structural and morphological properties of organo-montmorillonite clays. The configurations of surfactant in the organoclays have been further investigated and three different molecular environments for surfactant ODTMA within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. Changes in the spectra of the surfactant upon intercalation into clay have been investigated in details. Novel surfactant-modified montmorillonite results in the formation of new nanophases with the potential for the removal of organic contaminants from aqueous media and for the removal of hydrocarbon spills on roads.