O Reservatório Taiaçupeba, localizado no estado de São Paulo, na divisa dos municípios Mogi das Cruzes e Suzano, faz parte do Sistema Produtor Alto Tietê SPAT. A água deste reservatório é captada pela ETA da Sabesp para tratamento e distribuição, abastecendo 3,1 milhões de pessoas. Para se avaliar possíveis riscos à qualidade da água deste importante reservatório; foram coletados quatro perfis de solo e quatro testemunhos de sedimento na área de influência do reservatório. Este trabalho teve como objetivo avaliar a concentração de atividade dos radionuclídeos naturais 238U, 226Ra,210Pb, 232Th, 228Ra, 228Th e 40K e realizar a caracterização química inorgânica determinando os elementos As, Ba, Ce, Co, Cr, Cs, Eu, Hf, K, La, Lu, Nd, Rb, Sb, Sc, Se, Sm, Ta, Tb, Th, U, Yb e Zn no solo e sedimento marginal. As técnicas analíticas empregadas foram a espectrometria gama de alta resolução e a análise por ativação com nêutrons instrumental (INAA), repectivamente. Realisou-se a análise do fator de enriquecimento FE para avaliar a contribuição antrópica nas concentrações dos elemento químicos obtidos por INAA, utilizando como referência os valores da Crosta Continental Superior CCS. Analisou-se, também, a composição granulométrica, o conteúdo de água e o teor de matéria orgânica para auxiliar na interpretação dos resultados obtidos. Na análise granulométrica os perfis de solo apresentaram maiores percentuais de fração fina (silte + argila), enquanto que os testemunhos de sedimento apresentaram em sua maioria maiores percentuais de fração grossa (areia). Todos os perfis de solo apresentaram umidade praticamente constante, entre 10% e 20%. O sedimento apresentou variação no conteúdo de água, no geral reduzindo com a profundidade, sendo esta mais acentuada em um dos testemunhos. Em relação à matéria orgânica constatou-se maiores percentuais médios nos testemunhos de sedimento. No estudo das concentrações dos radionuclídeos naturais, verificou-se as maiores concentrações de atividade para os radionuclídeos 40K,232Th e 228Th, no solo, e 232Th e 210Pb, no sedimento. Em relação à caracterização química inorgânica do solo e sedimento foram determinados altos valores para os elementos As e Sb (40 mg.kg-1 e 2,9 mg.kg-1) quando comparados com os valores da CCS (1,5 mg.kg-1 e 0,2 mg.kg-1), respectivamente. Um dos testemunhos apresentou concentração elevadíssima para o elemento Zn (concentração máxima de 38157 mg.kg-1 e média de 6602,6 mg.kg- 1) quando comparada aos valores da crosta continental superior (71 mg.kg-1), indicando forte contribuição antrópica. Na análise do fator de enriquecimento, além dos elementos citados acima, outros elementos como Ce, Co, Cr, Cs, Eu Hf, La, Lu, Nd, Sm, Tb, Th, U e Yb também apresentaram contribuição antrópica. / The Taiaçupeba Reservoir, located in the state of São Paulo, on the border of the municipalities of Mogi das Cruzes and Suzano, is part of the Alto Tietê Producer System - SPAT. The water from this reservoir is captured by Sabesp\'s ETA for treatment and distribution, supplying 3.1 million people. In order to evaluate possible risks to the water quality of this important reservoir, four soil profiles and four sediment cores were collected in the area of influence of the reservoir. The aim of this work was to evaluate the concentration of the natural radionuclides 238U, 226Ra, 210Pb, 232Th, 228Ra, 228Th and 40K and to perform the inorganic chemical characterization determining the elements As, Ba, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Se, Sm, Ta, Tb, Th, U, Yb and Zn in soil profiles and marginal sediment cores. The analytical techniques used were high resolution gamma spectrometry and instrumental neutron activation analysis (INAA), respectively. The analysis of the enrichment factor - EF was performed to evaluate the anthropic contribution in the concentrations of the chemical elements obtained by INAA, using as reference the values of the Upper Continental Crust UCC. The granulometric composition, the water content and the organic matter content were also analyzed to aid in the interpretation of the obtained results. In the particle size analysis, the soil profiles presented higher percentages of fine fraction (silt + clay), while the sediment samples showed in the majority of the cores higher percentages of coarse fraction (sand). The soil samples presented almost constant moisture in all profiles, varying from 10% and 20%. The sediment cores presented variation in the water content, generally reducing with the depth. Regarding organic matter, it was observed a higher mean percentage in the the sediment cores. In the study of the natural radionuclide concentrations the highest values determined were verified for the radionuclides 40K, 232Th and 228Th in the soil samples and 232Th and 210Pb in the sediment samples. In relation to the inorganic chemical characterization of soil and sediment, high values for As and Sb elements (40 mg.kg-1 and 2.9 mg.kg-1) were determined when compared to the values of UCC (1.5 mg. kg-1 and 0.2 mg.kg-1), respectively. One of the sediment cores presented very high concentration for the element Zn (maximum concentration of 38157 mg.kg-1 and mean value of 6602.6 mg.kg-1), higher than the value of UCC (71 mg.kg-1), indicating a strong anthropogenic contribution. In the analysis of the enrichment factor, other elements such as Ce, Co, Cr, Cs, Eu Hf, La, Lu, Nd, Sm, Tb, Th, U and Yb also presented anthropogenic contribution.

Dans un contexte de transition énergétique et de lutte contre le réchauffement climatique, la production d’éthanol de seconde génération semble une voie très prometteuse afin de réduire notre dépendance aux énergies fossiles. Il existe 3 étapes clés pour la production de ce nouveau biocarburant : le prétraitement qui permet de déstructurer la matrice lignocellulosique afin de rendre la cellulose plus accessible aux enzymes, l’hydrolyse enzymatique qui a pour but de produire des sucres fermentescibles et la fermentation qui permet de transformer ces sucres en éthanol. Actuellement, le prétraitement considéré comme le plus efficace, et principalement retenu par les industriels, est le prétraitement par explosion à la vapeur. Cependant, certains aspects comme les effets physicochimiques induits par le prétraitement ainsi que leurs impacts sur les caractéristiques de la biomasse prétraitée restent encore mal compris.Schématiquement, le prétraitement par explosion vapeur peut se décomposer en deux étapes : la première se rapproche d’une cuisson acide réalisée à 150-200°C durant 5 30 min et permet principalement l’hydrolyse des hémicelluloses, alors que la seconde est une détente explosive qui permet un éclatement mécanique du substrat rendant potentiellement la cellulose plus réactive à l’hydrolyse enzymatique. Globalement les effets de ce type de prétraitement sur la biomasse lignocellulosique sont aujourd’hui bien connus mais la compréhension des différents phénomènes physico-chimiques ayant lieu en son sein reste limitée. En effet le découplage de l’étape de cuisson et de l’étape de détente est délicat car, la température du réacteur (qui impacte principalement les réactions de cuisson) est directement liée à sa pression (qui impacte principalement la détente) par la thermodynamique des phases.Ce travail de thèse se propose donc de mieux appréhender l’ensemble des phénomènes physico-chimiques ayant lieu durant le prétraitement par explosion à la vapeur en s’appuyant notamment sur une discrimination expérimentale des phénomènes chimiques (réactions de dépolymérisation) et des phénomènes physiques (détente explosive) ainsi que sur une caractérisation multi-techniques et multi-échelles de la biomasse lignocellulosique obtenue après ce type de prétraitement. L’objectif est aussi de comprendre quelles sont les principales caractéristiques de la biomasse qui expliquent les différences de réactivité observées lors de l’étape d’hydrolyse enzymatique et d’expliquer l’impact du prétraitement par explosion à la vapeur sur les propriétés physicochimiques et donc sur la réactivité. / In a context of energy transition and climate change challenge, the production of second generation ethanol seems to be a very promising way to reduce our dependence on fossil fuels. There are 3 key steps for producing this new biofuel: pretreatment to decompose the lignocellulosic biomass and to make cellulose more accessible to enzyme attacks, enzymatic hydrolysis to produce fermentable sugars and fermentation to convert these sugars into ethanol. Currently, the pretreatment considered to be the most efficient, and mainly retained for industrialization, is the steam explosion pretreatment. However, some aspects such as the physicochemical effects induced by pretreatment and their impacts on the characteristics of pretreated biomass remain misunderstood.Schematically, the steam explosion pretreatment can be separated into two stages: the first is similar to an acid cooking carried out at 150-200°C during 5-30 min and allows mainly the hydrolysis of hemicelluloses, while the second is an explosive release which allows a mechanical bursting of the substrate potentially making the cellulose more reactive to enzymatic hydrolysis. As a whole, the effects of this type of pretreatment on lignocellulosic biomass are now well known, but the understanding of the different physicochemical phenomena occurring within it remains limited. Indeed, decoupling the cooking stage and the expansion stage is complicated because the reactor temperature (which mainly impacts the cooking reactions) is directly related to its pressure (which mainly impacts the explosive release) by the phase thermodynamics.This thesis work aims to better understand all the physicochemical phenomena occurring during a steam explosion pretreatment, based in particular on experimental discrimination of chemical phenomena (depolymerization reactions) and physical phenomena (explosive release) as well as on a multi-technical and multi-scale characterization of the lignocellulosic biomass obtained after this type of pretreatment. The objective is also to understand what are the main characteristics of biomass that explain the differences in reactivity observed during the enzymatic hydrolysis step and to explain the impact of the steam explosion pretreatment on the physicochemical properties and therefore the reactivity.

A exposição a fontes naturais de radiação contribui com mais de 98% da dose de radiação normalmente recebida da população; esta dose é principalmente atribuída à incorporação de radionuclídeos naturais das séries de decaimento do 238U e 232Th que possuem meia-vidas relativamente longas. A qualidade da água para consumo humano deve ser constantemente analisada e, um parâmetro muito importante analisado é a radioatividade natural presente. Quando os radionuclídeos naturais estão presentes em águas minerais há uma maior preocupação, pois estas águas podem conter concentrações moderadamente elevadas de 226Ra, 228Ra e 222Rn originalmente dissolvidas e dos radionuclídeos 210Pb e 210Po, que embora apresentem menores concentrações, contribuem para um aumento da irradiação interna e externa dos indivíduos. As áreas de estudo do presente trabalho foram os Parques das Águas de Cambuquira e Marimbeiro e de uma fonte particular de uma fazenda localizados na cidade de Cambuquira, Minas Gerais, onde as águas minerais são frequentemente utilizadas para consumo humano e uso médico. Assim, o objetivo deste trabalho foi determinar as concentrações de atividade dos radionuclídeos 226Ra, 228Ra e 210Pb e 210Po, avaliar as doses efetivas comprometidas devido ao consumo e fazer a caracterização química inorgânica destas águas minerais. Os radionuclídeos foram determinados por medida alfa e beta total e espectrometria alfa, após separação radioquímica em coletas realizadas sazonalmente. Para a caracterização química inorgânica foram determinadas as concentrações dos elementos As, Ag, Ba, Ca, Cd, Co, Cr, Cu Fe, K, Mn, Ni, Se, Ti e V por fluorescência de raios X. As concentrações de atividades dos radionuclídeos variaram de 4 ± 1 mBq/l a 509 ± 32 mBq/l para 226Ra, de 3,7 ± 0,1 mBq/l a 631 ± 27 mBq/l para 228Ra, de 5 ± 1 mBq/l a 60 ± 5 mBq/l para 210Pb e de abaixo do limite de detecção da metodologia a 36 ± 2 mBq/l para o 210Po. A dose efetiva comprometida máxima em adultos foi de 0,12 mSv/a para 226Ra, 0,32 mSv/a para 228Ra, 0,03 mSv/a para 210Pb e para 210Po 0,031 mSv/a. Dentre os elementos analisados por fluorescência de raios X, os elementos Ag, As, Cd, Cr, Cu, Ni, Se e Ti apresentaram valores abaixo do limite mínimo de detecção da metodologia. Os elementos Ba e Co, considerados contaminantes nas águas minerais, apresentaram valores maiores do que estabelecido pela ANVISA e CONAMA para águas minerais, respectivamente. No entanto, trabalhos da literatura brasileira realizados com água mineral de em outros locais apresentaram valores próximos ao do presente estudo, mostrando que concentrações acima do limite podem representar uma anomalia natural do aquífero. / Exposure to natural sources of radiation contributes more than 98% of the radiation dose normally received from the population; this dose is mainly attributed to the incorporation of natural radionuclides from the 238U and 232Th decay series which have relatively long half-lives. The quality of the water for human consumption must be constantly analyzed and, a very important parameter analyzed is the presence of the natural radioactivity. When the natural radionuclides are present in mineral waters there is a greater concern because these waters may contain somewhat high concentrations of 226Ra, 228Ra and 222Rn originally dissolved and the radionuclides 210Pb and 210Po, which, although presenting lower concentrations, contribute to an increase in irradiation both internal and external. The study areas of the present work were the Water Parks of Cambuquira and Marimbeiro and a private spring of a farm located in the city of Cambuquira, Minas Gerais, where the mineral waters are frequently used for human consumption and medical use. Thus, the objective of this work was to determine the activity concentrations of the radionuclides 226Ra, 228Ra and 210Pb and 210Po, to evaluate the committed effective doses and to perform the inorganic chemical characterization of these mineral waters due to their consumption. The natural radionuclides were determined by gross alpha and beta measurement and alpha spectrometry, after radiochemical separation in samplings carried out seasonally; for the inorganic chemical characterization the elements As, Ag, Ba, Ca, Cd, Co, Cr, Cu Fe, K, Mn, Ni, Se, Ti and V concentrations were determined by X-ray fluorescence. The activity concentrations of the radionuclides varied from 4 ± 1 mBq/l to 509 ± 32 mBq/l for 226Ra, from 3.7 ± 0.1 mBq/l to 631 ± 27 mBq/l for 228Ra, 5 ± 1 mBq/(LID) to 36 ± 2 mBq/l for the 210Pb and below the detection limit to 60 ± 5 mBq/l for 210Pb. The maximum committed effective doses in adults for 226Ra was 0,12 mSv/y, 0,32 mSv/y for 228Ra, 0,03 mSv/y for 210Pb and 0,031 mSv/y for 210Po. Among the elements analyzed by X-ray fluorescence, the elements Ag, As, Cd, Cr, Cu, Ni, Se and Ti presented values below the minimum limit of detection. The elements, such as Ba and Co, considered contaminants in mineral waters, presented higher values than established by ANVISA and CONAMA for mineral waters, respectively. However, Brazilian literature studies with mineral water from other sites presented values similar to the present study, showing that concentrations above the limit may represent a natural anomaly of the aquifer.

As esculturas de cera do Museu Alpino, no Brasil, compostas por diversos materiais orgânicos e inorgânicos, apresentaram um tipo de degradação da superfície a qual foi investigada cientificamente através de metodologia diversificada baseada no uso de técnicas complementares, com cruzamento dos resultados. As matérias primas assim como os produtos de degradação foram caracterizadas físico-química e analiticamente. Foram empregadas as técnicas: análise térmica (termogravimetria, termogravimetria derivada e calorimetria exploratória diferencial); espectroscopia no infravermelho; análise elementar e microscopia eletrônica de varredura com analisador de dispersão de energia de raios X. A MEV/EDS foi utilizada para inspeção da micro morfologia da superfície e através dela foi possível identificar a presença de microorganismos que estavam causando a degradação físico-química pela forma como se fixaram na superfície através de suas hifas e por utilizarem os ácidos graxos presentes na cera como substrato metabólico. Os resultados de FTIR constataram a diminuição de ácidos graxos na superfície deteriorada em relação à superfície em bom estado. A TG/DTG e DSC permitiram avaliar o comportamento térmico das matérias primas e das amostras retiradas das obras de arte. Foi constatada a teoria da obra de arte como parte do ecossistema e a importância da utilização de políticas de preservação dos bens culturais por meio de ambientes controlados. / The waxy sculptures from Museum Alpino in Brazil, made of different organics and inorganics materials, presented a kind of surface degradation, which was scientifically investigated by multi-step methodology based on the use of complementary techniques with the interconnection of results. The raw materials as well as the degradation products were characterized physical-chemical and analytically. It was applied the following techniques: thermal analysis (thermogravimery, derivated thermogravimetry and differential scanning calorimetry); infrared spectroscopy; elemental analysis and scanning electronic microscopy with X ray energy dispersion system. The scanning electronic microscopy was used for the inspection of the micro morphology of the surface and after that it was possible to identify the presence of microorganisms which were causing the physical-chemical degradation analyzing the way they fixed their hyphae on the surface and the use of fat acids as metabolic substrate. Observing the FTIR results it was possible to notice the reduction of the fat acids on the deteriorated surface compared to the good surface. TG/DTG e DSC allowed to known the thermal behavior of the raw materials and the art works samples. It was possible to realize the theory of the work of art as part of the ecosystem and the importance of the cultural property\'s preservation policy by controlled ambient.

Dans l’industrie, les sources d’expositions aux particules ultrafines (PUF) sont nombreuses et connues depuis longtemps. Ces particules quelles soient manufacturées ou non intentionnelles (générées au cours de procédés industriels) présentent des propriétés singulières qui impliquent des effets sur la santé différents de ceux induits par des particules de plus grande taille (micrométrique). L’étude spécifique des PUF nécessite donc le développement de méthodes de prélèvement et d’analyse adaptées permettant d’obtenir des informations pertinentes complémentaires à la masse totale de poussières prélevées. Cette métrique semblerait insuffisante pour caractériser correctement les effets toxiques des PUF. La thèse a donc été menée dans l’optique de disposer de méthodes dédiées à l’analyse des nanoparticules et en particulier sur la caractérisation chimique des particules en fonction de leur taille (couplage entre dispositifs de prélèvement en fonction de la taille des particules et méthode d’analyse). Les méthodes développées ont ensuite été testées sur des échantillons provenant soit de sites et/ou procédés industriels (fonderie, projection thermique) soit d’essais en laboratoire par prélèvement sur banc de génération de PUF. / Expositions to nanoparticles (NPs) are known in industrial hygiene for a long time. Either from primary or secondary sources (industrial processes), these particles have specific properties which imply different toxicities compared to larger particles (micrometric) from the same material. Therefore NPs study requires adapted sampling and analytical technique development and more specifically methods allowing to access relevant information other than total dust mass. The latter seems not be sufficient for toxic effect assessment. Thus, this work has been conducted in order to dispose of analytical methods dedicated to NPs and especially on size-dependent particle chemical analysis. Then, the developed methods have been applied on samples collected either from industrial sites and/or processes (smelter, thermal projection), either from NP generation bench.

O Reservatório Taiaçupeba, localizado no estado de São Paulo, na divisa dos municípios Mogi das Cruzes e Suzano, faz parte do Sistema Produtor Alto Tietê SPAT. A água deste reservatório é captada pela ETA da Sabesp para tratamento e distribuição, abastecendo 3,1 milhões de pessoas. Para se avaliar possíveis riscos à qualidade da água deste importante reservatório; foram coletados quatro perfis de solo e quatro testemunhos de sedimento na área de influência do reservatório. Este trabalho teve como objetivo avaliar a concentração de atividade dos radionuclídeos naturais 238U, 226Ra,210Pb, 232Th, 228Ra, 228Th e 40K e realizar a caracterização química inorgânica determinando os elementos As, Ba, Ce, Co, Cr, Cs, Eu, Hf, K, La, Lu, Nd, Rb, Sb, Sc, Se, Sm, Ta, Tb, Th, U, Yb e Zn no solo e sedimento marginal. As técnicas analíticas empregadas foram a espectrometria gama de alta resolução e a análise por ativação com nêutrons instrumental (INAA), repectivamente. Realisou-se a análise do fator de enriquecimento FE para avaliar a contribuição antrópica nas concentrações dos elemento químicos obtidos por INAA, utilizando como referência os valores da Crosta Continental Superior CCS. Analisou-se, também, a composição granulométrica, o conteúdo de água e o teor de matéria orgânica para auxiliar na interpretação dos resultados obtidos. Na análise granulométrica os perfis de solo apresentaram maiores percentuais de fração fina (silte + argila), enquanto que os testemunhos de sedimento apresentaram em sua maioria maiores percentuais de fração grossa (areia). Todos os perfis de solo apresentaram umidade praticamente constante, entre 10% e 20%. O sedimento apresentou variação no conteúdo de água, no geral reduzindo com a profundidade, sendo esta mais acentuada em um dos testemunhos. Em relação à matéria orgânica constatou-se maiores percentuais médios nos testemunhos de sedimento. No estudo das concentrações dos radionuclídeos naturais, verificou-se as maiores concentrações de atividade para os radionuclídeos 40K,232Th e 228Th, no solo, e 232Th e 210Pb, no sedimento. Em relação à caracterização química inorgânica do solo e sedimento foram determinados altos valores para os elementos As e Sb (40 mg.kg-1 e 2,9 mg.kg-1) quando comparados com os valores da CCS (1,5 mg.kg-1 e 0,2 mg.kg-1), respectivamente. Um dos testemunhos apresentou concentração elevadíssima para o elemento Zn (concentração máxima de 38157 mg.kg-1 e média de 6602,6 mg.kg- 1) quando comparada aos valores da crosta continental superior (71 mg.kg-1), indicando forte contribuição antrópica. Na análise do fator de enriquecimento, além dos elementos citados acima, outros elementos como Ce, Co, Cr, Cs, Eu Hf, La, Lu, Nd, Sm, Tb, Th, U e Yb também apresentaram contribuição antrópica. / The Taiaçupeba Reservoir, located in the state of São Paulo, on the border of the municipalities of Mogi das Cruzes and Suzano, is part of the Alto Tietê Producer System - SPAT. The water from this reservoir is captured by Sabesp\'s ETA for treatment and distribution, supplying 3.1 million people. In order to evaluate possible risks to the water quality of this important reservoir, four soil profiles and four sediment cores were collected in the area of influence of the reservoir. The aim of this work was to evaluate the concentration of the natural radionuclides 238U, 226Ra, 210Pb, 232Th, 228Ra, 228Th and 40K and to perform the inorganic chemical characterization determining the elements As, Ba, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Se, Sm, Ta, Tb, Th, U, Yb and Zn in soil profiles and marginal sediment cores. The analytical techniques used were high resolution gamma spectrometry and instrumental neutron activation analysis (INAA), respectively. The analysis of the enrichment factor - EF was performed to evaluate the anthropic contribution in the concentrations of the chemical elements obtained by INAA, using as reference the values of the Upper Continental Crust UCC. The granulometric composition, the water content and the organic matter content were also analyzed to aid in the interpretation of the obtained results. In the particle size analysis, the soil profiles presented higher percentages of fine fraction (silt + clay), while the sediment samples showed in the majority of the cores higher percentages of coarse fraction (sand). The soil samples presented almost constant moisture in all profiles, varying from 10% and 20%. The sediment cores presented variation in the water content, generally reducing with the depth. Regarding organic matter, it was observed a higher mean percentage in the the sediment cores. In the study of the natural radionuclide concentrations the highest values determined were verified for the radionuclides 40K, 232Th and 228Th in the soil samples and 232Th and 210Pb in the sediment samples. In relation to the inorganic chemical characterization of soil and sediment, high values for As and Sb elements (40 mg.kg-1 and 2.9 mg.kg-1) were determined when compared to the values of UCC (1.5 mg. kg-1 and 0.2 mg.kg-1), respectively. One of the sediment cores presented very high concentration for the element Zn (maximum concentration of 38157 mg.kg-1 and mean value of 6602.6 mg.kg-1), higher than the value of UCC (71 mg.kg-1), indicating a strong anthropogenic contribution. In the analysis of the enrichment factor, other elements such as Ce, Co, Cr, Cs, Eu Hf, La, Lu, Nd, Sm, Tb, Th, U and Yb also presented anthropogenic contribution.

<p>Opisane su sinteze, fizičko-hemijske i strukturne karakteristike kompleksa Cu(II), Co(II), Co(III), Ni(II), Fe(III), Cr(III) Zn(II) i Cd(II) sa PLSC, PLTSC i PLITSC. Dobijene su dve nove protonovane forme liganda PLSC, kao i od ranije poznati neutralna forma PLSC i protonovana forma PLTSC ali u vidu monokristala pogodnih za rentgeno-strukturnu analizu i 37 kompleksa, od čega je 12 okarakterisano rentgeno-strukturnom analizom. U zavisnosti od pH sva tri liganda se mogu koordinovati kao neutralni, mono-, odnosno, dianjoni sa uobičajenim ONO, ONS i ONN setom donorskih atoma, respektivno, pri čemu neutralna i monoanjonska forma liganada postoji u obliku zwitter-jona. U slučaju PLTSC a na primerima dva dimerna kompleksa bakra nađen je i ređi tetradentatni ONSO način koordinacije, tj. uče&scaron;će i atoma kiseonika hidroksimetil grupe kao mostovnog atoma. Sva tri liganda sa Cu(II), nezavisno od stehiometrije Cu:ligand, daju mono(ligand) komplekse kvadratno-planarne, kvadratno-piramidalne ili oktaedarske strukture, a sa kobaltom mono- i bis(ligand) oktaedarske komplekse. Dobijenim mono(ligand) kompleksima Zn(II) sa sva tri liganda je pripisana najmanje tetra-, odnosno pentakoordinacija, dok je me&scaron;ovitim PLSC(PLTSC)/NCS i bis(ligand) kompleksima Cr(III), i mono(ligand) kompleksu Fe(III) sa PLTSC pripisuje oktaedarska struktura. Ni(II) sa PLTSC i PLITSC daje mono- i dinuklearne komplekse, dok Cd(II) sa istim ligandima gradi mono(ligand) komplekse. Sva jedinjenja su okarakterisana parcijalnom mikroanalizom, IR-spektrima i konduktometrijskim merenjima, a odabrani kompleksi rentgeno-strukturnom, termogravimetrijskom i toksikolo&scaron;kom analizom.</p> / <p>The work describes the syntheses, physico-chemical, structural and antibacterial characteristics of Cu(II), Co(II), Co(III), Zn(II), Ni(II), Fe(III), Cr(III) and Cd(II) complexes with semi-, thiosemi- and S-methylisothiosemicarbazones. The result of the syntheses was 2 new ligand forms and 37 complexes, of which 12 were characterized by X-ray structural analysis. Depending of the pH, all three ligands can be coordinated either as neutral, monoanion, or dianion, using ONO, ONS and ONN set of donor atoms, respectively, whereby the neutral and monoanionic forms of the ligands exist in the form of zwitter-ions. All three ligands form with Cu(II), irrespective of the stoichiometry Cu:ligand, give mono- and dinuclear complexes of square-planar, square-pyramidal and/or octahedral configuration and with cobalt mono- and bis(ligand) octahedral complexes. The obtained mono(ligand) complexes of Zn (II) with all three of ligands is attributed to the at least tetra-, or pentacoordination, while the mono- and bis(ligand) complexes of Cr(III) with PLSC and PLTSC, and mono (ligand)complex of Fe(III) with PLTSC attributable to octahedral structure. Ni(II) with PLTSC and PLITSC forms mono- and binuclear complexes, and Cd(II) with the same ligands forms mono(ligand) complexes. All the compounds were characterized by partial microanalysis, IR spectra and conductometric measurements, while some selected complexes were examined by X-ray structural, thermogravimetric and toxicological analysis.</p>

L’objectif de cette thèse est de développer des matériaux polymérisés par rayonnement ultra-violet possédant une bonne balance des propriétés thermomécaniques entre résistance à la température, rigidité (strength) et résistance à l’impact. Une direction vers cet objectif est l’utilisation de résines (meth)acrylate modifiées avec des thiols polyfonctionnels. Cependant, les thiol-ene en général sont sujets à un problème de polymérisation prématurée incontrôlée même à l’abri de la lumière. Ce problème doit être traité puisque celui-ci conditionne le succès des thiol-ene dans le domaine des photopolymères. La première partie de cette thèse concerne l’élaboration de résine (meth)acrylate modifiée par l’incorporation d’un polythiol, le pentaerythritol tetrakismercaptopropionate (PETMP), à différents ratio. Les propriétés thermomécaniques et photochimiques de ces résines sont à l’étude. La seconde partie traite du problème de polymérisation prématurée incontrôlée des thiol-ene. Une étude de stabilité thermique aboutissant à des résultats très encourageant est proposée. Finalement, la dernière partie porte sur la caractérisation des réseaux photo-réticulés par pyrolyse-GC/MS. La compréhension de la constitution des réseaux tridimensionnels devraient apportés des avancées dans l’élaboration de nouveaux matériaux. Une nouvelle méthode de caractérisation utilisant la pyrolyse-GC/MS directe à multi-étapes est développée. Enfin, des résultats sur l’application de la méthode sur des matériaux à base de (meth)acrylate difonctionnel photopolymérisés ainsi qu’une tentative de caractérisation de matériaux à base de polythiol/(meth)acrylates photopolymérisés sont reportés puis discutés. / This thesis fall within an approach aiming to develop UV-processed materials having a good thermo-mechanical properties balance between strength, temperature resistance and impact resistance. A direction toward this objective is the use of photocurable (meth)acrylate resins modified with polyfunctional thiols. Indeed, thiol-ene chemistry is known to have poor sensitivity toward oxygen inhibition, to improve the dimensional stability and toughness properties of photocured materials. However, thiol-ene resins are subjected to premature uncontrolled dark polymerization, an issue that has to be solved for their success in the photopolymers area. The first part of this work is focused on the thermo-mechanical and the photopolymerization properties investigation of a pentaerythritol tetrakismercaptopropionate (PETMP) modified (meth)acrylate based resin by looking at different ratio of polythiol/(meth)acrylate. The second part is dedicated to the understanding of the thermal instability of such systems and to the solving of this issue. Finally, a special interest is brought to the characterization of photopolymeric networks by pyrolysis-GC/MS. The lake of deep understanding and view about how the cured networks are really constituted due to the difficulty to analyze insoluble cured polymers, prevents improvements in the formulation of high performance materials. Further information on cured networks constitution could bring useful information for the elaboration of new materials. A new characterization method based on direct multi-step pyrolysis-GC/MS is developed and an attempt on the characterization of polythiol (meth)acrylate material by Py-GC/MS is reported and discussed.

L’hydroxyapatite est l'un des matériaux les plus fréquemment utilisés pour le traitement des maladies des tissus durs. Le zinc est impliqué dans chaque étape du métabolisme du tissu osseux et une carence en zinc peut déterminer l'apparition de l'ostéoporose. Le dopage de l'hydroxyapatite par des ions de zinc peut créer un meilleur matériau, avec des propriétés physico-chimiques supérieures. L'objectif de cette thèse est de créer de nouveaux matériaux biocéramiques avec des propriétés spécifiques qui pourraient permettre le développement de nouvelles applications dans le domaine médical. Une attention particulière a été portée à la caractérisation des propriétés biologiques et physico-chimiques. Dans cette thèse, une nouvelle méthode non destructive de caractérisation de nanoparticules de céramique a été développée. La thèse se compose de six chapitres. Les deux premiers décrivent les biomatériaux et les techniques de caractérisation physico-chimique et ultrasonore utilisées, les trois chapitres suivants présentent des résultats expérimentaux originaux et le dernier chapitre des conclusions générales. La nouveauté de cette étude réside dans la caractérisation de matériaux biocéramiques à base d'hydroxyapatite pour de possibles applications biomédicales. Une nouvelle méthode non destructive de caractérisation par ultrasons est présentée. Ces résultats pourraient contribuer à développer une technique rapide et efficace pour la caractérisation de matériaux céramiques, qui pourrait être utilisée dans le futur en complément des techniques communément utilisées dans le domaine médical, notamment dans le domaine orthopédique. / Hydroxyapatite is one of the most commonly used material used for treating hard tissue diseases. Zinc is involved in each stage of bone tissue metabolism and a lack of it may determine the onset of osteoporosis. Doping hydroxyapatite with Zn ions may cause an improvement of the hydroxyapatite properties, thus resulting a better material, with enhanced physico-chemical properties. Devices based on collagen and hydroxyapatite inhibit the development of bacterial pathogens, reducing the risk of post-surgical infections. The goal of this thesis was to create new bioceramic materials with specific properties which could allow development of new applications in the medical field. Special attention was paid to the characterization of the physico-chemical and biological properties. In this thesis are reported for the first time non-destructive, ultrasonic spectroscopy studies performed on ceramic solutions. The thesis consists of six chapters, the first two comprised of general aspects, the following three chapters present original experimental results and the last chapter presents general conclusions. The novelty of this study lies in the method of synthesis and characterization of bioceramic materials based on hydroxyapatite for possible biomedical applications. Furthermore, a new non-destructive method of characterization techniques based on ultrasounds is presented. The results presented in this study could create a premises of developing a rapid and effective technique for characterization of ceramic materials, which could be used in the future as a complementary technique widely used on different materials used in the medical field, especially in the orthopedic field.

[pt] O objetivo do presente estudo consistiu na obtenção, caracterização mecânica e química das fibras de bucha vegetal (Luffa cylindrica) utilizadas, e o emprego das mesmas como possível reforço de compósitos cimentícios. Inicialmente, as fibras de bucha foram encaminhadas à prensa mecânica para perder o seu formato cilíndrico, propiciando uma moldagem mais facilitada, dos posteriores compósitos. A partir daí, foram submetidas a ensaio de tração direta, dividindo-se entre filamento e tecido, difração de raios-x (DRX), espectroscopia de infravermelho (IV), microscopia eletrônica de varredura (MEV) e análise em microscópio digital, com posterior análise em software digital. A matriz foi dosada, respeitando uma substituição parcial de 50 porcento de cimento, por materiais pozolânicos, como 40 porcento de metacaulinita e 10 porcento de cinza volante, com o objetivo de diminuir a quantidade de Hidróxido de Cálcio (HC), produto oriundo da hidratação do cimento. Também foi utilizado superplasticante na confecção da pasta, para melhorar a fluidez e assegurar que toda a área do molde fosse preenchida, além de prover o encharcamento uniforme da fibra. A caracterização química matriz se deu através do ensaio de termogravimetria (TGA), o qual foi capaz de corroborar a baixa presença de HC, propiciando a incorporação de fibras vegetais nessa matriz. As propriedades mecânicas foram avaliadas a partir de ensaio de flow tabe, de resistência à compressão e à flexão. O composto com a matriz supracitada foi confeccionado com as fibras de bucha vegetal nas direções do carregamento e posteriormente encaminhados ao ensaio de flexão de três pontos. Para agregar valor à discussão, foi fabricado um compósito sanduíche com a fibra de sisal (Agave sisalana) em conjunto com a fibra de bucha. Os compósitos cimentícios reforçados por fibra de bucha, e o compósito sanduíche apresentaram valores de resistência 33 porcento maiores, em relação aos corpos de prova moldados apenas com a matriz (sem reforço). / [en] The objective of this study was to obtain, mechanical and chemical fibre characterization of Loofah (Luffa cylindrica) used, and the use of same as possible reinforcement of cementitious composites. Initially, Loofah fibres were forwarded to the mechanical press for losing your cylindrical format, providing a more facilitated, molding of composite posterior. From there, were subjected to direct tensile test, dividing her time between filament and fabric, x-ray diffraction (XRD), infrared spectroscopy (IV), scanning electron microscopy (SEM) and microscope analysis Digital, with further analysis in digital software. The array was dosed, respecting a partial substitution of 50 per cent cement, Pozzolanic materials, such as 40 per cent metacaulinite and 10 per cent fly ash, with the goal of reducing the amount of calcium hydroxide (CH), native of cement hydration product. Superplasticizer was also used in the making of the folder, to improve the fluidity and ensure that the entire area of the mold were filled equally, in addition to providing the drenching fiber uniform. Chemical characterization through array of Thermogravimetry (TGA), which was able to corroborate the low presence of CH, resulting in the incorporation of vegetable fibers in this array. The mechanical properties were evaluated from flow tabe test, compression and flexural strenght. The compound with the above-mentioned matrix was made with Loofah fibres in the directions of loading and subsequently forwarded to the three-point flexural test. To add value to the discussion, made a sandwich composite with sisal fiber (Agave sisalana) in conjunction with the Loofah fiber. The cementitious composites reinforced by loofah fiber, and sandwich composite presented values of maximum 33 per cent larger in relation to specimens only molded array (no reinforcement), although it is not an improvement as significant as found in other synthetic or natural fibers, already studied and some in use by industry.