Submitted by PAOLA ANDREA ESCOBAR DIAZ null (paitopink@hotmail.com) on 2018-03-26T01:18:57Z No. of bitstreams: 1 Dissertação Mestrado Paola Andrea Escobar Diaz.pdf: 1634986 bytes, checksum: bc533d62e487cc8174926d75306e2f98 (MD5) / Approved for entry into archive by Alexandra Maria Donadon Lusser Segali null (alexmar@fcav.unesp.br) on 2018-03-26T10:54:22Z (GMT) No. of bitstreams: 1 diaz_pae_me_jabo.pdf: 1634986 bytes, checksum: bc533d62e487cc8174926d75306e2f98 (MD5) / Made available in DSpace on 2018-03-26T10:54:22Z (GMT). No. of bitstreams: 1 diaz_pae_me_jabo.pdf: 1634986 bytes, checksum: bc533d62e487cc8174926d75306e2f98 (MD5) Previous issue date: 2018-03-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O uso contínuo de fertilizantes minerais na agricultura promove o excesso de nutrientes como fósforo, nitrogênio e potássio o que ocasiona danos ao ecossistema e leva à alteração da microbiota do solo. Além disso, existe uma baixa eficiência das plantas em absorver e utilizar esses nutrientes o que gera perdas da adubação mineral. Neste sentido o uso de bactérias promotoras de crescimento de plantas (BPCP) é uma alternativa promissora para melhorar a eficiência das plantas na utilização dos fertilizantes minerais. O presente trabalho teve por objetivo avaliar o potencial de dez isolados Bacillus (oito isolados de Bacillus subtilis, um isolado de Bacillus velezensis e um isolado de Bacillus amyloliquefaciens) quanto à sua capacidade de promoção de crescimento na cultura de algodão em condições de vaso em casa de vegetação. O experimento foi realizado em delineamento inteiramente casualizado com 11 tratamentos e cinco repetições. Os parâmetros avaliados foram altura da planta, massa seca da parte aérea e raiz, teores de clorofila nas folhas, nitrogênio e fósforo na planta e no solo. A massa seca total (parte aérea e raiz) foi maior nos isolados 248 e 290 (B. subtilis), e maiores valores de altura das plantas foram obtidos para o isolado 248. O teor de clorofila nas folhas foi superior nas plantas inoculadas com o isolado 290, indicando que o mesmo foi capaz de aumentar a atividade fotossintética das plantas de algodão. Os teores de nitrogênio na parte aérea e na raiz foram superiores nos tratamentos com os isolados 248 e 290, o que indica que houve estabelecimento dessas bactérias na rizosfera melhorando a disponibilidade e absorção de nitrogênio pela planta. O teor de fosforo na raiz foi maior em plantas que receberam o isolado 001 (B. amyloliquefaciens) o que indica que esse isolado favorece a absorção de fósforo pela planta. O isolado 248 apresentou maior quantidade de fósforo solúvel disponível no solo o que demostra que B. subtilis atua positivamente na solubilização do fósforo. A análise molecular do DNA ribossomal 16S de isolados obtidos do reisolamento a partir do solo e raiz das plantas do algodão confirmam a identidade das linhagens utilizadas. Finalmente, os isolados 248 e 290 de B. subtilis têm a capacidade de aumentar os teores de clorofila e nitrogênio nas plantas, altura e matéria seca, e também solubilizam fósforo, o que os torna agentes potencias para uso como bioinoculantes nas plantas de algodão. / The continuous use of mineral fertilizers in agriculture promotes the excess of nutrients as phosphorus, nitrogen and potassium in the ecosystems which causes damages and leads to the instability of the soil microbiota. Moreover, a low efficiency of the plants to absorb and use these nutrients causes losses of the mineral fertilization, but the use of plant growth promoting bacteria (PGPB) is a promising alternative to improve plant efficiency in the use of mineral fertilizers implying in the reduction of its application on the crops. This work aimed to evaluate the potential of ten Bacillus strains (eight of B. subtilis, one of B. velezensis and one of B. amyloliquefaciens) about their capacity to promote growth of cotton seedlings on greenhouse conditions. The experiment was carried out in a completely randomized design with 11 treatments and five replicates. The parameters evaluated were plant height, dry matter of aerial part and root, chlorophyll content in leaves, nitrogen and phosphorus in the plant and soil. The total dry matter (aerial part and root) was higher to the isolates 248 and 290 of B. subtilis, and higher values of plant height were obtained for the isolate 248. The chlorophyll content in leaves was higher in plants inoculated with the isolate 290 what indicates that this isolate was able to increase the photosynthetic activity of cotton seedlings. The nitrogen content in the aerial part and roots was higher at the treatments with the isolates 248 and 290 indicating that the bacteria were established in the rhizosphere improving the nitrogen availability and absorption by the plant. The phosphorus content in the roots was higher in seedlings treated with the isolate 001 of B. amyloliquefaciens, what demonstrates that this isolate favors its uptake by the plant. The isolate 248 provided the highest amount of soluble phosphorus available in the soil, which shows that B. subtilis acts positively on phosphorus solubilization. The molecular analysis of 16S Ribosomal DNA from isolates obtained from reisolation from the soil and roots of cotton seedlings confirms the identity of the strains used at the experiment. Finally, isolates 248 and 290 of B. subtilis are able to increase nitrogen and chlorophyll contents in the plants, high and dry matter, and also solubilize phosphorus, which make them potential agents for use as bioinoculants in cotton plants. / Capes:1590076

Made available in DSpace on 2014-12-17T15:01:18Z (GMT). No. of bitstreams: 1 DiegoAAG_partesautorizadas.pdf: 1805054 bytes, checksum: 0bbdfaaf4272f15a091664e96c012ed7 (MD5) Previous issue date: 2009-03-06 / This work presents studies related to the use of microemulsions in the solubilization of heavy crude oil fractions responsible by the formation of deposits. The first stage of the work was addressed to the construction of phases diagrams, with the intention of determining the area within which the microemulsion is formed. The following systems were studied: UNITOL L 90 n-Butanol - Water - Kerosene (system 1); UNITOL L 90 - n-Butanol - Water - Xylene (system 2); UNITOL L 90 n-Butanol - Water - Kerosene/Xylene 10% (system 3); UNITOL L 90 - Sec-Butanol - Water - Xylene (system 4). In parallel experiments of physical adsorption were carried out by the static method, with the intention of simulating natural conditions of reservoirs. Crude oil of the Fazenda Bel?m field (Rio Grande do Norte), was used as solute, xylene as solvent and the Assu sandstone (Rio Grande do Norte, Brazil) and Botucatu sandstone (Paran?, Brazil) as rock reservoirs. The curves of adsorption presented the S format type, in agreement with the classification proposed by Giles, Smith and Huitson (1974). The solubilization process was accomplished in the batch method, by varying the time of agitation, the microemulsions and the solid/solution ratio. The experiments showed that the microemulsions presented high efficiency in the solubilization of the crude oil adsorbed on the sandstones. System 2 presented an efficiency of 99% for the Assu sandstone and 97% for the Botucatu sandstone / No presente trabalho foi avaliado o desempenho das microemuls?es na solubiliza??o de fra??es pesadas do petr?leo, respons?veis pela forma??o de dep?sitos. A primeira fase do trabalho foi direcionada ? constru??o dos diagramas de fases, com o intuito de determinar a regi?o na qual a microemuls?o ? formada. Os seguintes sistemas foram estudados: UNITOL L 90 n-Butanol ?gua Querosene (sistema 1); Unitol L 90 n-Butanol ?gua Xileno (sistema 2); Unitol L 90 n-Butanol ?gua Querosene/Xileno 10% (sistema 3); Unitol L 90 Sec-Butanol ?gua Xileno (sistema 4). Em paralelo foram conduzidos experimentos de adsor??o f?sica pelo m?todo est?tico, com o intuito de simular condi??es naturais de reservat?rio. Utilizou-se ?leo bruto do campo de Fazenda Bel?m, (Petrobras - Rio Grande do Norte), xileno como solvente, arenito Assu (Rio Grande do Norte, Brasil) e arenito Botucatu (Paran?, Brasil) como rochas reservat?rio. As curvas de adsor??o foram enquadradas no formato S , de acordo com a classifica??o proposta por Giles, Smith & Huitson (1974). O processo de solubiliza??o foi realizado em regime de batelada, variando o tempo de agita??o, as microemuls?es e a raz?o arenito/microemuls?o. Ensaios mostraram que os sistemas apresentaram alta efici?ncia na solubiliza??o do ?leo bruto adsorvido sobre os arenitos. O sistema 2 apresentou uma efici?ncia de 99% para o arenito Assu e 97% para o arenito Botucatu

Submitted by (lucia.rodrigues@ufrpe.br) on 2016-08-11T12:22:48Z No. of bitstreams: 1 Michelangelo de Oliveira Silva.pdf: 667109 bytes, checksum: d1d78400e5eb31539cdab86c7d14b716 (MD5) / Made available in DSpace on 2016-08-11T12:22:48Z (GMT). No. of bitstreams: 1 Michelangelo de Oliveira Silva.pdf: 667109 bytes, checksum: d1d78400e5eb31539cdab86c7d14b716 (MD5) Previous issue date: 2011-02-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / The exploration and understanding of the mechanisms of bacteria-plant interaction may be used in management systems that seek a sustainable production of several crops in agriculture, mainly sugar cane, which has great importance in today's economy. Therefore, the objective was to evaluate the diversity of bacteria (endophytic and rhizoplane) associated with different varieties of cane sugar grown in the Northeast and select bacteria with potential to promote plant growth (nitrogen fixing and phosphate solubilizing) for a possible reduction of fertilizer. Endophytic bacteria, leaf and root, and rhizoplane were isolated from three commercial varieties (RB 92579, RB 867515 and RB 863129) of cane sugar grown in the Northeast, in areas with and without the application of Termiticide and in two seasons (4 and 10 months) of plant development. The bacteria were isolated in 10% TSA media and selective media NFB and selected based on their ability to solubilize inorganic phosphate and nitrogen fixation. At the end of the process were isolated about 410 strains in rich media (TSA) and about 245 isolated media NFB(diazotrophic), that for both harvests. In the interaction bacteria-cane sugar, the total population of yellow and white bacteria was influenced by the varieties of cane and evaluated by plant tissues, and its management, and, moreover, it was concluded that the varieties of sugarcane sugarcane grown in the Northeast have a bacterial community associated with potential application to plant growth promotion, since they have the ability to fix nitrogen, solubilize inorganic phosphate and produce AIA. Plant cane sugar grown in Pernambuco has a distinct community of endophytic bacteria in relation to other producing states, some being identified as the genus Burkholderia, Pantoea, Klebsiella, Pseudomonas and Enterobacter. / A exploração e o conhecimento dos mecanismos de interação bactéria-planta poderão ser utilizados em sistemas de manejo que busquem uma produção sustentável de diversas culturas de interesse agrícola, principalmente a cana-de-açúcar, que exerce grande importância na economia atual. Portanto, o objetivo deste trabalho foi avaliar a diversidade de bactérias (endofíticas e do rizoplano) associadas a diferentes variedades de cana-de-açúcar, cultivadas no Nordeste e selecionar bactérias com potencial em promover o crescimento vegetal (fixadoras de nitrogênio e solubilizadoras de fosfato), para uma possível redução de fertilizantes. Bactérias endofíticas, de folha e raiz, e do rizoplano foram isoladas de três variedades comerciais (RB 92579, RB 867515 e RB 863129) de cana-de-açúcar, cultivadas no Nordeste, em áreas com e sem aplicação de cupinicida e em duas épocas (4 e 10 meses) de desenvolvimento da planta . As bactérias foram isoladas em meio TSA 10% e no meio seletivo NFb e selecionadas quanto a sua capacidade de solubilizar fosfato inorgânico e fixar nitrogênio. No final do processo foram isoladas cerca de 410 isolados em meio rico (TSA) e cerca de 245 isolados em meio NFb (diazotroficas), isso para ambas épocas de coleta. Na interação bactéria-cana-de-açúcar, a densidade populacional total, de bactérias amarelas e brancas foi influenciada pelas variedades de cana avaliadas e pelos tecidos vegetais, e pelo manejo e, além disso, foi possível concluir que as variedades de cana-de-açúcar cultivadas no Nordeste apresentam uma comunidade bacteriana associada com potencial aplicação para a promoção de crescimento vegetal, pois possuem a capacidade de fixar nitrogênio, solubilizar fosfato inorgânico e produzir AIA. Planta de cana-de-açúcar cultivada em Pernambuco possui uma comunidade de bactérias endofíticas distinta em relação aos outros estados produtores, sendo algumas identificadas como dos gêneros: Burkholderia, Pantoea, Klebsiella, Pseudomonas e Enterobacter.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Espécies de arroz silvestre são colonizadas por bactérias diazotróficas, contudo, pouco se conhece sobre a colonização em Oryza glumaepatula (Steud). Este estudo teve como objetivo isolar e caracterizar bactérias diazotróficas de arroz silvestre em áreas de mata e cerrado no bioma amazônico. Amostras de plantas selvagens foram coletadas e utilizadas para o isolamento bacteriano, sendo as bactérias obtidas avaliadas quanto à formação de película em meio de cultura semi-sólido. Posteriormente, as que apresentaram a formação de película foram analisadas quanto a presença do gene nifH utilizando os iniciadores PolF/PolR e, as que foram positivas, caracterizadas através de Box-PCR, solubilização de fosfato de Ca e produção de ácido indol acético (AIA). Trinta e oito bactérias, cerca de 4% do total, formaram película e apresentaram produto de amplificação do gene nifH. A incidência de bactérias diazotróficas foi semelhante entre as áreas, porém maior número foi isolado na parte aérea das plantas. Além disso, mais de 30% das bactérias diazotróficas apresentaram produção de AIA e/ou solubilização de fosfato, sendo a maior concentração na parte aérea das plantas do cerrado. Nessa área ocorre maior diversidade genotípica de bactérias diazotrófica associadas ao arroz silvestre e maior número destas bactérias capazes de solubilizar fosfato de Ca e produzir AIA. / Species of wild rice are colonized by diazotrophic bacterias, however, little is known about the colonization in Oryza glumaepatula (Steud). This study aimed isolate and characterize diazotrophic bacterias of the wild rice from forest and cerrado areas in the Amazon biome. Samples of wild plants were collected for bacterial isolation, and semi-solid medium was used to assay the pellicles formation by the bacterias. Later, the nifH gene was also amplified by PCR using the primer set PolF/PolR and the bacterias, each ones were positive, characterized through Box-PCR, solubilization of calcium phosphate and production of indol acetic acid (AIA). Thirty eight bacterias, around 4% of the total, formed pellicles and also presented nifH gene amplification. A incidência de bactérias diazotróficas foi semelhante entre as áreas, porém maior número foi isolado na parte aérea das plantas. Além disso, mais de 30% das bactérias diazotróficas apresentaram produção de AIA e/ou solubilização de fosfato, sendo a maior concentração na parte aérea das plantas do cerrado. Nessa área ocorre maior diversidade genotípica de bactérias diazotrófica associadas ao arroz silvestre e maior número destas bactérias capazes de solubilizar fosfato de Ca e produzir AIA. The incidence of diazotrophic bacterias was similar between the areas, however, higher number was isolated from the aerial part of the plants. Furthermore, more than 30% of the diazotrophic bacterias produced AIA and/or solubilized phosphate, and the largest concentration of these bacteria was isolate in the aerial part of the plants from cerrado. In this area happens higher genotypic diversity of diazotrophic bacterias associated to the wild rice and also the larger number of these bacterias is capable producing AIA and solubilizing phosphate.

Os rejeitos de mineração provenientes do beneficiamento do minério, quando dispostos de maneira inadequada, podem causar a contaminação do solo e das águas superficiais e subterrâneas. Dependendo do tipo de minério tratado, tais rejeitos podem conter elevadas concentrações de metais potencialmente tóxicos e passar a atuar como fontes persistentes de liberação de tais metais através dos ecossistemas. Assim sendo, a caracterização desses rejeitos é extremamente importante. Neste contexto, foram realizadas caracterizações geológicas e geotécnicas nos rejeitos de mineração provenientes da região do Vale do Ribeira (município de Adrianópolis-PR), visando avaliar o grau de mobilidade e toxicidade dos metais contidos na porção superficial deste depósito. Para tanto, foram realizadas caracterizações mineralógicas (DRX e MEV/EDS), granulométricas, determinação dos parâmetros físico-químicos (pH, Eh e CE), além de ensaios que verificaram a mobilidade, especiação química e toxicidade das amostras: ensaios de solubilização, lixiviação, ensaio de variação de pH, extração sequencial e ecotoxicidade aquática envolvendo o organismo teste Daphnia similis. Além dos rejeitos foram realizadas análises mineralógicas e determinação dos parâmetros físico-químicos em amostras de estéril. A partir destas caracterizações, foi possível verificar que a composição mineralógica predominantemente no rejeito e no estéril é o carbonato, reflexo da litologia local. Tal composição refletiu também nos elevados valores de pH, que variaram de 7,6 a 8,0. Esses rejeitos apresentaram granulometria fina (predominância de areia muito fina, fina e silte), além de altas concentrações de metais, principalmente Pb (concentração média de 5.236,67 mg.kg-1 ) e Zn (7.726,53 mg.kg-1 ). Dos metais analisados, o Pb excedeu o valor preconizado na norma ABNT NBR 10.004:2004, tanto nos extratos lixiviados como nos solubilizados, para todas as amostras analisadas, o que permitiu classificar tais resíduos como Classe I - Perigoso. No ensaio de variação de pH, de forma geral, o Zn apresentou maior liberação na condição inicial mais ácida (pH 3), com média de liberação de 11,54 mg.L-1 após sessenta minutos de ensaio; embora nas outras condições também tenha ocorrido liberação considerável. A partir da extração sequencial, foi possível verificar que todos os metais (com exceção do Cu) estavam associados à fase de óxidos/hidróxidos, porém as fases consideradas de maior mobilidade (trocável e carbonática) estavam presentes em concentrações significativas para todos os metais analisados. As cinco amostras analisadas mostraram-se heterogêneas sendo que a RP5 e a RP7, apresentaram maior mobilidade dos metais Pb e Zn, além de terem apresentado maior toxicidade nos ensaios de ecotoxicidade. Para o ensaio de ecotoxicidade aquática, tais amostras apresentaram imobilidade dos neonatos até mesmo nas diluições menos concentradas (diluições contendo somente 6,2 e 3,1% de extrato solubilizado). Assim, concluiu-se que o rejeito pode ser considerado perigoso do ponto de vista ambiental, já que as altas concentrações de metais potencialmente tóxicos presentes estão passíveis de liberação e migração no ecossistema, podendo interagir com a biota aquática e terrestre. / Tailings from the ore processing when improperly disposed, can cause contamination of soil, surface water and groundwater. Depending on the treated ore, the mining waste may contain high concentrations of toxic metals and start acting as persistent metals sources to surrounding ecosystems. Therefore, the characterization of this material is extremely important. In this context, geological and geotechnical characterization were performed on tailings from Ribeira Valley (Adrianópolis-PR), in order to evaluate the mobility and toxicity of metals present in the superficial portion of the deposit. For the current paper the following tests were performed: mineralogical characterization (XRD and SEM/EDS), particle size distribution, determination of physical and chemical properties (pH, Eh and EC), solubilization and leaching tests, pH variation, sequential extraction and aquatic ecotoxicity were carried out. Besides the tailings analyzes, mineralogical characterization and pH measurements were also performed in samples from Perau (waste rock). The results showed mineralogical compositions predominantly carbonate in both tailing and Perau samples, as a reflection of the local lithology. This composition also reflected in the higher pH values, which ranged from 7.6 to 8.0. The tailing had fine particle size (predominance of silt, very fine and fine sand), and high concentrations of metals, especially Pb (average concentration of 5236.67 mg.kg-1) and Zn (7726.53 mg.kg-1). The metal Pb was above of the recommended value in ABNT NBR 10.004:2004 in leaching tests, solubilization tests and for all samples. This fact allowed the classification of the waste as Class I-Dangerous. In testing of pH variation, the Zn showed higher release in initial acidic condition (pH 3), releasing average 11.54 mg.L-1 after sixty minutes of test; although in others pH conditions have also been considerable release. In sequential extraction, the results found that all metals (except Cu) were associated with phase oxides/hydroxides, but the phases considered more mobile (exchangeable and carbonate) were also present in significant concentrations for all metals. The five samples were considered heterogeneous and two of them (RP5 and RP7) had greater mobility of Pb and Zn, besides a higher toxicity in ecotoxicity tests. In aquatic ecotoxicity test, the samples showed immobility of neonates organisms even in less concentrated dilutions (dilutions containing only 6.2 and 3.1% solubilized extract). In conclusion, the waste may be considered problematic for environment, because the high concentrations of toxic metals present in tailing can be released from it and migrate to the ecosystems, causing exposure to terrestrial and aquatic organisms.

The thesis presents work regarding amphiphilic molecules associated in aqueous solution or at the liquid/solid interface. Two main topics are included: the temperature-dependent behavior of micelles and the adsorption of dispersants on carbon nanotube (CNT) surfaces. Various NMR methods were used to analyze those systems, such as chemical shift detection, spectral intensity measurements, spin relaxation and, in particular, self-diffusion experiments. Besides this, small angle X-ray scattering (SAXS) was also applied for structural characterization.   A particular form of phase transition, core freezing, was detected as a function of temperature in micelles composed by a single sort of Brij-type surfactants. In mixed micelles, that phase transition still occurs accompanied by a reversible segregation of different surfactants into distinct aggregates. Adding a hydrophobic solubilizate shifts the core freezing point to a lower temperature. Upon lowering the temperature to the core freezing point, the solubilizate is released. The temperature course of the release curves with different initial solubilizate loadings is rationalized in terms of a temperature-dependent loading capacity.   The behavior of amphiphilic dispersant molecules in aqueous dispersions of carbon nanotubes (CNTs) has been investigated with a Pluronic-type block copolymer as frequent model dispersant. Detailed dispersion curves were recorded and the distribution of the dispersant among different available environments was analyzed. The amount of dispersed CNT was shown to be defined by a complex interplay of several factors during the dispersion process such as dispersant concentration, sonication time, centrifugation and CNT loading. In the dispersion process, high amphiphilic concentration is required because the pristine CNT surfaces made available by sonication must be rapidly covered by dispersants to avoid their re-attachment. In the prepared dispersions, the competitive adsorption of possible dispersants was investigated that provided information about the relative strength of the interaction of those with the nanotube surfaces. Anionic surfactants were found to have a strong tendency to replace Pluronics, which indicates a strong binding of those surfactants.   CNTs were dispersed in an epoxy resin to prepare nanotube-polymer composites. The molecular mobility of epoxy was investigated and the results demonstrated the presence of loosely associated CNT aggregates within which the molecular transport of epoxy is slow because of strong attractive intermolecular interactions between epoxy and the CNT surface. The rheological behavior is dominated by aggregate-aggregate jamming. / <p>QC 20180103</p>

Les solvants occupent une place prépondérante dans l’industrie chimique et se retrouvent au cœur de nombreuses applications telles que la formulation de produits phytosanitaires, d’encres ou de peintures, le nettoyage industriel ou les procédés d’extraction, de synthèse ou de séparation. L’épuisement des ressources pétrolières, le durcissement de la réglementation, et une prise de conscience collective motivent le développement d’alternatives à l’utilisation de solvants pétrochimiques. En effet, environ 45% des émissions de composés organiques volatils (COVs) en France proviennent de l’utilisation des solvants, qui, pour la plupart, présentent une empreinte environnementale et sanitaire peu favorable. Le panorama des solvants industriels amorce inévitablement une mutation, qui nécessite la recherche de solvants plus respectueux de l’environnement et des utilisateurs, au regard de leurs propriétés et de leur mode de production. Outre les liquides ioniques, les fluides supercritiques et les solvants fluorés qualifiés de solvants verts, les biosolvants sont apparus comme une solution alternative capable de répondre à un grand nombre de spécifications requises dans diverses applications. L’élaboration de biosolvants s’accompagne d’un changement de matière première, au profit de ressources renouvelables issues de la biomasse. Parmi les molécules plateforme biosourcées utilisées pour la synthèse de bioproduits, le furfural, obtenu par déshydratation des sucres contenus dans les rafles de maïs, a été sélectionné dans le cadre de cette étude visant à développer de nouveaux biosolvants, en collaboration avec la société Rhodia-Solvay (projet InBioSynSolv). Ainsi, afin de substituer des solvants conventionnels utilisés pour formuler des actifs phytosanitaires ou pour le nettoyage industriel, deux méthodologies, différentes de l’approche essais et erreurs, ont été étudiées. La première méthodologie, prédictive, se base sur la prédiction des propriétés avant la synthèse des molécules. La formulation inverse est, quant à elle, une méthodologie innovante qui permet de concevoir des molécules de biosolvants grâce à un laboratoire virtuel; les étapes de génération de structures moléculaires et de prédiction des propriétés, sont intégrées à un outil informatique d’aide au design moléculaire (CAMD) qui propose des solutions répondant aux spécifications visées. Dans un premier temps, ces méthodologies ont conduit à identifier un pool de molécules candidates dérivées du furfural et susceptibles de jouer le rôle de solvant pour les applications envisagées. Dans un deuxième temps, la faisabilité des filières de leur production a été étudiée, depuis la molécule plateforme jusqu’à l’utilisation du biosolvant au sein d’une formulation. Pour cela, les molécules candidates ont été obtenues selon différentes voies de synthèse, que l’on a caractérisées à l’aide de la détermination d’indicateurs verts. Une démarche d’éco conception a également contribué à la mise en place d’une approche multi critère intégrant les aspects techniques, environnementaux et socio- économiques. Enfin, la production d’échantillons a permis de vérifier expérimentalement les propriétés recherchées, et de valider l’intérêt des méthodologies de substitution de solvants utilisées, en termes de gain de temps et d’efficacité. Celles-ci pourront être généralisées au développement de différents bioproduits pour accompagner les évolutions des marchés auxquelles doit faire face l’industrie chimique. / The solvents play a significant role in the chemical industry and are at the heart of many applications such as the formulation of pesticides, inks or paints, industrial cleaning or extraction processes, synthesis and separation. The depletion of fossil resources, stricter regulations and collective awareness incite the development of alternatives to the use of petrochemical solvents. In fact, about 45% of emissions of volatile organic compounds (VOCs) come from the use of solvents, most of which have a very unfavorable environmental and health impact. The panorama of industrial solvents inevitably initiates a change, which requires the search for more eco friendly solvents in terms of their properties and their mode of production. In addition to the ionic liquids, supercritical fluids and fluorinated solvents, called green solvents, biosolvents emerged as an alternative capable of meeting a large number of specifications required in various applications. Developing biosolvents is accompanied by a change in raw material, from petroleum to renewable resources from biomass. Among the biobased platform molecules used for the synthesis of bioproducts, furfural, obtained by dehydration of sugars in corn cobs, was selected as part of this study to develop new biosolvents in collaboration with Rhodia-Solvay (InBioSynSolv project). Thus, to replace conventional solvents used in phytosanitary formulations or for industrial cleaning, two methodologies different from the tests and error approach, were studied. The first methodology, predictive, is based on the properties prediction before the synthesis of the molecules. The inverse formulation is, in turn, an innovative methodology to design molecules of biosolvents through a virtual laboratory. Stages of generation of molecular structures and properties prediction are integrated in a computer-aided molecular design tool (CAMD) providing solutions that meet the outlined specifications. First, these methodologies have led to identify a pool of candidate molecules derived from furfural that may act as a solvent for the intended applications. In a second step, the feasibility of their production chains has been studied from the molecule platform to the use of the biosolvent in a formulation. For this, the candidate molecules were obtained by different synthetic routes, which were characterized using the determination of green indicators. An eco-design approach has also contributed to take into account different criteria including technical, environmental and socio-economic aspects. Finally, with the production of samples, properties were experimentally verified, to validate the interest of solvents substitution methodologies in terms of time savings and efficiency. These could be generalized to the development of various bioproducts to make possible innovation in the chemical industry.

The thesis contains two parts. Part 1 describes the investigations on graphene and contains five sections. Section 1, gives a brief overview of graphene and other nanocarbons. The other four sections deal with various aspects of single-layer and few-layer graphene such as functionalization and solubilization, surface properties and gas adsorption, molecular charge transfer interaction and some properties and applications. Section 2 describes covalent and noncovalent functionalization and solubilization of few-layer graphene samples prepared by different methods as well as of single-walled carbon nanotubes (SWNTs). It includes covalent functionalization of graphene with organometallic reagents, noncovalent functionalization of graphene and SWNTs with surfactants as well as large aromatic molecules, and exfoliation of few-layer graphene by a water-soluble coronene carboxylate. Section 3 deals with surface properties and gas adsorption (mainly H2 and CO2) of few-layer graphenes. It is found that graphene samples with high surface area can adsorb even more than 3 wt% of H2 at high pressure which makes it promising material for gas-storage applications. Section 4 describes the molecular charge-transfer interaction of single and few-layered graphenes and SWNTs with different electron-donor and -acceptor molecules probed by both ITC measurements and Raman spectroscopy. Electron–acceptor molecules interact more strongly with graphene and SWNTs than the -donor molecules and nature of interaction of metallic SWNTs are different than the as-prepared ones. A Raman study of the interaction of single-layer graphene, prepared by micromechanical cleavage as well as chemical route, with an electron donor molecule such as tetrathiofulvalene (TTF) and an electron acceptor molecule such as tetracyanoethylene (TCNE) is examined. In Section 5, some properties and applications of graphene are discussed. These include fluorescence quenching phenomena observed with few-layer graphene samples on two fluorescent molecules such as coronene and perylene derivatives. Fabrication of a sensing device as well as of FETs prepared from doped and undoped few-layer and single-layer graphene samples forms part of this section. Part 2 of the thesis includes a brief introduction of hybrid open-framework material and synthesis, characterization and crystal structure of various open-framework metal carboxylates, starting with different transition and main group metals. The carboxylic acids used to form these frameworks vary such as simple aliphatic amino acids such as beta-alanine and aspartic acid or simple aliphatic hydroxyl carboxylic acid such as malic acid in its chiral and achiral forms or five-membered heterocyclic aromatic acid, such as imidazole dicarboxylic acid.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-01-22T11:04:31Z No. of bitstreams: 1 wesleytinocoesteves.pdf: 1817304 bytes, checksum: 6ff6e2f42ca29b6d9a247cd5c28895ef (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-01-25T18:50:19Z (GMT) No. of bitstreams: 1 wesleytinocoesteves.pdf: 1817304 bytes, checksum: 6ff6e2f42ca29b6d9a247cd5c28895ef (MD5) / Made available in DSpace on 2016-01-25T18:50:19Z (GMT). No. of bitstreams: 1 wesleytinocoesteves.pdf: 1817304 bytes, checksum: 6ff6e2f42ca29b6d9a247cd5c28895ef (MD5) Previous issue date: 2014-12-02 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O presente trabalho buscou estabelecer um método para a determinação de contaminantes inorgânicos em leite cru que fosse compatível com aplicações em larga escala, como os programas regulatórios de monitoramento de contaminantes em leite. Para tal, foi proposta uma abordagem utilizando a técnica de espectrometria de emissão atômica em plasma (ICP-AES) sem mineralização das amostras, que foram solubilizadas em solução contendo etanolamina e ácido cítrico. Estudos foram conduzidos a fim de estabelecer condições instrumentais em que fosse possível utilizar o preparo amostral proposto mantendo o compromisso com a sensibilidade, exatidão e desempenho analítico necessários a fim de se atingir os limites de detecção requeridos por legislações relacionadas à segurança alimentar. A proporção ideal de diluição da amostra na solução de etanolamina e ácido cítrico foi de 1:2 (amostra:solução) e os valores mais adequados dos parâmetros instrumentais foram 1300W para a radiofrequência do plasma, 0,50L.min-1 para a vazão do gás auxiliar e 0,60L.min-1 para a vazão do gás de nebulização. Os limites de quantificação obtidos para Cd, Co, Cr, Cu e Pb foram, respectivamente, 6,54, 6,57, 14,8, 14,3 e 27,4 μg.mL-1. / This study aimed to establish a method for the determination of inorganic contaminants in raw milk that was compatible with largescale applications, such as regulatory programs for the monitoring of contaminants in milk. For this purpose, an approach using the technique of atomic emission spectrometry (ICP-AES) with no mineralization of the samples, which was solubilized in a solution containing ethanolamine and citric acid, has been proposed. Studies were conducted in order to establish experimental conditions in which it was possible to use the proposed sample preparation and keeping the commitment to sensitivity, accuracy and the analytical performance required by legislations related to food safety. The ideal ratio of sample dilution was 1:2 (sample:solution) and the most suitable values for instrumental parameters were 1300W for the plasma radiofrequency power, 0.50L.min-1 for the flow of auxiliary gas and 0.60L.min-1 for the flow of nebulizer gas. The quantification limits obtained for Cd, Co, Cr, Cu and Pb were, respectively, 6.54, 6.57, 14.8, 14.3 and 27.4 μg.mL-1.

Geringe Wasserlöslichkeiten kleiner organischer Wirkstoffkandidaten, sogenannter Leitstrukturen, sind in der Medikamentenentwicklung häufig für das Scheitern vielversprechender Projekte verantwortlich. Um diese Kandidaten dennoch zur Marktreife bringen zu können, wurden verschiedene Strategien entwickelt. Neben der kostenintensiven Strukturoptimierung rücken Formulierungsadditive in den Fokus, die in der Lage sind, Wirkstoffe zu solubilisieren, transportieren und gezielt freizusetzen. In dieser Arbeit wird eine Hochdurchsatz-Screening-Methode präsentiert, die eine schnelle und arbeitsextensive Identifizierung maßgeschneiderter Binder für wasserunlösliche, niedermolekulare Wirkstoffe ermöglicht und mithilfe derer Löslichkeitsvermittler in Form von Peptid-Polymer-Konjugaten mit definierten Solubilisierungs- und Freisetzungseigenschaften realisiert werden können. Dazu werden Peptidbibliotheken in einem zweistufigen Prozess auf Wirkstoffbindung und auf Wirkstofffreisetzung durchsucht. Das Screening kann aufgrund einer innovativen on-chip Immobilisierung der Peptidbibliothek und der intrinsischen Fluoreszenz der niedermolekularen Wirkstoffe halbautomatisiert durchgeführt werden. Vielversprechende Peptidsequenzen können anschließend direkt on-chip mittels MALDI-ToF-MS/MS bzw. fragmentierungsfrei sequenziert und löslichkeitsvermittelnde Peptid-PEG-Konjugate hergestellt werden. In einem Testsystem wurden maßgeschneiderte Peptid-PEG-Konjugate mit unterschiedlichen Freisetzungseigenschaften für einen potentiellen Alzheimer-Wirkstoff realisiert und sowohl Solubilisierungseigenschaften, als auch die Freisetzungseigenschaften in einem vereinfachten Blutplasmamodell mittels Fluoreszenzanisotropie und Fluoreszenzkorrelationsspektroskopie bestätigt. In Zelltests mit einer Neuro-2a-Zelllinie konnten durch Zugabe der Wirkstoff-Transporter-Komplexe effektiv die Ausbildung der bei einer Alzheimer-Erkrankung auftretenden Tau-Protein-Aggregate bis zu 55 % reduziert werden. / Low water solubility of promising small organic drugs is one of the main reasons for failures during early drug development. Solubilizers promise to overcome these difficulties by solubilization, improved transport and final release of the potential drug candidates, which may result in an approval as a commercial drug. Here, a high-throughput screening method is presented, which is capable of identifying tailor-made peptide-polymer conjugates binding small molecule drugs, which can be used to act as solubilizers with precisely defined drug uptake and release properties. The screening is based on a two-dimensional process, which in a first step identifies strong binders and in a second, characterises their drug release. Due to its innovative on-chip immobilization of the peptide library and the intrinsic fluorescence of the small molecule drugs, the screening can be performed semi-automatically. Promising peptides can be sequenced directly by on-chip fragmentation-free or via MALDI-ToF-MS/MS and subsequently peptide-PEG conjugates can be synthesized. A screening against a high potential Alzheimer´s disease drug resulted in several tailor-made peptide-PEG conjugates with various drug uptake and release characteristics, which were confirmed in additional experiments. Here, loading capacities were determined and release properties analysed with a simplified blood plasma model utilizing fluorescence anisotropy and fluorescence correlation spectroscopy. Cell tests with a Neuro-2a cell line confirmed the effectiveness of the drug-transporter aggregates by reducing the tau-protein concentration by 55 % and inhibiting their aggregation, which is one of the key issues in Alzheimer´s disease.