CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / Laticifers plants have been studied by presenting a wide range of proteins related to plant defense in its latex. The aim of this study was to investigate, in tissue cultured in vitro, proteins and activities described for latex laticÃferas two species. Tissue callus and roots of Cryptostegia grandiflora were obtained by in vitro tissues culture protocols and subjected to histological analysis for laticifers characterization. Cultured tissue of Calotropis procera were used as comparative reference in the analysis. There wasnât any laticifer structure in callus or roots of C. grandiflora while in C. procera laticifers are formed in the roots. Soluble proteins were extracted from the cultured tissue and characterized using enzymatic assays, biochemical, immunological techniques and mass spectrometry. The presence of activity against phytopathogenic fungi was investigated and all data obtained were compared with the previously one determined for the plants studied latex. Callus and roots proteins of C. procera showed antifungal activity against pathogenic fungi. The percentage inhibition of the vegetative hyphae growth in the presence of callus and roots C. procera protein respectively were 75.5% and 82.6% for Fusarium solani, 76.7% and 57.1% for Rhizoctonia solani, 88.8% and 79.8% for Fusarium oxysporum, 93.7% and 90.2% for Colletotrichum lindemuthianum and 80.2% and 79.7% for Colletotrichum gloesporioides, however, showed no effect on Mucor sp. Callus and roots proteins of C. grandiflora showed no inhibitory effect on the hyphae growth or spores germination of assayed fungi. Through assays using fluorescent markers, it was demonstrated that proteins extracted from in vitro culture of C. procera interact with the membrane of C. gloesporioides causing leakage of cytoplasmic contents, possibly suggesting that its mechanism of action against fungi is related to the change in plasma membrane permeability. Also oxidative stress was observed in C. gloesporioides spores treated with callus and roots protein C. procera by hydrogen peroxide production. Protease inhibitors, chitinases, osmotins and proteases were detected in the C. procera callus and roots samples, however, osmotins and proteases were not observed in C. grandiflora callus and roots. The activity of antioxidant enzymes APX, G-POD and catalase were observed in tissue cultured in vitro of C. grandiflora. Considering that C. grandiflora laticifers proteases were demonstrated exert action against fungi, the results observed in this study suggest that the absence of antifungal activity in C. grandiflora cultured tissue is due to the absence of proteases in these tissues as well exclude chitinases and proteases inhibitors as antifungal proteins. The study concludes that the use of cultured tissues that do not differentiate laticifers is an interesting model to study activities associated to proteins founded in latex. Antifungal proteases present in C. grandiflora latex were not found in the tissues without laticifer formation. / Plantas laticÃferas tÃm sido estudadas por apresentarem uma grande diversidade de proteÃnas relacionadas à defesa vegetal em seu lÃtex. O objetivo deste trabalho foi pesquisar em tecidos cultivados in vitro, proteÃnas e atividades descritas para o lÃtex de duas espÃcies laticÃferas. Tecidos de calos e raÃzes de Cryptostegia grandiflora foram obtidos atravÃs de protocolos de cultura in vitro de tecidos e submetidos à anÃlise histolÃgica para caracterizaÃÃo de laticÃferos. Tecidos cultivados de Calotropis procera foram utilizados como referencial comparativo nas anÃlises. NÃo foi detectada qualquer estrutura laticÃfera em calos ou raÃzes de C. grandiflora enquanto que em C. procera laticÃferos se formam nas raÃzes. ProteÃnas solÃveis foram extraÃdas dos tecidos cultivados e caracterizadas por meio de ensaios enzimÃticos, tÃcnicas bioquÃmicas, imunolÃgicas e espectrometria de massas. A presenÃa de atividade contra fungos fitopatogÃnicos foi investigada e todos os dados obtidos foram comparados com dados previamente determinados para os lÃtex das espÃcies estudadas. ProteÃnas dos calos e raÃzes de C. procera, apresentaram atividade antifÃngica sobre fungos fitopatogÃnicos. Os percentuais de inibiÃÃo do crescimento vegetativo de hifas na presenÃa de proteÃnas de calos e raÃzes de C. procera, respectivamente, foram: 75,5% e 82,6% para Fusarium solani, 76,7% e 57,1% para Rhizoctonia solani, 88,8% e 79,8% para Fusarium oxysporum, 93,7% e 90,2% para Colletotrichum lindemuthianum e 80,2% e 79,7% para Colletotrichum gloesporioides, no entanto, nÃo demonstraram nenhum efeito sobre Mucor sp. As proteÃnas de calos e raÃzes de C. grandiflora nÃo apresentaram qualquer efeito inibitÃrio sobre o crescimento de hifas ou germinaÃÃo de esporos dos fungos avaliados. Por meio de ensaios com marcadores de fluorescÃncia, foi possÃvel demonstrar que as proteÃnas extraÃdas da cultura in vitro de C. procera interagem com a membrana de C. gloesporioides causando extravasamento do conteÃdo citoplasmÃtico, sugerindo que possivelmente seu mecanismo de aÃÃo contra fungos esteja relacionado à alteraÃÃo na permeabilidade da membrana plasmÃtica. TambÃm foi observado estresse oxidativo em esporos de C. gloesporioides tratados com proteÃnas de calos e raÃzes de C. procera atravÃs da produÃÃo de perÃxido de hidrogÃnio. Inibidores de proteases, quitinases, osmotinas e proteases foram detectados nas amostras de calos e raÃzes de C. procera, porÃm, osmotinas e proteases nÃo foram observadas em calos e raÃzes de C. grandiflora. A atividade das enzimas antioxidantes APX, G-POD e catalase foram observadas nos tecidos cultivados in vitro de C. grandiflora. Considerando que proteases laticÃferas de C. grandiflora foram demonstradas exercer aÃÃo contra fungos, os resultados observados nesta pesquisa sugerem que a ausÃncia de atividade antifÃngica em tecidos cultivados de C. grandiflora deve-se a ausÃncia de proteases nestes tecidos e ainda excluem quitinases e inibidores de proteases presentes como proteÃnas antifÃngicas. Em calos e raÃzes de C. procera, alÃm de proteases, outras proteÃnas tais como, quitinases, inibidores de proteases e osmotinas detectadas podem estar envolvidas na atividade antifÃngica observada, e/ou agir sinergicamente na defesa contra fungos. O estudo conclui que o uso de tecidos cultivados que nÃo diferenciam laticÃferos à um interessante modelo para estudar atividades associadas Ãs proteÃnas encontradas no lÃtex. Proteases antifÃngicas presentes no lÃtex de C. grandiflora nÃo foram encontradas nos tecidos sem formaÃÃo laticÃfera.

Although the application of surface treatments on bridge decks is expected to positively impact bridge deck condition, the effectiveness of specific surface treatments on extending bridge deck life has not yet been quantified on Utah bridge decks. Therefore, the objectives of this research were to develop and analyze deterioration curves for bare concrete bridge decks and decks with specific treatments commonly used in Utah. The scope of this study was determined by the types and extent of electronically available data, including selected static inventory information; maintenance, rehabilitation, and reconstruction histories; and National Bridge Inventory (NBI) condition ratings for the bridge decks. Bridge deck selection criteria and analysis procedures were developed to enable evaluation of the effects of surface treatments on bridge decks in Utah. Characteristics of a typical bridge were defined, and a list of typical bridges was produced to minimize potentially confounding effects of atypical bridge characteristics in comparisons of deterioration curves for monolithic concrete decks, decks with a bituminous overlay, decks with an epoxy overlay, and decks with a latex-modified concrete overlay. Climatic differences were taken into account by grouping bridges not only by overlay type, but also by Utah Department of Transportation region, which was used in this research as a general surrogate for latitude. Individual bridge deck deterioration curves were then combined to generate average deterioration curves aligned by deck construction time and average deterioration curves aligned by deck treatment time. To at least partially account for the potentially different effects of different treatment times, the bridge groups involving overlays were divided into two treatment time categories, early and late, for analysis. The average deterioration curves aligned by deck construction time suggest that certain treatments applied at certain times can achieve average NBI ratings greater than those for monolithic concrete during selected years of bridge deck life. The average deterioration curves aligned by deck treatment time suggest that certain treatments applied at certain times can achieve improvements in NBI ratings that correspond to apparent increases in bridge deck service life. Primarily because the NBI rating system is based mainly on visual inspection, the full benefits of early applications of surface treatments are not apparent in the results of this research. Supplemental perspectives may be gained about the performance of specific surface treatments by evaluating bridge deck deterioration in terms of delamination, half-cell potential, and chloride concentration, for example, which are direct measures of the deterioration process typically experienced by concrete bridge decks in Utah.

Coating colors are applied to the base paper in order to maximize the performance of the end product. Coating colors are complex colloidal systems, mainly consisting of water, binders, and pigments. To understand the behavior of colloidal suspensions, an understanding of the interactions between its components is essential.

In this thesis, I describe experiments that were designed to provide a better understanding of polymer diffusion during latex film formation. This step leads to the improvement of film mechanical properties. Polymer diffusion in these films was monitored by fluorescence resonance energy transfer. Current paint formulations contain Volatile Organic Compounds (VOCs) as plasticizers to facilitate polymer diffusion. The drawback of this technology is the release of VOCs to the atmosphere. VOCs are deleterious to the environment and contribute to smog and ground level ozone formation. The propensity of water, an indispensible part of any latex dispersion, to promote polymer diffusion was studied. Copolymers of poly (butyl acrylate-co-methyl methacrylate) and poly(ethylhexyl acrylate-co-tertiary butyl methacrylate) with similar glass transition temperatures but different hydrophobicity were compared. Polymer diffusion was monitored for films aged at different relative humidities. Water absorbed by the hydrophobic copolymer film was less efficient in promoting polymer diffusion than in the hydrophilic polymer. Only the fraction of water which is molecularly dissolved in the film participate actively in plasticization. Although water has low solubility in most latex polymers, molecularly dissolved water is more efficient than many traditional plasticizers. The possibility of modifying film formation behavior of acrylic dispersions with oligomers was studied by synthesizing hybrid polymer particles consisting of a high molecular weigh (high-M) polymer and an oligomer with the same composition. Oligomers with lower molecular weight are more efficient as diffusion promoters and have less deleterious effect on high-M polymer viscosity. A different set of hybrid particles were prepared in which the oligomer contained methacrylic acid units. The composition of the oligomer was tuned to be miscible with the high-M polymer when the acid groups were protonated but to phase separate when the acid groups were deprotonated. At basic pH, these particles adopt a core-shell morphology, with a shell rich in neutralized oligomers. After film formation, the oligomer shell retarded polymer diffusion. This retardation is expected to expand the time window during which the paint surface can be altered without leaving brush marks (open time). Short open time is a pressing problem in current technology.

In this thesis, I describe experiments that were designed to provide a better understanding of polymer diffusion during latex film formation. This step leads to the improvement of film mechanical properties. Polymer diffusion in these films was monitored by fluorescence resonance energy transfer. Current paint formulations contain Volatile Organic Compounds (VOCs) as plasticizers to facilitate polymer diffusion. The drawback of this technology is the release of VOCs to the atmosphere. VOCs are deleterious to the environment and contribute to smog and ground level ozone formation. The propensity of water, an indispensible part of any latex dispersion, to promote polymer diffusion was studied. Copolymers of poly (butyl acrylate-co-methyl methacrylate) and poly(ethylhexyl acrylate-co-tertiary butyl methacrylate) with similar glass transition temperatures but different hydrophobicity were compared. Polymer diffusion was monitored for films aged at different relative humidities. Water absorbed by the hydrophobic copolymer film was less efficient in promoting polymer diffusion than in the hydrophilic polymer. Only the fraction of water which is molecularly dissolved in the film participate actively in plasticization. Although water has low solubility in most latex polymers, molecularly dissolved water is more efficient than many traditional plasticizers. The possibility of modifying film formation behavior of acrylic dispersions with oligomers was studied by synthesizing hybrid polymer particles consisting of a high molecular weigh (high-M) polymer and an oligomer with the same composition. Oligomers with lower molecular weight are more efficient as diffusion promoters and have less deleterious effect on high-M polymer viscosity. A different set of hybrid particles were prepared in which the oligomer contained methacrylic acid units. The composition of the oligomer was tuned to be miscible with the high-M polymer when the acid groups were protonated but to phase separate when the acid groups were deprotonated. At basic pH, these particles adopt a core-shell morphology, with a shell rich in neutralized oligomers. After film formation, the oligomer shell retarded polymer diffusion. This retardation is expected to expand the time window during which the paint surface can be altered without leaving brush marks (open time). Short open time is a pressing problem in current technology.

Im Rahmen der Diplomarbeit wurde ein modernes System zur Erledigung typischer Geschäftsvorfälle des URZ entwickelt. Die Arbeit betrachtet den Einsatz von XML als Grundlage der Implementation und unterschiedliche XML-Applikationen auf ihre Verwendbarkeit zur Repräsentation von URZ-Dokumenten. Laufende Geschäftsvorfälle wurden anhand ausgewählter Dokumententypen analysiert und deren Strukturen und Inhaltstypen in XML definiert. Die Dokumentenerstellung wird durch eine Web-basierte Nutzerschnittstelle gewährleistet.

Reproduction de : Thèse de doctorat : Chimie organique et macromoléculaire : Lille 1 : 2004. / N° d'ordre (Lille 1) : 3448. Résumé en français et en anglais. Titre provenant de la page de titre du document numérisé. Bibliogr. p. 254-272.

It is necessary to understand the erodibility and hydrological response of mine-site slope forming materials (SFMs), because of increasing awareness of the environmental impacts of mining. Steep engineered slopes in high intensity rainfall environments present a serious erosion risk. Temporary surface stabilisers, such as polyacrylamides (PAMs) and polyvinylacrylic latex (PVALs) are potentially cost effective erosion control solutions. In this study PAM and PVAL efficacy to reduce runoff, leachate and erosion was assessed at two application rates, with and without gypsum on SFMs from an iron ore mine in Guinea (West Africa). NSPASS (near-surface photogrammetry assessment of slope forming materials’ surface roughness) is a novel method that integrates digital image capture and GIS. It is shown to detect and quantify surface micro-relief changes of 2-3 mm, not visible to the naked eye. As expected, soil and non-soil SFMs were significantly different in terms of their physical and chemical properties. Phase I of the study investigated the erodibility of ten SFMs, including soil, ore and waste-rock. The results indicate that the hydrological response to rainfall of most SFMs is to generate leachate. Weathered phyllite (PHY-WEA) is the most erodible SFM by both runoff and leachate. Multiple regression analysis demonstrated that magnetic susceptibility, mineralogy and dry aggregate distribution; parameters not commonly assessed in erosion studies, are important in explaining SFM erodibility and hydrological response. Phase II evaluated critically the effectiveness of three commercially available polymer solutions (two PAMs and one PVAL) at reducing runoff, leachate and erosion from four of the most erodible SFMs identified in Phase I. The results indicate that some PAM and PVAL treatments significantly reduce runoff, leachate and erosion. Polymer efficacy is highly dependent on the physical and chemical properties of the SFM, as well as the mechanism of polymer to SFM adsorption. Increasing the application rate of select treatments lowered leachate volumes, runoff and leachate total sediment loads. Contrary to previous studies, gypsum amendments did not significantly improve polymer efficiency. This research has added to our understanding of the erodibility and hydrological response of soil and non-soil SFMs. This is the first study to evaluate critically the efficacy of PVALs in controlling erosion from mine-site SFMs. Future studies should continue to optimise NSPASS performance in monitoring changes in surface micro-relief.

Ce travail de thèse traite de l'élaboration de nanoparticules luminescentes à based'organolanthanides pour des applications d'imagerie biomédicale ou de marquage pour la lutte anticontrefaçon. Les organolanthanides ont été incorporés sans liaison covalente afin de préserver leursremarquables propriétés de luminescence et leur stabilité chimique. Deux types de nanoparticulesont été étudiés, des particules de latex et des billes de silice qui ont toutes les deux été synthétiséesen milieu hétérogène.La silice a été synthétisée par un procédé sol-gel en microémulsion inverse. Deux organolanthanidesluminescents initialement dissous dans les micelles inverses ont été piégés physiquement dans lasilice amorphe pendant sa formation. Une nouvelle méthode basée sur la quantification de l'activitéd'un isotope radioactif de l'Eu(III) a été développée pour étudier l'incorporation desorganolanthanides. Les propriétés physico-chimiques des organolanthanides influencent directementleur localisation au sein des particules et l'efficacité d'incorporation. L'étude approfondie de cesnanoparticules a permis de mettre en évidence une amélioration de la relaxivité d'un complexe deGd(III) quand il est confiné dans la silice.Les particules de latex ont été synthétisées par polymérisation radicalaire en miniémulsion directe.Différents organolanthanides de structures ionique ou non ionique ont été incorporés efficacementpar simple dissolution dans le monomère. L'incorporation du complexe de structure ionique anécessité l'utilisation d'un tensioactif cationique afin de le maintenir à l'intérieur des gouttelettes etgarantir son incorporation dans les particules de latex. Ce système permet d'incorporer un grandnombre de complexes et aucun relargage n'est observé après plusieurs mois. Le ligand utilisé permeten plus d'exciter jusqu'à dix terre rares simultanément. En faisant varier la nature et la quantité desorganolanthanides incorporés, il est ainsi possible de générer des codes optiques complexes sousune excitation unique.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Partículas nanoestruturadas têm sido amplamente utilizadas como carga de reforço em matrizes elastoméricas, sendo substitutos eficazes das cargas convencionais, já consagradas, como o negro de fumo, mica, sílica. Em especial, as argilas têm mostrado grande potencial ao que se refere a melhor dispersão na matriz polimérica, em função de sua elevada razão de aspecto. Dentro do vasto universo de argilominerais, as argilas aniônicas, também conhecidas hidróxido duplo lamelar (HDL), apresentam como vantagem a possibilidade de ser projetada estruturalmente para as mais diversas finalidades, ao se modificar os ânions ou os cátions, ou até mesmo combiná-los na estrutura lamelar. E dentre os métodos existentes para se preparar compósitos a base de elastômero/argila, a co-coagulação do látex, é uma forma bastante eficaz e economicamente viável, uma vez que a borracha obtida após processo de coagulação já contém a carga incorporada. Este trabalho se dedicou a avaliar o processo de co-coagulação do látex de NBR e HDL, visando a obtenção de nanocompósitos. Para tanto HDL de composição Mg/Al-CO3 foi modificado com ânions DS, DBS e ST e foram preparadas suspensões aquosas, utilizando como ferramentas de dispersão ultraturrax e ultrassom de ponteira. As variáveis de processo avaliadas foram tipo e teor de HDL, tempo de mistura látex/suspensão aquosa de HDL, quantidade de coagulante e velocidade de agitação. Por fim, os coágulos obtidos foram formulados para avaliar a influência dos HDL na cinética de vulcanização e também para determinação das propriedades mecânicas convencionais. Os resultados obtidos comprovaram que a metodologia de dispersão de hidrotalcita ao látex nitrílico de modo prévio ao processo de coagulação é uma alternativa viável para a obtenção de nanocompósitos. O uso do ultrassom de ponteira como ferramenta na dispersão aquosa de HDL contribuiu para maior estabilidade da suspensão e o ajuste nos parâmetros do sistema de coagulação, levaram a obtenção de grumos uniformes do ponto de vista macroscópico e microscópico. As micrografias dos coágulos não vulcanizados obtidas por MEV-FEG confirmaram as informações apuradas a partir dos difratogramas de raios-X que apontou a formação de um sistema parcialmente esfoliado, em função da ausência dos picos característicos da hidrotalcita, além de indicarem a coexistência de partículas em dimensões micrométrica a nanométricas em uma mesma estrutura. A composição química do HDL, com a presença de átomos de magnésio e alumínio combinados com grupos hidroxila favoreceu a redução tanto o tempo de indução como de pré-cura. As propriedades mecânicas que se mostraram mais sensíveis ao grau de dispersão da carga foram a dureza, a deformação permanente à compressão (DPC) e o módulo de tração a 300% de deformação (E300), em especial para os compósitos contendo 10% m/m de HDL natural e modificado com estearato. A resistência à chama dos nanocompósitos de NBR-HDL vulcanizados apresentou um ligeiro aumento quando comparados à NBR pura, visto que esta é uma característica própria da hidrotalcita, decorrente da sua composição química / Nanostructured particles have been widely used as a reinforcing filler in rubber matrices and effective substitutes for, already established conventional fillers such as carbon black, mica and silica. In particular, clays have shown great potential when it comes better dispersed in the polymeric matrix due to its high aspect ratio. Within the vast universe of clay minerals, anionic clays, also known as layered double hydroxide (LDH), have the advantage of being able to be structurally designed for many different purposes, by modifying the anions or cations, or even combine them into lamellar structure. Among the existing methods to prepare elastomer-clay composites, the latex co-coagulation is an effective and economically viable, since method the rubber obtained after the coagulation process already contains the incorporated filler. This work was dedicated to evaluate the co-coagulation of NBR latex and LDH, aiming to obtain nanocomposites. This way, LDH with Mg/Al-CO3 composition was modified with anions dodecyl sulphate, dodecyl-benzene-sulphonate and stearate aqueous suspensions were prepared using ultraturrax as dispersion tools and the ultrasound probe. The process variables were evaluated in type and content of LDH, mixing time latex / aqueous suspension of LDH, quantity of coagulant and mixins speed. Finally, the clots obtained were formulated to verify the effect of LDH on the kinetics of vulcanization, and also for conventional determination of mechanical properties. The results obtained proved that the methodology of dispersion of the hydrotalcite in nitrile latex prior to the coagulation process is a viable alternative for obtaining nanocomposite. The use of ultrasound probe as a tool in the aqueous dispersion of LDH contributed to higher stability of the suspension and the adjusting the parameters of the coagulation system, led to obtainment of uniform clots of macroscopic and microscopic point of view. The micrographs of the clots obtained by SEM-FEG confirmed the information collected from the X-ray diffraction that showed the formation of a partially exfoliated system, due to the absence of the characteristic peaks of hydrotalcite, and indicated the coexistence of particles dimensions micrometric the nanometric within the same structure. The chemical composition of LDH in the presence of atoms of magnesium and aluminum combined with hydroxyl groups favored the reduction of both the induction time as pre-curing. The mechanical properties were more sensitive to the degree of dispersion of the charge were hardness, compression set, and tensile modulus at 300% strain (E300), particularly for composites containing 10% w/m for natural LDH and LDH modified with stearate. The flame resistance of nanocomposites NBR-LDH vulcanizates increased slightly compared to pure NBR, since this is a characteristic of hydrotalcite, due to its chemical composition