<p>PPO inhibitors are a valuable group of herbicides that provide soil-residual and foliar control of glyphosate resistant <em>Amaranthus</em> species. The ΔG210 mutation in the <em>PPX2</em> gene confers PPO-inhibitor resistance and has been present in the Midwest for more than a decade. Until recently, PPO-inhibitor resistance in waterhemp was attributable to just the ΔG210 mutation in the <em>PPX2</em> gene, but recently, several new PPO-resistant biotypes have been discovered in waterhemp and Palmer amaranth. A possible explanation is a change in PPO-inhibitor use patterns and commonly used active ingredients.</p> <p>A direct comparison of the ΔG210 mutation and a new mutation, R128G, was conducted in the greenhouse. Results indicate that the R128G mutation in waterhemp is not substantially better than the ΔG210 mutation with respect to conferring resistance to PPO inhibitors applied preemergence. Furthermore, there is no evidence that the utility of PPO inhibitors applied preemergence will diminish any further as a result of the R128G mutation increasing in frequency. A set of field trials was conducted to investigate how a new PPO inhibitor, trifludimoxazin, will select for resistant biotypes in the field. Overall, a greater number of resistant plants survived the foliar herbicide applications than emerged through soil applications. Trifludimoxazin did not increase the frequency of PPO-resistant individuals when applied to soil, but when applied to foliage, increased the frequency of PPO-resistant individuals by 2.5 to 2.6-fold, similar to other PPO inhibitors applied to foliage. In other experiments, investigations of waterhemp populations with unique resistance phenotypes were conducted. In populations that were more resistant than others, yet had the same ΔG210 mutation, there was no evidence of herbicide metabolism contributing to the greater resistance phenotype. In resistant populations that had no target site mutations, target site expression experiments and lipid peroxidation experiments were inconclusive. However, there was some evidence of increased target-site expression or increased antioxidant capacity as being causal mechanisms, although no mechanisms have been fully ruled out.</p>

La performance d'un projet de conception de produits manufacturés est souvent caractérisée par un ensemble d'indicateurs qui ne repose pas uniquement sur la performance du produit mais sur celle du triptyque produit processus et organisation (PPO). L’utilisation d’indicateurs de performance dans un projet de conception ne peut être efficace que si les liens de traçabilité entre les données sont formalisés. Durant le cycle de conception, de très nombreuses spécifications PPO, également appelées spécifications projet, sont déployées dans un environnement de conception collaborative. Ce déploiement consiste à transférer les spécifications de niveaux de détail donnés vers des niveaux de détail plus affinés (transfert interniveaux) et depuis des vues globales vers des vues particulières (transfert intervues). Ce travail propose de caractériser ces deux mécanismes de transferts, déjà introduits pour les spécifications géométriques, à l’ensemble des spécifications projet. La formalisation et la généralisation de ces mécanismes de transferts ont été identifiées pour un ensemble de modèles pour la conception collaborative (un modèle produit, deux modèles processus (un pour le système décisionnel et un pour le système technologique) et un modèle organisation). Ces modèles constituent ainsi un environnement PPO. Le système décisionnel et le système technologique y sont décrits comme deux aspects du système de conception : l’un s’intéressant à l’organisation et aux processus, l’autre travaillant sur le produit même au travers d’un processus de conception. Les transferts de spécifications y sont ainsi illustrés. La mise en place de perturbations dans un scénario de conception de turbine haute pression permet de mettre en évidence les liens de traçabilité entre les spécifications ainsi que les impacts des perturbations et des solutions censés les corriger. Un indicateur de performance énergétique ayant été défini, des perturbations sont simulées et des solutions sont proposées. La notion de compromis apparaît alors lorsque les solutions améliorent une caractéristique de l’indicateur de performance énergétique mais en dégrade une autre. / Design project performance of manufactured products is often characterised by a set of indicators which does not depend only on the product’s performance but also on that of the product process and organisation (PPO) triptych. The use of performance indicators in a design project can only be effective if the traceability links between the data are formalised. During the design cycle, a lot of PPO specifications, also called project specifications, are deployed in a collaborative design environment. This deployment consists in transferring the specifications from a given detail level towards finer ones (interlevel transfer) and from a global view towards particular ones (interview transfer). This work proposes to characterise these two mechanisms of transfers, already introduced for geometrical specifications, with the whole of project specifications. The formalisation and the generalisation of these mechanisms of transfers were identified for a set of models for collaborative design (one product model, two process models (one for the decision-making system and one for the technological system) and one organisation model). These models provide thus a PPO environment. The decision-making system and the technological system are described there as two aspects of design system: one concerned with the organisation and the processes, the other working on the product through a design process. Specifications transfers are thus illustrated there. The introduction of disturbances in a design scenario of a high-pressure turbine can highlight the traceability links between specifications and the impacts of the disturbances and the solutions to correct them. An energetic performance indicator has been defined, disturbances are simulated and solutions are proposed. The compromise notion appears then when the solutions go better a characteristic of the energetic performance indicator but degrade another one.

Neste trabalho, foram fabricados biossensores amperométricos a partir do uso da polifenol oxidase (PFO), obtida do abacate como fonte enzimática, imobilizada em filmes de polipirrol (PPI) e que foram eletrossintetizados em meio de três diferentes eletrólitos de suporte (NaCl e NaClO4 e NaDDS). O método de imobilização enzimática foi o da adsorção, sendo a solução de enzima adicionada à solução com o pirrol e o eletrólito durante o processo de eletropolimerização. Os filmes de PPI/PFO foram caracterizados por técnicas eletroquímicas, principalmente por voltametria cíclica. A detecção de compostos fenólicos (catecol e pirogalol) foi realizada pela técnica de cronoamperometria após se variar a concentração do analito. A morfologia dos filmes foi estudada por microscopia de força atômica (AFM), sendo observado que a presença da enzima no filme polimérico assim como o uso de diferentes eletrólitos de suporte levou a diferenças na superfície dos filmes. Além disto, verificou-se que o biossensor construído a partir do uso do NaCl, apresentava uma resposta mais eficiente, ou seja, ele foi capaz de detectar catecol e pirogalol em um menor limite de detecção. / In this study amperometric biosensors were manufactured from the use of polyphenol oxidase (PPO) obtained from avocado as a source of enzyme immobilized in polypyrrole (PPY) films that were electrosynthesized with three different support electrolytes (NaCl, NaClO4 and NaDDS). The method of enzyme immobilization was the adsorption. The PPO was added in the solution containing pyrrole and electrolyte during electropolymerization. The PPY/PPO films were characterized by electrochemical techniques mainly by cyclic voltammetry. Detection of phenolic compounds (catechol and pyrogallol) was performed by the technique of chronoamperometry after varying the concentration of the analyte. The morphology of the films was studied by the atomic force microscopy (AFM) and observed that the presence of the enzyme in the polymer film and the use of different electrolytes support led to differences in the surface of films. However it was found that the biosensor constructed from the use of NaCl showed more efficient response and it was able to detect catechol and pyrogallol in a lower limit of detection.

Nesta dissertação, a polifenol oxidase (PFO) como extrato bruto de abacate (Persea americana) foi imobilizada em filmes de polipirrol (PPI) sintetizados eletroquimicamente utilizando o glutaraldeído (GA) como um agente de ligação entrecruzada. Os filmes PPI e PPI/PFO-GA foram caracterizados por eletroquímica, principalmente voltametria cíclica, sendo avaliadas a eletroatividade e a reversibilidade eletroquímica. A detecção de compostos fenólicos em soluções padrão foi feita por cronoamperometria, tendo um controle sobre a concentração dos compostos. O processo de transferência de massa foi monitorado com uma microbalança de cristal de quartzo eletroquímica. Os resultados indicaram uma boa reprodutibilidade das medidas na detecção dos compostos fenólicos. A estabilidade do biossensor em uma solução tampão manteve-se durante 27 dias, um resultado aceitável já que é encontrado na literatura um tempo de vida estável para sistemas semelhantes em tomo de 30 dias / In this dissertation, polyphenol oxidase (PPO) as crude extract of avocado (Persea americana) was immobilized on electrochemical1y synthesized polypyrrole (PPY) films using glutaraldehyde (GA) as a crosslinking agent. PPY and PPY/PPO-GA films were electrochemical1y characterized, mainly by cyclic voltametry, where electroactivity and electrochemical reversibility were evaluated. The detection of phenolic compounds in standard samples was made by chronoamperometry with a control over the compound concentration. The process of mass transfer was monitored with an electrochemical quartz crystal microbalance (EQCM). Our results indicated a good repeatability of the measurements for the detection of phenolic compounds. The stability of biosensor in a buffer solution has remained for 27 days, a result acceptable since it is found in the literature a time of life stable for similar systems around 30 days

Field and labratory studies were conducted to determine the efficacy of saflufenacil alone and with mixture partners for burndown. Field studies were conducted in 2009 and 2010 to evaluate saflufenacil in mixtures with glyphosate, glufosinate, or paraquat for control of glyphosate-resistant (GR) horseweed prior to planting cotton. Saflufenacil and saflufenacil mixtures were applied 7 days before planting (DBP). Saflufenacil at 25 and 50 g ai ha-1 in mixture with all three non-selective herbicides provided similar GR horseweed control when compared to the current standard of glyphosate plus dicamba. Control of GR horseweed was also not different at the 25 and 50 g ai ha-1 of saflufenacil across all mixtures from the standard of glyphosate plus dicamba. Laboratory studies were initiated to determine the uptake and translocation of saflufenacil alone and when mixed with glyphosate and paraquat. It was found that glyphosate plus saflufenacil had a greater absorption of saflufenacil at 2 and 8 HAT. By 24 HAT there were not any differences between the amount of saflufenacil absorbed into GR horseweed between treatments. Translocation data also confirmed that the majority of saflufenacil stayed in the treated leaf at 72 HAT.

Emulsion polymerized mixed matrix (EPMM) membranes is a new category of membranes, which incorporate silica-based inorganic nanoparticles dispersed in continuous phase of an organic polymer. The uniqueness of the EPMM membranes comes from the fact that they may combine otherwise incompatible inorganic and organic phases. This is achieved by the synthesis of the inorganic nanoparticles from a silica precursor in a stable emulsion, in which an aqueous phase is dispersed in a continuous phase of the polymer solution. More specifically, the silica precursor soluble in the polymer solution polymerizes in contact with the aqueous phase, and consequently the latter acts as finely dispersed micro reactors. The objective of this work was to optimize the previously developed protocol for the synthesis of poly (2,6-dimethyl-1,4pheneylene oxide) (PPO) based EPMM membranes, and to characterize their physical and gas transport properties. In particular, the effects of inorganic loading and the membrane post-treatment protocol on the permeability and selectivity of the membranes were of interest. However, the results showed that the obtained permeation and separation were virtually not affected by the theoretical Si loading and the post-treatment protocol. Moreover, in comparison to the base PPO membranes, the observed O2 permeability and the O2/N2 permselectivity have generally decreased. The differential scanning calorimetry (DSC) analysis of the synthesized membranes showed an important scatter of the glass transition temperatures (Tg) of the EPMM membranes with the values generally lower than the Tg of the base PPO. Moreover, the inductively coupled plasma mass spectrometry (ICP-MS) showed the silica content in selected EPMM membranes to be far below the expected theoretical level. This, in combination with the 29Si nuclear magnetic resonance (29Si NMR) results, showed that most of the already low silica content comes from the unreacted silica source (tetraethylorthosilicate) and have led to the second phase of the project in which a modified synthesis protocol has been developed. The major differences of the modified protocol compared to the original one include the replacement of a surfactant, 1-octanol, by ethanol and using greater concentrations of the reactants. To study the effect of different parameters involved in the synthesis protocol, a Gravimetric Powder experiment, in which the inorganic polymerization is carried out in an emulsion with a pure solvent rather than a polymer solution, has been designed. The Gravimetric Powder experiments have confirmed polymerization of tetraethylorthosilicate (TEOS) in the emulsion system. Using the conditions, which resulted in the maximum production of the polymerized TEOS in the Gravimetric Powder experiments, one set of new EPMM membranes has been synthesized and characterized. The new EPMM membranes have the Tg of 228.2oC, which is distinctly greater compared to the base PPO, and contain one order of magnitude more of silica compared to the old EPMM membranes. More importantly, the 29Si NMR analysis has proven that the silica content in the new EPMM membranes originates from the reacted rather than unreacted TEOS. Interestingly, the observed conversion of TEOS in the new EPMM membranes, exceeding 20%, is greater than the largest conversion in the Gravimetric Powder experiments. The oxygen permeability in the new EPMM membrane of 33.8 Barrer is more than twice that of the base PPO membrane. Moreover, this increase in O2 permeability is associated with a modest increase in the O2/N2 permselectivity (4.75 versus 4.67).

Emulsion polymerized mixed matrix (EPMM) membranes is a new category of membranes, which incorporate silica-based inorganic nanoparticles dispersed in continuous phase of an organic polymer. The uniqueness of the EPMM membranes comes from the fact that they may combine otherwise incompatible inorganic and organic phases. This is achieved by the synthesis of the inorganic nanoparticles from a silica precursor in a stable emulsion, in which an aqueous phase is dispersed in a continuous phase of the polymer solution. More specifically, the silica precursor soluble in the polymer solution polymerizes in contact with the aqueous phase, and consequently the latter acts as finely dispersed micro reactors. The objective of this work was to optimize the previously developed protocol for the synthesis of poly (2,6-dimethyl-1,4pheneylene oxide) (PPO) based EPMM membranes, and to characterize their physical and gas transport properties. In particular, the effects of inorganic loading and the membrane post-treatment protocol on the permeability and selectivity of the membranes were of interest. However, the results showed that the obtained permeation and separation were virtually not affected by the theoretical Si loading and the post-treatment protocol. Moreover, in comparison to the base PPO membranes, the observed O2 permeability and the O2/N2 permselectivity have generally decreased. The differential scanning calorimetry (DSC) analysis of the synthesized membranes showed an important scatter of the glass transition temperatures (Tg) of the EPMM membranes with the values generally lower than the Tg of the base PPO. Moreover, the inductively coupled plasma mass spectrometry (ICP-MS) showed the silica content in selected EPMM membranes to be far below the expected theoretical level. This, in combination with the 29Si nuclear magnetic resonance (29Si NMR) results, showed that most of the already low silica content comes from the unreacted silica source (tetraethylorthosilicate) and have led to the second phase of the project in which a modified synthesis protocol has been developed. The major differences of the modified protocol compared to the original one include the replacement of a surfactant, 1-octanol, by ethanol and using greater concentrations of the reactants. To study the effect of different parameters involved in the synthesis protocol, a Gravimetric Powder experiment, in which the inorganic polymerization is carried out in an emulsion with a pure solvent rather than a polymer solution, has been designed. The Gravimetric Powder experiments have confirmed polymerization of tetraethylorthosilicate (TEOS) in the emulsion system. Using the conditions, which resulted in the maximum production of the polymerized TEOS in the Gravimetric Powder experiments, one set of new EPMM membranes has been synthesized and characterized. The new EPMM membranes have the Tg of 228.2oC, which is distinctly greater compared to the base PPO, and contain one order of magnitude more of silica compared to the old EPMM membranes. More importantly, the 29Si NMR analysis has proven that the silica content in the new EPMM membranes originates from the reacted rather than unreacted TEOS. Interestingly, the observed conversion of TEOS in the new EPMM membranes, exceeding 20%, is greater than the largest conversion in the Gravimetric Powder experiments. The oxygen permeability in the new EPMM membrane of 33.8 Barrer is more than twice that of the base PPO membrane. Moreover, this increase in O2 permeability is associated with a modest increase in the O2/N2 permselectivity (4.75 versus 4.67).

Subsidijos yra vienas iš sudėtingiausių ir daugiausia ginčų sukeliančių tarptautinės teisės klausimų. Viena vertus, vyriausybės teikia subsidijas siekdamos visiškai teisėtų nacionalinės ekonominės ir socialinės politikos tikslų. Tačiau, kita vertus, subsidijos gali sukelti nenumatytus tarptautinės prekybos iškraipymus. Dėl jų neigiamo poveikio subsidijos yra sudėtingo tarptautinės ir viršvalstybinės teisės normų rinkinio, kuriuo siekiama atskirti ir reguliuoti „nesąžiningas“ subsidijas, subjektas. Šiame magistro darbe nagrinėjama apsaugos nuo neigiamo subsidijų poveikio prekybos partnerių interesams problematika, ieškant atsakymų į klausimus, kodėl apsauga yra būtent tokia, ir ar subsidijų (ir joms atsverti taikomų kompensacinių muitų) naudojimą reglamentuojančios taisyklės yra pakankamos. / Subsidies are one of the most complicated and contentious questions in international law. On the one hand, subsidies are used by governments to serve fully legitimate objectives of national economic and social policy. On the other hand, however, subsidies may create unintended distortions in international trade. Due to adverse effects subsidies are the subject to an intricate set of legal rules of international and supra-national law, which attempts to distinguish and regulate „unfair“ subsidies. This master‘s thesis examines the issue of protection from adverse effects on the interests of trading partners, attempting to answer the questions, why this is the case and whether the disciplines governing the use of subsidies – and countervailing duties to offset them – is complete.

Emulsion polymerized mixed matrix (EPMM) membranes is a new category of membranes, which incorporate silica-based inorganic nanoparticles dispersed in continuous phase of an organic polymer. The uniqueness of the EPMM membranes comes from the fact that they may combine otherwise incompatible inorganic and organic phases. This is achieved by the synthesis of the inorganic nanoparticles from a silica precursor in a stable emulsion, in which an aqueous phase is dispersed in a continuous phase of the polymer solution. More specifically, the silica precursor soluble in the polymer solution polymerizes in contact with the aqueous phase, and consequently the latter acts as finely dispersed micro reactors. The objective of this work was to optimize the previously developed protocol for the synthesis of poly (2,6-dimethyl-1,4pheneylene oxide) (PPO) based EPMM membranes, and to characterize their physical and gas transport properties. In particular, the effects of inorganic loading and the membrane post-treatment protocol on the permeability and selectivity of the membranes were of interest. However, the results showed that the obtained permeation and separation were virtually not affected by the theoretical Si loading and the post-treatment protocol. Moreover, in comparison to the base PPO membranes, the observed O2 permeability and the O2/N2 permselectivity have generally decreased. The differential scanning calorimetry (DSC) analysis of the synthesized membranes showed an important scatter of the glass transition temperatures (Tg) of the EPMM membranes with the values generally lower than the Tg of the base PPO. Moreover, the inductively coupled plasma mass spectrometry (ICP-MS) showed the silica content in selected EPMM membranes to be far below the expected theoretical level. This, in combination with the 29Si nuclear magnetic resonance (29Si NMR) results, showed that most of the already low silica content comes from the unreacted silica source (tetraethylorthosilicate) and have led to the second phase of the project in which a modified synthesis protocol has been developed. The major differences of the modified protocol compared to the original one include the replacement of a surfactant, 1-octanol, by ethanol and using greater concentrations of the reactants. To study the effect of different parameters involved in the synthesis protocol, a Gravimetric Powder experiment, in which the inorganic polymerization is carried out in an emulsion with a pure solvent rather than a polymer solution, has been designed. The Gravimetric Powder experiments have confirmed polymerization of tetraethylorthosilicate (TEOS) in the emulsion system. Using the conditions, which resulted in the maximum production of the polymerized TEOS in the Gravimetric Powder experiments, one set of new EPMM membranes has been synthesized and characterized. The new EPMM membranes have the Tg of 228.2oC, which is distinctly greater compared to the base PPO, and contain one order of magnitude more of silica compared to the old EPMM membranes. More importantly, the 29Si NMR analysis has proven that the silica content in the new EPMM membranes originates from the reacted rather than unreacted TEOS. Interestingly, the observed conversion of TEOS in the new EPMM membranes, exceeding 20%, is greater than the largest conversion in the Gravimetric Powder experiments. The oxygen permeability in the new EPMM membrane of 33.8 Barrer is more than twice that of the base PPO membrane. Moreover, this increase in O2 permeability is associated with a modest increase in the O2/N2 permselectivity (4.75 versus 4.67).

Made available in DSpace on 2016-12-08T17:19:31Z (GMT). No. of bitstreams: 1 Cap 1.pdf: 76234 bytes, checksum: d1d164557af129d7e5c6e0be224fee30 (MD5) Previous issue date: 2007-07-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In view of that some environmental problems are associated to the industrial production, it becomes necessary to work and to apply concepts for the sustainability. Spite of complex system it s possible to accomplish an analysis for the sustainable development through method that support to obtain data and interpretation of the results. Life Cycle Assessment can be considered one of the most appropriate, that because it propose solutions for global environmental problems, once it includes all of the stages of the life cycle of a product or process, from: the extraction and processing of raw materials, production and packing, transport and distribution, use and recycling until the final disposition. LCA studies comprise four phases: the goal and scope definition, inventory analysis, impact assessment and interpretation the results. The objective of this research is to propose an appropriate systematic to accomplish the Inventory of Life Cycle Assessment for the Tampa de Relê EM that it s injected with a blend of poly (phenylene oxide) and polystyrene of high impact (PPO/PSHI), to support in a subsequent Life Cycle Assessment studies. This research was structured in the following stages: the goal and scope definition; analysis of the processes; obtaining of data for inventory analysis; impact assessment and interpretation the results, characterization of the material and mechanical and physical/chemical analyses. The inventory was accomplished considering all the inputs and outputs of each stage of the system in analysis and starting from the obtained data, they were identified the aspects and impacts environmental associates to it. The main environmental impacts obtained were the exhaustion of natural resources, contamination of the soil and atmospheric pollution. The analyses done in the virgin material and recycled, presented similar results in thermal resistance and properties mechanics and physical/chemical. / Em virtude da percepção, de que os alguns problemas ambientais estão associados à produção industrial, torna-se necessário trabalhar e aplicar conceitos para a sustentabilidade. Apesar de amplo e até mesmo complexo é possível realizar uma análise para o desenvolvimento sustentável através de ferramentas que auxiliam na coleta de dados e interpretação dos resultados. Entre elas, a Avaliação do Ciclo de Vida pode ser considerada uma das mais apropriadas, pois busca soluções para problemas ambientais globais, uma vez que inclui todas as etapas do ciclo de vida de um produto ou processo, desde: a extração e processamento de matérias-primas, fabricação e embalagem, transporte e distribuição, uso e reemprego, reciclagem ou reutilização até a disposição final. A ACV está estruturada sob uma metodologia que inclui: a definição do objetivo e escopo do estudo, análise do inventário, avaliação dos impactos ambientais e interpretações dos resultados. O objetivo geral deste trabalho é propor uma sistemática adequada para realizar o Inventário do Ciclo de Vida da Tampa de Relê EM injetada com uma blenda de poli (óxido de fenileno) e poliestireno de alto impacto (PPO/PSAI), para auxiliar uma posterior Avaliação do Ciclo de Vida completa. Assim, para realização deste trabalho foram seguidas as seguintes etapas: definição do objetivo e escopo do estudo; mapeamento dos processos e identificação das variáveis de análise; coleta de dados para realização do inventário do ciclo de vida; interpretação dos resultados obtidos; caracterização da blenda e execução de ensaios mecânicos e físico/químicos no material virgem e reciclado. O inventário foi realizado considerando todas as entradas e saídas de cada etapa do sistema em análise e a partir dos dados obtidos, foram identificados os aspectos e impactos ambientais associados a ele. Diante dos resultados do inventário, obteve-se como principais impactos ambientais, o esgotamento de recursos naturais renováveis e não renováveis, contaminação do solo e poluição atmosférica. Com relação as análises feitas no material virgem e reciclado, as amostras apresentaram resultados similares no que tange resistência térmica, mecânica e físico/química.