O objetivo deste trabalho é explorar a síntese e funcionalização de 1,2,3- triazóis empregando o uso de reações do tipo \"Click-chemistry\", que é uma abordagem para a síntese de diversos compostos com base em reações de formação de ligação carbono-heteroátomo, onde a reação é estereoespecífica, altamente eficiente e geralmente com elevados rendimentos e em alguns casos ausência de subprodutos. O composto 1,2,3-triazol, sendo o material de partida para a continuidade do projeto foi preparado a partir do álcool propargílico (4) em presença de uma azida orgânica (1) e utilizando cobre(I) como agente promotor. Após a obtenção de uma série de compostos 1,2,3-triazólicos (2), procedeu-se a etapa de tosilação da hidroxila e posterior cicloadição multicomponente de um novo 1,2,3-triazol formando compostos bis-triazólicos. Os bis-triazóis (5) obtidos foram testados frente a cepas fúngicas, responsáveis por dermatites, com resultados satisfatórios. Ainda essas estruturas poderão ser empregados como blocos construtores para a síntese de estruturas mais complexas. / The aim of this work has been exploring the synthesis and functionalization of 1,2,3-triazoles employing the use of \"click-chemistry\" concept, which is defined as an approach for synthesis of various compounds based on reactions of carbon-heteroatom bond formation, which the reaction is stereospecific, high-efficiently, commonly gives high yields and in some cases no by-products are formed. The compound 1,2,3-triazole, which is the main starting material for the next steps was prepared from propargyl alcohol (4) in the presence of an organic azide (1) and copper(I) as a reaction promoter. Subsequently with a series of 1,2,3-triazole (2n) prepared we proceeded to the next step which is the substitution of hydroxyl for a tosyl group and after that a multicomponent cycloaddition of a new 1,2,3-triazole compound forming bis-triazoles. Bis-triazoles (5) were tested against fungal strains, responsible for dermatitis, with delighted results, furhtermore this class of strutures can be used as building blocks to improve efficiency in some other more complex structure.

Submitted by Maicon Juliano Schmidt (maicons) on 2015-08-05T14:54:29Z No. of bitstreams: 1 Felipe Rodrigues Ferrary_.pdf: 7904559 bytes, checksum: c792687a5d6af3c5b496d85e12b9f21e (MD5) / Made available in DSpace on 2015-08-05T14:54:29Z (GMT). No. of bitstreams: 1 Felipe Rodrigues Ferrary_.pdf: 7904559 bytes, checksum: c792687a5d6af3c5b496d85e12b9f21e (MD5) Previous issue date: 2015-03-10 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O estudo a seguir tem por objetivo otimizar e tornar automatizado um sistema de manufatura que utiliza chapas como matéria prima. A preparação do processo de manufatura através do sistema CAM analisado atualmente possui diversas etapas que não possuem comunicação entre si, além disso, exige um alto nível de intervenção do usuário em suas tomadas de decisão. Esse processo deve ser unificado de forma a buscar um resultado aprimorado, com base nos critérios de otimização propostos. As etapas do processo de manufatura envolvendo chapas são analisadas ao longo do trabalho, passando por etapas iniciais como a definição das peças que devem ser produzidas, etapas intermediárias como o processo de otimização de peças (nesting) e sua respectiva parametrização, e a etapa final, ou seja, a obtenção do código NC para a produção das peças. Para otimizar tais etapas, é proposto um sistema de apoio à tomada de decisão, com características híbridas, formado por um sistema especialista e por técnicas de otimização, tais como metaheurísticas. O método proposto aprimora os resultados através da parametrização automatizada utilizando o sistema de apoio à tomada de decisão, definindo a melhor parametrização com base nos produtos a serem manufaturados, reduzindo assim a necessidade de decisões manuais e, por conseguinte, a interferência do usuário no processo e, ainda, eliminando a necessidade do mesmo ser um especialista. Essa automação deve analisar as possíveis chapas em estoque assim como parâmetros oferecidos pelo processo de nesting e buscar a melhor configuração para o processo, analisando possíveis permutações. Além disso, é proposta a adição de um novo componente nas etapas de manufatura, responsável por analisar as sobras aproveitáveis do processo e organizar a sucata gerada pelo mesmo, tornando-a disponível para ser reutilizada futuramente. Analisando o SAD implementado, foi possível observar que os resultados obtidos foram satisfatórios e, em muitos casos, superiores aos obtidos em outros testes realizados na literatura. Além disso, a aceitação do sistema pelos usuários que realizaram os testes de performance e viabilidade de uso foi considerada excelente. Conforme apontado pelos usuários, o número de parâmetros a ser selecionado reduziu drasticamente, tornando assim o sistema mais simples de ser utilizado. / The following work aims to optimize and make automated a manufacturing system that uses metal plates as raw material. The analysed process currently has several steps with no communication between each other, moreover requires a high level of user’s intervention in their decision making. This process must be unified in order to achieve the optimal result based on the optimization criteria proposed. The analysed processes throughout this work address all stages of the manufacturing process involving plates, going through the initial stages as the definition of the parts to be produced, intermediate steps as the process of optimizing parts (nesting) and its parameters and final step, i.e., obtaining the CN code for the production of parts. To optimize these steps, a method of hybrid solution using a system to support the decision making aided by an expert system and known optimization (such metaheuristics) is proposed. The proposed method will improve the results through an automated parameterization using the system to support the decisions making, defining the best parameter based on the products to be manufactured, thus reducing the need for manual decisions and therefore the user input in the process and eliminating the need for an expert to be the same. This automation should analyse the possible plates in stock as well as parameters offered by the nesting process and seek the best configuration for the process, analyzing possible permutations. Furthermore, we propose the addition of a new component in the steps of manufacturing, responsible for analysing the process remains usable and organize the scrap generated by it, making it available for reuse in the future. Through the proposed system, good and relevant results were obtained. In several cases the obtained results are better than results in the literature. In addition, the acceptance of the system by users who performed performance system tests was considered excellent. As pointed by these users, the number of parameters to be selected has drastically reduced, thus making the system simpler to use.

Muitos fármacos, principalmente os agonistas B-adrenérgicos, vêm sendo utilizados na produção animal e, devido às novas formas de pecuária intensiva, sua utilização tem crescido exponencialmente. Dentre os agonistas B-adrenérgicos, a Ractopamina (RAC) é o mais utilizado como agente repartidor de nutrientes, pois promove ganho de peso, eficiência alimentar, deposição de tecido muscular e rendimento da carcaça de suínos, bovinos, ovinos e perus. Neste contexto, o desenvolvimento de métodos analíticos capazes de detectar e quantificar a RAC na matéria-prima, no produto acabado, em pré-formulações enriquecidas com nutrientes e minerais e na ração é de suma importância no controle de qualidade do produto acabado comercializado por indústrias veterinárias, visando maior segurança para os animais e para o consumidor de carnes. Desta forma, este projeto tem como objetivo desenvolver e validar métodos analíticos capazes de quantificar o fármaco nestas 4 etapas (matéria-prima, produto acabado Ractosuin®, pré-mistura com complexo vitamínico-mineral e na mistura destes componentes com a ração). No primeiro capítulo deste trabalho está descrito o método para quantificação da RAC na matéria- prima e no produto acabado Ractosuin®. Este método apresentou-se linear no intervalo de concentração de 160,00 a 240,00 ug mL-1 (r> 0,99). Os coeficientes de variação nos estudos de precisão intra e interensaios foram inferiores a 2,0% e a exatidão intra e interensaios variaram de 97 a 100%. No segundo capítulo, foi utilizada a extração líquido-líquido e acetato de etila como solvente extrator para a análise da RAC no complexo vitamínico-mineral. A curva analítica foi linear no intervalo de concentração de 90,00 a 210,00 ug mL-1 (r > 0,99). Os coeficientes de variação nos estudos de precisão intra e interensaios foram inferiores a 1,5%, a exatidão intra e interensaios variaram de 98 a 102% e a recuperação ficou em torno de 94%. O terceiro capítulo mostra o método desenvolvido e validado para análise da RAC na ração. A RAC foi extraída da matriz utilizando a extração líquido-líquido com acetato de etila. A curva analítica apresentou-se linear no intervalo de concentração de 6,50 a 14,40 ug mL-1 (r > 0,99), o limite de detecção (LD) foi de 2,00 ug mL-1 e o limite de quantificação (LQ) foi de 4,00 ug mL-1. Os coeficientes de variação nos estudos de precisão intra e interensaios foram inferiores a 5,0%, a exatidão intra e interensaios variaram de 90 a 98% e a recuperação foi de 84%. Desta forma, os métodos desenvolvidos e validados podem ser aplicados em análises de rotina de controle de qualidade de indústrias veterinárias para a quantificação da RAC na matéria-prima, no produto acabado Ractosuin®, no complexo vitamínico-mineral e na ração. / Several drugs, especially B-adrenergic agonists, have been used in animal production and due to new forms of intensive livestock their use has grown exponentially. Among the B-adrenergic agonists, ractopamine (RAC) is the most used as a nutrient repartitioning agent, it promotes weight gain, feed efficiency, deposition of muscle and carcass yield of pigs, cattle, sheep and turkeys. In this context, the development of analytical methods able to detect and quantify RAC in the raw material, feed additive, in pre-formulation (feed additive) enriched with nutrients and minerals and in the ration is very important in quality control of pharmaceutical formulation marketed by veterinary industries for greater security for animals and to consumers of meat. Thus, this project aims to develop and validate analytical methods able to quantify the drug in these 4 stages (raw material, feed additive Ractosuin®, pre-mixed with vitamin mineral complex and the mixture of these components with the ration). In the first chapter of this work is described the method for quantification of RAC in the raw material and feed additive Ractosuin®. This method showed linearity over the concentration range from 160.00 to 240.00 ug mL-1 (r > 0.99). The coefficients of variation in studies of intra-and interassay precision were less than 2,0% and intra and interassay accuracy ranged from 97 to 100%. In the second chapter, we used liquid-liquid extraction and ethyl acetate as solvent extractor for the analysis of RAC in complex vitamin-mineral. The calibration curve was linear over the concentration range from 90.00 to 210.00 ug mL-1 (r > 0.99). The coefficients of variation in studies of intra and interassay precision were less than 1.5%, intra and interassay precision varied from 98 to 102% and the recovery was around 94%. The third chapter shows the method developed and validated for analysis of RAC in the ration. The RAC was extracted from the matrix by liquid-liquid extraction with ethyl acetate. The analytical curve was linear over the concentration range 6.50 to 14.40 ug mL-1 (r > 0.99), the limit of detection (LD) was 2.00 ug mL-1 and limit of quantification (LQ) was 4.00 ug mL-1.The coefficients of variation in studies of intra and interassay precision were less than 5.0%, intra and interassay accuracy ranged from 90 to 98% and the recovery was 84%. Thus, the methods developed and validated can be applied in routine analysis for quality control of veterinary industries for the quantification of RAC in the raw material, feed additive Ractosuin®, vitamin mineral complex and in the ration.

Le territoire belge est caractérisé par de nombreuses découvertes de Préhistoire ancienne, réparties sur un espace géographique restreint mais contrasté en termes de relief et de disponibilité des ressources minérales. Il est donc favorable à létude de la relation de lHomme à son Environnement par le biais des importantes différences régionales relatives aux types de sites représentés (grottes/plein air) ainsi quà la proximité et à la morphologie du silex disponible. Le rapport entre les populations néandertaliennes et chacun des types denvironnements rencontrés constitue le cur de ce travail, structuré en quatre parties intimement liées. La première partie est consacrée aux variations environnementales. Celles du substrat dabord, puisque quelques kilomètres à peine séparent les plaines riches en silex de Moyenne Belgique des profondes vallées de Haute Belgique. Variations chronologiques ensuite, puisque la sédimentation quaternaire eut une incidence tant sur laccessibilité des ressources lithiques que sur la préservation des traces archéologiques qui nous sont parvenues. Lhistorique des recherches est aussi abordé car les motivations et les contraintes des chercheurs qui se sont succédés depuis 1829 sont largement responsables de labondance mais aussi de la qualité très variable des documents. La deuxième partie concerne cette documentation. Nous avons identifié 437 lieux, inégalement répartis sur le territoire, qui ont livré des artefacts relatifs au Paléolithique moyen : 46 sites en contexte karstique (dont 16 majeurs) et 391 en plein air (dont 31 majeurs). Leur distribution tient tant à des paramètres taphonomiques et aux circonstances des découvertes quà des choix opérés par les Néandertaliens eux-mêmes. Deux environnements sont particulièrement favorisés : les plaines dont le substrat livre un silex abondant et les grottes du Bassin mosan. Lexamen de la position topographique des gisements montre des récurrences traduisant des choix liés à limplantation dans le paysage : les plateaux ou le haut des versants surplombant de petites vallées sont ainsi clairement privilégiés. La distribution chronologique des traces est aussi abordée, mettant notamment en évidence labondance de la documentation relative au Début Glaciaire weichselien, labsence de véritable occupation durant le Pléniglaciaire weichselien inférieur ainsi quune concentration de traces attribuables au Pléniglaciaire weichselien moyen tout à fait exceptionnelle pour le Nord-Ouest européen. En létat actuel des données, les datations situent les industries les plus récentes du Paléolithique moyen vers 38.000 B.P. (grotte Scladina) et les derniers Néandertaliens vers 36.000 B.P. ( Bètche-aux-Rotches à Spy). La troisième partie consiste en une étude approfondie dune dizaine dindustries lithiques dépendant de contextes environnementaux variés. Plusieurs tendances générales sen dégagent dans la manière dont les populations paléolithiques ont adapté leurs systèmes dacquisition et dexploitation des roches. Ainsi, des variations claires se marquent dans les systèmes dacquisition des roches exploitées selon un gradient nord-est sud-ouest. En Basse Belgique, lemploi de galets de silex local est couplé à limportation de nucléus et d'éclats provenant de Moyenne Belgique. En Moyenne Belgique, le silex disponible localement est employé prioritairement et le recours à dautres roches locales ou importées est tout à fait exceptionnel. En Haute Belgique, limportation de silex depuis la Moyenne Belgique combinée au recours à dautres matériaux disponibles localement constitue la règle. Ces variations dans les systèmes dacquisition génèrent de la diversité en termes de nature, de morphologie, de conditionnement et de disponibilité des matériaux mis en uvre par les tailleurs. Ces différents paramètres ont une incidence sur les choix techniques posés par les Néandertaliens lors de la phase de débitage. Sobservent ainsi des différences régionales importantes. Les sites de Haute Belgique procèdent doptions économiques qui se manifestent tant dans la réduction des blocs, comme au Trou du Diable à Hastière, que dans ladaptation des concepts de débitage à tel point quils en deviennent parfois atypiques comme lattestent les nombreux remontages de la grotte Scladina. À linverse, les sites de Moyenne Belgique témoignent dun usage dispendieux de la matière première et dune expression des concepts Levallois, Discoïde et Laminaire dans leur acception la plus stricte comme le montrent notamment les industries du gisement paléolithique dOtrange ou dObourg Canal. La quatrième partie est consacrée à une discussion des résultats et à une ouverture sur le reste de lEurope. Cette disparité des productions liée à la position géographique des gisements est particulièrement importante : des sites voisins mais diachroniques (couches 5 et 1A de la grotte Scladina) présentent entre eux plus danalogies que dautres pénécontemporains mais dépendant denvironnements contrastés (couches 1A de la grotte Scladina et WFL de Veldwezelt-Hezerwater). Dautres facteurs de variabilité se surimposent à cette diversité régionale : fonction des sites, traditions culturelles et techniques, variations paléoenvironnementales, chronologie. Des comparaisons sont opérées avec les résultats obtenus dans les régions limitrophes de la Belgique mais aussi à plus grande distance, des similitudes comportementales étant observées dans le sud de lEurope, dans des environnements qui évoquent par certains aspects le karst des vallées du Bassin mosan. Belgium is noted for its many ancient prehistoric sites which are spread over a limited geographic area. Despite its limited size, this area shows important regional contrasts in terms of topographic relief and availability of mineral resources. These factors in conjunction with important regional differences related to the types of sites represented (cave/open air) as well as the proximity and morphology of the available flint make this area favorable for the study of man's relationship with his environment. The connection between the Neanderthal populations and the types of environments encountered constitutes the focus of this study which is divided into four closely associated parts. The first part is devoted to environmental variation starting with the interface between the flint-rich plains of Middle Belgium and the deep valleys of Upper Belgium. Only a few kilometers separate these two contrasting environments. Chronological variations follow because quaternary sedimentation had as much impact on the accessibility of lithic resources as on site preservation. The history of the research from 1829 to the present is also addressed. The motives and constraints of the researchers are responsible for both the abundance of documentary evidence and for the extremely variable quality of these documents. The second part concerns the previously mentioned documentation. Artifacts attributable to the Middle Paleolithic have been recovered from 437 sites : 46 sites (16 major ones) are found in karstic contexts and 391 sites (31 major ones) are open air sites. The distribution of these sites is a direct result of taphonomic processes, circumstances of discovery, and choices made by the Neanderthals themselves. In particular, two environments were favored : the plains which have abundant flint resources and the caves of the Mosan Basin. Prehistoric Man's choice of sites appears to be linked to topographical position : plateaus or cliff tops overhanging small valleys were preferred. Chronological distribution is also examined. It notably shows an abundant documentation from the Beginning of the Weichselian Pleniglacial and an absence of occupation during the Lower Weichselien Pleniglacial It also shows a concentration of archaeological evidences related to the Middle Weichselian Pleniglacial which is very exceptional for Northwest Europe. Based on research to date, Scladina Cave (38.000 B.P.) gives the most recent date for Middle Palaeolithic industries and Betche-aux-Rochtes at Spy (36.000 B.P.) provides the date for the last Neanderthals. The third part consists of a detailed study of ten lithic industries and their environmental context. Several general tendencies were detected in the way Palaeolithic populations adapted their systems of acquisition and exploitation of rocks. Clear variations in the systems of acquisition and exploitation along a northwest/southeast gradient were noted. In Lower Belgium, the use of local flint pebbles was coupled with the importation of nuclei and flakes from Middle Belgium. In Middle Belgium, the available local flint was used almost exclusively. Recourse to other local rocks or to imports was very exceptional. In Upper Belgium, the importation of flint from Middle Belgium in combination with other locally available materials constituted the rule. These variations in the systems of raw material procurement generated diversity in terms of nature, morphology, conditioning, and availability of the nodules chosen by the knappers. These diverse parameters impacted the technical choices of the Neanderthals during the reduction or debitage stage. Other important regional differences were also observed. The sites of Upper Belgium exhibited economic options which manifested in the reduction of blocks (Trou du Diable at Hastière) and in extreme adaptations or manipulation of concepts of reduction such as those recognized in several refittings from Scladina Cave. The sites of Middle Belgium exhibited an extravagant use of the primary material and a strict expression of different concepts : mainly Levallois, also Discoid, and volumetric blade production (gisement paléolithique d'otrange, Obourg Canal). The fourth part is devoted to a discussion of the results and a preliminary comparison to the rest of Europe. The connection of the diversity in lithic productions and the geographic position of the sites is particularly important. Lithic industries from the two occupation layers of Scladina (layers 5 and 1A) present more analogies between themselves than other plenicomtemporaneous sites in different environments (lays 1A of Scladina and WFL of Veldwezelt-Hezerwater). Other factors of variability superimpose themselves in this diverse region : function of the sites, cultural traditions and techniques, palaeoenvironmental variations, chronology. Comparisons with the results obtained from regions bordering Belgium as well as those obtained from greater distances showed some behavioural similarities in southern Europe in environments which evoke aspects of the karst valleys of the Mosan Basin. Translation : Cheryl Roy, Department of Anthropology, Faculty of Social Sciences, Vancouver Island University

The Swedish pulp and paper industry is the third largest exporter of pulp and paper products worldwide. It is a highly energy-demanding and water-utilising industry, which generates large volumes of wastewater rich in organic material. These organic materials are to different extents suitable for anaerobic digestion (AD) and production of energy-rich biomethane. The implementation of an AD process within the wastewater treatment plant of a mill would increase the treatment capacity and decrease the overall energy consumption due to less aeration and lower sludge production and in addition produce biomethane. Despite the many benefits of AD it is only applied at two mills in Sweden today. The reason for the low implementation over the years may be due to problems encountered linked to the complexity and varying composition of the wastewaters. Due to changes in market demands many mills have broadened their product portfolios and turned towards more refined products. This has increased both the complexity and the variations of the wastewaters´ composition even further, as the above changes can imply an increased pulp bleaching and utilisation of more diverse raw materials within the mills. The main aim of this thesis was therefore to generate knowledge needed for an expansion of the biomethane production within the pulp and paper industry. As a first step to achieve this an evaluation of the biomethane potential and the suitability for AD of wastewaters within a range of Swedish pulp and paper mills was performed. Thus, around 70 wastewater streams from 11 different processes at eight mills were screened for their biomethane potential. In a second step, the impact of shifts in wood raw material and bleaching on the AD process and the biomethane production was investigated and further evaluated in upflow anaerobic sludge bed (UASB) reactors. The screening showed that the biomethane potential within the Swedish pulp and paper industry could be estimated to 700 GWh, which corresponds to 40% of the Swedish biomethane production during 2014. However, depending on the conditions at each specific mill the strategy for the establishment of AD needs to differ. For mills producing kraft pulp the potential is mainly found in wastewaters rich in fibres, alkaline kraft bleaching wastewaters and methanol-rich condensates. The biomethane potential within thermo-mechanical pulp- (TMP) and chemical thermo-mechanical pulp (CTMP) mills is mainly present in the total effluents after pre-sedimentation and in the bleaching effluents as these holds high concentrations of dissolved organic material. The screening further showed that the raw material used for pulp production is an important factor for the biomethane potential of a specific wastewater stream, i.e. hardwood (HW) wastewaters have higher potentials than those from softwood (SW) pulp production. This was confirmed in the lab-scale UASB reactor experiments, in which an alkaline kraft bleaching wastewater and a composite pulping and bleaching CTMP wastewater were used as substrates. AD processes were developed and maintained stable throughout shifts in wastewater composition related to changes in the wood raw materials between SW and HW for the kraft wastewater and spruce, aspen and birch for the CTMP wastewater. The lower biomethane production from SW- compared to HW wastewaters was due to a lower degradability together with a higher ratio of sulphuric compounds per TOC for the SW case. The impact of shifts between bleached and unbleached CTMP production could not be fully  evaluated in the continuous process mainly due to technical problems. However, due to the large increase in dissolved organic material when bleaching is applied, the potential biomethane production will increase during the production of bleached pulp compared to unbleached pulp. Based on the biomethane potentials obtained for one of the included CTMP mills, their yearly production of biomethane was estimated to 5-27 GWh with the lowest and the highest value corresponding to the production of unbleached spruce pulp vs. bleached birch pulp. Thus, the results of the investigations presented in this thesis show that the UASBreactor is suitable for AD of wastewaters within the pulp and paper industry. The results also show that challenges related to variations in the organic material composition of the wastewaters due to variations in wood raw materials could be managed. The outcome of the thesis work also imply that the production of more refined products, which may include the introduction of an increased number of raw materials and extended bleaching protocols, could increase the potential biomethane production, especially if the pulp production will make use of more HW. / Den svenska pappers- och massaindustrin är den tredje största exportören av massa och pappersprodukter och en viktig industriell aktör i Sverige. Det är en industri med hög energi- och vattenanvändning, som genererar stora mängder avloppsvatten rika på organiskt material. Detta organiska material kan via anaerob nedbrytning användas för att producera energirik biometan. Användandet av anaerob behandling, som ett steg i brukens vattenrening, genererar inte bara biometan utan kan också öka reningskapaciteten och minska energiförbrukning och kostnader tack vare minskat behov av luftning och minskad slamproduktion. Trots de många fördelarna med anaerob behandling är den idag bara tillämpad på två bruk i Sverige. En av orsakerna till detta kan vara processproblem som relaterats till avloppsvattnens komplexitet samt varierande sammansättning och flöden. Många pappers- och massabruk har utökat sina produktportföljer med bl a mer förfinade produkter, som en följd av en förändrad marknad. Dessa förändringar har ökat avloppsvattnens komplexitet och variation än mer, då ovan exempelvis kan medföra en ökad produktion av blekt massa samt att fler typer av träråvaror används vid ett och samma bruk. Huvudsyftet med föreliggande avhandling är att bidra med kunskap för en ökad produktion av biometan inom pappers- och massaindustrin. Som ett första steg genomfördes en övergripande utvärdering av ca 70 avloppsvattenströmmar från totalt 11 olika processer vid åtta svenska pappers- och massabruk med fokus på biometanpotential samt lämplighet för anaerob behandling. I ett andra steg utvärderades hur skiften i träråvara samt blekning påverkar biometanproduktionen samt processtabiliteten för en kontinuerlig anaerob nedbrytningsprocess i en UASBreaktor. Den initiala utvärderingen visade att den svenska pappers- och massaindustrin skulle kunna bidra med 700 GWh biometan per år, vilket motsvarar 40% av biometanproduktionen i Sverige under 2014. Beroende på utformningen av det enskilda bruket kommer strategier för implementering av anaeroba processer att se olika ut. För bruk som producerar sulfatmassa återfanns huvuddelen av biometanpotentialen i fiberrika avloppsvattenstömmar, alkaliska blekeriavlopp samt metanolrika kondensat. För bruk som producerar termomekanisk- (TMP) eller kemitermomekanisk (CTMP) massa föreligger biometanpotentialen framförallt i avloppsvatten rika på löst organiskt material såsom totalavlopp efter sedimentering och blekeriavlopp. Den initiala utvärderingen visade också att användandet av lövved ger en högre biometanpotential jämfört med barrved. Dessa resultat kunde bekräftas vid kontinuerliga experiment med anaerob nedbrytning i UASB-reaktorer, där ett alkaliskt blekeriavlopp från ett sulfatmassabruk och ett kombinerat massaproduktions- och blekeriavlopp från ett CTMP-bruk användes som substrat. Stabila anaeroba processer etablerades och bibehölls vid förändrad avloppsvattensammansättning på grund av skiften i träråvara (löv- och barrved för sulfatmassabruket samt gran, asp och björk för CTMP bruket). Den lägre produktionen av biometan för barrved jämfört med lövved kunde förklaras med en lägre nedbrytbarhet samt ett ökat svavelinnehåll i relation till mängden organiskt material. Skiften mellan avloppsvatten från blekt- och oblekt CTMP massa kunde inte utvärderas fullständigt i den kontinuerliga processen på grund av tekniska problem. Produktionen av blekt massa ökar dock mängden organiskt material i  avloppsvattnet, vilket medför att mer biometan kan produceras jämfört med då oblekt massa produceras. Baserat på biometanpotentialerna för ett av i studien ingående CTMP bruk uppskattas den årliga produktionen av biometan till 5-27 GWh, där den lägsta produktionen motsvarar oblekt granmassa och den högsta produktionen motsvarar blekt björkmassa. Sammanfattningsvis visar studien att UASB-reaktorer är lämpliga för anaerob behandling av avloppsvatten inom pappers- och massaindustrin. Vidare visar resultaten från de kontinuerliga försöken att de utmaningar som medförs av den varierande sammansättningen av avloppsvattnens organiska material knutet till träråvaran kan hanteras. Slutligen, breddade produktportföljer samt produktionen av mer förfinade produkter, vilket kan innebära en ökad massablekning och ett ökat användande av olika träråvaror, kan öka brukens potentiella biometanproduktion, särskilt om mer lövved används för massaproduktion.

The goal of this study is to research and substantiate the impact of drying environment on quality preservation in medicinal raw material, i. e. hyssop herb (Hyssopi herba). A complex impact of the drying environment factors (temperature and comparative ventilation intensity) of medicinal raw material, hyssop herb (Hyssopi herba), on the process of kinetics of its drying within a motionless layer, that was not researched until now, was determined. After the analysis of the medicinal raw material drying regularities the change of moisture in the object being dried was modelled. Both the comparative air flow and the dryer parameters impacted moisture exchange processes, drying time and medicinal raw material quality. Through the application of a complex dryer temperature and comparative airflow combination the environment favourable for medicinal raw material quality preservation is created. A close correlation between the mycobiotic contamination of medicinal raw material and the loss of essential oils was determined upon drying Hyssopi herba within a motionless layer. The theoretical fundamentals for designing medicinal raw material conservation technologies were developed. On the basis of the research findings, a pilot technology for medicinal raw material drying within a bulk motionless layer was developed. The technology was introduced in the medicinal raw material drying room of the Full House Community in village (Varėna district). / Darbo tikslas − ištirti ir pagrįsti vaistinės augalinės žaliavos − isopų žolės (Hyssopi herba) džiovinimo aplinkos įtaką kokybės išsaugojimui. Nustatyta iki šiol nenagrinėta kompleksinė džiovinimo aplinkos veiksnių (temperatūros ir lyginamojo ventiliavimo intensyvumo) įtaka vaistinės augalinės žaliavos − isopų žolės (Hyssopi herba) džiovinimo nejudančiame sluoksnyje proceso kinetikai. Išanalizavus vaistinės augalinės žaliavos džiovinimo dėsningumus, modeliuotas džiovinamo objekto drėgnio kitimas. Lyginamasis oro srautas ir džioviklio parametrai įtakojo drėgmės mainų procesus, džiovinimo trukmę ir vaistinės augalinės žaliavos kokybę. Taikant kompleksinį džioviklio temperatūros ir lyginamojo srauto derinį sukuriama vaistinės augalinės žaliavos kokybei išsaugoti tinkama aplinka. Nustatyta, kad džiovinant Hyssopi herba nejudančiame sluoksnyje yra glaudus ryšys tarp vaistinės augalinės žaliavos mikobiotinio užterštumo ir eterinių aliejų praradimo. Sukurti teoriniai pagrindai vaistinės augalinės žaliavos konservavimo technologijų projektavimui. Remiantis atliktais tyrimų rezultatais patobulinta vaistinės augalinės žaliavos storame nejudančiame sluoksnyje džiovinimo technologija, kuri įdiegta Pilnų namų bendruomenės vaistinės augalinės žaliavos džiovykloje, Varėnos r., Panaros k.

Vaistinių augalinių žaliavų ir fitopreparatų antioksidantinio aktyvumo tyrimams būtina taikyti optimizuotus ESC pokolonėlinius metodus bei validuoti jų metodikas, kurios leistų patikimai, tiksliai bei atkartojamai įvertinti antioksidantų sudėtį, pasiskirstymą ir stabilumą. Darbo tikslas – nuodugniai ištirti ir pritaikyti ESC pokolonėlinius metodus augalinių antioksidantų tyrimams, augalinės žaliavos ekstraktų bei jų preparatų antioksidantų sudėties ir aktyvumo įvertinimui. Nustatyta, kad reakcijos kilpos parametrai turi įtakos smailės aukščio ir bazinės linijos triukšmo santykiui. Atliktų validacijos eksperimentų rezultatai patvirtina ESC-DPPH ir ESC-ABTS pokolonėlinių metodų tinkamumą radikalus surišančių junginių nustatymui ir kiekiniam antiradikalinio aktyvumo įvertinimui. Optimizuotas ESC-FRAP pokolonėlinis metodas tinkamas kompleksiniuose mišiniuose esančių junginių redukcinių savybių nustatymui ir kiekiniam redukcinio aktyvumo įvertinimui. Nustatyti pagrindiniai antiradikalinio ir/arba redukcinio aktyvumo žymenys: Crataegus L. – chlorogeno rūgštis ir hiperozidas; Origanum L. ir Perilla L. – rozmarino rūgštis; Achillea L. – chlorogeno rūgštis ir 3,5-dikafeoilchino rūgštis; Fragaria L. – epigalokatechino galatas. Šie žymenys tinkami antioksidantinius junginius kaupiančių vaistinių augalinių žaliavų bei fitopreparatų kokybės kontrolei. / A study of antioxidant activity in medicinal herbal raw materials and phytopreparations requires the application of optimized HPLC post-column assays as well as validation of their methodologies that could allow for a reliable, accurate and reproducible evaluation of composition, distribution and stability of antioxidants. The aim of the work is to examine HPLC post-column assays and adjust them for research on plant antioxidants as well as assessment of composition and activity of herbal raw material extracts and their preparations. It was determined that reaction coil parameters have impact on the ratio of peak height and baseline noise. Evaluated validation results confirm the suitability of HPLC-DPPH and HPLC-ABTS post-column assays for the determination of radical scavenging compounds and quantitative evaluation of antiradical activity. Optimized HPLC-FRAP post-column assay can be applied for discriminating reducing active compounds in complex mixtures and quantitative evaluation of their reducing activity. Main radical scavenging and/or reducing activity markers were determined: Chlorogenic acid and Hyperoside for Crataegus L., Rosmarinic acid for Origanum L. and Perilla L., Chlorogenic acid and 3,5-dicaffeoylquinic acid for Achillea L., Epigallocatechin gallate for Fragaria L. These markers are applicable for the quality control of the herbal raw materials and phytopreparations containing antioxidants.

Made available in DSpace on 2014-12-17T14:07:04Z (GMT). No. of bitstreams: 1 ElialdoCS_TESE.pdf: 4625434 bytes, checksum: bec8d03e9004e11648c49c45f84ffe0f (MD5) Previous issue date: 2010-03-26 / Universidade Federal do Rio Grande do Norte / The dielectric porcelain is usually obtained by mixing various raw materials proportions and is used in the production of electronic equipment for various applications, from capacitors of high and low Power to insulators for low, medium, high and extra high voltage, which are used in distribution lines and transmission of electricity.This work was directed to the s tudy of technological properties of technic porcelain, made from raw materials extracted from pegmatites found in the regions of Serid? and the Alto Oeste of Rio Grande do Norte, which are made of kaolin, quartz and feldspar, abundant and high quality in these regions. The technic ceramics were obtained by mixing in appropriate levels, kaolin, feldspar, quartz and clay, the last item from a pottery in the city of Sao Gon?alo do Amarante, Rio Grande do Norte. During the development the following characterizations correlated to raw materials were made: laser particle sizing, x-ray diffraction, DTA and TG. The compositions studied were formed by uniaxial pressing at a pressure of 50 MPa and sintered at temperatures ranging from 1150 to 1350?C and levels (times) of sintering between 30, 60, 90 and 120 minutes. The characterization of the samples were taken from the analysis of weight loss, linear shrinkage, porosity, stoneware curve, bulk density, flexural strength of three points, SEM and X-ray diffraction, TMA, Dielectric and cross Resistivity. The studied materials can be employed in producing the objects used in electrical engineering such as: insulators for low, medium and high-voltage electrical systems, command devices, bushing insulation for transformers, power capacitors, spark plugs, receptacles for fluorescent and incandescent light bulbs and others / A porcelana diel?trica ? normalmente obtida atrav?s da mistura de diferentes mat?rias-primas, em propor??es adequadas, sendo utilizada na produ??o de equipamentos eletroeletr?nicos de diversas aplica??es, desde capacitores de alta e baixa pot?ncia, a isoladores para baixa, m?dia, alta e extra alta tens?o, que s?o utilizados em linhas de distribui??o e transmiss?o de energia el?trica. Neste trabalho, s?o estudadas as propriedades tecnol?gicas de uma porcelana diel?trica, formulada a partir de mat?rias-primas obtidas de pegmatitos encontrados nas regi?es do Serid? e do Alto Oeste do Rio Grande do Norte, sendo estas constitu?das de caulim, quartzo e feldspato, abundantes e de alta qualidade nestas regi?es, e de uma argila proveniente de uma cer?mica situada no munic?pio de S?o Gon?alo do Amarante, tamb?m no Estado do Rio Grande do Norte. As mat?rias-primas foram caracterizadas atrav?s de: granulometria a laser, difra??o de raios X, an?lise t?rmica diferencial e an?lise termogravim?trica. As amostras foram conformadas por prensagem uniaxial a uma press?o de 50 MPa, e sinterizadas ?s temperaturas de 1150, 1200, 1250, 1300 e 1350 ?C, com patamares de sinteriza??o de 30, 60, 90 e 120 minutos. Os ensaios tecnol?gicos realizados foram: an?lise da perda de massa, retra??o linear, porosidade, curva de gressifica??o, microscopia eletr?nica de varredura, difra??o de raios X, dilatometria, rigidez diel?trica, resistividade transversal e permissividade diel?trica. Os melhores valores de propriedades foram obtidos na temperatura de 1250 ?C, para as composi??es estudadas, n?o sofrendo varia??es significativas em seu comportamento com o tempo de sinteriza??o. Os materiais estudados podem ser empregados na obten??o de objetos usados em eletrot?cnica como por exemplo: isoladores de baixa, m?dia e alta-tens?o para redes el?tricas, dispositivos de comando, bucha de isolamento de transformador, capacitores de pot?ncia, vela de igni??o, recept?culos de l?mpadas incandescentes e fluorescentes e outros

Made available in DSpace on 2016-03-08T13:58:53Z (GMT). No. of bitstreams: 2 13.pdf: 24054067 bytes, checksum: f2cedc51d13f66361d03cd66f3c46b36 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2015 / Fundação Oswaldo Cruz. Instituto de Tecnologia em Fármacos/Farmanguinhos. Rio de Janeiro, RJ, Brasil. / A nimesulida é um fármaco anti-inflamatório não esteroidal (AINE), com seletividade preferencialmente para a COX-2. A nimesulida é um ácido fraco, praticamente insolúvel em água e está classificado como um fármaco de Classe II do Sistema de Classificação Biofarmacêutica. Além disso, apresenta polimorfismo, sendo descrito na literatura o polimorfo I e II, que demonstram algumas diferenças identificadas através da análise térmica, difração de raios X e RMN no estado sólido. Nesse trabalho, amostras do fármaco nimesulida obtidas de diferentes fabricantes, sendo duas amostras micronizadas e uma não micronizada, foram caracterizadas através de análise térmica, técnicas espectroscópicas, análise morfológica, ensaios de fluidez e avaliação biofarmacêutica. Com os resultados obtidos, verificou-se que as amostras são de um mesmo polimorfo, não apresentam boa fluidez e as variações dos tamanhos de partícula influenciam nos ensaios de avaliação biofarmacêutica. O delineamento das formulações e a escolha do processo produtivo foram conduzidos com base nos resultados obtidos nos ensaios de caracterização do fármaco. Os lotes galênicos foram avaliados através da realização de perfis de dissolução utilizando os parâmetros preconizados pela Farmacopeia Brasileira (FB 5, 2010) e comparados com o medicamento de referência Nisulid®. As formulações propostas apresentaram diferentes comportamentos de dissolução, podendo destacar a escolha do tensoativo, do aglutinante e as etapas de adição do tensoativo e desintegrante como fundamentais para a obtenção de resultados mais favoráveis. Foi selecionado o lote galênico que apresentou valores de cedência mais próximos do medicamento de referência e, em seguida, avaliou-se o comportamento em meios de dissolução contendo diferentes concentrações de tensoativo, com o objetivo de verificar se a concentração de 2% (v/v) de polissorbato 80, preconizado pela Farmacopeia Brasileira, estaria superestimando a biodisponibilidade do ativo em condições in vivo. Os resultados obtidos demonstraram que o percentual de tensoativo presente no meio de dissolução impacta diretamente na quantidade de fármaco dissolvida. A formulação selecionada demonstrou resultados promissores para prosseguir com a fabricação dos biolotes e realização do estudo de equivalência farmacêutica. / Nimesulide is a nonsteroidal antiinflammatory drug (NSAID), preferably with selectivity for COX-2. Nimesulide is a weak acid, almost insoluble in water and classified as a Class II drug Biopharmaceutical Classification System. Moreover, the literature has been described polymorph I and II, which show some differences identified by thermal analysis, diffraction X-ray and NMR in the solid state. In this study, drug nimesulide samples were obtained from different manufacturers, two micronized and one non-micronized samples were characterized by thermal analysis, spectroscopic techniques, morphological analysis, flowability and biopharmaceutical evaluation. The results showed that the samples belong to the same polymorph, do not have good flowability and particle size variations affect the biopharmaceutical evaluation tests. The design of the formulations and the choice of the production process were carried out based on the results obtained in the characterization of the drug tests. Pilot batches were evaluated by conducting dissolution profiles using the parameters established by the Brazilian Pharmacopoeia (FB 5, 2010) and compared with the reference Nisulid®. The proposed formulations show different dissolution behavior, and may highlight the choice of the surfactant, binder and adding steps of the surfactant and binding essential for obtaining most favorable results. The closest pilot batch dissolution values of the reference product was selected and then evaluated the behavior of dissolution media containing different concentrations of surfactant, in order to verify if the concentration of 2% (v/v) polysorbate 80, recommended by the Brazilian Pharmacopoeia, would be overestimating the bioavailability of the drug in vivo conditions. The results showed that the percentage of surfactant present in the dissolution medium directly impacts the amount of dissolved drug. The selected formulation demonstrated promising results to proceed with the manufacture of biobatches and the pharmaceutical equivalence study.

Made available in DSpace on 2016-07-01T11:59:28Z (GMT). No. of bitstreams: 2 license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) 6.pdf: 1983551 bytes, checksum: fa748c78d045ad8c560c9984c7c0d8de (MD5) Previous issue date: 2016 / Made available in DSpace on 2016-07-21T14:39:34Z (GMT). No. of bitstreams: 2 6.pdf: 1983551 bytes, checksum: fa748c78d045ad8c560c9984c7c0d8de (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2016 / Fundação Oswaldo Cruz. Instituto de Tecnologia em Fármacos/Farmanguinhos. Rio de Janeiro, RJ, Brasil. / A produção de medicamentos como a maioria da produção de produtos manufaturados, requer matérias-primas as quais necessitam inicialmente de um planejamento eficaz e depois um controle eficiente para que o produto final seja entregue nas condições requeridas. A falha no processo de aquisição dos insumos pode resultar negativamente em toda a cadeia produtiva. Farmanguinhos como Laboratório Farmacêutico Oficial (LFO) deve seguir a Lei nº 8.666 de 21 de junho de 1993, que trata do processo de aquisição, o que torna a atividade mais complexa assim como a atividade de Planejamento e Controle da Produção. Assim, o presente trabalho tem como objetivo principal analisar o sistema de suprimento de Farmanguinhos e propor melhorias no planejamento e controle de matérias-primas. Foi realizado um estudo descritivo tendo como estratégia metodológica o estudo de caso referente à Farmanguinhos. Foram realizados cálculos entre os tempos estimados e reais para cada etapa do processo produtivo de antirretrovirais no LFO em questão. Ademais, foram buscadas informações referentes a experiências de outros LFO e por fim foram elaboradas propostas de melhoria. No que tange ao atendimento ao cliente, Farmanguinhos não tem tido bom desempenho, uma vez que apenas 24% dos pedidos foram atendidos no prazo. Possui em tempo médio de atendimento para os anos 2010 a 2014 de 395 dias reais contra uma expectativa do principal cliente, o Ministério da Saúde, de 157 dias. O suprimento das matérias-primas corresponde a 88% do tempo total, sendo que só a requisição e a aquisição correspondem a 72% do tempo total. A primeira vista, a legislação rígida do serviço público parece ser o maior fator de atraso no sistema produtivo de Farmanguinhos. A lei veda a escolha de fornecedores e contratos de exclusividade por longos períodos a não ser em condições excepcionais. Ficando assim, na contramão das empresas de ponta no mercado privado que montam suas cadeias de suprimentos com empresas de sua escolha e com exclusividade. As propostas para tentar reduzir o tempo de suprimento passam pela qualificação de fornecedores e realização de Registro de Preços para aquisição das matérias-primas / The pharmaceutical production, as well as the manufactured products production, requires raw materials, which initially need an effective planning and then an efficient control to guarantee that the final product will be deliver in the required conditions. Failure to inputs of the acquisition process can result negatively on the entire commodity chain. Farmanguinhos, as Brazilian official pharmaceutical laboratories (LFO), should follow the Brazilian law no. 8666 of June 21, 1993, that treats about acquisition process, which makes the activity more complex and turn planning and production control complex too. Thus, this study objective to analyze Farmanguinhos supply chain system the Farmanguinhos and propose improvements in the planning and control of raw materials. It was conducted a descriptive study, having as a methodological strategy a case study of the Farmanguinhos. Calculations were make between theoretical and actual times for each stage of the antiretroviral production process at the LFO in question. In addition, information’s were show regarding the experiences of other LFO and finally improvement proposals were make. According to customer service, Farmanguinhos has not had good performance, only 24% of requests were delivery on time. Has a total average service time in the years 2010-2014 of 395 actual days against an expectation of the main customer, the Ministry of Health, of 157 days. The raw material supply correspond to 88% of the total time and, if we concentrate only the in request and in acquisition this correspond to 72% of the total time. At first glance, the rigid law of public service seems to be the longest delay factor in the productive system Farmanguinhos. The law prohibits the choice of suppliers and exclusive contracts for long periods unless in exceptional condition. Being against the leading companies in the private market that hires their supply chain with companies of your choice and being exclusive. The proposal try to reduce the leading time passes the qualification of suppliers and price record of accomplishment to purchase materials.