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Desenvolvimento de um m?todo inovador de forma??o de nanoemuls?es para libera??o modificada de praziquantel atrav?s da dilui??o de cristais l?quidosSouza, Izadora de 31 July 2015 (has links)
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Previous issue date: 2015-07-31 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Cristais l?quidos (CL) possuem um arranjo molecular bastante estruturado que combina propriedades dos estados l?quido e s?lido, bem como o fluxo dos l?quidos e a ordena??o da estrutura cristalina dos s?lidos. Foram testadas t?cnicas de alta e baixa energia para produzir CL, utilizando oleato de s?dio, fosfatidilcolina de soja, ?leo de soja, N-metilpirrolidona (NMP) e ?gua. As intera??es entre NMP e oleato de s?dio da formula??o foram investigadas. CL obtidos por t?cnica de alta energia foram caracterizados por microscopia de luz polarizada (MLP), reologia e tamanho de part?cula. MLP exibiu estruturas que sugerem presen?a de CL lamelares. Na reologia, as amostras apresentaram viscosidade newtoniana limitante nas curvas de fluxo e uma diminui??o no grau de estrutura??o nos testes oscilat?rios, quando a concentra??o de NMP diminu?a. Uma nova t?cnica para obter sistemas lip?dicos de libera??o de f?rmacos foi desenvolvida a partir da dilui??o de CL produzidos por baixa energia. CL foram produzidos por agita??o magn?tica e, posteriormente, foram dilu?dos com ?gua e solu??o aquosa de NMP 10%, a 25 ? C e 70 ?C, em que foram avaliados tamanho de got?cula e incorpora??o de praziquantel (PRZ). Os sistemas dilu?dos com ?gua apresentaram menor faixa de tamanho (165,22 ? 381,26 nm) e maior faixa de incorpora??o de PRZ (40,96 ? 43,44 mg/mL) quando comparadas com as dilu?das com a solu??o de NMP. N?o houve contribui??o da solu??o de NMP para a forma??o de got?culas menores e para a maior incorpora??o de PRZ. Houve um aumento na solubilidade do PRZ em sistemas dilu?dos com ?gua, aumentando a fra??o sol?vel de f?rmaco em at? 200 vezes quando comparada ? sua solubilidade em ?gua. Testes utilizando Espalhamento de raios-X a baixo ?ngulo e MLP comprovaram a transi??o da mesofase lamelar para sistemas com micelas vermiformes, confirmando o sucesso da nova t?cnica em obter sistemas lip?dicos de libera??o de f?rmacos atrav?s da dilui??o de CL. / Liquid crystalline mesophase (LC) have an organized molecular arrangement and combining properties of liquid and solid state as the flow of liquids and the ordered and crystalline structure of solids. High- and low energy techniques were used to produce LC. N-methylpyrrolidone (NMP) and sodium oleate interactions with the system were investigated. LC fabricated by high-energy method were characterized by polarizing light microscopy (PLM), rheology and droplet size. PLM showed structures that indicated lamellar phases. Surface tension no important difference between the samples was observed. Rheology showed a zero shear viscosity in flow curves with a shear-thinning behavior in oscillatory tests, which with increasing of NMP, there was a decrease in degree of structure. Novel method to obtain lipid based drug delivery system (LBDDS) were developed through LC dilution and drug-loading was tested. LC fabricated with low-energy method was diluted with water and NMP 10% aqueous solution, at 25 ?C and 70 ?C, which droplet size and drug loading were evaluated. The systems diluted with water showed lower range size (165.22 nm- 381.26 nm) and higher drug-loading (40.96 mg/mL - 43.44 mg/mL) when compared with systems diluted by NMP solution. NMP aqueous solution did not contribute to form smaller particle size and higher praziquantel-loading. An increment in the apparent solubility of Praziquantel was achieved from incorporation in dilution of LC with water, increasing the soluble drug fraction approximately 200-fold when compared with water solubility. Small angle X-ray scattering (SAXS) measurements and PLM comproved the transition from lamellar mesophase to worm-like micelle systems confirming the success of new techinique for obtain LBDDS from LC dilution.
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Avalia??o de catalisadores a base de carv?o da pir?lise do lodo de esgoto e carbetos de molibd?nio na transesterifica??o met?lica do ?leo de soja / Catalytic evaluation of coal derived from sewage sludge pyrolysis and molybdenum carbides materials from methyl transesterification reaction of soybeanAlexandrino, Angelinne Costa 29 September 2017 (has links)
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Previous issue date: 2017-09-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / H? d?cadas que a produ??o de combust?veis alternativos visando ? substitui??o do petr?leo e de seus derivados tem despertado o interesse de muitos pesquisadores em todo o planeta. Biodiesel ? uma alternativa renov?vel, o qual pode ser produzido a partir de ?leos residuais, gorduras animais e ?leos vegetais atrav?s do processo de transesterifica??o heterog?nea utilizando ?lcoois. Nesse contexto, catalisadores heterog?neos t?m se apresentado como potencial na produ??o de biodiesel em raz?o da possibilidade do seu reuso e por ser um processo mais limpo e eficiente. No presente trabalho, carv?o ativado obtido da pir?lise do lodo de esgoto (C.A), Mo2C, Mo2C/C.A e Ni (20%)-Mo2C/C.A foram avaliados no processo de transesterifica??o met?lica do ?leo de soja refinado visando ? produ??o de biodiesel. O carv?o do lodo foi tratado com o KOH no sentido de abrir os poros e promover maior ?rea especifica de contato, seguido de ativa??o f?sica. Os catalisadores a base de molibd?nio foram sintetizados a partir da rea??o g?s-s?lido utilizando como precursor heptamolibdato de am?nio e uma mistura de CH4/H2. Todos os materiais foram caracterizados utilizando as an?lises de TG, DRX, FRX, MEV, B.E.T e granulometria a laser. O processo de transesterifica??o foi avaliado em um reator de mistura constitu?do de um sistema de aquecimento e refluxo da fase alco?lica. Em temperatura constante de 65 oC, as condi??es operacionais estudadas para a rea??o foram: a natureza e concentra??o m?ssica (1 a 5%) do catalisador em rela??o ? massa do ?leo, a raz?o molar ?leo/?lcool (1/6 a 1/18), o pH do meio reacional (2,0 a 8,5), o tempo de rea??o (3 e 5 h) e a velocidade de agita??o da fase l?quida (450 e 600 rpm). Para todas as condi??es e demais catalisadores, o biodiesel foi produzido. A convers?o m?xima do ?leo de soja encontrada foi de 27,34%, no estudo cin?tico, para o catalisador Mo2C/C.A nas condi??es operacionais de 1% de catalisador, 6 h de rea??o, raz?o molar ?leo/?lcool de 1/12 e pH = 5. Na an?lise de caracteriza??o de uma amostra de biodiesel produzido o ponto de fulgor apresentou valor de 141 ?C, o qual est? acima do m?nimo especificado pela ANP. Um modelo cin?tico pseudo homog?neo foi utilizado, para o catalisador Mo2C/C.A atrav?s do qual foi mostrado que os resultados experimentais se ajustaram satisfatoriamente a uma cin?tica de 1? ordem, cuja constante cin?tica de velocidade teve como valor 0,0009 min-1. / For decades, the production of environment-friendly fuels, as alternative power sources for oil, has gained attention and interest of researchers worldwide. Biodiesel is a renewable alternative fuel that can be obtained from residual oils, animal fat and vegetable oils through heterogeneous transesterification reaction using alcohol. In this context, heterogeneous catalyst present potential for biodiesel production as they can be regenerated and provide a cleaner and more efficient process. In this work, several molybdenum carbide catalysts were tested for the transesterification reaction of soybean oil with methanol towards producing biodiesel. These catalysts were pure Mo2C, Mo2C supported over activated carbon (A.C), pure A.C and bimetallic Ni (20%)-Mo2C/A.C being this support produced from sewage sludge pyrolysis. The pyrolysis product was treated with KOH, in order to increase its porosity and promote a larger specific surface area, and later physically activated. Gas solid reaction with CH4 and H2 atmosphere was used to produce the studied molybdenum derived catalysts, and ammonium molybdate was used as molybdenum source in all cases. All catalysts were characterized in a TG, XDR, XFR, SEM, B.E.T and laser particle size analysis basis. Their activity towards transesterification reaction was evaluated by using a mixing reactor with temperature control and alcohol reflux at 65 ?C. The parameters that were manipulated for this experimental evaluation were: type and mass concentration of the catalyst (1 to 5%), oil/alcohol ratio (1/6 to 1/18), pH (2.0 to 8.5), reaction time (3 and 5h) and liquid phase agitation speed (450 and 600 rpm). For all conditions and other catalysts, biodiesel was produced. The maximum conversion found was 27.34% for the Mo2C/A.C catalyst under the operating conditions of 1% catalyst, 6 h reaction, oil/alcohol ration of 1/12 and pH = 5. In the characterization analysis of a sample of biodiesel produced the flash point presented a value of 141 ?C, which is above the minimum specified by the ANP. A pseudo homogeneous kinetics model was used, and experimental data presented agreement with a 1st order reaction with speed rate constant of 0,0009 min-1.
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Novo catalisador heterog?neo magn?tico SiO2/KI/?Fe2O3 para rea??o de transesterifica??o em ?leos vegetais para produ??o de biodieselMacedo, Alice Lopes 21 February 2017 (has links)
Data de aprova??o retirada da vers?o impressa do trabalho. / Incluir a Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) como ag?ncia financiadora. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-12-13T16:15:41Z
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Previous issue date: 2017 / Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) / A crescente demanda global por combust?veis l?quidos para transporte, gera??o de eletricidade, atividade industrial e produ??o agropecu?ria tem imposto planejamento de a??es direcionadas ao uso de fontes ambientalmente limpas de energia. Os derivados da biomassa s?o alternativas econ?mica e tecnicamente vi?veis aos de origem f?ssil, n?o renov?vel, ora dominantes na matriz energ?tica global. O biodiesel, l?quido formado por uma mistura de ?steres de ?cidos graxos, ? adequado ? opera??o em motores de combust?o interna de ciclo Diesel, em substitui??o ou em complemento ao petrodiesel, ou em outras m?quinas t?rmicas. O prop?sito central do presente trabalho foi o desenvolvimento de um catalisador s?lido economicamente vi?vel, quimicamente eficiente e ambientalmente limpo para a produ??o de biodiesel via processos de transesterifica??o de triacilglicer?is dos ?leos de maca?ba ou de soja, com metanol. Foi preparado o catalisador heterog?neo baseado em iodeto de pot?ssio impregnado em s?lica amorfa (SiO2; derivada de areia da constru??o civil) e misturada a um componente magn?tico sint?tico (maghemita, ?Fe2O3). As estruturas qu?mica, cristalogr?fica e hiperfina essenciais e as propriedades magn?ticas dos materiais precursores e do catalisador s?lido foram investigadas. O teor de ?steres e a composi??o dos biodieseis produzidos foram determinados por cromatografia de fase gasosa acoplada a espectr?metro de massa. A composi??o qu?mica do catalisador, verificada por espectroscopias de energia dispersiva sob feixe de el?trons e por fluoresc?ncia de raios X (FRX), confirmou a ocorr?ncia de Si, Fe, K, e I. As ?reas espec?ficas BET encontradas para os componentes individuais, SiO2, ?Fe2O3 e do catalisador SiO2/KI/?Fe2O3, foram 352, 102, e 19 m2 g-1, respectivamente. A significativa redu??o da ?rea espec?fica do catalisador aponta que os componentes foram efetivamente impregnados no suporte. A morfologia das part?culas visualizadas por microscopias eletr?nicas de varredura e de transmiss?o revela a textura esponjosa do catalisador SiO2/KI/?Fe2O3, similarmente ao suporte de s?lica; o ?xido de ferro magn?tico aparece como material altamente organizado, cristalino, disperso no suporte. Os dados M?ssbauer e da magnetometria do ?xido de ferro magn?tico puro e no catalisador confirmam ser a maghemita, resultando em uma magnetiza??o de satura??o do catalisador de 4,6 emu g-1. O catalisador SiO2/KI/?Fe2O3, usado na transesterifica??o de triacilglicer?is, na propor??o em massa em rela??o ao ?leo da am?ndoa de maca?ba de 4,5% e raz?o molar ?leo:metanol de 1:35, levou ? produ??o de 94,3 massa% de ?steres, ap?s 8 h de rea??o. Foi experimentalmente observado que a maghemita tem comportamento qu?mico-catal?tico sin?rgico com os demais componentes do catalisador. O SiO2/KI/?Fe2O3 foi reutilizado em seis rea??es consecutivas com ?leo de soja, na mesma propor??o do catalisador e raz?o molar ?leo:metanol de 1:35, com rendimentos de 94,5% e tempo reacional de 110 min, para o primeiro ciclo, e de 61,2% e 150 min, para o ?ltimo ciclo. O catalisador, antes e ap?s cada ciclo de reuso, e as al?quotas das rea??es foram analisados por FRX, que mostrou que n?o h? perda significativa dos componentes do catalisador. Os resultados demonstram uma perspectiva tecnol?gica que permite redu??o substantiva do volume de efluentes poluentes e utiliza??o de diferentes mat?rias-primas oleaginosas de alto potencial para a produ??o de biodiesel. / Tese (Doutorado) ? Programa de P?s-gradua??o em Biocombust?veis, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / The global demand for liquid fuels destined to propel automobile motors and for all other types of transport has been growing significantly over the last decades in response to the needs of the population for mobility. These fuels are also necessary for the generation of electricity to support industrial and agricultural activities. However, the principal concern involved in the generation of mechanical work involves the threat that the effluents from burning fuels, particularly those from fossil origin, impart to the environment. Biomass-derived fuels are energetically, economically and environmentally interesting alternatives to the non-renewable fossil fuels, which still dominate the global energy matrix. Biodiesel, a liquid that is composed of a mixture of esters of fatty acids, is mainly suitable for use in Diesel-cycle internal combustion engines, totally replacing or partially complementing petrodiesel. The main purpose of the present work was the development of an economically viable, environmentally clean and chemically efficient solid catalyst for the production of biodiesel via the transesterification reaction of triacylglycerols from maca?ba or soybean oil with methanol. The proposed heterogeneous catalyst was based on potassium iodide-impregnated particles of amorphous silica (SiO2; derived from construction sand) mixed with a synthetic magnetic iron oxide (maghemite, ?Fe2O3). The essential chemical, crystallographic and hyperfine structures and magnetic properties of the starting materials and of the solid catalyst mixture were assessed by physical laboratory techniques. The ester content and the chemical composition of the biodiesel produced were determined by gas chromatography coupled with mass spectrometry. The chemical composition of the catalyst, as determined by electron energy dispersive and X-ray fluorescence (FRX) spectroscopies, confirmed the occurrence of Si, Fe, K, and I. Specific BET surface areas for the SiO2 and ?Fe2O3 components and for the SiO2/KI/?Fe2O3 catalyst were found to be 352; 102 and 19 m2 g-1, respectively. The significant reduction in the specific area of the catalyst indicates that the solid components were intimately mixed and that KI was indeed impregnated on the support. The morphology of the particles, as visualized from the scanning and transmission electron microscopy images, reveals the spongy texture of the SiO2/KI/?Fe2O3 catalyst, which was quite similar to that of the initial silica support. The atomic framework of the magnetic iron oxide appeared to be a highly organized, crystalline nano-material, relatively well dispersed on the silica support. The M?ssbauer and magnetometric data for the pure magnetic iron oxide and for the catalyst confirm that the component is essentially maghemite. The resulting saturation magnetization of the catalyst mixture was 4.6 emu g-1. From the chemical point of view, this maghemite was found to act synergically with the other components of the catalyst and to significantly improve its catalytic activity. The transesterification reaction of triacylglycerols using the SiO2/KI/?Fe2O3 catalyst at a mass ratio corresponding to 4.5 mass% relative to the maca?ba kernel oil and a methanol:oil molar ratio 30:1 yielded 94.3 mass% of esters after 8 h of reaction. The SiO2/KI/?Fe2O3 catalyst was reused for six consecutive transesterification reactions of triacylglicerols in soybean oil employing the same mass proportion of the catalyst and a methanol:oil molar ratio 35:1. A 94.5% yield of esters was obtained after 110 min of reaction in the first cycle, and a 61.2% yield was obtained in the last reaction cycle after 150 min. The compositions of the catalyst before and after each reaction cycle, along with detection of residual chemical elements in the liquid mixture of esters formed, were duly monitored by FRX. There was no significant leaching of the catalyst components during the reactions. These results open a perspective for (i) a substantial reduction in the volume of polluting effluents and (ii) the use bio-oils from native Brazilian flora (maca?ba) as raw materials for the industrial production of biodiesel.
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Estudo da efic?cia do tensoativo sorbitano tween 80 veiculado em nanoemuls?o contendo ?leo de soja, como inibidor de corros?oRodrigues, Ciro Jos? Ferreira 30 August 2012 (has links)
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Previous issue date: 2012-08-30 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Nowadays, the use of chemicals that satisfactorily meet the needs of
different sectors of the chemical industry is linked to the consumption of
biodegradable materials. In this context, this work contemplated
biotechnological aspects with the objective of developing a more
environmentally-friendly corrosion inhibitor. In order to achieve this goal,
nanoemulsion-type systems (NE) were obtained by varying the amount of
Tween 80 (9 to 85 ppm) a sortitan surfactant named polyoxyethylene (20)
monooleate. This NE-system was analyzed using phase diagrams in which the
percentage of the oil phase (commercial soybean oil, codenamed as OS) was
kept constant. By changing the amount of Tween 80, several polar NE-OS
derived systems (O/W-type nanoemulsion) were obtained and characterized
through light scattering, conductivity and pH, and further subjected to
electrochemical studies. The interfacial behavior of these NE-OS derived
systems (codenamed NE-OS1, S2, S3, S4 and S5) as corrosion inhibitors on
carbon steel AISI 1020 in saline media (NaCl 3.5%) were evaluated by
measurement of Open Circuit Potential (OCP), Polarization Curves (Tafel
extrapolation method) and Electrochemical Impedance Spectroscopy (EIS). The
analyzed NE-OS1 and NE-OS2 systems were found to be mixed inhibitors with
quantitative efficacy (98.6% - 99.7%) for concentrations of Tween 80 ranging
between 9 and 85 ppm. According to the EIS technique, maximum corrosion
efficiency was observed for some tested NE-OS samples. Additionaly to the
electrochemical studies, Analysis of Variance (ANOVA) and Principal
Component Analysis (PCA) were used, characterization of the nanoemulsion
tested systems and adsorption studies, respectively, which confirmed the
results observed in the experimental analyses using diluted NE-OS samples in
lower concentrations of Tween 80 (0.5 1.75 ppm) / Atualmente, a utiliza??o de produtos qu?micos que atendam satisfatoriamente
as necessidades de diferentes setores da ind?stria qu?mica encontra-se
vinculada ao consumo de materiais biodegrad?veis. Neste contexto, o presente
trabalho foi desenvolvido contemplando aspectos biotecnol?gicos com o
objetivo de se desenvolver um inibidor de corros?o menos agressivo ao meio
ambiente. Para tanto, uma nanoemuls?o (denominada de NE-OS) foi obtida
com Tween 80 (polioxietileno (20) monooleato), ?leo de soja (OS) e ?gua
bidestilada. A modifica??o dos percentuais deste tensoativo sorbitano (entre 9
e 85 ppm) foi avaliada em diagramas de fases em que se manteve constante o
percentual da fase ?leo, possibilitando a forma??o do sistema NE-OS em
diferentes concentra??es. Desta forma, nanoemuls?es (NE-OS1, S2, S3, S4 e
S5) polares (do tipo O/A) foram caracterizadas (an?lise de dispers?o de luz,
condutividade e pH) e submetidas a estudos eletroqu?micos. O comportamento
interfacial destes sistemas nanoemulsionados como inibidores de corros?o na
presen?a de a?o-carbono AISI 1020, em meio salino (NaCl 3,5%) foi avaliado
pela determina??o do Potencial de Circuito Aberto (OCP), Curvas de
Polariza??o (obtidas pela extrapola??o das curvas de Tafel) e Espectroscopia
de Imped?ncia Eletroqu?mica (EIE). De acordo com os resultados obtidos pelas
an?lises das Curvas de Polariza??o, foi poss?vel caracterizar o sistema NE-OS
(e suas varia??es) como inibidores mistos com efici?ncias m?ximas de
inibi??es quantitativas (98,6% - 99,7%) para NE-OS1 e NE-OS2 (9 - 85 ppm do
tensoativo). No entanto, de acordo com a t?cnica EIE, as efici?ncias m?ximas
de inibi??es quantitativas foram observadas para v?rias amostras deste
sistema NE-OS. Como ferramentas adicionais aos estudos eletroqu?micos
foram realizados quimiom?tricos de An?lise de Vari?ncia (ANOVA) e An?lise de
Componentes Principais (PCA), utilizadas, respectivamente, para
caracteriza??o das nanoemuls?es e estudo de isotermas de adsor??o, que
confirmaram os resultados observados nas investiga??es experimentais em
que se utilizaram as nanoemuls?es dilu?das com o tensoativo em
concentra??es reduzidas (0,5 1,75 ppm)
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