Human tumor susceptibility gene 101, TSG101, exhibits a variety of functions including protein sorting, vesicular trafficking, and regulation of transcription, epithelial growth and differentiation. The upstream sequence of TSG101 gene shows a typical housekeeping TATA-less and Sp1 containing promoter. Our previous data indicated the essential role of TSG101 in skin keratinocyte differentiation that is under the regulation of PKC-Sp1 signaling. In this report, we investigated the correlation of TSG101 and Sp1 expression in the specimens of cervical intraepithelial neoplasia. Cervical intraepithelial neoplasia specimens used in this study were 129 paraffin blocks from 41 normal, 35 CIN I, 28 CIN II and 25 CIN III/CIS patients collected in Cancer Prevention and Screening Center at Kaohsiung from January 2005 to July 2007. The expression of TSG101 and Sp1 were analyzed by immunohistochemistry and digitally quantified by Image Pro-plus 6.1 Microimage software according to the method described by Eliane Pedra Dias et al. The quantified data were statistically analyzed using Spearman's rho coefficient and SPSS for Win, v.14 statistical software (SPSS Inc., Chicago, USA). Values were considered significantly different when the P value < 0.05. We found that TSG101 and Sp1 are expressed in cells of parabasal and intermediate layers in normal cervical epithelium, whereas their expressions in basal and superficial layers were either absence or reduced. Interestingly, the expressions of these two markers are significantly increased in more advanced progression stages (CIN II and CIN III/CIS) of cervical intraepithelial neoplastic specimens (P < 0.05). Congruous expression pattern of TSG 101 and Sp1 in normal cervical epithelium confirms the important of cellular Sp1 signaling in regulating TSG101 expression, which is essential during epithelial cell growth and differentiation. Our results also indicate upregulation of these two markers might be important for the progression of cervical intraepithelial neoplasia. Further analysis using more specimens should reveal the prognostic value of these two markers.

Made available in DSpace on 2014-06-12T15:07:48Z (GMT). No. of bitstreams: 2 arquivo1582_1.pdf: 452251 bytes, checksum: 5691474a22f46504567b67e2a9903c72 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2004 / A presente dissertação tem por objetivo analisar o papel desempenhado pelo CIN Centro de Inovação e Negócios, nas atividades de gestão, promoção e articulação dos programas SEBRAETEC no Estado de Pernambuco, em parceria com o SEBRAE, junto às Micro e Pequenas Empresas. A partir do estudo do ambiente de surgimento do CIN, busca-se avaliar as dificuldades que este vem enfrentando na gestão do referido programa de consultoria tecnológica frente às pequenas empresas. Para este fim, foram aplicados questionários e realizadas entrevistas junto aos atores individuais envolvidos nos projetos de consultoria

Made available in DSpace on 2015-04-14T13:59:08Z (GMT). No. of bitstreams: 1 389419.pdf: 856184 bytes, checksum: 75843de852363f22fd3691f46ed12cd5 (MD5) Previous issue date: 2007-02-28 / Este trabalho apresenta um estudo comparativo entre sistemas catal?ticos alternativos, acetilacetonatos met?licos (ferro, cobre, cromo e estanho), frente ao catalisador comercial dibutil dilaurato de estanho (IV), DBTDL, na s?ntese de poliuretanos obtidos a partir de rea??es entre o diisocianato de isoforona (IPDI) e os poli?is polipropilenoglicol/dietilenoglicol e 1,6-hexanodiol poliadipato. Os sistemas catal?ticos acetilacetonatos foram obtidos a partir da rea??o entre um sal met?lico e a acetilacetona, e caracterizados atrav?s da espectroscopia de infravermelho (IV) e espectroscopia eletr?nica de ultravioleta (UV) de acordo com a literatura. As rea??es de forma??o dos poliuretanos foram acompanhadas atrav?s do consumo de IPDI ao longo do tempo, verificado atrav?s da diminui??o da concentra??o de NCO utilizando o m?todo titulom?trico com dibutilamina e por IV atrav?s da diminui??o da banda caracter?stica de NCO livre, 2300-2200 cm-1. Atrav?s dos dados de IV determinou-se o comportamento cin?tico das rea??es, atrav?s do qual verificou-se que as rea??es realizadas com excesso de poli?l seguem comportamento cin?tico de pseudo-1? ordem, enquanto as rea??es realizadas em quantidade equivalente do diisocianato e do poli?l apresentaram comportamento cin?tico de 2? ordem

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-10-18T18:56:51Z No. of bitstreams: 1 TESE_JULIANA_PELISOLI_HOLZ_HOMOLOGA??O.pdf: 1545312 bytes, checksum: f915686f1b1663c40d8c1dba1f335b6d (MD5) / Rejected by Sheila Dias (sheila.dias@pucrs.br), reason: Devolvido devido ? falta da capa institucional no arquivo PDF. on 2018-10-19T12:03:09Z (GMT) / Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-10-19T20:35:58Z No. of bitstreams: 1 TESE_JULIANA_PELISOLI_HOLZ_HOMOLOGA??O_PUCRS.pdf: 1572906 bytes, checksum: 81eb2ad136f458f673745debe4a6fa13 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-10-22T11:20:21Z (GMT) No. of bitstreams: 1 TESE_JULIANA_PELISOLI_HOLZ_HOMOLOGA??O_PUCRS.pdf: 1572906 bytes, checksum: 81eb2ad136f458f673745debe4a6fa13 (MD5) / Made available in DSpace on 2018-10-22T11:30:50Z (GMT). No. of bitstreams: 1 TESE_JULIANA_PELISOLI_HOLZ_HOMOLOGA??O_PUCRS.pdf: 1572906 bytes, checksum: 81eb2ad136f458f673745debe4a6fa13 (MD5) Previous issue date: 2017-10-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Glyphosate is the most widely used herbicide in the world, due to its broad spectrum of action. But there is a need for reduction measures in its application, due to the risks associated with contamination of water and the environment. The development of controlled release systems appears as an alternative to minimize the application of this herbicide. This work aimed at the preparation of glyphosate-containing Poly (?-caprolactone) (PCL) microspheres. These were characterized as to their morphology, structure, physicochemical properties, and a bioassay was carried out to evaluate their use in rice cultivation, in order to create a possible alternative for the use of these herbicides in plantations. The PCL / glyphosate microspheres produced by the multiple emulsion technique and solvent evaporation were in the form of solid beads with mean sizes of 3 ?m ? 0.6 ?m. It was possible to incorporate 9.3% glyphosate in relation to the polymer mass in the formed particles, revealing an efficiency of incorporation IE of 30.9%. From the techniques used to quantify the incorporated glyphosate (UVvis, TGA and CHN), it can be stated that with the increase of glyphosate concentration in the formulation there is an increase in its IE. On the other hand, this increase leads to a decrease in the average size of the microspheres. The release of the herbicide from the microspheres was evidenced by bioassays, and in the assessment of the glyphosate release profile of the microspheres, it can be seen that approximately 17% of the herbicide was released into the medium, 0.01 M CaCl2 solution at room temperature, after 360 minutes of testing. This study allowed to affirm that the theoretical model described by Korsmeyer-Peppas is adequate to characterize the phenomenon of transport of glyphosate release from the microspheres, revealing an anomalous transport not governed by Fick diffusion. / O glifosato ? o herbicida mais utilizado no mundo, devido ao seu amplo espectro de a??o. Por?m existe a necessidade de medidas de redu??o na sua aplica??o, devido aos riscos associados ? contamina??o da ?gua e do meio ambiente. O desenvolvimento de sistemas de libera??o controlada surge como uma alternativa para minimizar a aplica??o deste herbicida. Este trabalho teve como objetivo a prepara??o de microesferas de Poli (?-caprolactona) (PCL) contendo glifosato. Estas foram caracterizadas quanto a sua morfologia, estrutura, propriedades f?sicoqu?micas, e ainda, realizou-se um bioensaio para a avalia??o do seu uso na cultura do arroz, a fim de criar uma poss?vel alternativa para o uso destes herbicidas em planta??es. As microesferas de PCL/glifosato produzidas atrav?s da t?cnica de emuls?o m?ltipla e evapora??o do solvente apresentaram a forma de esferas s?lidas com tamanhos m?dios de 3 ?m ? 0,6 ?m. Foi poss?vel incorporar 9,3% de glifosato em rela??o ? massa de pol?mero nas part?culas formadas, revelando uma efici?ncia de incorpora??o (EI) de 30,9%. A partir das t?cnicas utilizadas para quantifica??o do glifosato incorporado (UVvis, TGA e CHN), pode-se afirmar que com o aumento da concentra??o de glifosato na formula??o existe um aumento de sua EI. Por outro lado este aumento acarreta na diminui??o no tamanho m?dio das microesferas. A libera??o do herbicida das microesferas foi evidenciada atrav?s de bioensaios, e na avalia??o do perfil de libera??o do glifosato das microesferas, pode-se constatar que aproximadamente 17% do herbicida foi liberado para o meio, solu??o de CaCl2 0,01 M em temperatura ambiente, ap?s transcorridos 360 minutos de ensaio. Este estudo permitiu afirmar que o modelo te?rico descrito por Korsmeyer-Peppas ? adequado para caracterizar o fen?meno de transporte de libera??o do glifosato das microesferas, revelando um transporte an?malo n?o governado pela difus?o de Fick.

No description available.

Networks at various levels of the nervous system coordinate different motor patterns such as respiration, eye or hand movements and locomotion. Intrinsic rhythm-generating networks that are located in the spinal cord generate motor behaviors that underlie locomotion in vertebrates. These networks give a continuous and measurable coordinated rhythmic motor output and are referred to as locomotor central pattern generators (CPGs). Characterization of the mammalian locomotor CPG and its molecular control is depending on the identification of participating neurons and neuronal populations. In this thesis I present work where we have studied the significance of subpopulations of neurons in the formation and function of the left-right circuitry. In summary, we show that the axon guidance receptor DCC has a central role in the formation of spinal neuronal circuitry underlying left-right coordination, and that both Netrin-1 and DCC are required for normal function of the locomotor CPG. Commissural interneurons (CINs), which send their axons across the ventral midline in the spinal cord, play a critical role in left–right coordination during locomotion. A complete loss of commissural axons in the spinal cord, as seen in the Robo3 null mutant mouse, resulted in uncoordinated fictional locomotor activity. Removing CIN connections from either dorsal or ventral neuronal populations led to a shift from alternation to strict synchronous locomotor activity. Inhibitory dI6 CIN have been suggested as promising candidate neurons in coordinating bilateral alternation circuitry. We have identified that Dmrt3, expressed in inhibitory dI6 CINs, is a crucial component for the normal development of coordinated locomotor movements in both horses and mice. We have also concluded that the prominent hopping phenotype seen in hop/hop mice is a result of abnormal developmental processes including induction from the notochord and Shh signaling. Together, these findings increase our knowledge about the flexibility in neuronal circuit development and further confirm the role of dI6 neurons in locomotor circuits.

Ce travail vise à étudier un matériau biphasé métallique matrice/inclusion. Une méthode simple est proposée pour évaluer les propriétés élastiques d'une phase si les propriétés de l'autre phase sont connues. La méthode est basée à la fois sur un modèle d'homogénéisation inverse et sur les mesures de champs mécaniques par corrélation d'images numériques 2D. L'originalité de la méthode repose sur l'échelle étudiée, à savoir l'échelle de la microstructure du matériau : la taille caractéristique des inclusions est d'environ quelques dizaines de microns. L'évaluation est réalisée sur des essais de traction uniaxiale standards associés à un microscope longue distance. Cela permet d'observer la surface de l'échantillon à l'échelle de la microstructure au cours de la sollicitation mécanique. Tout d'abord, la précision de la méthode est examinée à partir de champs mécaniques 'parfaits' provenant des simulations numériques pour quatre microstructures : inclusions simples élastiques ou poreux ayant une forme sphérique ou cylindrique. Deuxièmement, cette précision est examinée sur les vrais champs mécaniques provenant des deux microstructures simples : une matrice métallique élasto-plastique contenant un ou quatre micro-trous cylindriques arrangés en un motif carré. Troisièmement, la méthode est utilisée pour évaluer les propriétés élastiques des inclusions de forme arbitraire dans un échantillon Zircaloy-4 oxydé présentant le gainage du combustible d'un réacteur à eau sous pression après un accident de perte de réfrigérant primaire (APRP). Dans toute cette étude, les phases sont supposées avoir des propriétés isotropes. / This work is focused on a matrix/inclusion metal composite. A simple method is proposed to evaluate the elastic properties of one phase while the properties of the other phase are assumed to be known. The method is based on both an inverse homogenization scheme and mechanical field's measurements by 2D digital image correlation. The originality of the approach rests on the scale studied, i.e. the microstructure scale of material: the characteristic size of the inclusions is about few tens of microns. The evaluation is performed on standard uniaxial tensile tests associated with a long-distance microscope. It allows observation of the surface of a specimen on the microstructure scale during the mechanical stress. First, the accuracy of the method is estimated on ‘perfect' mechanical fields coming from numerical simulations for four microstructures: elastic or porous single inclusions having either spherical or cylindrical shape. Second, this accuracy is estimated on real mechanical field for two simple microstructures: an elasto-plastic metallic matrix containing a single cylindrical micro void or four cylindrical micro voids arranged in a square pattern. Third, the method is used to evaluate elastic properties of inclusions with arbitrary shape in an oxidized Zircaloy-4 sample of the fuel cladding of a pressurized water reactor after an accident loss of coolant accident (LOCA). In all this study, the phases are assumed to have isotropic properties.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2016-08-09T13:56:09Z No. of bitstreams: 2 Dissertação - Kelly Deyse Segati - 2012.pdf: 1381150 bytes, checksum: 6c27c539f7ddade59c13124dfc688935 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-08-09T13:57:32Z (GMT) No. of bitstreams: 2 Dissertação - Kelly Deyse Segati - 2012.pdf: 1381150 bytes, checksum: 6c27c539f7ddade59c13124dfc688935 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-08-09T13:57:32Z (GMT). No. of bitstreams: 2 Dissertação - Kelly Deyse Segati - 2012.pdf: 1381150 bytes, checksum: 6c27c539f7ddade59c13124dfc688935 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2012-12-18 / Infection with Chlamydia trachomatis (CT) may be associated with persistent carcinogenic HPV types and the development of cervical neoplasia. There are indications that detection of CT serum antibodies rather than DNA is a better measure of cumulative exposure to CT or of exposure occurring several years prior to the development of cervical disease. The objective of this study was to compare the positivity for CT by ELISA and PCR and to correlate with the severity of cervical neoplasia in women with abnormal cervical smear. Between February 2007 and March 2009, 136 women were referred to the colposcopy clinic at the Santa Casa de Misericordia in Goiânia-GO. HPV DNA was detected by the polymerase chain reaction (PCR) and genotyping was performed by reverse line-blot hybridization assay. CT seropositivity was tested by ELISA for the detection of IgG antibodies and the detection of CT was done by PCR to amplify a sequence in the cryptic plasmid generating a fragment of 512 base pairs. The total prevalence of HPV infection was 85.2%. Seropositivity for CT was 26%. Thirty-one women 26.7 were tested positive for CT antibodies and HPV-DNA. Of these 10.3% had diagnosis of cervical intraepithelial neoplasia grade 1 (CIN1) or cervicitis, while 16.3% had histological diagnosis of CIN2 worse diagnosis. When employed PCR test positivity was found to be 8.8%. Eleven women 9.48% were tested positive for CT and HPV DNA. Of these 5.1% had diagnosis of cervicitis or CIN1 and 4.3% had a diagnosis of CIN2 or worse diagnosis. The agreement between serology and PCR tests for CT was considered poor (kappa=0.10 IC 95% 0.69-7.9). Taking as reference the cases negatives for HPV and CT, a positivity for HPV and CT seropositivity was significantly associated with a diagnosis of CIN2 or worse diagnosis, for all HPV types (OR=11.9 IC=2.00-91.5 p=0.0009) and types 16 and 18 (OR=7.50 IC=0.91-76.28 p=0.02). Significant association was observed after adjustment for HPV. A Borderline significance was observed considering other HPV types (OR=7.50 IC=0.91-76.28 p=0.02). CT seropositivity was associated with CIN2 worse diagnosis in women infected by HPV, mainly when the types 16 and 18 were involved. This study did not show any association between CT infection detected by PCR and CIN2 or worse diagnosis. These data support the hypothesis that seropositivity for CT compared to PCR positivity in HPV positive women, especially for types 16 and 18, is a better measure of previous exposure, which reflects a higher probability of association with the severity of cervical neoplasia. / A infecção por Chlamydia trachomatis (CT) pode estar associada com a persistência dos tipos de Papilomavírus humano (HPV) oncogênicos e desenvolvimento da neoplasia cervical. Há indicações de que a detecção de CT por sorologia seja uma melhor medida de exposição cumulativa ou da exposição passada quando comparada a detecção pela reação da polimerase em cadeia (PCR). O objetivo deste estudo foi comparar a positividade para CT pelos métodos de ELISA e PCR e relacionar com a gravidade da neoplasia cervical em mulheres com anormalidades citológicas. Entre fevereiro de 2007 e março de 2009, 136 mulheres, foram encaminhadas à Clínica de Colposcopia na Santa Casa de Misericórdia em Goiânia-GO por exame citológico alterado. A detecção de DNA do HPV foi realizada por PCR utilizando os iniciadores PGMY09/PGMY11, e a genotipagem foi realizada por hibridização reversa em pontos. A positividade para CT foi avaliada por ELISA para detecção de anticorpos IgG e por PCR empregando iniciadores cujo alvo é uma região de plasmídeo críptico, gerando um fragmento de aproximadamente 512 pares de bases. A prevalência total da infecção por HPV foi 85,2%. A positividade para CT por sorologia foi de 25%. Trinta e uma amostras 26,7% foram positivas para HPV e CT. Destas 10,3% tinham diagnóstico de neoplasia intraepitelial cervical grau 1 (NIC1) ou cervicite, enquanto 16,3% tinham diagnóstico histológico de NIC 2 ou pior diagnóstico. Quando empregado o teste de PCR a positividade encontrada foi de 8,8%. Onze amostras 9,48% foram positivas para HPV e CT por PCR, sendo que 5,1% das pacientes apresentavam diagnóstico de NIC1 ou cervicite e 4,3% tinham diagnóstico de NIC 2 ou pior diagnóstico. A concordância entre os testes de sorologia e PCR para CT foi considerado ruim (kappa=0,10 IC 95% 069-7.9). Tomando como referência casos negativos para HPV/CT, a positividade para HPV/CT por sorologia foi significantemente associada com diagnóstico de NIC2 ou pior diagnóstico, para todos os tipos de HPV (OR=11.9 IC=2.00-91.5 p=0.0009) e para os tipos 16 e 18 (OR=16.25 IC=2.28-148.57 p=0.0005). Uma associação limítrofe foi observada considerando outros tipos de HPV (OR=7.50 IC=0.91-76.28 p=0.02). Houve associação estatisticamente significante após o ajustamento para infeção por HPV entre as infecções pelos tipos 16 e 18 e soropositividade para CT com a gravidade da neoplasia cervical. Quando empregado o teste de PCR, não houve associação entre a coinfecção HPV/CT e a gravidade da neoplasia cervical. Estes dados reforçam a hipótese de que a soropositividade para CT quando comparada a positividade por PCR em mulheres HPV positivas, especialmente para os tipos 16 e 18, é uma melhor medida de exposição anterior, o que reflete maior probabilidade de associação com a gravidade da neoplasia cervical.

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-10-11T17:16:47Z No. of bitstreams: 1 Disserta??o Rafael Bitello Silva.pdf: 3894988 bytes, checksum: cf3a5e12050e0f5509ae1930f1b89181 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-10-17T12:16:39Z (GMT) No. of bitstreams: 1 Disserta??o Rafael Bitello Silva.pdf: 3894988 bytes, checksum: cf3a5e12050e0f5509ae1930f1b89181 (MD5) / Made available in DSpace on 2018-10-17T12:23:40Z (GMT). No. of bitstreams: 1 Disserta??o Rafael Bitello Silva.pdf: 3894988 bytes, checksum: cf3a5e12050e0f5509ae1930f1b89181 (MD5) Previous issue date: 2018-07-16 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / In this study the influence of different commercial curing agents of epoxy resin on film capacitors encapsulation was evaluated. A formulation with DGEBA epoxy resin was used with three different curing agent types: anhydride base, aliphatic amine base and polyamidoamine base. The curing reaction kinetic analysis of each epoxy system was performed by Osawa dynamic method by DSC according ASTM E968. The thermal properties of the epoxy systems were checked by TGA and DSC while the mechanical properties were measured by Shore D hardness and IZOD impact strength, also the a characterization by SEM was performed. The epoxy systems performance in capacitor was verified by qualification tests for film capacitors for automotive application based in AEC-Q200 D, as: exposure to the maximum capacitor operating temperture, exposure to thermal cycles and exposure to humidity. The capacitors were characterized by the capacitance variation while the effects in the epoxy systems were checked by their thermal and mechanical properties change. The systems based on aliphatic amine and polyamidoamine had lower activation energy and higher reaction velocity than the anhydride system. The performance of the capacitor against humidity was similar between the evaluated systems showing low loss of capacitance after the test, whereas against thermal cycles, even the aliphatic amine and polyamidoamine base systems were not affected by reduction of mechanical properties, they had their performance affected by cracks arising. Regarding the performance under exposure to the maximum operating temperature, the anhydride system presented the lowest capacitance loss in the capacitor, followed by the samples with polyamidoamine and aliphatic amine, respectively, which showed a significant reduction of the mechanical properties after prolonged exposure to the temperature of the test. / Neste estudo avaliou-se a influ?ncia de diferentes agentes de cura comerciais de resina ep?xi no encapsulamento de capacitores de filme. Foi utilizado uma formula??o de resina ep?xi DGEBA (diglicidil ?ter de bisfenol-A) com tr?s tipos diferentes de agente de cura: base anidrido, base amina alif?tica e base poliamidoamina. A an?lise da cin?tica da rea??o de cura de cada sistema ep?xi foi realizada pelo m?todo din?mico de Osawa, por DSC conforme ASTM E968. As propriedades t?rmicas dos sistemas ep?xi foram determinadas por TGA e DSC enquanto que as propriedades mec?nicas foram medidas atrav?s de dureza Shore D e resist?ncia ao impacto IZOD, al?m disto foi realizado caracteriza??o por MEV. O desempenho dos sistemas ep?xi no capacitor foi verificado pelos ensaios de qualifica??o de capacitores de filme para aplica??o automotiva baseados na norma AEC-Q200 D, sendo estes: exposi??o a temperatura m?xima do capacitor, exposi??o a ciclos t?rmicos e exposi??o a umidade. Os capacitores foram caracterizados pela varia??o de capacit?ncia enquanto que os efeitos nos sistemas ep?xi foram acompanhados pela altera??o em suas propriedades t?rmicas e mec?nicas. Os sistemas a base de amina alif?tica e poliamidoamina apresentaram menor energia de ativa??o e maior velocidade de rea??o que o sistema anidrido. O desempenho do capacitor frente a umidade foi similar entre os sistemas avaliados com baixa perda de capacit?ncia ap?s o ensaio, enquanto que frente aos ciclos t?rmicos, mesmo n?o apresentando redu??o de propriedades mec?nicas os sistemas base amina alif?tica e poliamidoamina tiveram seu desempenho afetado pelo aparecimento de trincas. Em rela??o ao desempenho sob exposi??o ? temperatura m?xima o sistema anidrido foi o que apresentou menor perda de capacit?ncia no capacitor, seguido das amostras com poliamidoamina e amina alif?tica, respectivamente, sendo que estas apresentaram redu??o significativa das propriedades mec?nicas ap?s exposi??o prolongada a temperatura do ensaio.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-09-12T19:05:23Z No. of bitstreams: 1 2017 - Amanda de Paula Alves.pdf: 2949048 bytes, checksum: 68f405efb8be6119401dfd85e1d5768a (MD5) / Made available in DSpace on 2017-09-12T19:05:23Z (GMT). No. of bitstreams: 1 2017 - Amanda de Paula Alves.pdf: 2949048 bytes, checksum: 68f405efb8be6119401dfd85e1d5768a (MD5) Previous issue date: 2017-02-23 / The large amount of glycerol, produced in the last decades, generated as a by product of biodiesel production is object of inumerous studies searching for different technologies for its purification. Crude glycerol obtained as a by-product in the transesterification process is composed of alcohol, water, inorganic salts, free fatty acids, mono-, di-, triglycerides, among other organic materials and wastes in different concentrations. It is of extreme importance the purification of glycerol in order to reduce environmental problems due to its accumulation. There are current effective technologies in purifying and refining crude glycerol. However, they are considered unfeasible for small and medium production units due to the high cost and high energy demand. In this way, it is essential that new purification routes of low cost and high efficiency, as well as new markets, be developed. The adsorption process is promising and very favorable technique to remove the contaminants from glycerin due to its low cost, simplicity of design and operation. In this point of view, the objective of this work was to select an adsorbent for the purification of crude glycerol obtained from the transesterification reaction of residual oil. The evaluation of the efficiency and the best operacional conditions were studied using three types of adsorbents: Pure-Flo Supreme B81 clarifying clay, activated charcoal and diatomaceous earth. Preliminary adsorption experiments were carried out using a synthetic solution of glycerin and soybean oil, in order to verify the influence of glycerin concentration in the solution, as well as the behavior of the glycerol contaminants in the adsorption process. In order to reach the objective, the influence and optimization of the process variables as temperature (298.15, 305.65 and 313.15 K), amount of adsorbent (1.2, 1.8 and 2.4 g) and glycerol concentration (30, 50 and 70% v/v) were evaluated through an experimental design. The most significant variable was glycerol concentration, and results indicated high glycerol content after purification: 97.25% for diatomaceous earth, 95.59% for activated carbon and 90.26% for clay. Through the optimization of these variables, experiments were carried out to study the thermodynamics and kinetics of the reaction. The equilibrium time was less than 60 minutes for the three adsorbents. The negative values of Gibbs free energy (?G) showed that the adsorption of the contaminants is a spontaneous process. The negative values for enthalpy change (?H) and positive entropy (?S) values for clay and activated carbon indicate an exothermic nature and that the contaminant molecules are more randomnless in the adsorbed state than in solution. The positive value of ?H for diatomaceus earth indicates that the adsorption process for this adsorbent is endothermic. The adsorption results obtained at 298.15, 305.65 and 313.15 K showed that the experimental data were well correlated with the Langmuir, Freundlich and Redlich-Peterson isotherms models. The purification of crude glycerol using the same adsorbents did not show an effective result. The results showed that the adsorbents were not able to adsorb the impurities, but rather a small amount of glycerol. The adsorption carried out for purification did not clarify the glycerin, concluding that only the adsorption process is not suitable for purification of the crude glycerol, and a pre-purification step is necessary for the previous removal of the contaminants. / O excedente de glicerol produzido nas ?ltimas d?cadas, gerado como subproduto da produ??o de biodiesel, est? associado a constantes pesquisas por fontes alternativas de energia e vem criando uma demanda na busca de diferentes tecnologias para sua purifica??o. A glicerina bruta obtida como subproduto no processo de transesterifica??o ? composta por ?lcool, ?gua, sais inorg?nicos, ?cidos graxos livres, mono-, di-, triglicer?deos, entre outras mat?rias org?nicas e res?duos em diferentes quantidades. ? de extrema import?ncia a purifica??o do glicerol, a fim de reduzir problemas ambientais devido ao seu ac?mulo. Existem tecnologias atuais eficazes na purifica??o e refino do glicerol bruto. Por?m, s?o consideradas invi?veis para pequenas e m?dias produ??es, devido ?s restri??es de custos e alta demanda energ?tica. Dessa forma, ? indispens?vel que novas rotas de purifica??o de menor custo e maior efici?ncia, assim como novos mercados, sejam desenvolvidos. A adsor??o desponta como uma t?cnica promissora e muito favor?vel para a remo??o dos contaminantes da glicerina, devido ao seu baixo custo, simplicidade de projeto e opera??o. Diante do exposto, o objetivo deste trabalho foi selecionar um adsorvente para a purifica??o do glicerol bruto obtido da rea??o de transesterifica??o de ?leo residual. Para a avalia??o da efici?ncia e escolha das melhores condi??es de purifica??o, foram avaliados tr?s tipos de adsorventes: argila clarificante Pure-Flo Supreme B81, carv?o ativado e terra diatom?cea. Experimentos de adsor??o foram realizados utilizando uma solu??o sint?tica de glicerina P.A. e ?leo de soja, com o intuito de verificar a influ?ncia da concentra??o da glicerina na solu??o, assim como o comportamento dos contaminantes do glicerol no processo de adsor??o. Para atingir o objetivo, avaliou-se a influ?ncia e otimiza??o das vari?veis de processo como temperatura (298,15, 305,65 e 313,15 K), quantidade de adsorvente (1,2, 1,8 e 2,4 g) e concentra??o de glicerol (30, 50 e 70% v/v) atrav?s de um planejamento experimental. A vari?vel mais significativa foi a concentra??o de glicerol, e resultados indicaram alto teor de glicerol ap?s a purifica??o: 97,25% para terra diatom?cea, 95,59% para carv?o e 90,26% para argila. Al?m disso, foram realizados experimentos para o estudo da termodin?mica e cin?tica da rea??o e o tempo necess?rio para o sistema alcan?ar o equil?brio foi inferior a 60 minutos para os tr?s adsorventes. Os valores negativos da varia??o da energia livre de Gibbs (?G) mostraram que a adsor??o dos contaminantes ? um processo espont?neo. Os valores negativos para varia??o de entalpia (?H) e os valores positivos de entropia (?S) para argila e carv?o ativado, indicam uma natureza exot?rmica e que as mol?culas dos contaminantes encontram-se mais desordenadas no estado adsorvido do que em solu??o. O valor positivo de ?H para a terra diatom?cea indica que o processo de adsor??o para esse adsorvente ? endot?rmico. As an?lises dos resultados de adsor??o obtidos nas temperaturas de 298,15, 305,65 e 313,15 K, mostraram que os dados experimentais foram bem correlacionados ?s isotermas de Langmuir, Freundlich e Redlich Peterson. Utilizando as mesmas vari?veis para o processo de adsor??o usando o glicerol bruto, os resultados mostraram que os adsorventes n?o foram capazes de adsorver as impurezas, mas sim glicerol. A adsor??o realizada para purifica??o n?o clarificou a glicerina, indicando que n?o houve remo??o das impurezas, concluindo que somente o processo de adsor??o n?o ? apropriado para purifica??o do glicerol bruto, sendo necess?rio uma pr?-purifica??o para pr?via remo??o de alguns contaminantes.