Made available in DSpace on 2015-04-14T13:36:01Z (GMT). No. of bitstreams: 1 462235.pdf: 2683765 bytes, checksum: dc15bd33e02ceefcb7c6427763878df3 (MD5) Previous issue date: 2014-08-11 / It is unclear how temperament is related to alcohol-related behavior in large population studies. We have used the Affective and Emotional Composite Temperament Scale (AFECTS) model to evaluate how emotional traits and affective temperaments are associated with alcohol use, abuse, and dependence in the general population. Data from 10,603 subjects (mean age=28.0?7.8yrs, 70.3% females) was collected anonymously by the Internet in Brazil using the AFECTS model and the Alcohol, Smoking and Substance Involvement Screening Test (ASSIST). Alcohol use was stratified into control, low use, abuse, and dependence groups. The analysis of dimensional traits showed that Volition and Coping were lower, and Sensitivity was higher, in the abuse and dependence groups, with no differences between the Control and the Low Use groups. Alcohol consumption was also associated with lower Control, Stability, and Caution, and higher with Anger, Anxiety, and Desire, with significant differences between all groups. Regarding affective temperament types, alcohol abuse and dependence were associated with euphoric and cyclothymic temperaments in both genders, which was mirrored by a lower frequency of both euthymic and hyperthymictypes. Only hyperthymics were overrepresented in the Control group for both genders. A global dysfunction of emotional traits and a predominance of cyclothymic and euphoric temperaments were associated with alcohol-related behavior. Prevention and treatment strategies may be developed more effectively if these traits are taken into account. / N?o est? claro na literatura como otemperamento associa-se a comportamentos relacionados ao consumo de ?lcool em grandes estudos populacionais. Utilizamos o modelo Affective and Emotional Composite Temperament Scale (AFECTS) para avaliar como tra?os emocionais e temperamentos afetivos relacionam-se ao uso, abuso e depend?ncia de ?lcool na popula??o geral. Dados de 10.603 participantes (m?dia de idade = 28.0 ? 7.8 anos, 70,3% mulheres) foram coletados anonimamente pela Internet no Brasil utilizando o modelo AFECTS e o Alcohol, Smoking and Substance Involvement Screening Test (ASSIST). Estratificamos os sujeitos de acordo com o consumo da subst?ncia, sendo os grupos respectivamente nomeados: controle (baix?ssimo uso), baixo uso, abuso e depend?ncia. As an?lises para tra?os emocionais mostraram que nos grupos de abuso e depend?ncia os n?veis de Vontade e Maturidade (Coping) foram mais baixos, enquanto que os escores de Sensibilidade estavam mais altos, sem diferen?as entre os grupos controle e baixo uso. O consumo de ?lcool foi tamb?m associado com baixo Controle, Estabilidade e Cautela, alta Raiva, Ansiedade e Desejo, apresentando diferen?as significativas entre todos os grupos. Com rela??o aos tipos de temperamento afetivo, abuso e depend?ncia de ?lcool foram associados com temperamentos euf?rico e ciclot?mico em ambos os sexos, acompanhados de uma menor freq??ncia dos tipos eut?mico e hipert?mico. Apenas os hipert?micos tiveram alta representatividade no grupo controle, tanto para homens quanto para mulheres. A exist?ncia de uma disfun??o global de tra?os emocionais e a predomin?ncia de temperamentos ciclot?mico e euf?rico foram associados a comportamentos relacionados ao consumo de ?lcool. Ressalta-se que estrat?gias de preven??o e tratamento podem ser desenvolvidas de forma mais eficaz,sendo estas caracter?sticas identificadas e consideradas.

Submitted by Setor de Tratamento da Informa??o - BC/PUCRS (tede2@pucrs.br) on 2016-07-26T14:25:23Z No. of bitstreams: 1 DIS_MARCOS_VINICIUS_FORTES_ALBA_COMPLETO.pdf: 1333852 bytes, checksum: c687fbcabc052faa5ed3567c986640e9 (MD5) / Made available in DSpace on 2016-07-26T14:25:23Z (GMT). No. of bitstreams: 1 DIS_MARCOS_VINICIUS_FORTES_ALBA_COMPLETO.pdf: 1333852 bytes, checksum: c687fbcabc052faa5ed3567c986640e9 (MD5) Previous issue date: 2016-02-15 / Nuclear Medicine enables, among other things, the visualization, characterization and quantification of biochemical processes, metabolism, biomarkers and receptors in vivo by molecular imaging. One of the methods of functional imaging available in this area is Positron Emission Tomography (PET), which depends on the administration of a radiopharmaceutical in the studied organism. One disease that can be studied by PET scan is multiple sclerosis (MS) through the access to the TSPO (Translocator protein) receptors density. The radiopharmaceutical [11C]-(R) -PK11195 has high affinity and selectivity for these receptors, which are increased in activated microglia cells in the case of MS. Therefore, the objective of this study was to develop and to validate the production process (synthesis, purification and quality control) of the radiotracer [11C]-(R)-PK11195 in the Radiopharmaceutical Production Center of the Brain Institute of Rio Grande do Sul (BraIns), allowing performing PET scans for the study of MS. The radioisotope was produced in the 16 MeV PETrace cyclotron (GE Healthcare) as [11C]CO2 via the nuclear reaction 14N (p, ?)11C after the bombardment of a gaseous target containing N2 and 0.5% of O2 with protons. The production was performed in the equipment TRACERlab FX-C Pro (GE Healthcare) to meet the requirements of Good Manufacturing Practices (GMP). The radiopharmaceutical quality control was carried out at the BraIns Quality Control Laboratory and the final product was tested for Identity and Radionuclidic Purity, Radiochemical Purity, Specific Activity, Residual Solvents, pH, Sterility, the Filtration Membrane Integrity and Bacterial Endotoxins. The synthesis was performed through the methylation of the precursor (R)-[N-desmethyl]PK11195 using [11C]CH3I (methyl iodide labeled with carbon-11) under the defined optimal conditions: 400 uL of dimethyl sulfoxide (DMSO), approximately 1 mg of precursor, approximately 10 mg of potassium hydroxide (KOH) at 40 ?C for 1 minute. The reaction mixture was then neutralized with 1 mol.L-1 hydrochloric acid and diluted with mobile phase (76% acetonitrile and 24% Milli-Q water). The diluted mixture was injected into a semi-preparative HPLC system for purification. Solid phase extraction (through Sep-Pak C18 cartridges - Waters) was used to remove the solvent. Product elution and formulation was conducted with 0.7 mL of ethanol and 6.3 ml of 0.9% saline (sterile and pyrogen free). Sterilization was performed by filtration on a 0.22 ?m pore membrane and, as well as the filling process, was carried out under laminar flow. The process steps could be optimized and fitted to the equipments and laboratories structure. Radiochemical yield of the process in relation to the [11C ]CH3I start activity was 15.5 ? 2.4 % ( 7471.5 ? 1283.8 MBq ; n = 39 ) . All batches were approved according to the specifications defined and tested in the quality control, reaching Radiochemical Purity levels greater than 99% and a Specific Activity of 39.7 ? 11.1 GBq / micromol , 10 minutes before the injection. All analytical methods were validated and met the requirements established by current regulations. Three consecutive batches were produced and approved by the quality control, so the process could be considered validated. The developed process was suitable for production of adequate doses of the radiopharmaceutical [11C]-(R)-PK11195 for clinical use at BraIns. The production of the radiopharmaceutical labeled with carbon-11 at the institute provides an additional tool for improving health services in the country and to improve the life quality of the patients. / A medicina nuclear possibilita, dentre outras coisas, a visualiza??o, caracteriza??o e quantifica??o de processos bioqu?micos, metab?licos, biomarcadores e receptores, in vivo, atrav?s da imagem molecular. Dentre as modalidades de imagem funcional dispon?veis nesta ?rea est? a Tomografia por Emiss?o de P?sitrons (PET), que depende da administra??o de um radiof?rmaco no organismo estudado. Uma das doen?as pass?veis de estudo atrav?s do exame PET ? a esclerose m?ltipla (EM), atrav?s do acesso ? densidade de receptores TSPO (Prote?na Translocadora). O radiof?rmaco [11C]-(R)-PK11195 possui alta afinidade e seletividade por estes receptores, aumentados nas c?lulas ativadas da micr?glia nos casos de EM. Portanto, o objetivo deste trabalho foi desenvolver e validar o processo produtivo (s?ntese, purifica??o e controle de qualidade) do radiof?rmaco [11C]-(R)-PK11195 no Centro de Produ??o de Radiof?rmacos do Instituto do C?rebro do RS (InsCer), possibilitando a realiza??o de exames PET para o estudo da EM. O radiois?topo foi produzido no C?clotron PETrace 16 MeV (GE Healthcare) na forma de [11C]CO2 atrav?s da rea??o nuclear 14N(p,?)11C, por meio do bombardeamento com pr?tons do alvo gasoso contento N2 e 0,5 % de O2. A produ??o foi realizada no equipamento TRACERlab FX-C pro (GE Healthcare) atendendo ?s exig?ncias de Boas Pr?ticas de Fabrica??o (BPF). O controle de qualidade do radiof?rmaco foi realizado no Laborat?rio de Controle de Qualidade do InsCer e o produto acabado foi submetido ?s an?lises de Identidade e Pureza Radionucl?dica, Pureza Radioqu?mica, Atividade Espec?fica, Solventes Residuais, pH, Esterilidade, Integridade da Membrana Filtrante e Teor de Endotoxinas. A s?ntese foi realizada atrav?s da metila??o do precursor (R)-[N-desmetil]PK11195 utilizando o [11C]CH3I (iodeto de metila marcado com carbono-11) sob as condi??es ?timas definidas: 400 ?L de dimetilsulf?xido (DMSO), aproximadamente 1 mg de precursor, aproximadamente 10 mg de hidr?xido de pot?ssio (KOH), a 40 ?C durante 1 minuto. A mistura de rea??o foi posteriormente neutralizada com ?cido clor?drico 1 mol.L-1 e dilu?da com fase m?vel (acetonitrila 76 % e ?gua Milli-Q 24 %). A mistura dilu?da foi injetada em sistema CLAE semi-preparativo para purifica??o. Extra??o de fase s?lida (atrav?s de cartuchos SepPak C18 ? Waters) foi utilizada para remo??o do solvente. A elui??o e formula??o do produto foi realizada com 0,7 mL de etanol e 6,3 mL de solu??o salina 0,9 % (est?ril e livre de pirog?nios). A esteriliza??o foi realizada atrav?s de filtra??o em membrana de poro de 0,22 ?m e, assim como o envase, ocorreu em fluxo laminar. As etapas do processo foram otimizadas e adequadas aos equipamentos e estrutura dos laborat?rios. O rendimento radioqu?mico do processo em rela??o ? atividade de [11C]CH3I de partida foi de 15,5?2,4 % (7471,5?1283,8 MBq; n=39). Todos os lotes produzidos foram aprovados quanto ?s especifica??es definidas e testadas no controle de qualidade, atingindo Pureza Radioqu?mica maior que 99 % e uma Atividade Espec?fica de 39,7?11,1 GBq/?mol, 10 minutos antes da inje??o. Todas as metodologias anal?ticas foram validadas e atenderam os crit?rios estabelecidos pela norma vigente. Tr?s lotes consecutivos foram produzidos e aprovados no controle de qualidade e o processo p?de ser considerado validado. O processo desenvolvido se mostrou adequado para produ??o do radiof?rmaco [11C]-(R)-PK11195 em doses suficientes para realiza??o de exames em pacientes no InsCer. A produ??o do radiof?rmaco marcado com carbono-11 no instituto disponibiliza mais uma ferramenta para melhoria dos servi?os de sa?de no pa?s e para melhoria da qualidade de vida dos pacientes.

Submitted by Setor de Tratamento da Informa??o - BC/PUCRS (tede2@pucrs.br) on 2016-09-12T16:18:06Z No. of bitstreams: 1 TES_MANUEL_ALVES_FALCAO_COMPLETO.pdf: 3543313 bytes, checksum: c6209bccf7d4cd318c874850a1bc853d (MD5) / Made available in DSpace on 2016-09-12T16:18:06Z (GMT). No. of bitstreams: 1 TES_MANUEL_ALVES_FALCAO_COMPLETO.pdf: 3543313 bytes, checksum: c6209bccf7d4cd318c874850a1bc853d (MD5) Previous issue date: 2016-03-30 / Chemotherapy is highlighted for the treatment of many classes of tumors, especially by new drug delivery nanosystems. The drug delivery nanosystems are focused on greater selectivity for abnormal tissue, decrease adverse effects, dose reduction and decreased frequency applications. Due to the scale of these systems, the EPR effect favors the permeabilization in blood vessels and retention in tumor tissue particles. This thesis performed vinblastine extractions from C. roseus using water and ethanol as co-solvents for CO2 at 300 bar and at different temperatures, those experiments showed the viability of this extraction method, subsequent extractions were optimized using ethanol. The results are compared to traditional extraction methods such as solid-liquid extraction the results found was up to 92.41%. Concluding that vinblastine extraction using carbon dioxide and ethanol mixtures at high pressure is possible. The PLGA nanoparticles containing vinblastine showed again the reproducibility of the nanoemulsion method of ensuring the production of homogeneous nanoparticles with and without drug and cell viability experiments show that the three formulations of PLGA nanoparticles containing vinblastine potentiated drug activity at the lower doses, 1 and 5 ?g/mL, compared to free drug. The studies of glycopolymers synthesis presented the novel synthesis of an ATRP initiator based on PLGA without using PEG spacers. This initiator may, in future studies, be used for modifying PLGA. Successive attempts monomer polymerization saccharide via ATRP in water and DMSO leads to the conclusion that this approach is not the most suitable for the syntheses of glycopolymers graft from a PLGA initiator without the use of PEG spacers. / A quimioterapia ? op??o terap?utica para o tratamento de diversas classes de tumores, principalmente pelos novos nanosistemas de libera??o modificada de f?rmacos. Os nanosistemas de libera??o modificada t?m como foco a maior seletividade aos tecidos anormais, a diminui??o de efeitos adversos, redu??o da dose e diminui??o da frequ?ncia de aplica??es. Devido a escala destes sistemas, o efeito EPR favorece a permeabiliza??o nos vasos sangu?neos e a reten??o de part?culas no tecido tumoral. Nesta tese foram realizadas extra??es de vimblastina a partir de C. roseus utilizando ?gua e etanol como cossolventes de CO2 a 300 bar e a diferentes temperaturas mostraram a viabilidade do m?todo de extra??o, posteriormente, as extra??es foram otimizadas utilizando etanol. Quando os resultados encontrados s?o comparados a m?todos tradicionais de extra??o como a extra??o s?lido-l?quido o resultado encontrado foi de at? 92,41% superior. Concluindo, que a extra??o de vimblastina utilizando misturas de di?xido de carbono e etanol a altas press?es ? poss?vel. As nanopart?culas de PLGA contendo vimblastina demonstraram a reprodutibilidade do m?todo de nanoemuls?o garantindo a produ??o de nanopart?culas homog?neas, com e sem f?rmaco. Os experimentos de viabilidade celular mostraram que as tr?s formula??es de nanopart?culas de PLGA contendo vimblastina potencializaram a atividade do f?rmaco para as doses mais baixas, 1 e 5 ?g/mL, em rela??o ao f?rmaco livre. Os estudos realizados de s?ntese de glicopol?meros apresentaram a s?ntese in?dita de um iniciador de ATRP baseado em PLGA sem o uso de espa?adores de PEG. Este iniciador pode, em futuros estudos, ser utilizado para a modifica??o de PLGA. As sucessivas tentativas de polimeriza??o de mon?meros de sacar?deos via ATRP em ?gua e DMSO leva a conclus?o que esta metodologia n?o ? a mais adequada para s?nteses glicopol?meros conjugados a PLGA sem o uso de espa?adores de PEG.

Made available in DSpace on 2016-04-28T14:59:48Z (GMT). No. of bitstreams: 1 2009 - Luiz Carlos Vianna Reis Junior.pdf: 505730 bytes, checksum: 85fc6aba67104fc7876da3de318aed17 (MD5) Previous issue date: 2009-02-19 / This experiment was accomplished in the Animal Nutrition and Pastures Department in the Institute of Animal Science of the Rural Federal University of Rio de Janeiro. The effects of increasing levels of urea addition were evaluated on the chemical-bromatologic and microbiologic composition of Coast-cross hay. The hay was treated with 5 levels of urea (0, 0,5, 1,0, 1,5 e 2,0% of dry matter), during 28 and 35 days. The experimental design used was the completely randomized with five treatments in a split-plot design, two ammonization periods (28 and 35 days) and three replications. Urea (45% N) was used and diluted in the proportion 1 to 4 parts of water. The treated hay was stored in sealed plastic bags (3kg/bag) and, when opened, samples were collected for chemical and microbiological analysis. It was verified that the crude protein levels increased linearly in function of higher doses of urea and period, which suggested an elevation of the nitrogen level available in the material. The addition of urea promoted a significant reduction (P<0,05) on the levels of neutral detergent insoluble protein (NDIP) and acid detergent insoluble protein (ADIP). There was no influence of the ammonization on the levels of neutral detergent fiber (NDF) and hemicelluloses (HEM). The increasing levels of urea were efficient on the reduction of colonies generator unities, keeping them under tolerable levels aiming the preconized limits to vegetable health. The present experiment showed that the process of ammonization is efficient on the improvement of the chemical composition of coast-cross hay. / Este trabalho foi realizado no Departamento de Nutri??o Animal e Pastagens, do Instituto de Zootecnia da Universidade Federal Rural do Rio de Janeiro. Avaliaram-se os efeitos da adi??o de ureia em n?veis crescentes sobre a composi??o qu?mico-bromatol?gica e microbiol?gica do feno de coast-cross. O feno foi tratado com 5 n?veis de ureia com base na mat?ria seca durante 28 e 35 dias de amoniza??o. O delineamento experimental utilizado foi o inteiramente casualisado com um arranjo em parcelas subdivididas, com cinco tratamentos (0, 0,5, 1,0, 1,5 e 2,0% de ureia na mat?ria seca), dois per?odos de amoniza??o (28 e 35 dias) e tr?s repeti??es. Foi utilizada ureia pecu?ria (45% N), dilu?da na propor??o de 4 partes de ?gua para cada parte de ureia. O feno tratado foi armazenado em sacos pl?sticos (3 kg feno/saco), lacrado e ap?s abertura, foram coletadas amostras para as an?lises qu?micas e microbiol?gicas do material. Verificou-se efeito linear positivo (P<0,05) para os teores de prote?na bruta em fun??o dos n?veis crescentes de ureia, sugerindo uma eleva??o nos teores de nitrog?nio dispon?vel no material amonizado. A adi??o de ureia promoveu redu??o significativa (P<0,05) nos teores de prote?na insol?vel em detergente neutro e prote?na insol?vel em detergente ?cido. Os n?veis crescentes de ureia foram eficientes na diminui??o das unidades formadoras de col?nias, reduzindo-as a n?veis aceit?veis ao limite preconizado como par?metro de higiene para vegetais. N?o houve influ?ncia da amoniza??o sobre os teores de fibra em detergente neutro, hemicelulose para os n?veis de ureia utilizados. O presente trabalho mostrou que o processo de amoniza??o ? eficiente na melhoria da composi??o qu?mica do feno de coast-cross.

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2016-08-24T14:57:04Z No. of bitstreams: 1 2011 - Denise Bilibio.pdf: 1776424 bytes, checksum: 7a2458925cc528e896bf5d4baac6f571 (MD5) / Made available in DSpace on 2016-08-24T14:57:04Z (GMT). No. of bitstreams: 1 2011 - Denise Bilibio.pdf: 1776424 bytes, checksum: 7a2458925cc528e896bf5d4baac6f571 (MD5) Previous issue date: 2011-09-26 / Basic education has a strategic role in building a nation, and vocational teaching needs to articulate culture, knowledge, technology and work for the training of professionals prepared for new challenges in a globalized and competitive world. This way, the teaching-learning process search for methodological alternatives that make the process more dynamic and flexible. Then, it was used Interactive Methodology to promote the construction of knowledge in the process of teaching-learning chemistry applied to the technical course in agribusiness. The used theoretical contributions to this work was of Dialectical-Hermeneutical Circle (CHD) of Guba; Lincoln (1989) with adjustments and the Hermeneutic Analysis-Dialectics (AHD) of Minayo (1996). The survey was developed in Campus IFRS ? Erechim, with two classes of the technical course in agribusiness, subsequent mode. For the application of CHD, the actors of the process need to be familiar with the subject to practice the dialogue and knowledge building, as well as the use of small groups also provide the dialogue. In this research, it was used together the CHD and projective methods of interview, allowing the methodology? structure, data collection and monitoring the processes of knowledge?s construction of students through the establishment of dialogue from their own experiences. The results achieved in the survey showed that chemistry is still taught in the traditional way that aims to memorization; the use of Interactive Methodology is an innovative tool, that could be able to be used in technical education in agribusiness, especially teaching applied chemistry, forming critic professionals / A educa??o b?sica possui papel estrat?gico na constru??o de uma na??o e o ensino profissionalizante precisa articular cultura, conhecimento, tecnologia e trabalho para a forma??o de profissionais preparados para novos desafios em um mundo globalizado e competitivo. Desta forma, o processo ensino-aprendizagem precisa buscar alternativas metodol?gicas capazes de tornar o processo mais din?mico e vers?til. A Metodologia Interativa consiste numa alternativa para promover a constru??o do conhecimento no processo de ensino aprendizagem de qu?mica aplicada ao curso t?cnico em agroind?stria, tendo como aportes te?ricos para este trabalho a utiliza??o do Circulo hermen?utico-dial?tico (CHD) de Guba; Lincoln (1989) com adapta??es e a An?lise hermen?utica-dial?tica (AHD) de Minayo (1996). A pesquisa foi desenvolvida no IFRS ? Campus Erechim, com duas turmas do Curso T?cnico em Agroind?stria, modalidade subseq?ente. Observou-se que para a aplica??o do CHD, os atores do processo precisam estar familiarizados com o assunto para a efetiva??o do di?logo e constru??o do conhecimento, assim como a utiliza??o de pequenos grupos tamb?m propiciam o di?logo. A utiliza??o conjunta, nesta pesquisa, do CHD e de m?todos projetivos de entrevista permitiu a estrutura??o da metodologia a coleta de dados e o acompanhamento dos processos de constru??o do conhecimento dos alunos atrav?s do estabelecimento do di?logo a partir de suas experi?ncias. Os resultados alcan?ados na pesquisa demonstraram que a disciplina de qu?mica, ainda ? trabalhada dentro de um ensino tradicional que visa ? memoriza??o, e que a utiliza??o da Metodologia Interativa constitui-se em uma ferramenta inovadora, capaz de ser utilizada no ensino t?cnico em agroind?stria, em especial no ensino de qu?mica aplicada contribuindo para a forma??o profissionais cr?ticos.

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2017-01-20T11:19:55Z No. of bitstreams: 1 2016 - Michel Braga Garcia.pdf: 2199692 bytes, checksum: 4e890f95e489a3e9ea5a095b493dce78 (MD5) / Made available in DSpace on 2017-01-20T11:19:55Z (GMT). No. of bitstreams: 1 2016 - Michel Braga Garcia.pdf: 2199692 bytes, checksum: 4e890f95e489a3e9ea5a095b493dce78 (MD5) Previous issue date: 2016-04-06 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Studies on Atmospheric Chemistry allow the understanding of chemical behavior of different atmospheric pollutants towards oxidant agents in troposphere. Among these agents, OH radicals, ozone and nitrate radicals are the most important. In coastal zones, chlorine atoms are also important specie for the chemical removal of primary and secondary pollutants. This work aims the kinetic study of the gas phase reaction between chlorine atom and formaldehyde, H2CO + Cl ? HCO + HCl. The reaction was described at HF, MP2, CCSD, QCISD and DFT (B2PLYP, MPW2PLYP and MPWKCIS1K) levels. Basis set effect was also explored and the aug-cc-pVDZ (ACCD) and aug-cc-pVTZ (ACCT) basis set were adopted. Geometry optimizations and vibrational frequencies calculations were performed for reactants and products. A prebarrier complex was located at all levels of theory, stabilized with respect the isolated reactants by ca. 4 kcal mol-1. Saddle points were located and characterized by their imaginary frequencies. Energy barriers were predicted as ca. 1 kcal mol-1, in agreement with experimental results (0.7 ? 1.0 kcal mol-1). Rate coefficients were calculated in the range from 100 to 500 K, adopting the canonical variational method, as available in the kcvt code. The calculated kinetic parameters, rate coefficients (k, 298 K, expressed in 10-11 cm3 molecule-1 s-1), activation energy (Ea, expressed in kcal mol-1) and Arrhenius preexponential factor (A, expressed in 10-11 cm3 molecule-1 s-1) were: k = 4.89, Ea = 0.25 and A = 7.45. The results suggest that a reaction dynamics is well described by a mechanism taking into account a prebarrier intermediate. Canonical variational rate coefficients were predicted in good agreement with experimental data, validating the proposal for the reaction mechanism introduced in this study / Os estudos em Qu?mica Atmosf?rica permitem entender o comportamento qu?mico de diversos poluentes atmosf?ricos frente a agentes oxidantes presentas na troposfera. Entre esses agentes, radicais OH, oz?nio e nitrato s?o os mais importantes. Ainda em zonas costeiras, ?tomos de cloro tornam-se tamb?m importantes esp?cies para a remo??o qu?mica de poluentes prim?rios e secund?rios. Este trabalho visa o estudo cin?tico da rea??o H2CO + Cl ? HCO + HCl em fase gasosa. A rea??o foi descrita em n?veis HF, MP2, CCSD, QCISD, DFT (B2PLYP, MPW2PLYP e MPWKCIS1K) Tamb?m o efeito da base foi explorado e, para tanto, as bases aug-cc-pVDZ (ACCD) e aug-cc-pVTZ (ACCT) foram adotadas. C?lculos de otimiza??o de geometria e frequ?ncia vibracionais foram feitos para reagentes e produtos. Foram vistos tamb?m para todos os n?veis de c?lculo a forma??o de um pr?-complexo estabilizado, em rela??o aos reagentes isolados, por cerca de 4 kcal mol-1. Ponto de sela tamb?m foram otimizados e identificados pela frequ?ncia vibracional imagin?ria. Barreiras de energia foram previstas em cerca de 1 kcal mol-1, em acordo com a previs?o da literatura, 0,7 - 1,0 kcal mol-1. Os coeficientes de velocidade foram calculados na faixa de 100 ? 500 K a partir da teoria do estado de transi??o variacional com auxilio do programa kcvt. Os par?metros cin?ticos encontrados, coeficientes de velocidade (k, 298 K, expressos em 10-11 cm3mol?cula-1s-1), energia de ativa??o (Ea, expresso em kcal mol-1) e fator pr?-exponencial (A, expresso em 10-11 cm3mol?cula-1s-1) foram: k298K = 4,89, Ea = 0,25 e A = 7,45. Os resultados sugerem que a din?mica da rea??o ? bem descrita a partir de um mecanismo que contempla a participa??o de um intermedi?rio pr?-barreira. Resultados de coeficientes de velocidade variacionais can?nicos obtidos neste trabalho se mostraram satisfat?rios quando comparados a dados experimentais validando a proposta de mecanismo trazida nesse trabalho.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-02-13T16:48:50Z No. of bitstreams: 1 2016 - MATHEUS GOMES SILVA.pdf: 2058072 bytes, checksum: 65bd3fe4a96ed7ef6c405b0ab87a8edd (MD5) / Made available in DSpace on 2017-02-13T16:48:50Z (GMT). No. of bitstreams: 1 2016 - MATHEUS GOMES SILVA.pdf: 2058072 bytes, checksum: 65bd3fe4a96ed7ef6c405b0ab87a8edd (MD5) Previous issue date: 2016-07-27 / The Hidrogen sulfide is one of the substances most dangers in the oil and gas production. The H2S causes great economic losses to industries and so their removal is desired. The use of the triazine to remove the H2S has been extensively documented in the literature. However, the number of products that present the physical and chemical properties desired to act as H2S scavenger, available in the market, is reduced. For this reason, the search by molecules that act in removing of H2S has been the object of research in the worldwide. The goal of this work was investigate the thermal stability of two different H2S scavengers: 1,3,5-tris (hydroxyethyl) hexahydro-s-triazine (commercial) and 1,3,5-tris (hydroxypropyl) hexahydro-s-triazine (synthesized in our laboratory ) when they are subject to processing condition in a pilot plant. To achieve this goal was built a pilot plant capable of simulating some operating conditions of the pre-salt exploration, such as temperature, shear rate and residence time. The thermal stability (degradation) of the triazines was investigated by monitoring the conductivity of the samples. For comparison purposes were performed condutimetry tests of samples in bench tests in the laboratory and pilot plant at temperatures of 30?C, 40?C, 50?C, 60?C and 80?C. For both triazines, the conductivity values obtained in the pilot plant is much higher than those found in bench tests: 65.1 S/cm (2C) and 65.1 S/cm (3C) and 45.5 S/cm (2C), and 32.1 S/cm (3C) respectively. The results showed that the conductivity values are strongly affected by the processing time, being more evident differences in their bench tests. The results of monitoring the conductivity of the samples allowed to verify that the 1,3,5-tris (hydroxyethyl) hexahydro-s-triazine (commercial) and 1,3,5-tris (hydroxypropyl) hexahydro-s- triazine (synthesized in our laboratory) does not undergo degradation under the process conditions which have been subjected, either in bench tests or plant pilot. / O sulfeto de Hidrog?nio ? uma das subst?ncias mais perigosas na produ??o de petr?leo e g?s. O H2S provoca grandes perdas econ?micas para as ind?strias e assim a sua remo??o ? desejada. O uso da triazina para remover o H2S tem sido extensivamente documentado na literatura. No entanto, o n?mero de produtos que apresentam propriedades f?sicas e qu?micas desejadas para actuar como eliminador de H2S, dispon?vel no mercado, ? reduzida. Por esta raz?o, a busca por mol?culas que atuem na remo??o de H2S tem sido o objeto de pesquisa no mundo inteiro. O objectivo deste trabalho foi o de investigar a estabilidade t?rmica de duas diferentes sequestrantes de H2S: 1,3,5-tris (hidroxietil) hexa-hidro-s-triazina (comercial) e 1,3,5-tris (hidroxipropil) hexa-hidro-s-triazina (sintetizada em laborat?rio), quando eles est?o sujeitos a condi??o de processamento em uma planta piloto. Para atingir este objetivo foi constru?da uma planta piloto capaz de simular algumas condi??es de processamento da explora??o do pr?-sal, tais como temperatura, taxa de cisalhamento e tempo de resid?ncia. A estabilidade t?rmica (degrada??o) das triazinas, foi investigada atrav?s da monitoriza??o da condutividade das amostras. Para fins de compara??o foram realizados testes condutimetria de amostras em ensaios de bancada de laborat?rio e na planta piloto nas temperaturas de 30?C, 40?C, 50?C, 60?C e 80?C. Para ambas as triazinas, os valores de condutividade obtidos na instala??o piloto ? muito mais elevado do que aqueles encontrados no banco: 65,1 S/cm (2c) e 65,1 S/cm (3C) e 45,5 S/cm (2C), e 32,1 S/cm (3C), respectivamente. Os resultados mostraram que os valores de condutividade s?o fortemente afetados pelo tempo de processamento, sendo as diferen?as mais evidentes em seus testes de bancada. Os resultados da monitoriza??o da condutividade das amostras permitiram verificar que o 1,3,5-tris (hidroxietil) hexa-hidro-s-triazina (comercial) e 1,3,5-tris (hidroxipropil) hexa-hidro-triazina S- (sintetizado no nosso laborat?rio) n?o sofre degrada??o sob as condi??es de processo que foram sujeitos, tanto em testes de bancada ou planta piloto

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-02-13T18:29:35Z No. of bitstreams: 1 2016 - Jos? Messias Ribeiro J?nior.pdf: 2014751 bytes, checksum: f6fdac1f2a0f681e038143bedfe908ed (MD5) / Made available in DSpace on 2017-02-13T18:29:35Z (GMT). No. of bitstreams: 1 2016 - Jos? Messias Ribeiro J?nior.pdf: 2014751 bytes, checksum: f6fdac1f2a0f681e038143bedfe908ed (MD5) Previous issue date: 2016-08-30 / CENPES / Petrobras / This work has aimed to evaluate the predictive ability of simplified mathematical models to describe the dynamics of the thickening of solids in drilling fluids. In the early stages, settling experiments of barite and calcite in water-based fluids at graduated cylinders were done at initial volumetric concentrations of 6.7%, 12% and 20%, while the change of interface height was measured on the time steps. The first data modelling approach has used conservation laws, considering the relative velocity between the solid and the liquid phase as function of volumetric concentration of solids. This way, the conservation laws used to simulate these systems were based in mass conservation law and in the flux density functions. For the accuracy evaluation in the numerical data provided by conservation laws, this work has used the interface height variation through a period of time, which was determined by experiments as an auxiliary variable, to imply the prediction quality provided by the proposed model, because there was not any equipment available to determine the spatial profiles of solids concentration. Through this procedure, it was found that conservation laws was capable of predict the interface variation through a period of time with relative errors below 10%, except in regions of rapid increase of local concentration. In the second approach of modelling was used a simplified model consisting of the continuity equation and the momentum equation, considering the interaction forces between the solid and liquid phases. The simplified model describe the variation of the interface height through a period of time in several sedimentations, and the displayed results were quite satisfactory and with relative errors lower than the results showed by the conservation laws. In the final stage of this work, the simplified model was used in the simulation of time and spatial concentration profile of the barite suspended in the BR-Mul fluid, which is a real drilling fluid often used by Petrobras. The concentration profiles obtained by simulation were compared with the experimental data reported by authors from Faculty of Chemical Engineering in Federal University of Uberlandia (FEQ/UFU). In this case study, it was possible to directly compare the model output with the experimental data, and the results has showed that the relative error of the model was lower to the fluid with the highest concentration suspensions of barite, specially in the points near to the compacted zone. However, the experimental methodology used in FEQ/UFU has exhibit much imprecision in the regions of high solids concentration, because of the experimental error in the gamma ray emitter. / O presente trabalho teve como objetivo avaliar a capacidade de predi??o de modelos matem?ticos simplificados para descrever a din?mica de sedimenta??o de s?lidos adensantes em fluidos de perfura??o. Na etapa inicial deste trabalho, foram realizados experimentos de sedimenta??o de suspens?es aquosas de barita e de calcita em colunas de vidro, com concentra??es volum?tricas iniciais de 6; 7%, 12% e 20% para cada s?lido, e a varia??o da altura da interface entre a zona de clarificado e a zona de concentra??o constante foi registrada ao longo do tempo. A primeira abordagem fez uso de modelos conservativos, cuja velocidade relativa entre o s?lido e o fluido ? somente fun??o da concentra??o volum?trica local do s?lido. Dessa forma, os modelos conservativos utilizados para simular esses sistemas foram baseados nas leis de conserva??o da massa e em fun??es de densidade de fluxo. Para avaliar a acur?cia dos resultados fornecidos pelos modelos conservativos, utilizou-se a varia??o da altura da interface de clarifica??o ao longo do tempo, como vari?vel auxiliar para inferir a qualidade das predi??es fornecidas pelo modelo, visto que n?o se dispunha de equipamentos para determinar os perfis espaciais de concentra??o de s?lidos. Atrav?s deste procedimento, verificou-se que os modelos conservativos foram capazes de predizer a varia??o temporal da interface de clarifica??o com erro relativo menor que 10% na maior parte do tempo, exceto na regi?o que a concentra??o local aumenta rapidamente. Na segunda abordagem utilizou-se um modelo simplificado, composto pela equa??o da continuidade e pela equa??o do movimento, considerando as for?as de intera??o entre as fases s?lido e l?quido. O modelo simplificado descreve a varia??o temporal da interface de clarifica??o dos sistemas de sedimenta??o simples, com valores bastante satisfat?rios e com erro relativo menor do que os resultados exibidos pelos modelos conservativos. Na etapa final deste trabalho, este mesmo modelo foi avaliado na simula??o dos perfis temporais e espaciais da concentra??o de barita na sedimenta??o no fluido BR-Mul, que ? um fluido real de perfura??o bastante utilizado pela Petrobras. Os perfis de concentra??o obtidos por simula??o foram comparados a dados experimentais obtidos na Faculdade de Engenharia Qu?mica da Universidade Federal de Uberl?ndia (FEQ/UFU). Neste estudo de caso, foi poss?vel comparar diretamente a sa?da do modelo aos dados experimentais, e os resultados mostraram que o erro relativo do modelo foi menor para o fluido com a maior concentra??o inicial de barita, sobretudo nos pontos que se encontram pr?ximos da regi?o de compacta??o. No entanto, a metodologia experimental utilizada na FEQ/UFU apresenta elevada imprecis?o em regi?es com alta concentra??o de s?lidos, devido ao erro experimental introduzido na utiliza??o do equipamento emissor de raios gama.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-02-15T17:02:45Z No. of bitstreams: 1 2009 - William Pereira.pdf: 3794972 bytes, checksum: 64fbf9758bbf44329031caf3b369b79a (MD5) / Made available in DSpace on 2017-02-15T17:02:45Z (GMT). No. of bitstreams: 1 2009 - William Pereira.pdf: 3794972 bytes, checksum: 64fbf9758bbf44329031caf3b369b79a (MD5) Previous issue date: 2009-10-22 / CAPES / The present study has two specific phases: Early, was studied the isathine irradiation with the presence of diisopropil-phosphoril-dimethylidrazone (diisopfh), in chloroform, at room temperature and 300nm. The structure of photo-product was elucidated by GC/MS, IR, NMR 1H, 13C and 31P, as well as hety-cosy, homo-cosy and other techniques. The proposal mechanism involve a bi-radical from triplet excited state of isathine that react with C=N of the diisopfh and has a ring expansion. The successive pass would be thermal and with propanone elimination, as thermal rearrangement on phosphoric derivates described in the literature. In a second phase was studied, by Laser Flash Photolysis, the kinetic effect of the six aromatic derived of phosphoril-hidrazone (H, p-Cl, p-NO2, p-CN, p-NMe2 e p-CO2H) on the triplet excited state of four aromatic ketones: Xanthone, Tioxanthone, Benzophenone and Benzyl. The observed process to quencher, in all cases, was energy transference, because the rate constants are in the order of 1010M-1s-1. In this form was possible to estimate the energy of triplet excited state of these six phosphoril-hidrazone derivates. / O presente estudo divide-se em duas etapas bem distintas: Inicialmente, estudou-se a irradia??o de isatina na presen?a de diisopropil-dimetilfosforilidrazona (diisopfh) em clorof?rmio, a temperatura ambiente e comprimento de onda de 300nm. H? forma??o de um produto majorit?rio cujo peso molecular corresponde ? soma dos reagentes, diminu?do de 58g/mol. A estrutura deste produto foi elucidada por CG/EM, IV e RMN de 1H, 13C e 31P, al?m de t?cnicas como homocosy, hetycosy e outros. Prop?e-se um mecanismo via bi-radical formado a partir do estado excitado triplete da isatina com a liga??o C=N do composto diisopfh e conseq?ente expans?o do anel isat?nico; levando ? forma??o de um prov?vel produto fotoqu?mico prim?rio resultante de cicloadi??o. Numa segunda etapa, por processo t?rmico de elimina??o de propanona, similar a processo descrito na literatura por Olah, levaria a forma??o do fotoproduto detectado (derivado fosforil-benzodiazep?nico). Numa segunda etapa, estudou-se, por Fot?lise por Pulso de laser, o efeito cin?tico da presen?a de seis derivados arom?ticos de fosforilidrazona (H, p-Cl, p-NO2, p-CN, p-N (CH3)2 e p-CO2H) sobre o estado excitado triplete de quatro cetonas arom?ticas: tioxantona, xantona, benzofenona e benzil, todos em solu??o de acetonitrila. As constantes de velocidades obtidas (da ordem de difus?o da acetonitrila 1,9x1010 M-1s-1) indicam que o processo de supress?o de estado excitado se faz por transfer?ncia de energia. Desta forma foi poss?vel estimar a energia de estado excitado triplete destes derivados arom?ticos de fosforilidrazona.

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-05-09T11:39:47Z No. of bitstreams: 1 2012 - Filipe Arantes Furtado.pdf: 4817236 bytes, checksum: 027c11b973e31fc0617693a998446e3e (MD5) / Made available in DSpace on 2017-05-09T11:39:47Z (GMT). No. of bitstreams: 1 2012 - Filipe Arantes Furtado.pdf: 4817236 bytes, checksum: 027c11b973e31fc0617693a998446e3e (MD5) Previous issue date: 2012-07-26 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / The main objective of this work was the development of a methodoly using the Solid Phase Microextraction (SPME) on determinations of thermodynamic equilibrium data of liquid and polymeric mixtures. Three methodologies were proposed for determination of infinite dilution activity coefficient of solutes in liquid mixtures (??). The ?? values were determined for 9 hydrocarbons in the solvent furfural at temperatures of 25, 35 and 45 ?C. The liquid-gas partition coefficients were also determined in each studied temperature. On the experiments involving liquid mixtures, high sorption of solvent was observed, which may lead to swelling the polymer coating phase. Statistical tests were conducted after each experiments to measure possible damages on fiber coatings. There was also proposed a methodology using the SPME to determine the Flory Huggins parameter of the nine hydrocarbons used as solutes in polydimethylsiloxane (PDMS) and polyacrylate (PA). The Flory parameter were determined at temperature range of 25 to 80 ?C for the PDMS and 50 to 90 ?C for the PA. The proposed methodologies were evaluated through comparison of the obtained data with literature. All the results agreed with literature data. The Hildebrandt solubility parameter for PA was not available on literature and was determined on these experiments for the first time / O principal objetivo deste trabalho foi o desenvolvimento de uma nova metodologia para determina??o de dados de equil?brio termodin?mico em misturas l?quidas e polim?ricas. Tr?s metodologias foram propostas utilizando a Microextra??o em Fase S?lida (SPME) para determina??o dos coeficientes de atividade em dilui??o infinita (??) de sistemas l?quidos. Os valores de ?? de 9 hidrocarbonetos foram determinados em furfural nas temperaturas de 25, 35 e 45 ?C. Foram determinados valores de coeficiente de parti??o l?quid-g?s (KLg) em cada uma das temperaturas estudadas. Nos experimentos envolvendo as misturas l?quidas, foi observada uma alta taxa de sor??o de solvente podendo ocasionar o inchamento e poss?vel quebramento das fibras de SPME. Para verificar o poss?vel inchamento, foram conduzidos testes estat?sticos antes e depois de cada amostragem. Foi proposto ainda uma metodologia para determinar os par?metros de Flory em polidimetilsiloxano (PDMS) e poliacrilato (PA) utilizando a SPME. Nesse caso, os mesmos 9 hidrocarbonetos tiveram seus par?metros de Flory determinados na faixa de temperatura 25 a 80 ?C para o PDMS e de 50 a 90 ?C para o PA. As metodologias foram avaliadas atrav?s da compara??o dos dados obtidos com dados da literatura. Todos os resultados foram satisfat?rios, sendo ainda obtidos os valores dos par?metros de solubilidade de Hildebrandt, que para o poliacrilato, eram inexistentes na literatura