Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2017-02-15T16:34:59Z No. of bitstreams: 1 2016 - Vitor dos Santos Almeida.pdf: 2652432 bytes, checksum: 7f27ae8d8b345f1dc55ee863302bfda7 (MD5) / Made available in DSpace on 2017-02-15T16:34:59Z (GMT). No. of bitstreams: 1 2016 - Vitor dos Santos Almeida.pdf: 2652432 bytes, checksum: 7f27ae8d8b345f1dc55ee863302bfda7 (MD5) Previous issue date: 2016-04-15 / The analysis of mixtures is a common place challenge in the laboratory. Conventional methods demand a previous treatment which may be time consuming. At present, Nuclear Magnetic Resonance may be employed for the analysis of mixtures by using the DOSY (diffusion ordered spectroscopy) technique, whereby the different components of a mixture are separated by their diffusion coefficients. Pitches, in general, are products which are employed as starting material for the production of a variety of carbon materials, such as anodes for the production of aluminum, graphite electrodes for the steel industry, and carbon fibers. Pitches obtained from coal tar, itself a residue in the production of coke, are the most traditionally used. However, it is a carcinogen and therefore has had its use greatly diminished. Petroleum pitches, which are produced from decanted oil, may be a safer and less expensive alternative. The decanted oil is a heavy fraction obtained from catalytic cracking of petroleum. The difficulties in controlling its processing are derived from its complex composition, which includes paraffins, aromatic and heteroaromatic compounds. The present work investigates the analysis by NMR-DOSY of a mixture of model compounds present in decanted oil. Thus, a mixture of Tetracosane, Phenanthrene, 9-Mehylanthracene, Pyrene, Carbazole, 9-metil Carbazol, Dibenzothiophene, Dibenzofuran, Hexadecane, 1-Methylnaphthalene, Thiophene, Tetrahydrofuran was analyzed by NMR with an Avance III 500 MHz NMR spectrometer equipped with a BBO probe with a gradient on z-axis, at 20?C. To help in the separation by diffusion, the following polymers were used: poly-(ethyleneglycol), poly-(vinylpyrrolidone), poly-(dimethylsiloxan), poly-(butylmethacrylate) e poly-(vinylacetate).The shift reagent Eu(fod)3 was also employed. The results from DOSY-INEPT experiments show that poly-(butylmethacrylate) is the matrix which afforded the best separation of the different components of the mixture, followed by poly-(vinylacetate), poly-(ethyleneglycol) and finally, poly-(vinylpyrrolidone), which showed satisfactory results / Um grande desafio, muitas das vezes at? comum nos laborat?rios, ? a an?lise de misturas. Os m?todos convencionais em sua maioria exigem um tratamento pr?vio das misturas, o que demanda tempo, al?m de interferir diretamente no equil?brio do sistema. Hoje em dia, a t?cnica de Resson?ncia Magn?tica Nuclear pode ser usada na an?lise de misturas medindo-se o coeficiente de difus?o dos componentes da mistura, permitindo a obten??o dos espectros de cada componente individualmente por meio de um experimento r?pido que n?o interfere na mistura em si. O experimento mais comum ? o DOSY, do ingl?s Espectroscopia de Difus?o Ordenada. Piches, em geral, s?o produtos que s?o empregados como mat?rias-primas na produ??o de uma variedade de materiais de carbono, tais como: anodos de carbono para produ??o de alum?nio, eletrodos de grafite para a ind?stria sider?rgia e fibras de carbono. Piches obtidos a partir do alcatr?o da hulha, res?duo da produ??o de coque metal?rgico, s?o os tradicionalmente mais usados, mas apresentam alto potencial carcinog?nico e tem demanda decrescente em fun??o de novas tecnologias empregadas nas coquerias. Piches de petr?leo, produzidos a partir de ?leos decantados, podem potencialmente constituir uma alternativa mais segura e com maior disponibilidade. O ?leo decantado ? uma fra??o pesada obtida nas unidades de craqueamento catal?tico fluido no refino de petr?leo, e o controle de seu processamento ? dificultado pela complexidade de sua composi??o, que inclui compostos paraf?nicos, homoarom?ticos e heteroarom?ticos. O presente trabalho se prop?em a investigar a an?lise por RMN de uma mistura de padr?es de subst?ncias representativas dos tipos de compostos presentes no ?leo decantado. Assim, foram escolhidos padr?es de Tetracosano, Fenantreno, 9-metil Antraceno, Pireno, Carbazol, 9-metil Carbazol, Dibenzotiofeno, Dibenzofurano, Hexadecano, 1-metil Naftaleno, Tiofeno, Tetrahidrofurano. Todos os experimentos foram realizados no laborat?rio de RMN do PPGQ-UFRRJ a 20?C com o espectr?metro de RMN de 500 MHz Bruker Avance III, equipado com sonda BBO, gradiente no eixo z. Para auxiliar na separa??o dos componentes da mistura foram usados o pol?mero poli-(etilenoglicol), poli-(vinilpirrolidona), poli-(dimetilsiloxano), poli-(metacrilato de butila) e poli-(acetato de vinila), al?m do reagente de deslocamento Eu(fod)3. Os resultados obtidos a partir dos experimentos de DOSY-INEPT mostraram que o pol?mero PMAB foi a matriz que mais auxiliou na separa??o dos componentes da mistura em quest?o no presente trabalho, sendo seguido pelas matrizes PAV, PEG e PVP, que tamb?m apresentaram resultados satisfat?rios

Submitted by PPG Medicina e Ci?ncias da Sa?de (medicina-pg@pucrs.br) on 2018-07-20T19:52:55Z No. of bitstreams: 1 M?RCIA_CRISTINA_GON?ALVES_DE_OLIVEIRA_MARAES.pdf: 3458644 bytes, checksum: 005c22fed45246220ed1f2e0de9490a9 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-07-30T12:47:18Z (GMT) No. of bitstreams: 1 M?RCIA_CRISTINA_GON?ALVES_DE_OLIVEIRA_MARAES.pdf: 3458644 bytes, checksum: 005c22fed45246220ed1f2e0de9490a9 (MD5) / Made available in DSpace on 2018-07-30T12:58:07Z (GMT). No. of bitstreams: 1 M?RCIA_CRISTINA_GON?ALVES_DE_OLIVEIRA_MARAES.pdf: 3458644 bytes, checksum: 005c22fed45246220ed1f2e0de9490a9 (MD5) Previous issue date: 2017-08-30 / Abstract: Today, the incidence of prostate cancer is considered high, however, unlike other malignant tumours, there is an expressive number of cases in which prostate cancer does not progress to clinical disease. The management of patients with prostate cancer should be individually fitted due to the broad behaviour spectrum of this cancer, ranging from low grade tumours with low aggressive biological characteristics to high grade tumours with metastatic capacity. The possibility of predicting the future behavior of the disease allows the selection of the most appropriate conduct for each case. Studies have shown that mpMRI (multiparametric Magnetic Resonance Imaging) has a high negative predictive value for clinically significant prostate cancer, indicating that its application as a screening method and as assessment method of disease progression is promising. To standardize the protocols and reports of prostate mpMRI, the PI-RADS v2 (Prostate Imaging Reporting and Data System version 2) was launched in 2015. Multiparametric Magnetic Resonance Imaging standardized by PI-RADSv2 has been taking a prominent place in the management of prostate cancer, but the specificity and positive predictive value still need to be improved. Purpose: To assess whether the ADC (Apparent diffusion coefficient) value and tumour ADC ratio associated with PI-RADS v2 may increase accuracy in predicting clinically significant prostate cancer. Materials and methods: 91 individuals with suspected prostate cancer were retrospectively studied through mpMRI imaging standardized by PI-RADS v2, obtaining the ADC value from the tumour and the contralateral tissue. The findings were correlated to anatomopathological study (biopsy, prostatectomy or transurethral resection). Results: Accuracy, sensitivity, specificity, positive predictive value and negative predictive value for the consensus between the two reviewers using PI-RADS v2, category 3 associated with categories 4 and 5 for the detection of clinically significant cancer were 70.3%, 97.4%, 50.9%, 58.7% and 96.4% (p <0.001), respectively. The association of the ADC value (<0.795x10-3) to categories 3, 4 and 5 of the PI-RADSv2, in turn, demonstrated accuracy, specificity and positive predictive value of 78.9%, 84.9% and 76.5%; and the association with the tumour ADC ratio (<0.62) presented 77.5%, 86.5% and 77.4% of accuracy, specificity and positive predictive value, respectively. Conclusion: The association of the ADC value and the tumour ADC ratio to the PI-RADS v2 in mpMRI increases the accuracy, specificity and positive predictive value in the detection of aggressive prostate cancer, and may help in the screening of individuals who would undergo invasive procedures and radical therapy, or conservative management, as active surveillance or watchful waiting. / Introdu??o: ? considerada alta a incid?ncia de c?ncer de pr?stata na atualidade, contudo, diferentemente de outras neoplasias, existe um n?mero expressivo de casos em que o c?ncer de pr?stata n?o evolui para a doen?a cl?nica. Por este motivo, o manejo dos pacientes com neoplasia prost?tica deve ser moldado individualmente face ao amplo espectro que varia desde tumores de baixo grau, com caracter?sticas biol?gicas de baixa agressividade, a tumores de alto grau, com capacidade metast?tica. A possibilidade de prever o comportamento futuro da doen?a permite a sele??o da conduta mais adequada para cada caso. Estudos vem comprovando que a Resson?ncia Magn?tica multiparam?trica (RMmp) apresenta um alto valor preditivo negativo para o c?ncer de pr?stata com signific?ncia cl?nica, indicando que sua aplica??o como m?todo de triagem e na avalia??o da progress?o da doen?a ? promissora. Para padronizar os protocolos e os relat?rios da RMmp da pr?stata foi lan?ado em 2015 o PI-RADS v2 (?Prostate Imaging Reporting and Data System? vers?o 2). A RMmp padronizada pelo PI-RADS v2 vem assumindo um lugar de destaque no manejo do c?ncer de pr?stata, contudo, ainda s?o considerados baixos a Especificidade e o Valor Preditivo Positivo. Objetivos: Avaliar se o valor de ADC (?Apparent diffusion coefficient? = Coeficiente de Difus?o Aparente) e a raz?o tumoral do ADC associados ao PI-RADS v2 podem aumentar a acur?cia da RMmp na predi??o do c?ncer de pr?stata com signific?ncia clinica. Materiais e m?todos: Foram estudados retrospectivamente 91 indiv?duos com suspeita de c?ncer de pr?stata, submetidos a RMmp padronizada pelo PI-RADS v2, obtendo-se o ADC quantitativo da les?o e do tecido contralateral. Os achados foram correlacionados ao estudo anatomopatol?gico (bi?psia, prostatectomia ou ressec??o transuretral). Resultados: A acur?cia, sensibilidade, especificidade, valor preditivo positivo e valor preditivo negativo para o consenso entre os dois avaliadores utilizando a RMmp padronizada pelo PI-RADS v2, com a categoria 3 associada as categorias 4 e 5 para a detec??o do c?ncer com signific?ncia cl?nica foram 70,3%; 97,4%; 50,9%; 58,7% e 96,4% (p<0,001), respectivamente. A associa??o do valor do ADC (<0,795x10-3) ?s categorias 3, 4 e 5 do PI-RADS v2, por sua vez, demonstrou acur?cia, especificidade e valor preditivo positivo de 78,9%; 84,9% e 76,5%; e a associa??o com a raz?o tumoral do ADC (< 0,62), apresentou 77,5%; 86,5% e 77,4% de acur?cia, especificidade e valor preditivo positivo, respectivamente. Conclus?o: A associa??o do valor do ADC e da raz?o tumoral do ADC ao PI-RADS v2 na RMmp aumenta a acur?cia, especificidade e valor preditivo positivo na detec??o do c?ncer agressivo da pr?stata, podendo auxiliar na triagem dos indiv?duos e na decis?o entre a conduta agressiva, com procedimentos invasivos e terapia radical, ou a conduta conservadora, com vigil?ncia ativa ou observa??o.