by Cheung Kit Hing. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 175-199). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstracts --- p.ii / Table of Contents --- p.vi / List of Figures --- p.xviii / List of Plates --- p.xxii / List of Tables --- p.xxiii / Abbreviations --- p.xxv / Equations --- p.xxviii / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- The chemistry of azo dyes --- p.1 / Chapter 1.2 --- Azo dyes classification --- p.2 / Chapter 1.3 --- Environmental concerns and toxicity --- p.4 / Chapter 1.3.1 --- Toxicity of azo dyes --- p.5 / Chapter 1.3.2 --- Carcinogenicity --- p.5 / Chapter 1.3.3 --- Ecotoxicity --- p.11 / Chapter 1.3.3.1 --- Toxicity to microorganisms --- p.12 / Chapter 1.3.3.2 --- Toxicity towards vertebrates --- p.13 / Chapter 1.4 --- Treatment of azo dyes --- p.13 / Chapter 1.4.1 --- Physical treatment --- p.14 / Chapter 1.4.1.1 --- Adsorption --- p.14 / Chapter 1.4.1.2 --- Membrane technology --- p.15 / Chapter 1.4.2 --- Chemical treatments --- p.15 / Chapter 1.4.2.1 --- Chlorination --- p.16 / Chapter 1.4.2.2 --- Fenton's reaction --- p.16 / Chapter 1.4.2.3 --- Ozonation --- p.16 / Chapter 1.4.2.4 --- Coagulation --- p.17 / Chapter 1.4.3 --- Biological treatments --- p.17 / Chapter 1.4.3.1 --- Activated sludge process --- p.18 / Chapter 1.4.3.2 --- Biodegradation --- p.18 / Chapter 1.4.3.3 --- Biosorption --- p.21 / Chapter 1.4.3.3.1 --- Modeling of sorption --- p.24 / Chapter 1.4.3.3.1.1 --- Langmuir sorption model --- p.24 / Chapter 1.4.3.3.1.2 --- Freundlich sorption model --- p.25 / Chapter 1.4.4 --- Advanced oxidation processes --- p.25 / Chapter 1.4.4.1 --- Photocatalytic oxidation --- p.26 / Chapter 1.4.4.2 --- Titanium dioxide (TiO2) --- p.26 / Chapter 1.4.4.3 --- Mechanism of photocatalytic oxidation using photocatalyst TiO2 --- p.28 / Chapter 1.4.4.4 --- Photocatalytic oxidation of s-triazine containing compounds --- p.30 / Chapter 1.4.4.5 --- Photocatalytic oxidation of Procion Red MX-5B --- p.31 / Chapter 1.4.4.6 --- Cyanuric acid --- p.32 / Chapter 1.4.4.6.1 --- Application --- p.32 / Chapter 1.4.4.6.2 --- Toxicity --- p.32 / Chapter 1.4.4.6.3 --- Photocatalytic oxidation resistance --- p.34 / Chapter 1.4.4.6.4 --- Biodegradation --- p.35 / Chapter 1.4.4.7 --- Enhancement of photocatalytic oxidation by using sorbent immobilized with TiO2 --- p.35 / Chapter 1.4.4.7.1 --- Sorption --- p.35 / Chapter 1.4.4.7.2 --- Immobilization of TiO2 --- p.37 / Chapter 1.4.8 --- Integration of treatment methods --- p.39 / Chapter 2. --- Objectives --- p.41 / Chapter 3. --- Materials and methods --- p.42 / Chapter 3.1. --- Sorption --- p.42 / Chapter 3.1.1 --- Chemical reagents --- p.42 / Chapter 3.1.2 --- Determination of Procion Red MX-5B --- p.42 / Chapter 3.1.3 --- Sampling --- p.44 / Chapter 3.1.4 --- Isolation of Procion Red MX-5B-sorbing bacteria --- p.44 / Chapter 3.1.5 --- Screening of Procion Red MX-5B sorption ability --- p.44 / Chapter 3.1.6 --- Identification of isolated bacterium --- p.46 / Chapter 3.1.7 --- Optimization of cell yield and sorption capacity --- p.47 / Chapter 3.1.7.1 --- Preparation of cell culture of Vibrio sp. --- p.47 / Chapter 3.1.7.2 --- Growth phase --- p.47 / Chapter 3.1.7.2.1 --- Growth curve --- p.47 / Chapter 3.1.7.2.2 --- Dye sorption capacity --- p.47 / Chapter 3.1.7.3 --- Initial pH --- p.48 / Chapter 3.1.7.3.1 --- Growth curve --- p.48 / Chapter 3.1.7.3.2 --- Dye sorption capacity --- p.48 / Chapter 3.1.7.4 --- Temperature --- p.49 / Chapter 3.1.7.4.1 --- Growth curve --- p.49 / Chapter 3.1.7.4.2 --- Dye sorption capacity --- p.49 / Chapter 3.1.7.5 --- Glucose concentrations --- p.49 / Chapter 3.1.7.5.1 --- Growth curve --- p.49 / Chapter 3.1.7.5.2 --- Dye sorption capacity --- p.50 / Chapter 3.1.8 --- Optimization of sorption process --- p.50 / Chapter 3.1.8.1 --- Preparation of sorbent --- p.50 / Chapter 3.1.8.2 --- Dry weight of sorbent --- p.50 / Chapter 3.1.8.3 --- Temperature --- p.50 / Chapter 3.1.8.4 --- Agitation rate --- p.50 / Chapter 3.1.8.5 --- Salinity --- p.51 / Chapter 3.1.8.6 --- Initial pH --- p.51 / Chapter 3.1.8.7 --- Concentration of Procion Red MX-5B --- p.51 / Chapter 3.1.8.8 --- Combination study of salinity and initial pH --- p.51 / Chapter 3.2. --- Photocatalytic oxidation reaction --- p.52 / Chapter 3.2.1 --- Chemical reagents --- p.52 / Chapter 3.2.2 --- Photocatalytic reactor --- p.52 / Chapter 3.2.3 --- Optimization of sorption and photocatalytic oxidation reactions using biomass of Vibrio sp.immobilized in calcium alginate beads --- p.54 / Chapter 3.2.3.1 --- Effect of dry weight of immobilized cells of Vibrio sp. --- p.54 / Chapter 3.2.3.1.1 --- Sorption --- p.55 / Chapter 3.2.3.1.2 --- Photocatalytic oxidation --- p.56 / Chapter 3.2.3.2 --- Effect of UV intensities --- p.57 / Chapter 3.2.3.3 --- Effect of TiO2 concentrations --- p.57 / Chapter 3.2.3.3.1 --- Sorption --- p.57 / Chapter 3.2.3.3.2 --- Photocatalytic oxidation --- p.57 / Chapter 3.2.3.4 --- Effect of H202 concentrations --- p.57 / Chapter 3.2.3.5 --- Effect of the number of beads --- p.58 / Chapter 3.2.3.5.1 --- Sorption --- p.58 / Chapter 3.2.3.5.2 --- Photocatalytic oxidation --- p.58 / Chapter 3.2.3.6 --- Effect of initial pH with and without the addition of H2O2 --- p.58 / Chapter 3.2.3.7 --- Control experiments for photocatalytic oxidation of Procion Red MX-5B --- p.59 / Chapter 3.2.3.8 --- Combinational study of UV intensities and H2O2 concentrations --- p.59 / Chapter 3.2.3.9 --- Photocatalytic oxidation of Procion Red MX-5B under optimal conditions --- p.59 / Chapter 3.2.3.10 --- "Sorption isotherms of calcium alginate beads immobilized with 70 mg Vibrio sp. and 5,000 mg/L TiO2" --- p.59 / Chapter 3.3 --- Biodegradation --- p.60 / Chapter 3.3.1 --- Chemical reagents --- p.60 / Chapter 3.3.2 --- Sampling --- p.60 / Chapter 3.3.3 --- Enrichment --- p.60 / Chapter 3.3.4 --- Isolation of cyanuric acid-utilizing bacteria --- p.61 / Chapter 3.3.5 --- Determination of cyanuric acid --- p.61 / Chapter 3.3.6 --- Screening of Procion Red MX-5B sorption ability --- p.61 / Chapter 3.3.7 --- Screening of cyanuric acid-utilizing ability --- p.61 / Chapter 3.3.8 --- Bacterial identification --- p.63 / Chapter 3.3.9 --- Growth and cyanuric acid removal efficiency of the selected bacterium --- p.63 / Chapter 3.3.10 --- Optimization of reaction conditions --- p.64 / Chapter 3.3.10.1 --- Effect of salinity --- p.64 / Chapter 3.3.10.2 --- Effect of cyanuric acid concentrations --- p.65 / Chapter 3.3.10.3 --- Effect of temperature --- p.65 / Chapter 3.3.10.4 --- Effect of agitation rate --- p.65 / Chapter 3.3.10.5 --- Effect of initial pH --- p.66 / Chapter 3.3.10.6 --- Effect of initial glucose concentration --- p.66 / Chapter 3.3.10.7 --- Combinational study of glucose and cyanuric acid concentrations --- p.66 / Chapter 3.4 --- Detection of cyanuric acid formed in photocatalytic oxidation reaction --- p.66 / Chapter 3.5 --- "Integration of sorption, photocatalytic oxidation and biodegradation" --- p.67 / Chapter 4. --- Results --- p.68 / Chapter 4.1. --- Sorption --- p.68 / Chapter 4.1.1 --- Determination of Procion Red MX-5B --- p.68 / Chapter 4.1.2 --- Isolation of Procion Red MX-5B-sorbing bacteria --- p.68 / Chapter 4.1.3 --- Screening of Procion Red MX-5B sorption ability --- p.68 / Chapter 4.1.4 --- Identification of isolated bacterium --- p.72 / Chapter 4.1.5 --- Optimization of cell yield and sorption capacity --- p.72 / Chapter 4.1.5.1 --- Growth phase --- p.72 / Chapter 4.1.5.1.1 --- Growth curve --- p.72 / Chapter 4.1.5.1.2 --- Dye sorption capacity --- p.72 / Chapter 4.1.5.2 --- Initial pH --- p.75 / Chapter 4.1.5.2.1 --- Growth curve --- p.75 / Chapter 4.1.5.2.2 --- Dye sorption capacity --- p.75 / Chapter 4.1.5.3 --- Temperature --- p.75 / Chapter 4.1.5.3.1 --- Growth curve --- p.75 / Chapter 4.1.5.3.2 --- Dye sorption capacity --- p.79 / Chapter 4.1.5.4 --- Glucose concentrations --- p.79 / Chapter 4.1.5.4.1 --- Growth curve --- p.79 / Chapter 4.1.5.4.2 --- Dye sorption capacity --- p.79 / Chapter 4.1.6 --- Optimization of sorption process --- p.82 / Chapter 4.1.6.1 --- Dry weight of sorbent --- p.82 / Chapter 4.1.6.2 --- Temperature --- p.82 / Chapter 4.1.6.3 --- Agitation rate --- p.86 / Chapter 4.1.6.4 --- Salinity --- p.86 / Chapter 4.1.6.5 --- Initial pH --- p.86 / Chapter 4.1.6.6 --- Concentration of Procion Red MX-5B --- p.90 / Chapter 4.1.6.7 --- Combination study of salinity and initial pH --- p.90 / Chapter 4.2. --- Photocatalytic oxidation reaction --- p.94 / Chapter 4.2.1 --- Effect of dry weight of immobilized cells of Vibrio sp. --- p.94 / Chapter 4.2.1.1 --- Sorption --- p.94 / Chapter 4.2.1.2 --- Photocatalytic oxidation --- p.96 / Chapter 4.2.2 --- Effect of UV intensities --- p.96 / Chapter 4.2.3 --- Effect of TiO2 concentrations --- p.96 / Chapter 4.2.3.1 --- Sorption --- p.96 / Chapter 4.2.3.2 --- Photocatalytic oxidation --- p.101 / Chapter 4.2.4 --- Effect of H2O2 concentrations --- p.101 / Chapter 4.2.5 --- Effect of the number of beads --- p.101 / Chapter 4.2.5.1 --- Sorption --- p.105 / Chapter 4.2.5.2 --- Photocatalytic oxidation --- p.105 / Chapter 4.2.6 --- Effect of initial pH with and without the addition of --- p.105 / Chapter 4.2.7 --- Control experiments for photocatalytic oxidation of Procion Red MX-5B --- p.109 / Chapter 4.2.8 --- Combinational study of UV intensities and H202 concentrations --- p.112 / Chapter 4.2.9 --- Photocatalytic oxidation of Procion Red MX-5B under optimal conditions --- p.112 / Chapter 4.2.10 --- "Sorption isotherms of calcium alginate beads immobilized with 70 mg Vibrio sp. and 5,000 mg/L Ti02" --- p.112 / Chapter 4.3 --- Biodegradation --- p.116 / Chapter 4.3.1 --- Isolation of cyanuric acid-utilizing bacteria --- p.116 / Chapter 4.3.2 --- Determination of cyanuric acid --- p.116 / Chapter 4.3.3 --- Screening of Procion Red MX-5B sorption ability --- p.116 / Chapter 4.3.4 --- Screening of cyanuric acid-utilizing ability --- p.116 / Chapter 4.3.5 --- Bacterial identification --- p.118 / Chapter 4.3.6 --- Growth and cyanuric acid removal efficiency of the selected bacterium --- p.118 / Chapter 4.3.7 --- Optimization of reaction conditions --- p.122 / Chapter 4.3.7.1 --- Effect of salinity --- p.122 / Chapter 4.3.7.2 --- Effect of cyanuric acid concentrations --- p.122 / Chapter 4.3.7.3 --- Effect of temperature --- p.126 / Chapter 4.3.7.4 --- Effect of agitation rate --- p.126 / Chapter 4.3.7.5 --- Effect of initial pH --- p.132 / Chapter 4.3.7.6 --- Effect of initial glucose concentration --- p.132 / Chapter 4.3.7.7 --- Combinational study of glucose and cyanuric acid concentrations --- p.132 / Chapter 4.4 --- Detection of cyanuric acid formed in photocatalytic oxidation reaction --- p.137 / Chapter 4.5 --- "Integration of sorption, photocatalytic oxidation and biodegradation" --- p.137 / Chapter 5. --- Discussion --- p.141 / Chapter 5.1 --- Sorption --- p.141 / Chapter 5.1.1 --- Isolation of Procion Red MX-5B-sorbing bacteria --- p.141 / Chapter 5.1.2 --- Screening of Procion Red MX-5B sorption ability --- p.141 / Chapter 5.1.3 --- Identification of isolated bacterium --- p.141 / Chapter 5.1.4 --- Optimization of cell yield and sorption capacity --- p.142 / Chapter 5.1.4.1 --- Growth phase --- p.142 / Chapter 5.1.4.1.1 --- Growth curve --- p.142 / Chapter 5.1.4.1.2 --- Dye sorption capacity --- p.143 / Chapter 5.1.4.2 --- Initial pH --- p.146 / Chapter 5.1.4.2.1 --- Growth curve --- p.146 / Chapter 5.1.4.2.2 --- Dye sorption capacity --- p.146 / Chapter 5.1.4.3 --- Temperature --- p.146 / Chapter 5.1.4.3.1 --- Growth curve --- p.146 / Chapter 5.1.4.3.2 --- Dye sorption capacity --- p.147 / Chapter 5.1.4.4 --- Glucose concentrations --- p.147 / Chapter 5.1.4.4.1 --- Growth curve --- p.147 / Chapter 5.1.4.4.2 --- Dye sorption capacity --- p.147 / Chapter 5.1.5 --- Optimization of sorption process --- p.148 / Chapter 5.1.5.1 --- Dry weight of sorbent --- p.148 / Chapter 5.1.5.2 --- Temperature --- p.148 / Chapter 5.1.5.3 --- Agitation rate --- p.149 / Chapter 5.1.5.4 --- Salinity --- p.149 / Chapter 5.1.5.5 --- Initial pH --- p.150 / Chapter 5.1.5.6 --- Concentration of Procion Red MX-5B (MX-5B) --- p.152 / Chapter 5.1.5.7 --- Combination study of salinity and initial pH --- p.153 / Chapter 5.2. --- Photocatalytic oxidation reaction --- p.153 / Chapter 5.2.1 --- Effect of immobilized cells of Vibrio sp. --- p.153 / Chapter 5.2.1.1 --- Sorption --- p.153 / Chapter 5.2.1.2 --- Photocatalytic oxidation --- p.154 / Chapter 5.2.2 --- Effect of UV intensities --- p.155 / Chapter 5.2.3 --- Effect of TiO2 concentrations --- p.155 / Chapter 5.2.3.1 --- Sorption --- p.155 / Chapter 5.2.3.2 --- Photocatalytic oxidation --- p.156 / Chapter 5.2.4 --- Effect of H2O2 concentrations --- p.156 / Chapter 5.2.5 --- Effect of the number of beads --- p.157 / Chapter 5.2.5.1 --- Sorption --- p.157 / Chapter 5.2.5.2 --- Photocatalytic oxidation --- p.158 / Chapter 5.2.6 --- Effect of initial pH with and without the addition of --- p.158 / Chapter 5.2.7 --- Control experiments for photocatalytic oxidation of Procion Red MX-5B --- p.160 / Chapter 5.2.8 --- Combinational study of UV intensities and H202 concentrations --- p.161 / Chapter 5.2.9 --- Photocatalytic oxidation of Procion Red MX-5B under optimal conditions --- p.161 / Chapter 5.2.10 --- "Sorption isotherms of calcium alginate beads immobilized with 70 mg Vibrio sp. and 5,000 mg/L Ti02" --- p.161 / Chapter 5.3 --- Biodegradation --- p.162 / Chapter 5.3.1 --- Isolation of cyanuric acid-utilizing bacteria --- p.162 / Chapter 5.3.2 --- Determination of cyanuric acid --- p.163 / Chapter 5.3.3 --- Screening of Procion Red MX-5B sorption ability --- p.163 / Chapter 5.3.4 --- Screening of cyanuric acid-utilizing ability --- p.163 / Chapter 5.3.5 --- Bacterial identification --- p.163 / Chapter 5.3.6 --- Growth and cyanuric acid removal efficiency of the selected bacterium --- p.164 / Chapter 5.3.7 --- Optimization of reaction conditions --- p.165 / Chapter 5.3.7.1 --- Effect of salinity --- p.165 / Chapter 5.3.7.2 --- Effect of cyanuric acid concentration --- p.165 / Chapter 5.3.7.3 --- Effect of temperature --- p.166 / Chapter 5.3.7.4 --- Effect of agitation rate --- p.167 / Chapter 5.3.7.5 --- Effect of initial pH --- p.167 / Chapter 5.3.7.6 --- Effect of initial glucose concentration --- p.167 / Chapter 5.3.7.7 --- Combinational study of glucose and cyanuric acid concentrations --- p.168 / Chapter 5.4 --- Detection of cyanuric acid formed in photocatalytic oxidation reaction --- p.170 / Chapter 5.5 --- "Integration of sorption, photocatalytic oxidation and biodegradation" --- p.171 / Chapter 5.6 --- Recommendations --- p.171 / Chapter 6. --- Conclusions --- p.173 / Chapter 7. --- References --- p.175 / Appendix --- p.200

Typescript. / Thesis (Ph. D.)--University of Hawaii, 1970. / Bibliography: leaves [215]-226. / Microfilm. / xix, 226 l diagrs

Orientador: Maria Aparecida Carvalho de Medeiros / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia / Made available in DSpace on 2018-08-27T04:43:14Z (GMT). No. of bitstreams: 1 Vilella_KellyAdrianaRibeiroTagliaferro_M.pdf: 2403765 bytes, checksum: 91f29c165c5f2b7217d7fc43cb9b5daf (MD5) Previous issue date: 2015 / Resumo: Os resíduos de herbicidas triazínicos são compostos com moderada toxicidade, altamente persistentes no ambiente, contaminando os mananciais e águas subterrâneas e são muito utilizados em várias culturas, inclusive da cana-de-açúcar. Os herbicidas atrazina e simazina foram oxidados com 'H IND.2O IND.2' na presença de catalisadores biomiméticos (metaloporfirinas de ferro e rutênio) e os produtos gerados na reação foram analisados via cromatografia gasosa (GC, do inglês gás chromatography) associada à espectrometria de massas (MS, do inglês mass spectrometry), buscando elucidar os subprodutos. As reações de oxidação dos herbicidas triazínicos e os subprodutos gerados foram monitoradas por espectrofotometria na região do ultra violeta e visível (UV-Vis) e cromatografia gasosa (GC), utilizando-se o detector de captura de elétrons (ECD, do inglês elétron capture detector). Os rendimentos das reações de oxidação das triazinas com 'H IND.2O IND.2' e catalisadas pelas metaloporfinas de ferro (Fe(FTTPCl)) e rutênio (Ru(OCTTPP)), variaram de acordo com as condições de reações catalíticas. Foi observado que houve degradação significativa dos analitos (94,70% para a atrazina e 92,60% para a simazina utilizando a (Fe(FTTPCl)) e; 94,38% para a atrazina e 67,19% para a simazina utilizando a (Ru(OCTTPP))) e também foi observado a transformação dos herbicidas nos subprodutos desetilatrazina (DEA) e o deisopropilatrazina (DIA). Os dados de monitoramento das reações catalíticas por UV-Vis revelaram as estabilidades dos catalisadores (Fe(FTTPCl)) e (Ru(OCTTPP)), nas condições oxidantes das reações. Os resultados obtidos com a cromatografia gasosa acoplada com a espectrometria de massas (GC-MS), utilizando a técnica de ionização por impacto de elétrons ¿ (EI, do inglês electron ionization), full scan, com o modo positivo (EI+), associado a este pico revelaram o pico do íon molecular (m/z= 215, associado ao herbicida atrazina [M]+ e os principais fragmentos (m/z): 200(associado ao íon [M ¿ CH3]+), 173 e 138; sendo que o espectro de massa obtido após a reação de oxidação revelou o desaparecimento do pico associado aos herbicidas e formação de novos picos, associados a fragmentos de subprodutos. Similarmente, a identificação da simazina foi obtida com o modo positivo (EI+), tendo sido revelado o pico do íon molecular (m/z= 201) e os principais fragmentos (m/z): 186, 173 e 138 / Abstract: Waste triazine herbicides are compounds with moderate toxicity, highly persistent in the environment, contaminating water sources and groundwater are widely used in various cultures, including the cane sugar. The atrazine and simazine herbicides were oxidized with 'H IND.2O IND.2' in the presence of biomimetic catalysts (iron and ruthenium metalloporphyrins) and the products generated in the reaction were analyzed by gas chromatography (GC) associated with mass spectrometry (MS), to elucidate the by-products. The oxidation reaction of the triazine herbicide and by-products generated were monitored by spectrophotometry in the ultraviolet region and visible (UV-Vis) and gas chromatography (GC), using electron capture detector (ECD). Proceeds from the triazines oxidation reactions with 'H IND.2O IND.2' catalyzed by iron and metalloporphyrins (Fe (FTTPCl)) and ruthenium (Ru (OCTTPP)), varied according to the conditions of catalytic reactions. It was observed that there was significant degradation of the analytes (94.70% to 92.60% for atrazine and simazine using the (Fe(FTTPCl)) and; 94.38% to 67.19% for atrazine and simazine using the (Ru(OCTTPP))) and was also observed the transformation of herbicides in desethyl atrazine products (DEA) and the deisopropil atrazine (DIA). The monitoring data of catalytic reactions by UV-Vis revealed the stability of the catalysts (Fe(FTTPCl)) and (Ru(OCTTPP)) in oxidizing conditions of the reactions. The results obtained with gas chromatography coupled with mass spectrometry (GC-MS) using the electron impact ionization technique (EI), full scan, positive mode (EI+), associated this peak revealed molecular ion peak (m/z = 215, associated with atrazine [M]+ and major fragments (m/z): 200 (associated with the ion [M - CH3]+), 173 and 138, and the mass spectrum obtained after the oxidation reaction revealed the disappearance of the peak associated with the herbicides and formation of new peaks associated with byproducts fragments. Similarly, the identification of simazine was obtained in the positive mode (EI+) and been revealed molecular ion peak (m / z = 201) and the principal fragments (m / z): 186, 173 and 138 / Mestrado / Tecnologia e Inovação / Mestra em Tecnologia

FAK (kinase d’adhésion focale) est une protéine tyrosine kinase cytoplasmique, qui a un rôle clé dans la cascade de signalisation médiée par les intégrines et les récepteurs aux facteurs de croissance. Elle régule de nombreux processus cellulaires et le dérèglement de ce système est impliqué dans de nombreuses pathologies, en particulier dans les cancers. L’implication de FAK aux différentes étapes de la progression tumorale ne peut plus être remise en question, pourtant aucun inhibiteur n’est utilisé aujourd’hui en clinique. D’autre part certaines zones d’ombre restent encore dans les différents rôles de FAK et des inhibiteurs sélectifs devraient permettre de les étudier. Nous avons donc choisi de développer une première famille d’inhibiteurs de FAK de type diarylamino-1,3,5-triazinique à partir des données structurales pour accéder à une petite banque de composés. L’étude de cette première série et notamment les résultats de co-cristallisation nous ont permis de concevoir quatre nouvelles familles, plus originales d’inhibiteurs de l’activité kinase de FAK, dont le meilleur composé présente une CI50 de 35 nM. Les meilleurs inhibiteurs de FAK obtenus présentent un fort potentiel anti-angiogénique sur les cellules HUVEC en termes de croissance et formation de microvaisseaux. Certains dérivés possèdent un fort effet anti-tumoral, de l’ordre de 20 nM pour les meilleurs, sur plusieurs modèles cellulaires cancéreux (ex: glioblastome, cancer du côlon, …). Par ailleurs, certains de nos inhibiteurs de FAK ont montré une restauration de la sensibilité à TRAIL (Tumor-necrosis-factor Related Apoptosis Inducing Ligand) des cellules cancéreuses résistantes (PANC-1, MCF-7 et SKOV-3). / FAK (Focal Adhesion Kinase) is a non-receptor protein tyrosine kinase. FAK participates in growth factor receptor-mediated and integrin signaling pathway and plays essential roles in many cellular functions and the dysfunction of this system is involved in many pathologies, in particular in cancer. The implication of FAK in the various stages of the tumoral progress is widely studied but no inhibitors are used in therapy today. And some roles of FAK need to be clarify ant that why we need to develop selective inhibitors of FAK. As a part of our research program aimed at the development for new inhibitors of FAK, we have synthesized a series of novel diarylamino-1,3,5-triazine derivatives. The study of this first series in particular the structural studies allowed us to design four new families, more original of FAK inhibitors with an IC50 of 35 nM for the best compounds. This compounds show a high angiogenic potential on HUVEC cells and anti-tumor activity on a variety of cellular models (eg : colon, brain). Besides, some of our inhibitors of FAK restores sensitivity to TRAIL-induced apoptosis in resistant cancer cells line (PANC-1, MCF-7 and SKOV-3).

Membrane assisted passive sampler (MAPS) is an informative, cost-effective and environmentally friendly approach for monitoring of ionisable organic compounds in water bodies. The sampler uses no organic solvent. By adjusting the pH of the acceptor phase, both acidic chlorophenols and basic triazine model compounds were extracted. The sampler was optimized under laboratory conditions followed by field applications on the same compounds. The optimised parameters were temperature of the water body, turbulence, protective cover, biofouling, matrix effects such as humic substances, degree of trapping in the acceptor phase and exposure time. It was found that the sampling kinetics of most of the tested analytes are dependent on temperature and on the hydrodynamic conditions. Also, a strong dependence of the sampling rates reduction on sample matrix and protective cover used was noted. The chemical uptake of both the acidic chlorophenols and basic triazine compounds into the passive sampler remained linear and integrative through out the exposure periods. The amounts quantified in the MAPS had relative standard deviations mostly between 10 % and 20 % (from repeat determinations) and did in no case exceed 30 %. The behaviour of the MAPS to monitor ionisable triazine compounds in dam water of the Hartebeespoort was compared to Chemcatcher and solid phase extraction technique with C18 sorbents of spot samples. Similarly, the behaviour of the MAPS to monitor ionisable chlorophenol compounds in wastewater of the Goudkoppies Wastewater Treatment Plant was compared to solid phase extraction technique. There were no triazine and chlorophenol compounds detected in any of the deployed passive samplers in the field applications. The same results were obtained in grab samples extracted with solid phase extraction under laboratory conditions. However, data from laboratory studies support the feasibility of MAPS to measure the freely dissolved fraction of ionisable organic chemicals in water. Using water from the Hartebeespoort dam spiked with 50 μg L-1 triazine, the detection limits of triazine compounds ranged from 11.38 to 61.86 μg L-1 for direct injection, 1.082 to 23.077 μg L-1 for MAPS, 0.892 to 5.769 μg L-1 for Chemcatcher and 1.482 to 7.410 μg L-1 for SPE. While using water from Goudkoppies Wastewater Treatment Plant spiked with 100 μg L-1 chlorophenols, the detection limits of the passive sampler were comparable with that of solid phase extraction and were around 1.5 μg L-1. Estimation and interpretation of enrichment factors in the passive samplers and SPE were generally comparable ranging from 46 to 295 for chlorophenol compounds. Also, for triazine compounds, the obtained enrichment factors in the passive samplers and SPE are generally comparable with the exception of enrichment factors of propazine, ametryn terbuthylazine, prometryn and terbutryn compounds which were higher for the MAPS ranging from 46 to 65.

<p>Primenom tečne hromatografije na obrnutim fazama<br />ispitano je retenciono pona&scaron;anje 14 novosintetisanih<br />derivata s-triazina na tankom sloju RP C-18 i silika gelu<br />impregniranim parafinskim uljem. Kao pokretne faze<br />kori&scaron;ćene su dvokomponentne sme&scaron;e vode i organskih<br />rastvarača. Izračunate su R_M^0&nbsp;vrednosti i ispitana je<br />korelacija sa različitim deskriptorima i prediktorima<br />biolo&scaron;ke aktivnosti.</p> / <p>Retentional behaviour of 14newly syntetised derivates&nbsp;of s-triazine on RP C-18 and paraffin oil-impregnated&nbsp;silica gel suport had been investigated using thin-layer&nbsp;<br />chromatography. As a mobilephases were used two-component water based mobile &nbsp;phases. Calculated R_M^0&nbsp;values were corelated to various molecular descriptors&nbsp;<br />as well as biological activity indicators.</p>

ABSTRACT Anaplastic lymphoma kinase (ALK) is a tyrosine kinase receptor, which plays a pivotal part in the development of the central nervous system. Aberrant expression of full-length ALK occurs in neuroblastoma and chromosomal translocation or inversion of the ALK gene can generate novel fusion-ALK proteins that possess constitutive kinase activity and contribute to oncogenic processes. One of the well-studied fusion proteins is nucleophosmin (NPM-ALK), which draws a lot of attention for medicinal chemists to design small molecules as kinase inhibitors for this target. In this dissertation, [1, 2, 4]-Dihydrotriazine dimers as competitors of the lead compound NVP-TAE684 targeting NPM-ALK have been designed and synthesized. Molecular modelling studies show that those dihydrotriazine dimers have a great potential to be better kinase inhibitors. Chapter two describes imaging in the drug discovery and development arena. One of important imaging techniques is positron emission tomography (PET). PET is a radionuclide based molecular imaging technique, which can be used for early detection, characterization, "real time" monitoring of diseases, and investigation of the efficacy of drugs. Fluorine-18 (18F) based molecular probes for PET imaging still remain big challenging to prepare but have gained increased interest by radiochemists in the past two decades. In this study, a novel approach to introduce fluorine into a molecular probe has been discovered based on boron chemistry. A few novel fluorine capture reagents have been synthesized and described in this Chapter.

Thesis (Ph. D.)--University of Washington, 1996. / Vita. Includes bibliographical references (leaves [135]-144).

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Made available in DSpace on 2014-10-09T12:53:32Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:56Z (GMT). No. of bitstreams: 0 / O presente trabalho apresenta os dados obtidos no estudo para o desenvolvimento de método multirresíduo de pesticidas dos grupos de benzimidazol (carbendazim, tiabendazol e tiofanato metílico), carbamatos (aldicarbe, aldicarbe sulfona, aldicarbe sulfóxido, carbaril, carbofurano, metomil, metiocarbe, pirimicarbe, propoxur) e triazinas (atrazina e simazina) em amostras de milho verde. Os pesticidas foram extraídos em acetona, sob agitação, diluídos em água e injetados no sistema LC/MS/MS. A técnica analítica de quantificação e confirmação utilizada foi a Cromatografia Líquida acoplada à Espectrometria de Massas em Tandem com ionização por Electrospray no modo positivo. A validação do método multirresíduo foi submetida em conformidade com a norma EC/2002/657 da Comunidade Européia. Para quantificação dos analitos utillizouse as curvas analíticas dos princípios ativos, nas concentrações que variaram de 0,04 a 8,0 ng/ml, correspondentes a 2,0 a 400 ?g.kg-1 na amostra. Para o estudo da recuperação, os pesticidas foram avaliados em cinco níveis, de ½ Limite de quantificação (LOQ) a 5 LOQ, correspondentes a níveis de fortificação de 4,0 a 200 ?g.kg-1 . Os resultados da recuperação apresentaram, em níveis aceitáveis, na faixa de 80 a 110% e com precisão satisfatórias, CV <=20%, com exceção de aldicarbe e de aldicarbe sulfona. Os limites de quantificação do método variaram de 8 a 40 ?g.kg-1 e os limites de detecção do método, de 0,2 a 2,9 ?g.kg-1. Os limites de quantificação do método atendem aos limites máximos de resíduos da legislação brasileira em vigor. Nas amostras estudadas, não foram encontrados resíduos de pesticidas acima do limite de quantificação do método. Por outro lado, todos os pesticidas, exceto carbaril e pirimicarbe, foram detectados em todas as amostras e em níveis acima dos limites de detecção do método. A alta incidência da presença de resíduos de pesticidas se deve possivelmente ao uso inadequado de agrotóxico, quando não autorizado o seu uso para a cultura de milho no Brasil ou proveniente de alguma contaminação, como o tratamento de agrotóxicos aplicados em outras culturas plantadas no mesmo solo. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP