Les maladies cardio-vasculaires liées à l'athérosclérose sont pourvoyeuses d’une importante morbi-mortalité dans les pays développés. Une détection plus précoce des modifications des parois vasculaires, via des techniques de diagnostic non invasives, pourrait sensiblement améliorer leur prise en charge. L'échographie est largement utilisée comme outil de dépistage des maladies cardiovasculaires. Cependant, sa faible sensibilité limite son utilisation. Le développement d’agent de contraste spécifique permettant de résoudre ce problème semble donc primordial. Le fucoidane est un ligand polysaccharidique sulfaté ayant une forte affinité pour la P-sélectine. Exprimée au niveau de la surface des plaquettes activées et des cellules endothéliales, cette dernière est impliquée dans la pathogénèse précoce des maladies cardiovasculaires. Le but de ce projet de thèse a été de développer un agent de contraste injectable ciblant la P-sélectine via le fucoidane dans le but de réaliser une modalité d’imagerie moléculaire de faible coût, simple et spécifique des pathologies artérielles. Trois types d'agents de contraste ont été développés : 1) Des nanoparticules associées à du bromure de perfluorooctyle (PFOB), fonctionnalisées par du fucoidane. Elles ont été capables de se fixer à la P-selectine et une amélioration du contraste a été observée présentaient une mauvaise échogénicité dans la circulation sanguine, probablement en raison de leur faible teneur en PFOB et de leur très petite taille. 2) Afin d’améliorer l’échogénicité, des microcapsules contentant du PFOB dans leur coeur ont été développées. Celles-ci se sont également liées à la P-sélectine même en condition de dans un modèle animal de maladie artérielle. Cependant, ces produits flux sanguin. Des résultats dans les zones où la P-sélectine était exprimée. Malheureusement, l'augmentation du ont montré que ces m icrocapsules étaient présentes contraste était toujours insuffisante pour être suffisamment discriminante. 3) Des microbulles fonctionnalisées par du fucoidane, ont été conçues pour surmonter ce problème d’échogénicité. Elles ont montré une augmentation significative du signal acoustique en condition de flux sanguin. De plus, ces microbulles se sont accumulées à la surface des parois artérielles riches en thrombus. Ces derniers résultats indiquent que ces microbulles, en tant qu'outil d'imagerie moléculaire ultrasonore, pourraient être très intéressantes pour les futures études des maladies artérielles. / Cardiovascular diseases due to atherosclerosis remain a major morbidity in developed countries. Their treatment could be substantially improved with early detection of the vascular Ultrasonography is widely used as a screening tool in clinic to detect cardiovascular diseases. However, its low resolution requires the development of targeted acoustic tracers to improve the contrast degree. Fucoidan is a sulfated polysaccharide ligand with a high affinity for P-selectin, which was found to be expressed on the activated non- pathological changes by invasive diagnostic techniques. platelets and endothelial cells and involved in the early pathogenesis of cardiovascular diseases. The aim of this doctoral project was to develop injectable, low-cost and simple contrast agents, functionalized with fucoidan as efficient acoustic tracers of P-selectin for ultrasound molecular imaging of arterial pathologies. Three types of contrast agents have been developed: 1) Fucoidan functionalized nanoparticles loaded with perfluorooctyl bromide (PFOB). They could bind to P-selectin and exhibit contrast enhancement in animal models of arterial disease. However, these products showed poor echogenicity in blood stream due probably to low content of PFOB and their very small size. 2) Fucoidan functionalized microcapsules with PFOB core were developed to improve the PFOB encapsulation efficiency. They could bind to P-selectin in arterial flow conditions, and microcapsules were located in the regional expression of P-selectin. Unfortunately, results revealed that these the contrast enhancement was still insufficient to be observed. 3) To address echogenicity problems, fucoidan functionalized polymer microbubbles were designed to replace PFOB. They showed strong signal enhancement under flow conditions and could accumulate on the surface of platelets-rich thrombus. These results indicated that these microbubbles, as ultrasound molecular imaging tools, could be very interesting for the future study of arterial diseases.

The presence of micropollutants, particularly pesticides, in surface waters across Canada has been of concern not only for their environmental impact, but also for their potential effects on human health and recalcitrant nature to conventional water treatment methods. Although ozone has been mainly applied for disinfection of drinking water, oxidation of trace organics by ozonation has been considered potentially effective. In an effort to meet increasingly stringent drinking water regulations, different solid catalysts have been used to enhance the removal of water contaminants by ozonation. In spite of the increasing number of data demonstrating the effectiveness of heterogeneous catalytic ozonation, the influence of different factors on the efficiency of micropollutants oxidation is still unclear.<p> In the present work, application of three solid catalysts in ozonation of two model micropollutants in pure water was examined using a laboratory-scale reaction system over a range of operating conditions. The three catalysts investigated were activated carbon, alumina, and perfluorooctyl alumina, and the two model micropollutants were the pesticides atrazine and 2,4-dichlorophenoxyactic acid. The effects of solution pH, presence of a radical scavenger, pesticide adsorption on catalyst, and catalyst dose on micropollutant removal were investigated. Solution pH was found to significantly influence the catalyst ability to decompose ozone into free hydroxyl radicals. The effect of these free radicals was markedly inhibited by the radical scavenger resulting in a negative impact on pesticides degradation. In general, the removal rate of pesticides was found to increase with increasing doses of catalyst.<p> In the ozonation process in the presence of activated carbon, atrazine removal rates increased four and two times when using a catalyst dose of 0.5 g L-1 at pH 3 and 7, respectively, whereas observed reaction rates for 2,4-D increased over 5 times in the presence of 1 × 10-4 M tert-butyl alcohol at pH 3. In the ozonation system catalyzed by 8 g L-1 alumina, the observed reaction rate constant of atrazine removal notably improved at neutral pH by doubling the micropollutant removal rate. For the pesticide 2,4-D in the presence of 1 × 10-4 M tert-butyl alcohol at pH 5, the observed removal rate was over ten times higher than that for the non-catalytic ozonation process using also using a catalyst dose of 8 g L-1. Modification of alumina to produce perfluorooctyl alumina resulted in a material able to significantly adsorb atrazine, while not exhibiting affinity for adsorption of 2,4-D. In spite of its adsorptive properties, perfluorooctyl alumina was found to enhance neither molecular ozone reactions nor ozone decomposition into hydroxyl radicals. Thus, the observed removal rates for atrazine and 2,4-D by ozonation in the presence of perfluorooctyl alumina did not increase significantly.

The presence of micropollutants, particularly pesticides, in surface waters across Canada has been of concern not only for their environmental impact, but also for their potential effects on human health and recalcitrant nature to conventional water treatment methods. Although ozone has been mainly applied for disinfection of drinking water, oxidation of trace organics by ozonation has been considered potentially effective. In an effort to meet increasingly stringent drinking water regulations, different solid catalysts have been used to enhance the removal of water contaminants by ozonation. In spite of the increasing number of data demonstrating the effectiveness of heterogeneous catalytic ozonation, the influence of different factors on the efficiency of micropollutants oxidation is still unclear.<p> In the present work, application of three solid catalysts in ozonation of two model micropollutants in pure water was examined using a laboratory-scale reaction system over a range of operating conditions. The three catalysts investigated were activated carbon, alumina, and perfluorooctyl alumina, and the two model micropollutants were the pesticides atrazine and 2,4-dichlorophenoxyactic acid. The effects of solution pH, presence of a radical scavenger, pesticide adsorption on catalyst, and catalyst dose on micropollutant removal were investigated. Solution pH was found to significantly influence the catalyst ability to decompose ozone into free hydroxyl radicals. The effect of these free radicals was markedly inhibited by the radical scavenger resulting in a negative impact on pesticides degradation. In general, the removal rate of pesticides was found to increase with increasing doses of catalyst.<p> In the ozonation process in the presence of activated carbon, atrazine removal rates increased four and two times when using a catalyst dose of 0.5 g L-1 at pH 3 and 7, respectively, whereas observed reaction rates for 2,4-D increased over 5 times in the presence of 1 × 10-4 M tert-butyl alcohol at pH 3. In the ozonation system catalyzed by 8 g L-1 alumina, the observed reaction rate constant of atrazine removal notably improved at neutral pH by doubling the micropollutant removal rate. For the pesticide 2,4-D in the presence of 1 × 10-4 M tert-butyl alcohol at pH 5, the observed removal rate was over ten times higher than that for the non-catalytic ozonation process using also using a catalyst dose of 8 g L-1. Modification of alumina to produce perfluorooctyl alumina resulted in a material able to significantly adsorb atrazine, while not exhibiting affinity for adsorption of 2,4-D. In spite of its adsorptive properties, perfluorooctyl alumina was found to enhance neither molecular ozone reactions nor ozone decomposition into hydroxyl radicals. Thus, the observed removal rates for atrazine and 2,4-D by ozonation in the presence of perfluorooctyl alumina did not increase significantly.

Ozonation is an efficient method to degrade refractory organics in textile wastewaters. In recent years, catalytic ozonation is applied to reduce ozone consumption and to increase chemical oxygen demand and total organic carbon (TOC) removal efficiencies. The ozonation of two industrial dyes, namely Acid Red-151 (AR-151) and Remazol Brilliant Blue R (RBBR) was examined separately both in a semi-batch reactor and also in a fluidized bed reactor (FBR) by conventional and catalytic ozonation with alumina and perfluorooctyl alumina (PFOA) catalysts. The conventional and catalytic ozonation reactions followed a pseudo-first order kinetics with respect to the dye concentration. The highest COD reductions were obtained in the presence of the catalysts at pH=13, with alumina for AR-151 and with PFOA for RBBR. Residence time distribution experiments were performed to understand the degree of liquid mixing in the reactor. The behaviour of the FBR was almost equivalent to the behaviour of one or two completely stirred tank reactors in series in the presence of the solid catalyst particles. The volumetric ozone-water mass transfer coefficients (kLa) were found at various gas and liquid flow rates and catalyst dosages in the FBR. A model was developed to find kLa in the reactor by comparing the dissolved O3 concentrations in the experiments with the model results. kLa increased significantly by the increase of gas flow rate. Higher catalysts dosages at the fluidization conditions yielded higher kLa values indicating higher rates of mass transfer. Dye ozonation experiments without catalyst and with alumina or PFOA catalyst were conducted at different conditions of the inlet dye concentration, gas and liquid flow rates, inlet ozone concentration in the gas, catalyst dosage, particle size and pH. The dye and TOC removal percentages were increased with the increase of gas flow rate and with the decrease of both the liquid flow rate and inlet dye concentration. The addition of the catalyst was beneficial to enhance the TOC degradation. The ozone consumed per liter of wastewater was much lower when the catalyst was present in the reactor. In terms of TOC removal and O3 consumption, the most efficienct catalyst was PFOA. According to the organic analysis, the intermediate by-products were oxalic, acetic, formic and glyoxalic acids in RBBR and AR-151 ozonation. The dye and dissolved ozone concentration profiles were predicted from a developed model and the model results were compared with the experimental results to obtain the enhanced kLa values. The presence of the chemical reaction and the catalysts in the FBR, enhanced the kLa values significantly. The enhancement factor (E) was found as between 0.97 and 1.93 for the non-catalytic ozonation and 0.96 and 1.53 for the catalytic ozonation at pH = 2.5. The dimensionless number of Hatta values were calculated between 0.04-0.103 for the sole ozonation of RBBR and AR-151 solutions. According to the calculated Ha values, the reaction occurred in the bulk liquid and in the film being called as the intermediate regime in the literature.

Textile wastewaters are highly colored and non-biodegradable having variable compositions of colored dyes, surfactants and toxic chemicals. Recently, ozonation is considered as an effective method that can be used in the treatment of industrial wastewaters / catalytic ozonation being one of the advanced oxidation processes (AOPs), is applied in order to reduce the ozone consumption and to increase the chemical oxygen demand (COD) and total organic carbon (TOC) removals. In this study, catalytic ozonation of industrial textile wastewater (ITWW) obtained from AKSA A.S. (Yalova, Istanbul) textile plant has been examined in a three phase fluidized bed reactor at different conditions. The effects of inlet chemical oxygen demand concentration (CODin), pH, different catalyst types [perflorooctyl alumina (PFOA) and alumina] and catalyst dosage on ozonation process were determined. Moreover, the changes in the organic removal efficiencies with gas to liquid flow rate ratio were investigated. The dispersion coefficients (DL) and volumetric ozone-water mass transfer coefficients (kLa) were estimated at various gas and liquid flow rates in order to observe the effect of liquid mixing in the reactor on ozonation process. It was observed that increasing both gas and liquid flow rates by keeping their ratio constant provided higher organic removal efficiencies due to the higher mixing in the liquid phase. The dyes present in ITWW sample were known to be Basic Blue 41 (BB 41), Basic Red 18.1 (BR 18.1) and Basic Yellow 28 (BY 28). The &ldquo / absorbance vs. concentration&rdquo / calibration correlations were developed to estimate the amounts of these colored dyes in the ITWW sample. This provided the opportunity to examine the degradation of each dye in this wastewater separately. While PFOA catalyst was found to increase the removal efficiency of BY 28 at an acidic pH of 4, alumina yielded highest color removals for BB 41 and BR 18.1 at a pH of 12. The highest TOC and COD reductions being 24.4% and 29.5%, respectively, were achieved in the catalytic ozonation of the ITWW using alumina as the catalyst at a pH of 12 and at a gas to liquid flow rate ratio of 1.36 (QG = 340 L/h, QL = 250 L/h). At the same conditions, also the highest overall color removal in terms of Pt-Co color unit, namely 86.49%, were obtained due to the lower BY 28 concentration in the WW sample than those of the BB 41 and BR 18.1. In addition, the oxidation of BB 41, BR 18.1 and BY 28 dyes were investigated in a semi-batch reactor by sole and catalytic ozonations with alumina and PFOA catalyst particles. The sole and catalytic ozonation reactions followed a pseudo-first order kinetics with respect to dye concentration. The highest TOC and COD removals being 58.3% and 62.9%, respectively, were obtained at pH of 10 for BB 41 and 55.2% and 58.8%, respectively, for BR 18.1 with alumina catalyst. On the other hand, for BY 28 PFOA catalyst yielded highest TOC and COD reductions being 61.3% and 66.9%, respectively, at pH of 4.

Environmental regulations have imposed limitations on a wide variety of organic and inorganic pollutants in industrial textile wastewaters. There are several degradation methods used in literature studies. Among these methods ozonation is one of the most considered way to degrade refractory chemicals in textile wastewaters. In recent years, catalytic ozonation as being one of the advanced oxidation processes (AOPs), is applied to reduce the ozone consumption and to increase the Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) removals. Ozonation and catalytic ozonation of single and mixed dye solutions have been examined both in a semi-batch reactor and also in a three phase fluidized bed reactor. The dyes that are used in this study are Basic Blue 41 (BB-41), Basic Yellow 28 (BY-28) and Basic Red 18.1 (BR-18.1), these dyes are obtained from AKSA A.S. (Yalova, Istanbul) textile plant. In order to measure the concentration of each dye in the mixed dye solution, &ldquo / absorbance vs. concentration&rdquo / calibration correlations were developed. The effect of inlet dye concentration, inlet gas and liquid flow rates, pH, catalyst type [perflorooctyl alumina (PFOA) and alumina] and catalyst dosage were determined experimentally. Catalyst characterization analyses were done in order to determine the maximum number of times that the catalyst can be used and it was found to be 3 times. Gas washing bottle experiments are conducted to find the v amount of ozone required to oxidize one mole of each dye used in the study. Oxidation of BB-41, BR-18.1 and BY-28 dyes were investigated in a semi-batch reactor as single dye solutions by sole and catalytic ozonation with alumina and PFOA catalyst particles. The highest TOC and COD removals being 58.3% and 62.9%, respectively, were obtained at pH of 10 for BB-41 and 55.2% and 58.8%, respectively, for BR-18.1 with alumina catalyst. On the other hand, for BY-28 PFOA catalyst yielded highest TOC and COD reductions being 61.3% and 66.9%, respectively, at pH of 4. Minimum fluidization velocity (uL,min), the hold-up values of gas, liquid and solid phases, the dispersion coefficients (DL), and volumetric ozone-water mass transfer coefficients (kLa) were estimated at various gas and liquid flow rates in order to observe the effect of liquid mixing in the reactor on ozonation process. While PFOA catalyst was found to be effective in oxidizing BY-28 in acidic conditions (pH=4), BR-18.1 and BB-41 are degraded in alkaline medium (pH=10) with alumina catalyst better compared to acidic conditions. For catalytic ozonation reactions in fluidized bed reactor, the highest dye removals in mixed dye solution were observed for BY- 28 being 99.29% for gas flow rate (QG) of 340 L/h, liquid flow rate (QL) of 150 L/h and pH=4, initial dye concentration being 30 mg/L of each dye with PFOA catalyst, while for BR-18.1 and BB-41 being 95.39% and 97.95% respectively for QG = 340 L/h, QL = 150 L/h and pH=10, initial dye concentration being 30 mg/L of each dye with alumina catalyst. The highest TOC and COD reductions, 25.2% and 32.4%, respectively, were achieved in the catalytic ozonation of the mixed dye using PFOA as the catalyst at a pH of 4 and at a gas to liquid flow rate ratio of 2.26 (QG = 340 L/h, QL = 150 L/h). Highest dye removals were obtained at the same gas and liquid flow rates as those of the highest TOC and COD reductions in the experiments. Empirical TOC removal equations were obtained as a function of inlet TOC concentration, solution pH, gas and liquid flow rates.

The aim of this study was to develop an analytical method for fluorinated silanes. Furthermore, as a secondary aim, to explore if there would be possible to detect 1H,1H,2H,2H-perfluorooctyl triethoxysilane (6:2 PTrEtSi) and 1H,1H,2H,2H-perfluorodecyl triethoxysilane (8:2 PTrEtSi) in two different matrices, sludge and cosmetic extract. The method development included experiments using LC-MS, LC-MS/MS, UPC2, GC-MS and APGC-MS/MS and was carried out using standards containing 6:2 PTrEtSi and 8:2 PTrEtSi. The analytical method that worked best for the compounds was GC-MS/MS and an analytical method using APGC-MS/MS was developed for fluorinated silanes. The IDL for 6:2 PTrEtSi was 0.0012 μg/mL and 1.32 μg/mL for 8:2 PTrEtSi. This makes the developed method suitable for high contaminated samples, such as extracts from cosmetic products. It was concluded that a method using LC as the analytical instrument would not work for the two target compounds since they were too reactive with the mobile phase. However, LC could be a good choice for siloxanes, compounds that are formed from hydrolysis and condensation of fluorinated silanes. The samples analyzed in this study were three sludge extracts and one extract from a cosmetic product. 6:2 PTrEtSi was expected to be detected in the cosmetic sample since the compound was stated on the table of contents of the cosmetic product. No detection of 6:2 TrEtSi or 8:2 TrEtSi could be made in either of the samples. The reason for this was suspected to be transformation or degradation of the compounds into other compounds. Therefore, a full scan of the cosmetic sample using LC-MS/MS was included in the experiment as an addition to verify the suspicions that compounds such as siloxanes could have been formed. An interesting peak was discovered with m/z 947 which could be a disiloxane of 6:2 PTrEtSi.

The most important substances of the group of perfluorinated compounds are perfluorooctyl sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorooctane sulphonamide (FOSA). Perfluorinated compounds have special physical and chemical properties, which make them valuable for usage in different industrial branches. These properties, which make them so useful are also the reason, why they are so harmful for the environment. The target of theoretical part of the diploma thesis was processing of literature searche on the topic: Evaluation of environmental load by perfluorinated compounds. In the experimental part was developed and optimized a method that was used for the identification and quantification of selected pollutants contained in real soil samples.