Les spirocétals sont des sous-unités présentes dans de nombreuses molécules naturelles d’intérêt biologique. Pour accéder à ces structures, la spirocyclisation d’éthers d’énol en milieu acide est une méthode de choix. L’application de la réaction de Julia-Kocienski à des lactones a permis d’obtenir exo-glycals et éthers d’énol exo-cycliques tri- et tétrasubstitués. Selon l’hétérocycle porté parla sulfone engagée, l’un ou l’autre des diastéréoisomères de l’éther d’énol peut être obtenu préférentiellement. La spirocyclisation des produits formés, si elle est réalisée dans des conditions thermodynamiques, mène au [6.6]-spirocétal le plus stable. Des conditions permettant d’obtenir le diastéréoisomère cinétique ont également été étudiées. Les spirocétals ainsi préparés ont été utilisés en synthèse totale. Par exemple, le fragment spirocétal de la Broussonetine H, ainsi que l’unité iminosucre, ont été obtenus efficacement de façon énantiopure. Enfin, les spirocétals diversement substitués ont permis de préparer plusieurs analogues du Bistramide A. Ce métabolite marin est un agent anticancéreux puissant qui se lie à l’actine pour bloquer la division cellulaire mais des interactions avec PKC-TM, notamment impliquant l’apoptose, sont à l’étude / Spiroketals are often found as structural subunits of many biologically active natural compounds. One of the more powerful methods to access this structure is the acid-catalyzed cyclization of enol ethers. The reaction of Julia-Kocienski reagents with lactones allows us to synthesize various tri- and tetrasubstituted exo-glycals and exo-cyclic enol ethers. It is possible to obtain preferentially either one or the other of the two diastereoisomeric enol ethers by varrying the heterocycle moiety of the sulfone. These enol éthers are cyclized under thermodynamic conditions leading to the more stable [6.6]-spiroketal but other conditions may allow us to obtain the kineticisomer. Thermodynamic spiroketals were used in total synthesis. For example, both fragments ofBroussonetine H (one iminosugar and one spiroketal) have been readily and effectively prepared.Finally, diversely substituted spiroketals have been synthesized to prepare analogues of Bistramide A.This marine metabolite is a powerful antitumor agent that binds to actin and thus blocks cell divisionalthough some interactions involving PKC-TM are actually under study.

La quinocarcine appartient à la famille des tétrahydroisoquinoléines, produits naturels qui constituent de puissants agents cytotoxiques et possèdent de nombreuses activités biologiques telles qu'antitumorales et antibiotiques. Son intérêt biologique ainsi qu'un faible rendement d'extraction du milieu naturel ont fait d'elle une cible attrayante en synthèse organique. Dans le but d'effectuer la synthèse totale de la quinocarcine, plusieurs stratégies ont été envisagées pour construire la structure tétracyclique ABCD. Ces stratégies se sont appuyées sur différentes étapes clé comme des réactions de Pictet-Spengler ou des cyclisations de type Mannich, mettant en jeu une espèce N-acyliminium ainsi que différents types de nucléophiles, à savoir un malonate, un énamide et un éther d'énol silylé. La première stratégie qui utilise en motif malonate comme nucléophile pour réaliser la réaction de type Mannich n'a pas permis de construire le motif diaza-bicyclo-[3.2.1]-octane. Cependant, la synthèse énantiosélective de tétrahydroisoquinoléines fonctionnalisées a pu être effectuée de façon efficace. D'autre part, une voie de synthèse asymétrique de l'acide -carboxy-L-glutamique (L-Gla) a été mise au point au laboratoire. La deuxième stratégie que nous avons étudiée fait intervenir des nucléophiles de type énamides. Nous avons rencontré, là encore, des problèmes de réactivité. Malgré nos efforts, il n'a pas été possible d'activer sans dégradation la fonction énamide pour généner le motif pyrrolidine souhaité par addition sur un N-acyliminium. Néanmoins, une méthodologie de synthèse utilisant une oléfination de Wittig a été développée pour préparer des acides α-aminés comportant le motif énamide en β. La troisième stratégie utilise un éther d'énol silylé comme partenaire nucléophile pour réaliser la réaction de Mannich. Un intermédiaire clé tricyclique comportant le motif éther d'énol silylé a pu être synthétisé. Des essais sont actuellement en cours enfin de réaliser l'étape déterminante de cyclisation.

This thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis. Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated. Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems. A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2’-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands. Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved. <b>Kewords:</b>asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.

The environmental occurrence and behaviour of the brominated flame retardant (BFR) decabromodiphenyl ethane (dbdpe) has only been studied to a limited extent. It is structurally similar to decabromodiphenyl ether (decaBDE), which makes it conceivable that dbdpe may also become an environmental contaminant of concern. A method for environmental analysis and comparative assessments of dbdpe and decaBDE was developed. Both BFRs were studied in: a mass balance of the Henriksdal WWTP in Stockholm (Paper I); an international survey of sewage sludge (Paper II); sediment along a transect from Henriksdal WWTP to the outer archipelago of Stockholm and from isolated Swedish lakes (Paper III); and a benthic food web from the Scheldt estuary (Paper IV). Dbdpe was found in sludge from every country surveyed, indicating that it may be a worldwide concern. The WWTP mass balance showed that virtually all of the BFRs were transferred from wastewater to sludge. A small fraction was emitted via the effluent, confirming emissions to the aquatic environment. In the marine sediment, the BFR levels close to the WWTP outfall were high. They decreased along the transect to low levels in the outer archipelago. The study of lake sediment showed a widespread presence of dbdpe in the Swedish environment and provided evidence that it originates from long range atmospheric transport. In the food web, dbdpe did bioaccumulate to a small extent which was similar to decaBDE. The transfer of the BFRs from sediment to benthic invertebrates was low, while transfer from prey to predator was higher. Biodilution was observed rather than biomagnification. This work suggests that the persistence, the susceptibility to long range atmospheric transport, and the potential for bioaccumulation are similar for dbdpe and the regulated decaBDE that it is replacing. Thus, there is a risk that a problematic environmental pollutant is being replaced with a chemical that is equally problematic. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.

Heavy-duty trucks are in idle operation during long periods of time, providing the vehicles with electricity via the alternator at standstill. Idling trucks contribute to large amounts of emissions and high fuel consumption as a result of the low efficiency from fuel to electricity. Auxiliary power units, which operate independently of the main engine, are promising alternatives for supplying trucks with electricity. Fuel cell-based auxiliary power units could offer high efficiencies and low noise. The hydrogen required for the fuel cell could be generated in an onboard fuel reformer using the existing truck fuel. The work presented in this thesis concerns hydrogen generation from transportation fuels by autothermal reforming focusing on the application of fuel cell auxiliary power units. Diesel and dimethyl ether have been the fuels of main focus. The work includes reactor design aspects, preparation and testing of reforming catalysts including characterization studies and evaluation of operating conditions. The thesis is a summary of five scientific papers. Major issues for succeeding with diesel reforming are fuel injection, reactant mixing and achieving fuel cell quality reformate. The results obtained in this work contribute to the continued research and development of diesel reforming catalysts and processes. A diesel reformer, designed to generate hydrogen to feed a 5 kWe polymer electrolyte fuel cell has been evaluated for autothermal reforming of commercial diesel fuel. The operational results show the feasibility of the design to generate hydrogen-rich gases from complex diesel fuel mixtures and have, together with CFD calculations, been supportive in the development of a new improved reformer design. In addition to diesel, the reforming reactor design was shown to run satisfactorily with other hydrocarbon mixtures, such as gasoline and E85. Rh-based catalysts were used in the studies and exhibit high performance during diesel reforming without coke formation on the catalyst surface. An interesting finding is that the addition of Mn to Rh catalysts appears to improve activity during diesel reforming. Therefore, Mn could be considered to be used to decrease the noble metal loading, and thereby the cost, of diesel reforming catalysts. Dimethyl ether is a potential diesel fuel alternative and has lately been considered as hydrogen carrier for fuel cells in truck auxiliary power units. The studies related to dimethyl ether have been focused on the evaluation of Pd-based catalysts and the influence of operating parameters for autothermal reforming. PdZn-based catalysts were found to be very promising for DME reforming, generating product gases with high selectivity to hydrogen and carbon dioxide. The high product selectivity is correlated to PdZn interactions, leading to decreased activity of decomposition reactions. Auxiliary power systems fueled with DME could, therefore, make possible fuel processors with very low complexity compared to diesel-fueled systems. The work presented in this thesis has enhanced our understanding of diesel and DME reforming and will serve as basis for future studies. / QC 20100804

A new class of &pi / -conjugated monomers was synthesized with combination of electron donating and electron-withdrawing heterocyclics to understand the effects of structural differences on electrochemical and optoelectronic properties of the resulting polymers. Electron deficient benzotriazole, substititued with benzyl from two available sites, coupled with stannylated electron donating groups, ethylenedioxythiophene (EDOT) and thiophene (Th), to yield four different monomers / 1-benzyl-4,7-di(thiophen-2-yl))-2H-benzo[d][1,2,3] triazole (BBTA), 2-benzyl-4,7-di(thiophen-2-yl))-2H-benzo[d][1,2,3] triazole (BBTS), 1-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b]dioxin-5-yl)-2H-benzo [d][1,2,3]triazole (BBTEA), 2-benzyl-4,7-bis(2,3-dihydrothieno[3,4-b]dioxin-5-yl)-2H-benzo [d][1,2,3]triazole (BBTES). Furthermore, EDOT and thiophene terminated napthalene-2,3-crown ether containing monomers, 14,19-di(thiophen-2-yl)-naphtho[2,3-b][1,4,7,10,13] pentaoxacyclo pentadecane (TNCT), 14,19-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-naphtho[2,3-b][1,4,7,10,13]pentaoxacyclopenta decane (ENCE), were synthesized to observe the effect crown ether moiety on the final electrochemical and optoelectronic properties of resultant polymers. Cyclic voltammetry, UV-Vis-NIR spectroscopy and colorimetry techniques were employed to examine electrochemical and optoelectronic properties of all monomers and polymers. Experimental results showed that alteration of substituent, substitution position and donor groups&rsquo / strength lead to obtain polymers with different redox behaviors, optical band gaps and different number of achievable colored states.

Biotreatment for air pollution control can generally be categorized as biofilter, bioscrubbing and biotrickling filter systems. Generally, biotreatments could be effective and more economical treatment for containment waste gas if designed and operated properly. A two stage down-flow biofilter (2.18 m in height and 0.4 m¡Ñ0.4 m in cross-sectional area) was constructed to develop a biofilter packed only with fern chips for the removal of air-borne propylene glycol monomethyl ether acetate (PGMEA). Both stages were packed with fern chips of 0.30 m in height and 0.40 m ¡Ñ0.40 m in cross section. Fern chips could avoid the shortcomings of traditional media, such as compaction, drying, and breakdown, which lead to the performance failure of the biofilters. In addition, the fern chip medium has the following merits: (1) simplicity in composition, (2) low pressure drop for gas flow (< 20 mmH2O m-1), (3) simple in humidification, nutrient addition, pH control, and metabolite removal, (4) economical (USD$ 174 ¡V 385 m-3), and (5) low weight (wet basis around 290 kg m-3). Results indicate that with operation conditions of media moisture content controlled in the range of 50 ¡V 74%, media pH of 6.5 ¡V 8.3, EBRT (empty bed retention time) of 0.27 ¡V 0.4 min, influent PGMEA concentrations of 100 to 750 mg m-3, volumetric organic loading of < 170 g m-3 h-1, and nutrition rates of Urea-N 66.0 g m-3.day-1, KH2PO4-P 13.3 g m-3.day-1 and milk powder 1.0 g m-3 day-1, the fern-chip packed biofilter could achieve an overall PGMEA removal efficacy of around 94%. Instant milk powder or liquid milk was essential to the good and stable performance of the biofilter for PGMEA removal. An activated sludge aeration basin (20 cm i.d., 140 cm height) equipped with either a coarse air diffuser (a plastic pipe perforated with 56 orifices of 2 mm in diameter) or a fine diffuser (porous plastic type with 100-micrometer pores) was utilized to treat an air-borne hydrophobic VOC (toluene, 700 ¡V 800 mg m-3). The purposes of this study were to test the influences of both MLSS and diffuser type on the VOC removal efficiency. Results show that higher MLSS (mixed liquor suspended solids) such as 10,000 ¡V 40,000 mg L-1 in the mixed liquor did not enhance greatly the transfer and removal of the introduced toluene. Instead, activated sludge basins with a normal MLSS (e.g., 2,000 ¡V 4,000 mg L-1) in the mixed liquor and an efficient gas diffusion system with volumetric VOC transfer coefficient of around 10 ¡V 15 h-1 can be used for the removal of hydrophobic VOCs from the introduced gas. For achieving a removal of over 95% of the introduced toluene or similar hydrophobic VOCs, commercial air diffusers for aerobic biological wastewater treatment basins can be used with a submerged liquid depth of over 0.40 m over the diffusers and an aeration intensity (air flow rate/basin cross-sectional area) of lower than 5.0 m3 m-2 h-1.

<p>This thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis.</p><p>Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated.</p><p>Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems.</p><p>A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2’-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands.</p><p>Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved.</p><p><b>Kewords:</b>asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.</p>

<p>Heavy-duty trucks are in idle operation during long periods of time, providing the vehicles with electricity via the alternator at standstill. Idling trucks contribute to large amounts of emissions and high fuel consumption as a result of the low efficiency from fuel to electricity. Truck manufacturers are working to develop equipment using auxiliary power units to supply the trucks with electricity, which operate independently of the main engine. Fuel cell-based auxiliary power units could offer high efficiencies and low noise and vibrations. The hydrogen required for the fuel cell can be generated in an onboard fuel reformer. This thesis is devoted to hydrogen generation from dimethyl ether, DME, by autothermal reforming focusing on the application of fuel cell auxiliary power units. In the search for alternative fuels, DME has lately been identified as a promising diesel substitute.</p><p>The first part of the thesis gives an introduction to the field of DME reforming with a literature survey of recent studies within the area. Included are also results from thermodynamic equilibrium calculations.</p><p>In the following parts of the thesis, experimental studies on autothermal reforming of DME are presented. A reformer constructed to generate hydrogen to feed a 5 kW_e polymer electrolyte fuel cell is evaluated with emphasis on trying to work close to a practically viable process, i.e. without external heating and using gas mixtures resembling real conditions. Additional experiments have been conducted to investigate the use of catalytic oxidation of dimethyl ether as a heat source during startup. The results of these studies are presented in Paper I.</p><p>In the second experimental study of this thesis, which is presented in Paper II, Pd-based monolithic catalysts are evaluated at small scale for use in autothermal reforming of DME. A screening of various catalyst materials has been performed followed by a study of the influence on the product composition of varying operating parameters such as oxygen-to-DME ratio, steam-to-DME ratio, and temperature.</p>

The market for polyamide desalination membranes is expected to continue to grow during the coming decades. Purification of alternative water sources will also be necessary to meet growing water demands. Purification of produced water, a byproduct of oil and gas production, is of interest due to its dual potential to provide water for beneficial use as well as to reduce wastewater disposal costs. However, current polyamide membranes are prone to fouling, which decreases water flux and shortens membrane lifetime. This research explored surface modification using poly(ethylene glycol) diglycidyl ether (PEGDE) to improve the fouling resistance of commercial polyamide membranes. Characterization of commercial polyamide membrane performance was a necessary first step before undertaking surface modification studies. Membrane performance was found to be sensitive to crossflow testing conditions. Concentration polarization and feed pH strongly influenced NaCl rejection, and the use of continuous feed filtration led to higher water flux and lower NaCl rejection than was observed for similar tests performed using unfiltered feed. Two commercial polyamide membranes, including one reverse osmosis and one nanofiltration membrane, were modified by grafting PEGDE to their surfaces. Two different PEG molecular weights (200 and 1000) and treatment concentrations (1% (w/w) and 15% (w/w)) were studied. Water flux decreased and NaCl rejection increased with PEGDE graft density ([microgram]/cm2), although the largest changes were observed for low PEGDE graft densities. Surface properties including hydrophilicity, roughness and charge were minimally affected by surface modification. The fouling resistance of modified and unmodified membranes was compared in crossflow filtration studies using model foulant solutions consisting of either a charged surfactant or an oil in water emulsion containing n-decane and a charged surfactant. Several PEGDE-modified membranes demonstrated improved fouling resistance compared to unmodified membranes of similar initial water flux, possibly due to steric hindrance imparted by the PEG chains. Fouling resistance was higher for membranes modified with higher molecular weight PEG. Fouling was more extensive for feeds containing the cationic surfactant, potentially due to electrostatic attraction with the negatively charged membranes. However, fouling was also observed in the presence of the anionic surfactant, indicating hydrodynamic forces are also responsible for fouling. / text