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The first part of this thesis describes the efficient synthesis of several hypervalent iodine(III) compounds. Electron-rich diaryliodonium salts have been synthesized in a one-pot procedure, employing mCPBA as the oxidant. Both symmetric and unsymmetric diaryliodonium tosylates can be isolated in high yields. An in situ anion exchange also enables the synthesis of previously unobtainable diaryliodonium triflates. A large-scale protocol for the synthesis of a derivative of Koser’s reagent, that is an isolable intermediate in the diaryliodonium tosylate synthesis, is furthermore described. The large-scale synthesis is performed in neat TFE, which can be recovered and recycled. This is very desirable from an environmental point of view. One of the few described syntheses of enantiopure diaryliodonium salts is discussed. Three different enantiopure diaryliodonium salts bearing electron-rich substituents are synthesized in moderate to high yields. The synthesis of these three salts shows the challenge in the preparation of electron-rich substituted unsymmetric salts. The second part of the thesis describes the application of both symmetric and unsymmetric diaryliodonium salts in organic synthesis. A metal-free efficient and fast method for the synthesis of diaryl ethers from diaryliodonium salts has been developed. The substrate scope is wide as both the phenol and the diaryliodonium salt can be varied. Products such as halogenated ethers, ortho-substituted ethers and bulky ethers, that are difficult to obtain with metal-catalyzed procedures, are readily prepared. The mild protocol allows arylation of racemization-prone a-amino acid derivatives without loss of enantiomeric excess. A chemoselectivity investigation was conducted, in which unsymmetric diaryliodonium salts were employed in the arylation of three different nucleophiles in order to understand the different factors that influence which aryl moiety that is transferred to the nucleophile. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Accepted. Paper 5: Submitted. Paper 6: Manuscript.</p>

Polybrominated diphenyl ethers (PBDEs) are a widely used class of flame retardants that are important sources for contamination in the marine environment. Sediments serve as a large reservoir for PBDEs due to their large sorption capacity. This research assessed the presence and distribution of PBDEs in Hillsborough Bay, a subdivision of Tampa Bay, FL, by determining levels in surface sediment samples, creating a historical profile of the contaminant in a sediment core taken from within the bay, and investigating sediment characteristics that control their distribution. Compositional patterns and temporal distributions of 8 of the 209 congeners of PBDEs (BDE-28, -47, -99, -100, -153, -154, -183 and 209) were determined in sediment surface samples and a sediment core collected throughout the study area. Contaminant concentrations varied spatially due to proximity to sources and the spatial variability of physical processes that suspend or remove contaminants from the water column. Concentrations in the bay also varied in time with factors such as wind, precipitation, and subsequent freshwater runoff. PBDE contamination in surficial sediments from various regions of Tampa Bay is not well correlated with sediment grain size or organic matter content, but these factors may be more important in suspended sediments which may control the fate of these contaminants in the bay. The results from this investigation can be used in understanding the extent of PBDE pollution, identifying sources, as well as implementing management strategies for Hillsborough Bay.

Thesis (MTech. degree: Environmental Management.)--Tshwane University of Technology, 2012. / Determines the presence and levels of common brominated flame retardants (BFRs) in surface water and sediments in Jukskei River catchments with the aim of identifying potential pollution sources using Geographical Information System (GIS) land use map in order to provide baseline data required to protect water resources against such hazardous chemicals.

Thesis (DTech. degree: Environmental Management)--Tshwane University of Technology, 2012. / Discusses polybromobiphenyls (PBBs) and polybromodiphenyl ethers (PBDEs) are among brominated flame retardants commonly used as additive flame retardants and are now well-known pollutants. They can easily be released from household and office materials if present and tend to settle on dust. Of all the PBDEs congeners, the detection of BDE-209 is considerably more difficult than the lower congeners. Furthermore, there is no available data on the presence of PBBs and PBDEs in indoor dust in South Africa, and, therefore, it was deemed necessary to conduct the present study.

Fluorine incorporation has become increasingly important in pharmaceutical applications. Upon fluorination and incorporation of fluorinated moieties such as trifluoromethoxy groups, many small molecules become more bioavailable and metabolically stable and additionally can better cross the blood-brain-barrier. This thesis describes the development of a method mediated by silver salts for the synthesis of pharmaceutical-like trifluoromethoxylated compounds via \(C-OCF_3\) bond formation. Additionally the synthesis of 3-deoxy-3-fluoromorphine via late-stage fluorination of morphine is described as well as in vitro and in vivo evaluation of 3-deoxy-3-fluoromorphine as a potential analgesic. / Chemistry and Chemical Biology

The phosphine crown ether, 16-(4'diphenylphosphinophenyl)-1,4,7,10,13-pentaoxa-16azacyclooctadecane (III), was synthesized using a reaction scheme beginning with n-phenyldiethanolamine and the dichloride of tetraethylene glycol, with an overall yield of 4%. Platinum and Palladium complexes of the ligand, of the form MC12L2, were synthesized as well. 13C NMR and picrate extraction data indicate III and IV (the crown-5 analog) both moderately bind sodium (14%, 15%) and potassium ions (17%, 28%). Compound V (a crown-5, triphenylphosphine-based ligand) will bind both sodium and potassium ions as well (18%, 6%). When IV is complexed to nickel carbonyl (Ni(CO)3), the addition of sodium and potassium ions cause the Al carbonyl stretching frequency to increase slightly (0.3 cm-1, 0.2 cm 1). For comparison, the addition of a proton causes the A1 carbonyl stretching frequency to increase 5.2 cm-1. However, the shift in the A1 carbonyl stretching frequency upon the addition of sodium or potassium ions indicates that ion binding by the crown ether is communicated to the phosphorus and finally to the carbonyl groups.Ball State UniversityMuncie, IN 47306 / Department of Chemistry

Dans ce travail, nous choisissons, dans l'optique de mieux comprendre le rôle joué par les éthers de cellulose dans les mortiers monocouches, d'utiliser la rhéomètrie pour identifier les mécanismes d'action de ces molécules au sein d'une pâte de ciment. Nous développons ainsi les protocoles et l'analyse associée nous permettant, à partir de mesures macroscopiques, d'affiner notre compréhension de ces molécules à une échelle microscopique. Puis, nous extrapolons de nos résultats les conséquences d'une modification du dosage ou des paramètres moléculaires de l'éther dans le cas du mortier monocouche et de sa mise en œuvre. Dans une première partie, nous étudions l'influence de l'ajout d'éthers sur la viscosité du fluide interstitiel d'une suspension cimentaire et le rôle de ce paramètre sur la rétention d'eau. Dans une deuxième partie, nous étudions l'effet des éthers de cellulose sur le seuil d'écoulement et la déformation critique de pâtes de ciment et le rôle de ces paramètres sur la capacité d'adhésion du mortier. Dans une troisième partie, nous étudions l'effet des éthers de cellulose sur la viscosité d'une pâte de ciment et le rôle de ce paramètre sur la facilité de lissage

The fate and bioaccumulation of a contaminant entering the marine environment through wastewater outfalls depends on the contaminant’s persistence and affinity for particles. The physical characteristics of the receiving environment, e.g. current velocity, sedimentary processes, and the availability of organic carbon are also important. However, these latter effects are not usually evaluated quantitatively. This thesis investigates the near-field accumulation in sediment and biota of particle-reactive polybrominated diphenyl ethers (PBDEs) entering coastal waters via two municipal outfalls: one discharging into a high energy, low sedimentation environment near Victoria, B.C., Canada; the other into a low energy, high sedimentation environment near Vancouver, B.C. We used 210Pb profiles in sediment box cores together with an advection-diffusion model to determine surface mixing and sedimentation rates, and to model the depositional history of PBDEs at these sites. A particularly important finding of this study is that the very high energy environment to the southeast of the Victoria outfall accumulates PBDEs despite not having net sediment accumulation. Although the discharge of PBDEs was much lower from the Victoria outfall than from Vancouver, some sediment PBDE concentrations were higher near Victoria. Most PBDEs were dispersed beyond the near-field at both sites, but a greater proportion was captured in the sediment near the Vancouver outfall where rapid burial was facilitated by inorganic sediment supplied from the nearby Fraser River. Clearly, treating wastewater to the same level, regardless of local oceanographic conditions, will not result in a uniform environmental footprint. Total PBDE concentrations in benthic invertebrate communities were higher near Vancouver than Victoria, despite lower concentrations in sediments, and correlated with organic carbon normalized sediment concentrations. Principal Components Analysis suggested uptake of individual PBDE congeners was determined by sediment properties (TOC, grain size), whereas PCB congener uptake was governed by physico-chemical properties (octanol-water partitioning coefficient). Our results suggest that sediment quality guidelines for PBDEs and likely PCBs may be more relevant if corrected to TOC content in sediment. In addition, where enhanced wastewater treatment increases the ratio of PBDEs to particulate organic carbon in effluent, nearfield benthic invertebrates may face increased PBDE accumulation. This underlines the need for source control of persistent organic contaminants, which cannot be broken down by conventional wastewater treatment. / Graduate

Summary Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants. The addition of these chemicals to electrical and electronic equipment, building materials, carpet and textiles reduces flammability and therefore harm and destruction caused by unwanted fire. These chemicals are now internationally ubiquitous in the environment and humans because of their increased usage and physical and chemical properties of persistence and lipophilicity. Although Australian data on both the concentrations and the sources and exposure pathways was limited, a preliminary study of PBDEs in 10 pools of human blood serum revealed that concentrations of PBDEs in Australia were comparatively higher than most countries with the exception of Canada and the USA. The aim of this project was to determine the concentrations of PBDEs in the Australian population and to examine the possible sources and pathways of exposure in humans. Experimental evaluation of PBDE exposure matrices included samples of: sediment (n=46), air (n=19), dust (n=19), surface wipes (n=10) and human milk (157 samples combined into 17 pools, n=10 individual samples); and the general population using human blood serum (10552 samples combined into 169 pools). With accumulating evidence regarding age differences in PBDE concentrations, the scope of this project was broadened to include a focus on infants and young children. This study found that PBDE contamination was widespread in the Australian environment and human population. In sediment, PBDEs were relatively low at the majority of sites with mean ± standard deviation and median ΣPBDE concentrations across all sites of 4707 ± 12580 and 305 pg g-1 dw, respectively. There were elevated concentrations found downstream of sewerage treatment plants; in areas dominated by industrial and urban land-use types; and in estuarine compared to freshwater environments. PBDEs were detected in air, dust and surface wipes. Concentrations on the whole were found to be higher indoors compared to outdoors and in offices compared to homes. ΣPBDE concentrations ranged from 0.5 -179 pg/m3 for homes and 15 - 487 pg/m3 for offices and at the two outdoor sites the concentrations were 1.7 and 6.8 pg/m3. PBDEs were detected on 9 out of 10 surfaces (e.g. television, refrigerator, DVD player) sampled and ranged from non-detectable to 5985 pg/cm2 while in dust, ΣPBDEs ranged from 87 - 733 ng/g dust in homes and 583 - 3070 ng/g dust in offices. PBDEs were detected in all individual and pooled samples of human milk and blood serum and the ΣPBDE and BDE-47 concentrations ranged from 5.5 to 103 and 0.6 to 55 ng/g lipid, respectively. There were no regional differences in concentrations in human milk or blood serum and in general PBDE concentrations were higher in males than in females. Although no temporal trend was apparent in samples of human milk or blood serum collected between 2002 and 2008, the ban on penta- and octa-BDE commercial products in several countries has only been in place since 2004. Hence, effects of the ban may not be reflected in human body burden for several years. The concentrations of PBDEs were found to be highest in young children aged 2 – 5 years of age where concentrations were up to 10 times greater than those detected in adults. Congener profiles for sediment, air, dust and surface wipes were mostly dominated by BDE-209. In human milk and serum, BDE-47 was dominant while BDE-209 contributed only 3% in human milk and was not determined in serum. Concentrations of PBDEs found in Australian human and environmental samples were lower than those reported from North America but higher than those reported from Europe and Asia. The results of modeling and the assessment of matched samples of human milk, indoor air and dust showed that body burden could be partly explained by exposure via food, air, dust and human milk as well as clearance (half-life) data. However, the higher than expected concentrations in young children indicated that there are likely to be missing sources and exposure pathways and/ or the clearance data is inaccurate. The results of this thesis provide baseline data on PBDE concentrations in Australia and will prove important for long term monitoring of the effect of changes in usage rates of these chemicals. It is important to understand the specific sources and exposure pathways of PBDEs in infants and young children in order to identify intervention methods whereby exposure to this vulnerable population can be reduced. In terms of the future use of PBDEs or other flame retardant chemicals, it is important that the risk-benefit ratio is regulated so that the minimization of human exposure and potential associated negative health effects is balanced with the reduction of harm caused by fire.