1,1,1-trichloro-2,2-bis(4-chlorophenyl)-ethane (DDT) residues (DDTr) are widespread and persistent environmental contaminants, and have been classed as priority pollutants by the United Nations Environment Programme (UNEP). DDTr are potent endocrine disrupting molecules, and have been associated with reproductive abnormalities in juvenile alligators and rats. Microorganisms that metabolise DDTr both aerobically and anaerobically have been isolated and characterised. Bacteria that degrade DDTr aerobically typically utilise a dioxygenase to initiate degradative reactions through ring-hydroxylation, and convert DDTr to 4-chlorobenzoate without further degradation. Terrabacter sp. strain DDE-1 was isolated from DDTr-contaminated soil from Canterbury, New Zealand, and aerobically degrades 1,1-dichloro-2,2-bis-(4-chlorophenyl)-ethylene (DDE) to 4-chlorobenzoate, when grown in the presence of biphenyl (BP). The intermediates of degradation were inferred to be the end products of dioxygenase activity. Sequencing of a large linear plasmid, pBPH-1, from strain DDE-1 identified a cluster of genes with high levels of sequence similarity to BP-degradation genes from Rhodococcus spp. and Pseudomonas spp. This plasmid is lost at high frequency producing the plasmid-cured strain MJ-2, which has lost the ability to degrade BP or DDE. The aim of this study was to confirm that DDE-degradation in strain DDE-1 is encoded by the bph operon located on pBPH-1. No genetic systems to study gene function in either DDE-1 or MJ-2 could be developed using an array of broad-host range vectors. However, heterologous expression of the bph genes in Rhodococcus erythropolis strain TA422 was successful, with the recombinant strain TA425, obtaining the ability to utilise BP and DDE as a sole source of carbon and energy. DDE-1 was shown to convert indole to indigo, but MJ-2 could not, indicating that the biphenyl dioxygenase located on pBPH-1 is responsible for this activity. The bph genes from strain DDE-1 also conferred the ability to produce indigo from indole on strain TA425, confirming successful expression of the functional biphenyl dioxygenase in this strain. Despite several attempts to show quantitative degradation in strain TA425 using gas chromatography, the results were inconclusive Further analysis is needed to provide unequivocal evidence of DDE-degradation by strain TA425. Attempts to express the bph genes in rhizosphere-colonising bacteria, such a Rhizobium spp. or Pseudomonas spp., were unsuccessful, as evidenced by the inability to produce indigo, hence the lack of a functional biphenyl dioxygenase. However, RT-PCR did indeed indicate that P. aeruginosa strain Fin1 produced a bphA1 transcript, indicating that an error is occurring post-transcriptionally in these strains, to prevent production of the functional enzyme. New Zealand has recently been shown to contain hotspots of DDTr-contamination. The second aim of this study was to determine the prevalence of DDTr-degrading bacteria and to gain insight into the types of bacteria that inhabit sites contaminated with DDTr. To investigate this, culture-dependent and culture-independent techniques were employed. Enrichment for DDTr-degrading bacteria yielded species of Rhodococcus and Ralstonia using DDTr-overlayer plate assays. The polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE) were used to amplify and analyse the 16S rDNA and 16S rRNA for the identification of dominant and active bacteria in soil samples. The results of this analysis identified bacteria such as Williamsia spp. and Gordonia spp. that degrade other types of pollutants. This analysis did not identify a predominance of Rhodococcus or Ralstonia spp., or other bacteria that have been shown to degrade DDTr. To identify ecologically relevant members of the bacterial communities in DDTr-contaminated soils, and potentially important metabolic pathways, identification of ring-hydroxylating dioxygenase (RHD) genes was performed. PCR and restriction fragment length polymorphism (RFLP) analysis were employed together with phylogenetic analyses. The results showed that the RHD genes identified, clustered separately to those genes previously characterised from cultivated bacteria. Among these genes, one phylogenetic group was most closely related to the dioxygenase genes from Ralstonia eutropha H850, which is potent PCB-degrading bacterium that possesses a dioxygenase with a wide substrate range for many types of heavily chlorinated, PCB congeners. The identification of a predominance of genes with similarity to phenyl-propionate dioxygenases has been not been recognised previously in soil studies.

<p>Polychlorinated biphenyls, PCBs, were used in elastic sealants in buildings during the years1956-1973. Studies of PCB have revealed that it is harmful for humans and animals,especially water-living predators and other top-predators. It is also a persistent organicpollutant and remains in the environment for a very long time. To reduce the levels of PCB inthe environment, it has to be removed from the buildings. According to Swedish law, theproperty holder has to decontaminate sealants with a PCB level of 500 mg/kg or above. Themunicipalities are the supervising authority and they shall follow up the decontaminations toassure that the PCB has been properly removed from the buildings. The PCBdecontaminationin Eskilstuna municipality has not been a prioritised work, hence, there isPCB left in the buildings which need to be removed. To facilitate the decontamination-work,a plan of action has been developed. This plan will assist the inspector in prioritising thedifferent cases.</p>

The synthesis and optoelectronic properties of biphenyl based conjugated copolymers with varying acceptor units in the polymer backbone were investigated. The well known Donor-Acceptor Theory was used to establish the synthetic pathway for the structural modifications. Solubility issues regarding biphenyl polymer was solved by copolymerizing with soluble units. For this purpose / poly 4-(biphenyl-4-yl)- 4&rsquo / -tert butylspiro[benzo[d]imidazole-2,1&rsquo / -cyclohexane] (P1), poly 4-(biphenyl-4-yl)- 2- dodecyl-2H-benzo[d][1,2,3]triazole (P2) and poly(4-(5-(biphenyl-4-yl)-4-hexylthiophen- 2-yl)-2-dodecyl-7-(4-hexylthiophen-2-yl)-2H-benzo[d][1,2,3]triazole (P3) were synthetized using Suzuki coupling process. Electrochemical properties of these polymers were examined by cyclic voltammetry, spectroelectrochemistry and kinetic studies. Polymers P2 and P3 showed both p- and n-doping behaviors and multicolored electrochromic states. Optical studies revealed that emission color of biphenyl is tuned from blue to orange and the polymers are good candidates for light emitting diode applications. OLED application of P3 was established and outputs of the device were increased by energy transfer studies. The preliminary investigation indicated that P3 possesses promising efficiencies.

Polychlorinated biphenyls, PCBs, were used in elastic sealants in buildings during the years1956-1973. Studies of PCB have revealed that it is harmful for humans and animals,especially water-living predators and other top-predators. It is also a persistent organicpollutant and remains in the environment for a very long time. To reduce the levels of PCB inthe environment, it has to be removed from the buildings. According to Swedish law, theproperty holder has to decontaminate sealants with a PCB level of 500 mg/kg or above. Themunicipalities are the supervising authority and they shall follow up the decontaminations toassure that the PCB has been properly removed from the buildings. The PCBdecontaminationin Eskilstuna municipality has not been a prioritised work, hence, there isPCB left in the buildings which need to be removed. To facilitate the decontamination-work,a plan of action has been developed. This plan will assist the inspector in prioritising thedifferent cases.

Polychlorinated biphenyls (PCBs) are carcinogenic persistent contaminants. Although their manufacturing in North America ceased in the late 1970s, their high heat resistance made their use widespread over their production lifetime. As a result, PCB contamination has occurred globally and in particular has plague brownfield redevelopment in urban environments. The remediation of PCB contaminated soil or sediments has historically been dealt with through the expensive and unsustainable practice of excavation followed by off-site disposal or incineration. One potential technology that has shown some success with on-site remediation of PCB contamination is solvent extraction. Solvent extraction is technically simple; it involves excavating the contaminated soil, placing it in a vessel and adding solvent. The PCBs are extracted by the solvent and the treated soil is returned for use on site. Although successful at removing a large quantity of PCBs from some soils, this technology can be improved upon by extracting additional PCB mass and making the extraction more efficient and suitable for colder climates. This thesis aimed to identify the factors controlling PCB extraction with solvents in order to optimize PCB extraction as it is applied on different soil types and in various climates. The research investigated the impact of elevated moisture contents (≤ 20% by weight) on solvent extraction efficiency, the effects of low temperatures (<5ºC) on solvent extraction, and developed a kinetic model to represent PCB solvent extraction. As past research has shown, weathered PCB in soil is more difficult to remove. Contaminated field samples from Southern Ontario, Canada were used for this work, rather than synthetically prepared samples. The impact of elevated moisture contents and low temperature on extraction efficiency was determined through a series of screening experiments using polar and non-polar solvents at both 20ºC and 4ºC. It was hypothesized that improved extractions may be possible with combinations of polar and non-polar solvents. Based on the results of these screening experiments, a factorial experiment was designed using solvent combinations to further assess the role of moisture contents and low temperatures. The role of PCB mass distribution among grain sizes was also evaluated to see if optimization based on grain size separation is possible. Finally, experiments were performed to generate data suitable for the development of a kinetic model that incorporates key factors affecting solvent extraction. Four suitable solvents for solvent extraction in Ontario were identified through a literature review and these were used for this work: isopropyl alcohol (polar), ethanol (polar), triethylamine (non-polar) and isooctane (non-polar). Triethylamine outperformed isooctane and performed best on its own rather than in combination with polar solvents. An interaction between soil moisture content and choice of polar solvent (isopropyl alcohol versus ethanol) was established: a given polar solvent achieves optimal PCB extraction at a specific moisture content range. Temperature was also identified as significantly influencing PCB extraction. Although it was determined that PCBs were distributed unevenly amongst grain sizes, a simple relationship between grain size and fractional organic carbon or organic content was not found. A simple two-compartment kinetic model was developed which is suitable for predicting the PCB concentrations extracted up to 24 hours. The model incorporates both temperature and soil to solvent ratio in order to estimate PCB concentration extracted.

Polychlorinated biphenyls (PCBs) are carcinogenic persistent contaminants. Although their manufacturing in North America ceased in the late 1970s, their high heat resistance made their use widespread over their production lifetime. As a result, PCB contamination has occurred globally and in particular has plague brownfield redevelopment in urban environments. The remediation of PCB contaminated soil or sediments has historically been dealt with through the expensive and unsustainable practice of excavation followed by off-site disposal or incineration. One potential technology that has shown some success with on-site remediation of PCB contamination is solvent extraction. Solvent extraction is technically simple; it involves excavating the contaminated soil, placing it in a vessel and adding solvent. The PCBs are extracted by the solvent and the treated soil is returned for use on site. Although successful at removing a large quantity of PCBs from some soils, this technology can be improved upon by extracting additional PCB mass and making the extraction more efficient and suitable for colder climates. This thesis aimed to identify the factors controlling PCB extraction with solvents in order to optimize PCB extraction as it is applied on different soil types and in various climates. The research investigated the impact of elevated moisture contents (≤ 20% by weight) on solvent extraction efficiency, the effects of low temperatures (<5ºC) on solvent extraction, and developed a kinetic model to represent PCB solvent extraction. As past research has shown, weathered PCB in soil is more difficult to remove. Contaminated field samples from Southern Ontario, Canada were used for this work, rather than synthetically prepared samples. The impact of elevated moisture contents and low temperature on extraction efficiency was determined through a series of screening experiments using polar and non-polar solvents at both 20ºC and 4ºC. It was hypothesized that improved extractions may be possible with combinations of polar and non-polar solvents. Based on the results of these screening experiments, a factorial experiment was designed using solvent combinations to further assess the role of moisture contents and low temperatures. The role of PCB mass distribution among grain sizes was also evaluated to see if optimization based on grain size separation is possible. Finally, experiments were performed to generate data suitable for the development of a kinetic model that incorporates key factors affecting solvent extraction. Four suitable solvents for solvent extraction in Ontario were identified through a literature review and these were used for this work: isopropyl alcohol (polar), ethanol (polar), triethylamine (non-polar) and isooctane (non-polar). Triethylamine outperformed isooctane and performed best on its own rather than in combination with polar solvents. An interaction between soil moisture content and choice of polar solvent (isopropyl alcohol versus ethanol) was established: a given polar solvent achieves optimal PCB extraction at a specific moisture content range. Temperature was also identified as significantly influencing PCB extraction. Although it was determined that PCBs were distributed unevenly amongst grain sizes, a simple relationship between grain size and fractional organic carbon or organic content was not found. A simple two-compartment kinetic model was developed which is suitable for predicting the PCB concentrations extracted up to 24 hours. The model incorporates both temperature and soil to solvent ratio in order to estimate PCB concentration extracted.

This thesis is composed of two parts. The palladium-catalysted synthesis of 2-arylphenols and carbazoles via carbon-hydrogen (C-H) bond activation is described. Treatment of 2-phenoxypyridines with two and a half equivalents of potassium aryltrifluoroborate and 10 mol % of Pd(OAc)2 in the presence of two equivalents of Ag2CO3, one equivalent of p-benzoquinone (BQ), and four equivalents of DMSO with (or without) H2O at 130-140 oC for 48 h in dried CH2Cl2 gave the ortho-arylated 2-phenoxypyridines in modest to excellent yields. The investigation of kinetic isotope effect (kH/kD) is determined to be 5.25, which indicates that C-H bond cleavage occurs in the rate-determining step. 2-(Biphenyl-2-yloxy)pyridines was treated with methyl trifluoromethanesulfonate and subsequently sodium methoxide to give the 2-arylphenols to demonstrate the pyridine is a removable directing group. On the other hand, a novel one-pot synthesis for N-pyridylcarbazoles by the reaction of N-phenylpyridin-2-amines with potassium aryltrifluoroborates using Pd(OAc)2 as the catalyst is presented. For instance, reaction of N-phenylpyridin-2-amines with four equivalents of potassium aryltrifluoroborate under the optimal reaction condition gave N-pyridylcarbazoles in 67% yield along with N-(biphenyl-2-yl)pyridin-2-amine in 13% yield. The investigation of kinetic isotope effect (kH/kD) for first C-H bond activation/C-C bond formation step is determined to be 2.14, and that of the second C-H bond activation/C-N bond formation steps is 1.18. On the basis of KIE analysis, it might indicate that first C-H activation undergo direct C-H bond cleacage, and second step should be via electrophilic aromatic substitution.

Thesis (M. Phil.)--University of Hong Kong, 2001. / Includes bibliographical references (leaves 81-86).

published_or_final_version / Chemistry / Master / Master of Philosophy

Cardiovascular disease remains the leading cause of death in Western societies. Endothelial dysfunction is one of the initiating steps in the development of atherosclerosis. While there is a strong correlation with a person’s genetics, lifestyle factors including smoking, physical activity, and diet can significantly increase a person’s susceptibility to the development of atherosclerosis. In addition to these lifestyle factors, there is a strong body of evidence linking exposure to environmental pollutants including persistent organic pollutants such as polychlorinated biphenyls to increased cardiovascular disease and mortality. It has been well-established that exercise protects against cardiovascular disease, but whether exercise can modulate PCB-induced cardiovascular inflammation and dysfunction is unknown. To investigate the effects of exercise on PCB-induced cardiovascular disease, two murine models of atherosclerosis, the ApoE-/- and the LDLr-/- mouse were utilized. Risk factors for cardiovascular disease including adiposity, glucose intolerance, hyperlipidemia, hypertension, oxidative stress, and inflammation, were assessed in these two models as well as mean atherosclerotic lesion size. Exercise positively modulates several risk factors associated with cardiovascular disease including hypertension, hyperlipidemia, adiposity and obesity, systemic levels of oxidative stress, inflammation, and glucose tolerance. Exercise significantly reduced mean lesion size in vehicle-treated animals. To assess the mechanism of protection of exercise in chapter 4, vascular reactivity studies were performed to measure endothelial function after exposure to PCB 77. Exercise prevented PCB-impaired endothelial function implicating the role of superoxide as a cause of impairment. Exercise upregulated phase II antioxidant enzymes. The work in this dissertation demonstrates several protective properties of exercise against PCB-induced cardiovascular disease; however, additional studies are needed to determine if exercise enhances metabolism and excretion of these environmental pollutants.