Thesis (MTech (Environmental Management))--Cape Peninsula University of Technology, 2015. / This study was conducted to investigate the occurrence of PAH degrading microorganisms in two river systems in the Western Cape, South Africa, and their ability to degrade two PAH compounds (acenaphthene and fluorene). A total of 19 bacterial isolates were obtained from the Diep- and Plankenburg Rivers. These microorganisms were first identified phenotypically on various selective and general media (such as nutrient agar, Eosine Methylene Blue and Mannitol Salts Agar), followed by staining and biochemical testing, followed by molecular identification using 16S rRNA and PCR. The isolates were then tested for acenaphthene and fluorene degradation first at flask scale and then in a Stirred Tank Bioreactor at varying temperatures (25ºC, 30ºC, 35ºC, 37ºC, 38ºC, 40ºC and 45ºC). All experiments were run without the addition of supplements, bulking agents, biosurfactants or any other form of biostimulants. Four of the 19 isolated microorganisms were identified as acenaphthene and fluorene degrading isolates. Three of the four microorganisms identified as PAH degrading isolates were Gram negative isolates. Results showed that Raoultella ornithinolytica, Serratia marcescens, Bacillus megaterium and Aeromonas hydrophila efficiently degraded fluorene (99.90%, 97.90%, 98.40% and 99.50%) and acenaphthene (98.60%, 95.70%, 90.20% and 99.90%) at 37ºC, 37ºC, 30ºC and 35ºC, respectively. The degradation of fluorene was found to be more efficient and rapid compared to that of acenaphthene and degradation at Stirred Tank Bioreactor scale was more efficient for all treatments. Throughout the biodegradation experiments, there was an exponential increase in microbial plate counts ranging from 5 x 104 to 9 x 108 CFU/ml. The increase in plate count was observed to correlate with the efficient degradation temperature profiles and percentages. The PAH degrading microorganisms isolated during this study significantly reduced the concentrations of acenaphthene and fluorene and can be used on a larger, commercial scale to bioremediate PAH contaminated river systems. Other factors that influence the optimal expression of biodegradative potential of microorganisms other than temperature and substrate (nutrient) availability, such as pH, moisture and salinity will be investigated in future studies, as well as the factors contributing to the higher fluorene degradation compared to acenaphthene. Furthermore, the structure and toxicity of the by-products and intermediates produced during microbial metabolism of acenaphthene and fluorene should be investigated in further studies.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of requirements for the degree of Master of Science. Johannesburg 2014 / Polycyclic Aromatic Hydrocarbons (PAHs) are environmental contaminants which are formed during combustion of organic material such as coal, petroleum compounds and meat. Other sources of PAHs include automobile exhaust, coal tar and crude oil. Natural sources of PAHs include volcanoes, forest fires. Some PAHs are known to be carcinogenic and toxic. They are available to aquatic organisms such as fishes through contaminated sediments and other marine organisms. Due to their toxicity, it is essential to study and monitor PAHs in the environment. In this study, the quechers extraction method was developed and optimised for the extraction of 5 PAHs (Naphthalene, acenaphthene, phenanthrene, fluoranthene, and pyrene). The optimised parameters were the extraction speed, extraction time, volume of solvent, type of solvent, the mass of salt (MgSO4), the mass of fish used for extraction, mass of sorbent (PSA) and the type of sorbent used. After optimisation, the optimised QuEChERS extraction method was then compared to the Soxhlet extraction method. Firstly by spiking with different concentration and comparing the recoveries. Recoveries obtained where similar, this shows that the QuEChERS method is efficient for extraction of PAHs. The optimised QuEChERS extraction method and Soxhlet extraction were applied for analysis of PAHs in real fish samples. Fish samples were obtained from two dams, Jericho dam in Mpumalanga and Hartbeespoort dam in Gauteng. The result obtained for both extraction method were compared. The concentration of PAHs obtained for both methods were similar. Naphthalene was not detected in Hartbeespoort dam. The concentration of PAHs in Hartbeespoort and Jericho dam using QuEChERS extraction method range from 0.8 μg/kg to 739 μg/kg and 0.8 μg/kg to 7.4 μg/kg respectively. Acenaphthene and phenanathrene were not detected in all fish sample from Jericho dam, while pyrene was not detected in some of the fish samples from Jericho dam. Application of Soxhlet extraction to real sample gave concentration ranging from 1.9 μg/kg to 908 μg/kg for Hartbeespoort dam and 1.2 μg/kg to 18.7 μg/kg for Jericho dam. High concentration of PAHs was obtained from Hartbeespoort dam.

Orientador: Altair Benedito Moreira / Banca: Eduardo Alves de Almeida / Banca: Ronaldo José Torres / Resumo: Hidrocarbonetos Policíclicos Aromáticos (HPA) fazem parte de uma classe de compostos denominados Substâncias Tóxicas Persistentes, tendo como principais características elevada toxicidade e persistência no ambiente, sendo as fontes petrogênicas, pirogênicos e biogênicas as que mais contribuem para o aporte destes compostos. A Bacia Hidrográfica do Turvo/Grande (BHTG) é caracterizada por pequenos parques industriais e intensa atividade agrícola com destaque a cana-de-açúcar, que vem acompanhada por processos de queimadas. Neste contexto, este trabalho teve como principal objetivo utilizar a determinação de 1-hidróxipireno em bílis de peixes como biomarcador de exposição para HPA e também determinar o histórico destes em sedimentos de rios da BHTG. As coletas de amostras de peixe (160 amostras) e sedimento (superficial e profundidade) nos rios Preto (CAPRP), Turvo (PORTUR e RTURG) e Grande (RGRANDE) foram feitas em dois períodos distintos: fevereiro e julho de 2010. A determinação do 1-hidroxipireno nas amostras de bílis de peixes foi realizada de acordo com o método proposto por Ariase et alii (1993). Os HPA dos sedimentos foram extraídos de acordo com o método 3540C (EPA) e a quantificação foi realizada empregando Cromatografia Líquida de Alta Eficiência com detector de Fluorescência (HPLC-DF). As concentrações do 1-hidróxipireno no ponto RTURG da coleta de fevereiro de 2010 variaram na faixa de 210 a 1025 µg L-1, com valor médio de 780 ± 281 µg L-1. Para as amostras de peixes coletadas em julho de 2010 no ponto CAPRP, os valores estiveram na faixa de 397 - 6463 µg L-1, com valor médio de 1300 ± 1130 µg L-1. Para os pontos PORTUR e RTURG, os valores médios de concentração de 1-hidróxipireno na bílis dos peixes foram... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Polycyclic Aromatic Hydrocarbons (PAHs) constitute a class of compounds denominated as Persistent Toxic Substances, having as main characteristics high toxicity and persistence in the environment, being that the sources petrogenic, pyrogenic and biogenic contribute most to the intake of these compounds. Turvo/Grande watershed (BHTG) is characterized by a small industrial facilities and intensive agriculture especially sugarcane activity, which is accompanied by the burning process. In this context, this work aimed to use the determination of 1-hydroxypyrene in fish bile as a biomarker of exposure to PAHs and also determine the history of these in the sediments from BHTG rivers. The sampling of fish (160 samples) and sediment (surface and deep) in the Preto (CAPRP), Turvo (PORTUR e RTURG) e Grande (RGRANDE) rivers, were made in two distinct periods: February and July of 2010. The determination of 1-hydroxypyrene in fish bile samples was performed according to the method proposed by Ariase et alii (1993). PAHs were extracted of the sediments according to the method 3540C (EPA) and the quantification was performed using high performance liquid chromatography with fluorescence detector (HPLC-FD). Concentrations of 1-hydroxypyrene is fish bile samples collected in RTURG (February 2010) ranged from 210 to 1025 µg L-1, the average values 780 ± 281 µg L-1. For fish samples collected in CAPRP in July 2010 , values ranged 397-6463 µg L-1, with an average of 1300 ± 1130 µg L-1. For PORTUR and RTURG, the mean concentration of 1-hydroxypyrene in fish bile were 1643 ± 744 µg L-1 and 588 ± 183 µ g L-1, respectively. PAHs concentration along the sediment profile showed similar behavior. In general, for all PAHs there was a trend of reduction with increasing depth in sediment cores. The total concentration... (Complete abstract click eletronic access below) / Mestre

Thesis advisor: Lawrence T. Scott / Thesis advisor: James P. Morken / Expeditious establishment of molecular complexity in a stereoselective manner is a prominent goal in organic synthesis. In this regard, multicomponent coupling reactions have received substantial attention due to their ability to access complex molecules from simple starting materials in a single step. Chapter 1 is a comprehensive review on catalytic bismetallative multicomponent reactions. The scope of this process in terms of both bismetallic reagents and the pi components are broad enough to be generally applied to more elaborate synthetic sequences. Particularly, contemporary applications of the bismetallative multicomponent coupling reactions, in which high enantio- and/or diastereoselectivities are displayed, have enabled the study of this area to make a significant step forward. Chapter 2 presents nickel-catalyzed coupling reactions of aldehyde, diene, and a diboron reagent in the presence of a trialkyl phosphine ligand. Compared to borylation reactions with one pi-component, these borylative multicomponent reactions (involving two pi components) lead to formation of a new C-C bond between the pi components as well as generation of highly functionalized, stereodefined products. Chapter 3 describes a remarkable turnover in regioselectivity of the borylative multicomponent coupling when PCy3 is replaced with P(SiMe3)3. In particular, the products from the reactions with P(SiMe3)3 feature three contiguous stereocenters and an alpha-chiral allylboronate. The effect of P(SiMe3)3 ligand on the product selectivity is intriguing. According to the experimental and computational results, it has an ability to act as an electron acceptor, which will facilitate reductive elimination from the intermediate nickel complex during the course of the reaction. In Chapter 4, we show that borylative ketone-diene coupling reactions can be accomplished in high yields and with excellent levels of diastereocontrol. This reaction occurs in a predictable fashion, yet with regioselection that is distinct from related aldehyde-diene coupling reactions. The reaction products from these coupling processes, which possess tertiary alcohol functionality and an allylic alcohol moiety, are particularly well suited for the preparation of polyketide natural products. Chapter 5 presents investigations on bowl-shaped geodesic polyarenes, which are the missing links between the "classic" planar polycyclic aromatic hydrocarbons (PAHs) and the spheroidal fullerenes. The present study has shown that open geodesic polyarenes can feature chemistry inherent to both classes of aromatics. The curved pi system induces unequal environments on the two faces of circumtrindene, significant strain energy to the molecule, and non-identical bond lengths. Along with the electronic effects, the stereoelectronic effect enabled the site-selective functionalization with fullerene-type chemistry. On the other hand, the edge carbons, which are not present in fullerenes, still possess reactivity of common planar PAHs. Chapter 6 describes the intermolecular oxidative cyclotrimerization reactions of alkenes and aromatic compounds with DDQ and trifluoromethanesulfonic acid. The Scholl-type oxidation reactions involving alkenes have never been demonstrated. Moreover, the DDQ/acid system has never been used for the intermolecular oxidative cyclization reactions. This convenient non-metallic reagent system (DDQ/TfOH) is advantageous over the metal-based Scholl-type oxidants because it eliminates the possibility of halogenation of aromatic compounds and the reduced oxidant can be reoxidized. In Chapter 7, the regioselective formation of cyclic trimers from substituted benzenes and heteroaromatic compounds is demonstrated. This DDQ/TfOH method provides a simple and convenient synthetic route toward star-shaped oligomers containing triphenylene or isotruxene cores. Furthermore, the experimental outcome suggests that this oxidative process proceeds by an electron transfer mechanism. This is the first experimental evidence for mechanistic details on the Scholl-type oxidation. / Thesis (PhD) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Polycyclic aromatic hydrocarbon (PAH) compounds, which are common to coal tar and coal-tar-based products, are ubiquitous environmental contaminates with carcinogenic effects to human health and aquatic life. Transport of PAHs via solid phase particulate motion, gaseous phase volatilization, and aqueous phase dissolution into urban waterbodies of PAH compounds from coal-tar-based pavement sealant products has been studied. Pavement rejuvenators are products applied to increase the usable life of pavement. Coal-tar-based rejuvenators contain a significantly larger mass fraction of coal-tar with respect to coal-tar-based sealants, but pavement rejuvenators have not been as extensively studied as pavement sealants. Chemical analysis of detached pavement material treated with coal-tar-bases, asphalt-based, and bio-based rejuvenators was conducted with gas chromatography – mass spectrometry (GC/MS) analysis for 16 PAH compounds and two aromatic heterocyclic organic compounds following extraction with methylene chloride. Detached pavement material was collected from 19 simulated asphalt surface abrasion experiments that used a model mobile load simulator (MMLS) test apparatus that replicated surface challenges from vehicular traffic. The MMLS test apparatus configuration allowed asphalt disc samples treated with different rejuvenation products, to be tested and for detached material to be collected and quantified prior to GC/MS analysis. Test cases evaluated the influence of rejuvenation product type and cure time, as well as the effect of sand application (simulating sand application during slippery winter storm conditions) had on detached particulate and ultimate PAH compound loading. The average mass of particulate detachment from samples following a 48 hour cure time, for the asphalt-based and coal-tar-based rejuvenator products were 0.347 g and 0.480 g, respectively. This mass of detached material was lower than that from pavement treated with bio-based rejuvenator and the control (not treated), which had 4.858 g and 2.567 g of detached particulate material, respectively. When the product cure time was increased to three weeks, which was significantly long enough to capture effects of compound volatilization, average particulate detachment increased to 0.882 g for the coal-tar-based rejuvenator and decreased for the bio-based rejuvenator to 2.600 g. Six tests performed with a single application of winter storm sand after a 48 hour product cure time showed an increase in average particulate detachment to 1.450 g and 0.617 g for pavement treated with the asphalt-based and coal-tar-based rejuvenators, respectively. Conversely, under the same conditions, a reduction in average detached particulate to 3.749 g was observed for the bio-based product. Detached particulate material quantities for each test case were used with the respective cumulative concentration of 16 PAH compounds quantified to make an assessment on the potential PAH compound contamination via solid phase particle transport. The average PAH compound concentration in particulate detached from pavement treated with a coal-tar-based rejuvenator was 3062.8 mg PAH per kg of particulate. This was an order of magnitude higher than the average PAH concentration measured in particulate detached from the two control pavement samples and the two asphalt-based samples after a 48 hour cure time, which were 322.1 and 508.1 mg PAH per kg detached particulate, respectively. PAH compound concentrations were also normalized by the surface area of pavement treated with a rejuvenator to determine the potential PAH compound contamination per unit area. Normalized results for each rejuvenator type were averaged to make an overall evaluation of the potential rejuvenator specific PAH compound loading. The coal-tar-based, bio-based, and asphalt-based rejuvenators had a normalized cumulative solid-phase PAH compound release of 2.35, 0.88, and 0.17 mg PAH per square foot of pavement rejuvenated, respectively. In addition, carbazole was quantified in all pavement samples treated with the coal-tar-based rejuvenator at an average concentration of 125.6 mg carbazole per kg detached particulate. Acridine was quantified in detached particulate from five of seven coal-tar-based test performed at an average concentration (excluding non-detection samples) of 42.1 mg acridine per kg detached particulate.

No description available.

Aldol cyclotrimerizations have been used to achieve the rational chemical synthesis of both fullerenes and fullerene fragments in the past. Under certain conditions this reaction produces the corresponding cyclotetramer which has sometimes been regarded as an undesired byproduct. This work details efforts to synthesize and use these cyclotetramers toward a synthesis of a C240 fullerene fragment. One principal focus in this work is tridecacyclene, a cyclic tetramer of acenaphthylene given its name by our group for its thirteen rings. Relatively low yields for the synthesis of tridecacyclene and its derivatives drove us to investigate the mechanism of its formation and attempt to optimize its production. During this process, novel dione products were isolated from the attempted cyclotetramerization of two dimeric species. Characterization of these products by X-ray crystallography gave valuable insight into the reaction pathway, leading us to a new proposed mechanism of formation for the cyclotetramerization products observed in these aldol reactions. β-hydroxy-α-diazoketones are suitable progenitors to vinyl cation intermediates whose use in chemical synthesis is relatively unexplored. As part of an extensive project to develop the chemistry of vinyl cations for use in carbon-carbon bond forming reactions to build important molecular scaffolds, a range of β-hydroxy-α-diazoketones containing a pendent nucleophilic alkene were synthesized. Treatment of these compounds with Lewis acids gave either lactone or cyclopentenone products depending on the substrate used. Proposed herein is a mechanism involving a key acylium intermediate which, depending on the position of the pendent alkene, results in different product outcomes. In a collaborative effort to further investigate the known anti-cancer properties of fusarochromanone, a fungal metabolite that is isolated from Fusarium-infected feed from cold climates, a large-scale synthesis of this natural product was explored. An efficient, scalable synthesis of the previously prohibitively expensive amidochromanone starting material has been achieved and its elaboration to fusarochromanone has been demonstrated.

Exposure to polycyclic aromatic hydrocarbons such as benzo[a]pyrene (B[a]P) has been determined to be a risk factor for various forms of human cancer. PAH DNA adducts have been shown to cause mutations, but carcinogenesis is also accompanied by alterations in gene expression. Inhibiting individual cytochrome P450s could clarify the interaction of P450s and other enzymes in the activation of polycyclic aromatic hydrocarbons to DNA binding intermediates. Phosphorodiamidate morpholino oligomers (PMOs), a class of antisense agents were targeted against cytochrome P450 1A1 (CYP1A1) and cytochrome P450 1B1 (CYP1BI). No significant inhibition of enzyme activity or expression was observed with any PMO used as measured by ethoxyresorufin-O-deethylase (EROD) activity and immunoblots. It was demonstrated that BPDE may react with PMOs in vitro, and PMOs may be segregated in lysosomes, blocking their efficacy. Nonspecific effects by the PMO on CYP1A1 activity were observed. These observations indicate multiple confounding effects in the use of PMOs for this purpose. Many of the genes regulated by histone deacetylases are involved in proliferation, cell function, and differentiation, and HDAC inhibitors are of great interest in cancer research. To probe epigenetic regulation of CYP1A1, MCF-7 cells were treated with two HDAC inhibitors, suberoylanilide hydroxamic acid (SAHA) and trichostatin A (TSA). SARA and TSA increased EROD activity and in RT-PCR. SARA and TSA reduced B[a]P induced CYP1A1 and CYP1B1 mRNA levels. B[a]P DNA binding was not significantly altered by SAHA or TSA treatment. To assay global protein expression changes after treatment with PAR, MCF-7 cells were treated with B[a]P, DB{a,1]P, coal tar extract (SRM 1597) and diesel exhaust extract (SRM 1975), Proteins were separated by two-dimensional electrophoresis, and analyzed using PDQuest. Spots of interest were excised and identified by matrix assisted laser desorption/ionization time of flight time of flight mass spectroscopy. Alterations in expression of heat shock proteins, cytoskeletal proteins, DNA associated proteins, and glycolytic and mitochondrial proteins were observed. Universally increased expression was observed for tubulin alpha and myosin light chain alkali, cyclophilin B, heterogeneous nuclear riboprotein B1, and alpha enolase. Additional proteins exhibiting change in expression included histone H2A.1, heat shock protein 70-2, galectin-3, nucleoside diphosphate kinase, ATP synthase, and electron transfer flavoprotein. / Graduation date: 2004

Urban centers are major sources of contaminants to the surrounding air, water and soils. Above all, combustion-derived carbonaceous aerosols, especially black carbon (BC) and associated polycyclic aromatic hydrocarbons (PAHs), make significant contributions to the pollution in these systems. Here sedimentary records are used to produce a series of historical reconstructions of such contaminants to the Houston Ship Channel (HSC) system and compare these to point source inputs of hydrophobic organic contaminants (HOC). Analytical data on total organic carbon (TOC), BC, PAHs, dioxins and lignin (likely discarded from a pulp and paper mill along the Channel) were determined. This multi-proxy approach revealed that over the last several decades, HOC inputs to the system have been derived from a complex mixture of combustion processes, industrial point-sources, and oil spills. In particular, widespread dioxin contamination was observed throughout the study region with a particular site of the HSC showing total concentrations over 20,000 pg/g and 5000 pg toxic equivalent (TEQ)/g dry weight of sediment. Using two models based on sorption constants of total OC and BC, porewater concentrations were estimated to be lower than expected, at 20 pg/L and 5 pg TEQ/L. These values, however, are recognized as being extremely high for freely dissolved concentrations in porous media. The pulp and paper waste pit has recently been declared a Superfund site based on dioxin concentrations alone. The relationship between lignin biomarkers and dioxins observed in these sediments confirms that discharges of pulp and paper effluents were responsible for such high dioxin levels. Concentrations of BC, amorphous OC, and TOC were then used to calculate sediment binding of dioxins in sediments of the HSC. Our study found BC to be extremely low in HSC sediments (0.04 to 0.20%) indicating minimal dioxin sorption capacity. This suggests strong potential for fluxes of dioxins from sediments to the water column both through passive diffusion and physical mixing during natural and anthropogenic sediment remobilization events in this shallow system (hurricanes, storms, and dredging). The purposeful addition of BC to these sediments might be promising as a remediation strategy.

We report the application of our rhodium-catalyzed nucleophilic ring-opening methodology to the enantioselective synthesis of nitrogen-substituted polycyclic heterocycles. By using a cationic Rh(I) triflate catalyst in the presence of the chiral Josiphos ligand PPF-PtBu2, the ring opening reactions on dihydrooxaquinoline and dihydrooxaisoquinoline using different nucleophiles afford access to multiple dihydroquinolines and dihydroisoquinolones in high yield and high enantioselectivity (up to 99% total yield and >99%ee). A variety of nucleophiles were shown to be compatible with the catalytic system. The electronic effects in the new ring opening reactions were investigated using a variety of nucleophiles. It was found that reactivity and enantioselectivity of the ring opening products depends on the electronic effects as well as the position of the substituents on the substrates. Good yields and high ee of regioisomeric products are obtained using electron donating substituents, whereas electron withdrawing substituents decelerate the reactions.