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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.

Abstract This study investigated the distributions of polyclic aromatic hydrocarbons (PAHs) in the sediment cores collected from continental shelf of Gaoping submarine canyon. The sediment cores were analyzed for PAHs to reconstruct historical contamination record of these compounds and to find out the possible sources, trends and fluxes. The average concentrations of £U50 and £U16 PAHs ranged from 568 to 816 ng/g and from 169 to 256 ng/g, respectively. Except for sediment cores L10 and L26, the high molecular weight PAHs (4-6 ring PAHs) were found dominant in 1960s-2006, while the low molecular weight PAHs (2-3 ring PAHs) were found dominant before 1960s. Results from diagnostic ratios and hierarchical cluster analysis (HCA) both suggested that sources of PAHs in the cores of southern continental shelf were primarily from petrogenic, while those in the cores of northern continental shelf were from pyrogenic and petroleum combustion. There is a significant increasing of total PAH concentrations between 1930-1950, suggesting that might be an evident during the World War II. Due to increase of importing fossil fuel and the growth of heavy industrials in Gaoping area, the total concentrations of PAHs showed an increasing trend again since 1950s in the core from continental shelf of Gaoping submarine canyon. In addition, during 1990-2006, the total concentrations of PAHs showed a decreasing trend might result from the environmental protection laws. It is noteworthy that in L28 and L29 sediment cores, the increase of total PAH concentrations recorded during 1990-2006 may be due to the dumping of the sludge from dredged Kaohsiung harbor sediments. Comparing with the sediment quality guidelines (SQG), the PAH concentrations in the northern continental shelf sediment samples were higher than the Threshold Effect Level (TEL) value, suggesting there might be an adverse biological effects caused by PAHs. Keywords¡GPolycyclic aromatic hydrocarbons (PAHs), Kaohsiung harbor, Sediment quality guidelines (SQG)

Polycyclic aromatic hydrocarbons (PAHs) are one of major classes of organic pollutants. As semi-volatile organic compounds, PAHs can be transported in the atmosphere and scavenged according to various processes (dry and wet deposition). Atmospheric deposition is an important pathway for the transfer of pollutants from atmosphere to the terrestrial and water surfaces. The objective of this research is to quantify the dry and wet deposition of the atmospheric PAHs in the Kaohsiung coastal area. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were also performed with diagnostic ratios to determine the potential sources of PAHs. The mean dry and wet deposition fluxes of atmospheric total suspended particles (TSP) during the study period (January-December 2010) were estimated to be 44.3 (6.60-384) and 211 (56.1-738) mg/m2d, respectively. The annual mean total PAH fluxes in dry and wet deposition were 1500 (749-3760) and 8470 (2280-46000) ng/m2d, respectively. Both concentrations and dry deposition fluxes of TSP were much higher during dust storm. During Ghost Month, however, they were comparable with other sampling events. By comparing with literatures, the total PAH concentrations of TSP were relatively low during Ghost Month, suggesting that wind direction and precipitation might be plausible. The ratio of PM2.5/PM10 had a relatively low value during dust storm, indicating that coarse particle might be predominant. In addition, during dust storm, both TSP dry deposition velocity and total PAH dry deposition velocity were higher than other sampling events. Our findings in this study showed that previous attempts in literature to estimate total PAH dry deposition fluxes by using TSP dry deposition velocity and PAH concentrations could lead to overestimate fluxes in the field. TSP dry deposition fluxes were positively correlated with atmospheric total TSP concentrations and TSP dry deposition velocity, but were correlated negatively with intensity of precipitation. In addition, TSP dry deposition velocity showed a positive correlation with TSP concentrations. Total PAH dry deposition fluxes were correlated positively with atmospheric total particulate concentrations and total PAH dry deposition velocity, but negatively with intensity of precipitation and temperature. However, TSP and total PAH fluxes in wet deposition were both correlated positively with intensity of precipitation. Diagnostic ratios showed that diesel exhaust was the main source of combustion-derived PAHs in the study. HCA and PCA analysis indicated that emissions from the ships and vehicles, and fuel used were the main sources of combustion-derived PAHs, while during special events, such as dust storm and Ghost Month, suggesting a different source of PAHs.

Cores and sediment traps collected from Kao-ping Canyon were used to reconstruct historical record of PAHs contamination and find out the possible sources, distributions, trends and flux of PAHs. The sedimentary record of PAHs shows that the average concentration of total PAHs was 310 ng/g dry wt. (264¡ã364 ng/g) which was lower than coasts of the other countries. According to diagnostic ratios and statistical analysis, we identify sources of PAHs and suggest that all up-cores were dominated by petrogenic sources, but all down-cores except for C980 and S1 were tended to pyrogenic or mixed sources. In contrast, both C980 and S1 were showed higher perylene/£UPAHs (%), which suggests that biogenic sources dominate in C980 and S1. In comparison with sediment quality guidelines (SQGs), the PAHs concentrations of all sediment cores weren¡¦t exceeded the criteria, which suggests that no evident adverse biological effects exist caused by PAHs in Kao-ping Canyon. It shows that the transition from coal to petroleum fuel use corresponding to the total concentrations of PAHs decrease recorded during 1893-1935 period in the sediment core. A PAHs concentration peak also recorded during the World War ¢º, 1893-1935. Because of increase of importing fossil fuel and the growth of heavy industrials in Kao-Ping area, the total concentrations of PAHs were shown evidence of increase again since 1950s in the core from Kao-ping Canyon. The average PAHs flux in the upper and lower mooring deployed in Kao-ping Canyon were 66 and 108 £gg/m2/d, respectively, which were higher than coasts of the other countries. The PAHs sources of sinking particles were dominated by petrogenic sources which were as similar sources as all up-cores.

Turning back to look Kaohsiung city¡¦s development and history of exploitation, both of them had a close relationship with the Love River and Chianjen River. Along the rivers, there are numerous industrial estates and large population. The basin of the rivers is important in politics and economy to Kaohsiung. However, the development of Kaohsiung also causes organic pollution, such as polycyclic aromatic hydrocarbon (PAHs), released to water system. Furthermore, some of these pollutants are carcinogenic, so that this topic is quite important. This study investigates PAHs concentrations and seasonal variations in sediments and suspended solids of these two rivers. Total PAHs concentrations varied from 110 to 4300(ng g-1 dry wt) in sediments and 1500 to 7000(ng g-1 dry wt) in suspended solids of the Love River. Total PAHs concentrations of sediments and suspended solids of the Chianjen River exhibited in the range of 230-3900 (ng g-1 dry wt) and 490-9200 (ng g-1 dry wt), respectively. The average PAHs concentration during rain/ dry season of the Chianjen River is significantly higher than those of the Love River. Compared with global data in literature, level of total PAHs concentrations in sediments and suspended solids of the Love River and Chianjen River belongs to moderate pollution. Total PAHs and total organic carbon (TOC) is significantly related except suspended solids of the Chianjen River. However, the relationship between total PAHs concentrations and mean particle size is not significant because of inequilibrium resulted from different sources. Referring to Sediment quality guidelines (SQGs), most of stations are in safe range, only total PAHs concentrations at station L8 in rainy season is significantly higher than the standard ERL value. For each individual compound, the concentrations of many low-molecular-weight PAHs are higher than their standard ERL¡BLET and LAET values. The result of HCA shows that in both dry and rain season, these two rivers¡¦ sediments and suspended solids are separated into upstream and downstream groups. It is believed that the existence of an intercept device set up in midstream of both rivers is the reason. The PAHs in sediments of the Love River is mainly contributed from automobile exhaustion, while suspended solids in the Love River is mainly contributed from petrogenic source. However, both sediments and suspended solids in the Chianjen River are mainly contributed from combustion pollution.

Substantial environmental contamination has occurred from coal tar creosote and pentachlorophenol (C5P) in wood preserving solutions. The present studies focused on the characterization and remediation of these contaminants. The first objective was to delineate a sequence of biological changes caused by chlorinated phenol (CP) exposure. In Clone 9 cells, short-term exposure to 10 ?M C5P decreased pH, GJIC, and GSH, and increased ROS generation. Long-term exposure caused mitochondrial membrane depolarization (25 ?M), increased intracellular Ca2+ (50 ?M), and plasma membrane depolarization (100 ?M). Cells were affected similarly by C5P or 2,3,4,5-C4P, and similarly by 2,3,5-C3P or 3,5-C2P. Endpoints were affected by dose, time, and the number of chlorine substituents on specific congeners. Thus, this information may be used to identify and quantify unknown CPs in a mixture to be remediated. Due to the toxic effects observed due to CP exposure in vitro, the objective of the second study was to develop multi-functional sorbents to remediate CPs and other components of wood preserving waste from groundwater. Cetylpyridinium-exchanged low pH montmorillonite clay (CP-LPHM) was bonded to either sand (CP-LPHM/sand) or granular activated carbon (CP-LPHM/GAC). Laboratory studies utilizing aqueous solution derived from wood preserving waste indicated that 3:2 CP-LPHM/GAC and CP-LPHM/sand were the most effective formulations. In situ elution of oil-water separator effluent indicated that both organoclay-containing composites have a high capacity for contaminants identified in wood preserving waste, in particular high molecular weight and carcinogenic PAHs. Further, GAC did not add substantial sorptive capacity to the composite formulation. Following water remediation, the final aim of this work was to explore the safety of the parent clay minerals as potential enterosorbents for contaminants ingested in water and food. Calcium montmorillonite and sodium montmorillonite clays were added to the balanced diet of Sprague-Dawley rats throughout pregnancy. Based on evaluations of toxicity and neutron activation analysis of tissues, no significant differences were observed between animals receiving clay supplements and control animals, with the exception of slightly decreased brain Rb in animals ingesting clay. Overall, the results suggest that neither clay mineral, at relatively high dietary concentrations, influences mineral uptake or utilization in the pregnant rat.

A high-volume air sampler (PS-1) was used to measure the concentrations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of Kaohsiung coast, PAHs diagnostic ratios,Hierarchical Cluster Analysis (HCA) and Principal Component Analysis (PCA) were employed to determine the potential sources of PAHs. The results show that the lowest concentrations of PAHs occurred in May (2.62 ngm-3), while the highest occurred in December (36.4 ngm-3). The nighttime concentrations of PAHs are higher than daytime with average night / day ratio of 1.65. The PAHs was more distributed in gas phase with proportions between 64.1 to 93.7 %. The 2, 3-Ring PAHs were mostly present in the gaseous phase (96.2 and 96.5 % respectively), 4-Ring also present dominantly in the gaseous phase (73.0 %), 5-Ring present mostly in the particle phase (80.2 %), 6, 7-Ring PAHs were mostly present in particulate phase (97.4 and 97.7 % respectively). During the Ghost Festiva and Asian dust storm events, atmospheric concentrations of PAHs and PAHs/TSP ratios were both found increased. It is found that gaseous and particulate PAHs correlate negatively with ambient temperature(r=-0.62, -0.57). Results from analyses of diagnostic ratios, HCA and PCA, the major sources of pollution include gasoline, diesel exhaust and industrial emission.