Hui Chi Wai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 81-84). / Abstracts in English and Chinese. / Chapter I. --- Abstract --- p.ii / Chapter II. --- Acknowledgements --- p.iv / Chapter III. --- Table of contents --- p.v / Chapter IV. --- Introduction --- p.1 / Chapter A. --- Synthesis of tetraphenylene --- p.1 / Chapter B. --- Structural characteristics of tetraphenylene --- p.3 / Chapter C. --- Inclusion properties of tetraphenylene --- p.5 / Chapter D. --- Synthesis of substituted tetraphenylenes --- p.7 / Chapter 1. --- Electrophilic aromatic substitution approach --- p.7 / Chapter 2. --- Substituted biphenyl approach --- p.8 / Chapter 3. --- Substituted biphenylene approach --- p.10 / Chapter 4. --- Bis acetylene approach --- p.10 / Chapter E. --- "Synthesis of dibenzo［α ,e］cyclooctene (42) and its derivatives" --- p.14 / Chapter F. --- "Synthesis of 5,6,11,12-tetradehydrodibenzo［α ,e］cyclooctene (8) and its derivatives" --- p.16 / Chapter G. --- The aim of the present research --- p.21 / Chapter V. --- Results and discussion --- p.26 / Chapter A. --- Synthetic strategy --- p.26 / Chapter B. --- "Preparation of 1,10-dimethoxydibenzo［α ,e］cyclooctene (79)" --- p.28 / Chapter C. --- "Preparation of l，12-dimethoxytribenzo［α, c,e］cyclooctene (96)" --- p.33 / Chapter D. --- "Preparation of 1,4,5,16-tetrahydroxytetraphenylene (72) and its derivatives" --- p.44 / Chapter VI. --- Conclusion --- p.57 / Chapter VII. --- Experimental section --- p.58 / Chapter VIII. --- References --- p.81 / Chapter IX. --- Appendix --- p.85 / Chapter A. --- List of NMR Spectra --- p.86 / Chapter B. --- List of X-ray crystallographic data --- p.104

No description available.

Woo, On Ting. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 102-121). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / Table of Contents --- p.vi / List of Figures --- p.ix / List of Plates --- p.xiv / List of Tables --- p.xv / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- General characteristics --- p.1 / Chapter 1.2 --- Sources of PAHs --- p.6 / Chapter 1.3 --- Adsorption of PAHs --- p.7 / Chapter 1.4 --- Environmental fate of PAHs --- p.9 / Chapter 1.4.1 --- Transformation --- p.10 / Chapter 1.4.1.1 --- PAHs in atmosphere --- p.10 / Chapter 1.4.1.2 --- PAHs in water --- p.11 / Chapter 1.4.1.3 --- PAHs in soil and sediment --- p.12 / Chapter 1.4.2 --- Route of entry into human --- p.13 / Chapter 1.5 --- Toxicity of PAHs on human --- p.14 / Chapter 1.5.1 --- Cancer --- p.14 / Chapter 1.5.2 --- Other health effects - acute effects --- p.16 / Chapter 1.5.3 --- Other health effects - chronic effects --- p.16 / Chapter 1.5.3.1 --- Respiratory effect --- p.16 / Chapter 1.5.3.2 --- Dermal effect --- p.17 / Chapter 1.6 --- Treatment methods of PAHs --- p.17 / Chapter 1.6.1 --- Incineration --- p.17 / Chapter 1.6.2 --- Bioremediation --- p.18 / Chapter 1.6.3 --- Chemical oxidation --- p.19 / Chapter 1.6.4 --- Combined biological-chemical treatment --- p.22 / Chapter 1.6.5 --- Advanced oxidation processes --- p.23 / Chapter 1.6.5.1 --- Photocatalytic oxidation --- p.24 / Chapter 1.6.5.2 --- Operation parameters of PCO --- p.26 / Chapter 1.7 --- PAH contamination in Hong Kong --- p.27 / Chapter 2 --- Objectives --- p.28 / Chapter 3 --- Materials and methods --- p.29 / Chapter 3.1 --- Chemicals --- p.29 / Chapter 3.2 --- Photocatalytic reactor --- p.30 / Chapter 3.3 --- Ultrasonic extraction of PAHs --- p.32 / Chapter 3.4 --- Quantification of PAHs --- p.32 / Chapter 3.5 --- Photocatalytic reactivity of PAHs --- p.34 / Chapter 3.6 --- The effect of acetone on performance of PCO --- p.35 / Chapter 3.7 --- Identification of intermediates of PAHs --- p.36 / Chapter 3.8 --- Toxicity test --- p.38 / Chapter 3.9 --- Study of mixture effect --- p.40 / Chapter 4 --- Results and discussion --- p.42 / Chapter 4.1 --- Quantification of PAHs --- p.42 / Chapter 4.2 --- Extraction efficiency of PAHs --- p.42 / Chapter 4.3 --- Photocatalytic reactivity of PAHs --- p.44 / Chapter 4.4 --- The effect of acetone on performance of PCO --- p.52 / Chapter 4.5 --- Identification of intermediates --- p.62 / Chapter 4.5.1 --- PCO degradation of naphthalene --- p.62 / Chapter 4.5.2 --- PCO degradation of acenaphthylene --- p.66 / Chapter 4.5.3 --- PCO degradation of phenanthrene --- p.69 / Chapter 4.5.4 --- PCO degradation of anthracene --- p.72 / Chapter 4.5.5 --- PCO degradation of benzo[a]anthracene --- p.75 / Chapter 4.5.6 --- PCO degradation of pyrene --- p.78 / Chapter 4.6 --- Toxicity test --- p.80 / Chapter 4.7 --- Study of mixture effect --- p.87 / Chapter 5 --- Conclusions --- p.99 / Chapter 6 --- References --- p.102 / Chapter 7 --- Appendices --- p.122

No description available.

Sedimentary organic matter contains many compounds that have no obvious biogenic precursors, so their formation and occurrence are of geochemical interest. The first part of this thesis (chapters 2-5) discusses the results obtained from studying hydrocarbon racemates. Some of the compounds identified are also suggested as intermediates in the formation of alkylnaphthalenes identified in chapters 6-7. The second part of this thesis (chapters 6-11) covers the identification of a range of alkylnaphthalenes and alkylphenanthrenes in sedimentary organic matter. Possible pathways for the formation of these hydrocarbons are outlined and their application as probes into the processes of petroleum formation are described.In chapter 2 the use of permethylated cyclodextrin capillary gas chromatography columns to separate hydrocarbon racemates are reported. Chapter 3 reports the synthesis of 1,2,2,5-tetramethyltetralin and 1,2,2,5,6-pentamethyltetralin and identifies them as racemates in crude oil. They are proposed as intermediates in the formation of sedimentary alkylnaphthalenes (identified in chapters 6 and 7).The identification of isodihydro-ar-curcumene in sedimentary organic matter is described in chapters 4 and 5. It co-occurs in crude oil with dihydro-ar-curcumene and is suggested to originate from this compound via a sedimentary rearrangement process. Chiral GC-MS techniques have been used to show the presence of both enantiomers of these compounds in crude oils. The elution order of the enantiomers has been established using reference compounds of known configuration. The effects of maturity and biodegradation on dihydro-ar-curcumene and isodihydro-ar-curcumene enantiomers is reported. Optically pure dihydro-ar-curcumene from natural products undergoes rapid racemisation in the subsurface, yielding a racemic mixture before the onset of significant oil formation. ++ / 1,2-Alkyl shifts on the aromatic ring also begin at an early stage to yield isodihydro-ar-curcumene and these processes continue with increasing maturity. Laboratory experiments using proton and clay catalysts (Lewis acid catalyst) show that the alkyl shift reaction is catalysed by both proton and Lewis acids, and racemisation is only catalysed by Lewis acids. A moderately biodegraded crude oil has been shown to be depleted in the R enantiomer of dihydro-ar-curcumene and an extensively degraded oil has dihydro-ar-curcumene depleted relative to isodihydro-ar-curcumene.The identification of a number alkylnaphthalenes and their possible origins in sedimentary organic matter is described in chapters 6 and 7. In chapter 6 a previously unreported tetramethylnaphthalene (TeMN) was identified in petroleum. This compound is structurally similar to bicyclic compounds of microbial origin and these are suggested as a likely source, via a tetralin intermediate identified in chapter 3. In chapter 7 isomeric pentamethylnaphthalenes previously unreported in sedimentary organic matter are reported. These isomeric pentamethylnaphthalenes (PMNs) were identified in a number of crude oils and sediments, ranging in age from Proterozoic to Tertiary. 1,2,3,5,6-PMN is suggested to form predominantly from the aromatisation of drimanoid precursors via 1,2,2,5,6-pentamethyltetralin identified in chapter 3. In laboratory experiments, the other pentamethylnaphthalenes were generated from 1,2,3,5,6-PMN in proportions that reflect the relative stability of the isomers. By analogy, the other PMNs in sediments are suggested to arise via acid catalysed isomerisation or transalkylation processes. A maturity parameter was developed based on laboratory experiments in conjunction with observed distributions of pentamethylnaphthalenes.The formation of alkylnaphthalenes and alkylphenanthrenes through a ++ / methylation process is discussed in chapters 8-10. Several crude oils and shales which contain anomalously high concentrations of 1,6-dimethylnaphthalene, 1,2,5-trimethylnaphthalene, 1,2,7-trimethylnaphthalene, 1,2,3,5-tetramethylnaphthalene, 1,2,3,5,6-pentamethylnaphthalene, 2-methyl-6-isopropyl-1(4-methylpentyl)naphthalene, phenanthrene, 1-methylphenanthrene, 1,7-dimethylphenanthrene and retene have been shown to contain relatively high concentrations of their corresponding methylated counterparts. In laboratory experiments carried out under mild conditions, each of the alkylnaphthalenes and alkylphenanthrenes have been shown to be methylated in specific positions when heated with a methyl donor in the presence of a clay catalyst. These observations have been interpreted as evidence for a sedimentary methylation process.The effect of biodegradation on alkylnaphthalenes and alkylphenanthrenes formed from sedimentary methylation is described in chapter 11. Land-plant-derived aromatic hydrocarbons with a range of susceptibilities to reservoir biodegradation have been identified in crude oils. These compounds are the result of reactions of natural products involving aromatisation, rearrangement and methylation in the sediments (chapters 9 and 10). They are therefore suggested as markers for land-plants in severely biodegraded oils in which most of the other biologically derived compounds cannot be recognised. The order of biodegradability of these compounds has been assessed relative to their non-methylated counterparts namely 6-isopropyl-2-methyl-1-(4-methylpentyl)naphthalene and retene. The order of degradation of the four compounds is : retene < 9-methylretene ~ 6-isopropyl-2-methyl-1-(4-methylpentyl)naphthalene > 6-isopropyl-2,4-dimethyl-1-(4-methylpentyl)naphthalene. These results have been used to assess that a crude oil is a mixture of severely biodegraded and ++ / less biodegraded crude oil.

Typewritten copy / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, 1955

4-Aminobiphenyl is an aromatic amine compound that is present in cigarette smoke, diesel exhaust, cooking oil fumes and dye intermediates. It is a well-known human bladder carcinogen and liver carcinogen in experimental animals that is metabolically activated by liver CYP1A1/2. We have used the “Accelerated Cytotoxicity Mechanism Screening” (ACMS) techniques to analyze the molecular cytotoxic mechanisms of 4-aminobiphenyl. Hepatocyte exposure to an inflammatory system significantly increased hepatocyte susceptibility to 4-aminobiphenyl. 4-Aminobiphenyl- induced cytotoxicity and lipid peroxidation were both prevented by altering cellular redox status and with the addition of antioxidants. Toxicity was increased with the depletion of hepatocyte GSH levels and by inhibiting N-acetyltransferase. These results will provide more insight into the cytotoxic and genotoxic mechanisms of 4-aminobiphenyl and also suggest that inflammation may be responsible for an increase in arylamine carcinogenesis.

4-Aminobiphenyl is an aromatic amine compound that is present in cigarette smoke, diesel exhaust, cooking oil fumes and dye intermediates. It is a well-known human bladder carcinogen and liver carcinogen in experimental animals that is metabolically activated by liver CYP1A1/2. We have used the “Accelerated Cytotoxicity Mechanism Screening” (ACMS) techniques to analyze the molecular cytotoxic mechanisms of 4-aminobiphenyl. Hepatocyte exposure to an inflammatory system significantly increased hepatocyte susceptibility to 4-aminobiphenyl. 4-Aminobiphenyl- induced cytotoxicity and lipid peroxidation were both prevented by altering cellular redox status and with the addition of antioxidants. Toxicity was increased with the depletion of hepatocyte GSH levels and by inhibiting N-acetyltransferase. These results will provide more insight into the cytotoxic and genotoxic mechanisms of 4-aminobiphenyl and also suggest that inflammation may be responsible for an increase in arylamine carcinogenesis.

The distribution of hydrophobic ionogenic organic compounds (HIOC's) between aqueous and nonaqueous phases has been investigated. The HIOC's are aniline and methyl substituted anilines. The aqueous phases are methanol-water mixed solvents with varying pH and ionic strength. The nonaqueous phases are silica and alkyl derivatized silica with ethyl- (C-2), octyl- (C-8), and octadecyl- (C-18) silanes. A gas-liquid equilibration method has been developed to determine the Henry's law constants and the activity coefficients of methyl anilines in methanol-water mixed solvents. The logarithm of the Henry's law constants vary quadratically with the volume fraction of methanol. The chromatographic study has been performed to investigate the effect of three mobile phase factors, fraction of methanol, pH, and ionic strength, on the retention of methyl anilines on different stationary phases. The logarithm of mass distribution ratios, log k's, of methyl anilines vary linearly with the volume fraction of methanol. The ratios of H / k' of methyl anilines increase with increase in methanol in the mobile phase, indicating an increase in the activity coefficients in the stationary phases. This observation is found to be true for different methyl anilines in different stationary phases. A partition model is presented to describe the effect of pH and ionic strength on the retention of HIOC's in the mobile phase. The variation in log k' among neutral and ionic methyl anilines can be explained by linear free energy relationships. Equations are established to predict retention of neutral or ionized methyl anilines from their octanol-water partition coefficients at any methanol content in the mobile phase. Acid dissociation constants of methyl anilines determined from the dependence of log k' on pH are in close agrement with those determined by potentiometric titrations. The effect of ionic strength on the retention of both neutral and ionic species of methyl anilines is negligible. That is, the contribution from electrostatic energy and salting out effect are not significant. The chromatographic study is extended to study the retention of methyl anilines on silica as a function of pH and methanol at a constant ionic strength. The dependence of retention on pH is qualitatively interpreted from an ion exchange reaction between the dissociated silanol groups in the surface and the ionized methyl anilines. The effect of methanol on the retention of methyl anilines and of pyridine on silica is described by a quadratic relationship between the log k' and volume fraction of methanol. / Graduation date: 1990

Thesis (Ph. D.)--West Virginia University, 2008. / Title from document title page. Document formatted into pages; contains xi, 215 p. : ill. Includes abstract. Includes bibliographical references (p. 94-104).