Experimental mole fraction solubilities of benzil, thianthrene, trans-stilbene, thioxanthen-9-one, diphenyl sulfone and dibenzothiophene sulfone are determined in pure noncomplexing and complexing solvents. Predicted solubility values are calculated for benzil, thianthrene, trans-stilbene and thioxanthen-9-one using expressions derived from Mobile Order theory. Large deviations between experimental and predicted solubilities in alcohol solvents exist, therefore optimized solute - solvent association constants are determined. Previously measured thianthrene solubilities in five binary alkane + cyclohexane solvent mixtures are compared with values predicted from Mobile Order theory using the measured solubility in each of the pure solvents as input parameters. The experimental mole fraction solubility of benzil in eight binary alcohol + 1-octanol solvent mixtures are also measured and compared with predicted values.

A variable temperature ^13 C and ^199 Hg NMR study has been conducted for diphenyl-, bis(o-tolyl)-, bis(m-tolyl)-, and bis(2, 6-xylyl)mercury in dimethyl sulfoxide and 1,1,2,2 tetrachloroethane; ^13 C T1 relaxation times are reported as a function of temperature. Barriers to rotation of the aryl rings are obtained. Chemical shifts and couplings in CDCl_3 are given for bis(p-tolyl)-, bis(2, 5-xylyl)-, bis(mesityl)-,phenyl(o-tolyl)-, phenyl(m-tolyl)mercury, and the compounds listed above. The steric interactions of these aryl mercury compounds are discussed.

La variante « glyoxylique » de la réaction de Perkin permet de lier entre eux deux fragments aromatiques par un pont maléique. La rigidification de cet intermédiaire flexible mène à des systèmes aromatiques polycycliques étendus par création des liaisons carbone-carbone manquantes. Cette stratégie requiert l'utilisation d'acides arylacétiques et arylglyoxyliques, et l’utilisation d'unités bifonctionnelles a auparavant permis la synthèse de cibles variées allant des phénacènes plans aux (poly)hélicènes très distordus, mais aussi des macrocycles conjugués. Afin d'étendre la taille et la variété des molécules obtenues à l'aide de cette stratégie, des méthodes générales de protection/déprotection sont développées. Une dissymétrisation efficace des unités bifonctionnelles mène à des nouveaux précurseurs monoprotégés qui sont ensuite assemblés par la réaction de Perkin en oligomères de taille contrôlée possédant encore des fonctions chimiques réactives aux extrémités après déprotection. L'utilisation de ces derniers lors d'une deuxième réaction de Perkin donne alors accès à de longs précurseurs flexibles, d’au moins cinq unités, qui donneront ensuite de très longs phénacènes, de grands macrocycles mais aussi des cyclo-tris[5]hélicènes qui présentent une géométrie de Möbius persistante et une aromaticité de Möbius. / The “glyoxylic” variant of the Perkin reaction allows to link two aromatic fragments by a maleic bridge. The stiffening of the obtained flexible intermediate by the creation of the missing carbon-carbon bonds leads to extended polycyclic aromatic systems. This strategy relies on the use of arylacetic and arylglyoxylic acids, and the use of bifunctional units has previously allowed the synthesis of a variety of targets spanning from flat phenacenes to strongly distorted (poly)helicenes, as well as of conjugated macrocycles. This approach is generalized here by developing protection/deprotection techniques in order to enhance the size and the variety of the molecules that can be obtained by this strategy. These techniques enable an efficient dissymetrization of bifunctional units and the recycling of symmetrical side products. The new monoprotected building blocks are connected by Perkin reactions to yield oligomeric intermediates with reactive functions at their extremities after deprotection. Several of these intermediates are assembled in a second Perkin reaction to obtain long phenacenes, large macrocycles and also cyclo-tris[5]helicenes with persistent Möbius geometry and Möbius aromaticity.

Cubatão, o maior pólo industrial da américa latina também já foi uma das cidades mais poluídas do mundo. Os 30 anos de intensa atividade industrial vêm pressionando o meio ambiente com substâncias tóxicas e afetando gravemente a saúde da população. Dentre as substâncias contaminantes mais importantes da região estão os derivados de petróleo como o benzeno, tolueno, etilbenzeno e xilenos. Conhecidos como BTEX, eles são produzidos e utilizados em larga escala e a contaminação ocorre frequentemente através de vazamentos. Nos solos, devido à sua solubilidade em água, essas substâncias podem se espalhar por longas distâncias a partir do ponto afetado contaminando locais distantes. Já foi comprovada a capacidade de micro-organismos de sobreviver e até utilizar BTEX como fonte de carbono. Os micro-organismos adaptados catabolizam os contaminantes transformando-os em substâncias menos tóxicas e até mesmo eliminando-os do ambiente, capacidade de grande interesse econômico e ambiental. Nessa linha, nossa proposta visa o estudo das comunidades microbianas de solos afetados e não afetados por BTEX. Para isso foi utilizada a metagenômica como abordagem de estudo identificando-se diferenças qualitativas e quantitativas nas estruturas microbianas de três diferentes locais do município de Cubatão, sendo um deles afetado diretamente por BTEX. Pelo método utilizado e aqui desenvolvido, foi possível identificar um panorama metabólico geral identificando-se genes relevantes e o potencial de degradação de hidrocarbonetos aromáticos de micro-organismos conhecidos e desconhecidos, revelando melhor o potencial metabólico dos solos identificados. Os resultados apresentados podem contribuir para um melhor entendimento da dinâmica in situ de uma comunidade microbiana afetada por BTEX assim como melhorar o conhecimento sobre a comunidade microbiana de um local altamente impactado como Cubatão. / Cubatão is the largest industrial site in Latin America and was in the past one of the most polluted cities in the world. 30 years of intense industrial activity has pushed environmental limits with toxic substances and has severely affected the inhabitants\' health. Among the contaminants found in the region, the petroleum derivatives benzene, toluene, ethylbenzene and xylenes are the most important. Known collectively as BTEX, they are produced and used at a large scale and contamination frequently occurs. Because it is highly soluble in water, when in soil BTEX can spread long distances from the original contamination site, thus affecting large areas. Some microorganisms are known to live in contaminated environments and use contaminants such as BTEX as a unique carbon source for energy production. They catabolize contaminants into less dangerous products or even eliminate them from environment, a feature which has great commercial and environmental interest. We therefore compared the microbial communities in soils which were affected and un-affected by BTEX contamination. To this end, we used a metagenomics approach and developed a comparison method to identify microorganisms and degradation potential of soils studied. We found qualitative and quantitative differences in microbial structures from three different sites in Cubatão County, one of which is contaminated with BTEX. We constructed a metabolic overview identifying important genes, degradation potential and microorganisms related to BTEX degradation. The results presented here could contribute to understanding the in situ dynamics of a BTEX affected microbial community as well as improving our knowledge of the microbial community of Cubatão, a highly environmentally impacted place.

Chan, Chung Yin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 77-80). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.V / Abstract --- p.vi / Chapter Chapter 1 - --- Introduction --- p.1 / Chapter 1.1 --- Definition of Aromatic Bond Activation --- p.1 / Chapter 1.2 --- History of Carbon-Fluorine Bond Activation --- p.1 / Chapter 2.2.1 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1970s --- p.1 / Chapter 2.2.2 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1980s --- p.2 / Chapter 2.2.3 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1990s --- p.3 / Chapter 2.2.4 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 2000s --- p.6 / Chapter 1.3 --- Difficulties and Challenges in Aromatic Bond Activation Applications of Aromatic Carbon Fluorine Bond Activation --- p.6 / Chapter 2.2.1 --- Thermodynamic Estimations --- p.7 / Chapter 2.2.2 --- Competitive Aromatic Bond Activation --- p.9 / Chapter 1.3.2.1 --- Competitive Aromatic Carbon-Hydrogen and Carbon-Halogen Bond Activation --- p.10 / Chapter 1.3.2.2 --- Competitive Aromatic Carbon-Hydrogen and Carbon-Fluorine Bond Activation --- p.15 / Chapter 1.4 --- Mechanistic Investigations of Aromatic CFA --- p.17 / Chapter 2.2.1 --- Oxidative Addition --- p.17 / Chapter 2.2.2 --- Nucleophilic Aromatic Substitution --- p.18 / Chapter 2.2.3 --- Fluorine Atom Abstraction --- p.19 / Chapter 2.2.4 --- "1,2-Addition" --- p.19 / Chapter 1.5 --- Mechanistic Investigations of Aromatic Carbon-Hydrogen Bond Activation --- p.20 / Chapter 2.2.1 --- Oxidative Addition --- p.20 / Chapter 2.2.2 --- Electrophilic Aromatic Substitution --- p.21 / Chapter 2.2.3 --- "1,2-Addition" --- p.21 / Chapter 1.6 --- Applications of Aromatic Carbon-Fluorine Bond Activation --- p.22 / Chapter 1.7 --- Applications of Aromatic Carbon-Hydrogen Bond Activation --- p.23 / Chapter 1.8 --- Structural Features of Iridium Porphyrins --- p.23 / Chapter 1.9 --- Obj ectives of the Work --- p.25 / Chapter Chapter 2 - --- Competitive Aromatic Carbon Fluorine and Carbon Hydrogen Bond Activation by Iridium(III) Porphyrins --- p.26 / Chapter 2.1 --- C-F Activation of Fluorobenzene by Rhodium(III) Porphyrins --- p.26 / Chapter 2.2 --- Preparation of Starting Materials --- p.26 / Chapter 2.2.1 --- Preparation of Tetratolylporphyrin --- p.26 / Chapter 2.2.2 --- Preparation of Iridium(III) Porphyrin Carbonyl Chloride --- p.27 / Chapter 2.3 --- Base Effect of Carbon-Fluorine Bond Activation --- p.27 / Chapter 2.4 --- Solvent Effect of Carbon-Fluorine Bond Activation --- p.30 / Chapter 2.5 --- Temperature Effect --- p.31 / Chapter 2.6 --- Concentration Effect of Carbon-Fluorine Bond Activation --- p.33 / Chapter 2.7 --- Activations of Fluorobenzenes --- p.33 / Chapter 2.8 --- Electronic Effect --- p.36 / Chapter 2.9 --- Mechanistic Studies --- p.38 / Chapter 2.9.1 --- Activation of Fluorobenzene --- p.38 / Chapter 2.9.2 --- Reaction between Ir(ttp)H and Fluorobenzene --- p.40 / Chapter 2.9.3 --- Reaction between Ir2(ttp)2 and Fluorobenzene --- p.41 / Chapter 2.9.4 --- "Reaction between Ir(ttp)""K+ and Fluorobenzene" --- p.42 / Chapter 2.9.5 --- Reaction between Ir(ttp)Me and Fluorobenzene --- p.44 / Chapter 2.10 --- Proposed Mechanism for CFA --- p.45 / Chapter 2.11 --- Proposed Mechanism for CHA --- p.47 / Chapter 2.12 --- Kinetic and Thermodynamic CFA and CHA Products --- p.47 / Chapter 2.13 --- Summary --- p.48 / Chapter Chapter 3 - --- Experimental Section --- p.49 / Reference --- p.77 / Chapter Appendix I - --- Spectra --- p.81

Microbial biodegradation is the primary mechanism by which petrogenic hydrocarbons (PHCs) are removed from the environment. Though hydrocarbon biodegradation is widely studied in marine systems, knowledge of how it occurs in freshwater systems is still lacking. The Peace-Athabasca Delta (PAD), located in northeastern Alberta, is an ideal location to study microbial hydrocarbon degradation since it has a long history of exposure to PHCs. What’s more, these PHCs are predominately sourced from bituminous deposits and are therefore relevant to the Canadian Oil Sands Industry. This thesis investigated the genetic potential for hydrocarbon degradation of PHCs via metagenomic reconstruction of microbial communities in lakes of the Peace and Athabasca Deltas, as well as reference lakes in the nearby boreal uplands. In order to properly evaluate the microbial community and its potential for hydrocarbon degradation, a comprehensive analysis of PHCs (including n-alkanes, polycyclic aromatic compounds (PACs), and petroleum biomarkers of terpanes, hopanes, and steranes) was performed. PHC analysis showed that n-alkanes in lake sediments from all three regions were highly similar and predominately biogenic, while PAC composition was significantly different in each region. Restricted-drainage lakes of the Athabasca Delta had the highest concentrations of PACs from petrogenic sources. Closed-drainage lakes in the Peace Delta had lower concentrations of PACs that likely originated from a mixture of pyrogenic and petrogenic sources. Closed-drainage lakes in the boreal upland region had the lowest concentrations of PACs likely sourced from pyrogenic wood combustion with traces of petrogenic PACs, possibly from atmospheric deposition of dust. Petroleum biomarkers of terpanes, hopanes, and steranes were successfully used to identify the long-range fluvial, and possibly atmospheric, transport of bituminous compounds more than one hundred kilometers from their potential source. This validates the future use of these biomarkers in environmental forensics. Microbial communities in all three regions under study were highly diverse, and their composition was significantly different in both sediment and water. Targeted gene analysis identified a total of 3885 genes involved in the degradation of n-alkanes and PACs in sediment and water. The results show that organic carbon, nitrogen, and sulfur content, as well as PAC and short-chain alkane concentrations were important chemical predictors of change in degradation gene composition. Furthermore, genes for anaerobic degradation of PHCs were identified in syntrophic bacteria, methanogens, nitrate and sulfate reducers, demonstrating the potential for syntrophic hydrocarbon degradation in PAD lakes. Though this thesis confirms the genetic potential for hydrocarbon degradation in PAD and boreal upland lakes, further research is necessary to determine whether these microbial communities can actively degrade the PHCs present in these lakes.

Lee, Man Ho. / Thesis submitted in: October 2008. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 78-83). / Abstracts in English and Chinese. / Table of Contents --- p.ii / Acknowledgements --- p.iv / Abbreviations --- p.v / Abstract --- p.vi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Definition of Aromatic Bond Activation --- p.1 / Chapter 1.2 --- Application of Aromatic Carbon Fluorine Bond Activation --- p.1 / Chapter 1.3 --- Mechanistic Schemes Involved in Aromatic Bond Activation --- p.2 / Chapter 1.4 --- Difficulties in Aromatic Bond Activation --- p.7 / Chapter 1.5 --- Competitive Bond Activations --- p.20 / Chapter 1.6 --- Structural Features of Rhodium Porphyrins --- p.27 / Chapter 1.7 --- Objective of the Work --- p.28 / Chapter Chapter 2 --- Competitive C-F and C-H Activation of Fluorobenzenes by Rhodium(III) Porphyrins / Chapter 2.1 --- C-F Activation of Fluorobenzene by Rhodium(III) Porphyrins --- p.29 / Chapter 2.2 --- Preparation of Starting Materials --- p.29 / Chapter 2.3 --- Base Effect of CFA --- p.30 / Chapter 2.4 --- Solvent Effect of CFA --- p.32 / Chapter 2.5 --- Temperature Effect of CFA Reaction --- p.34 / Chapter 2.6 --- Activations of Fluorobenzene --- p.35 / Chapter 2.7 --- Electronic Effect of Carbon-Fluorine Bond Activations --- p.38 / Chapter 2.8 --- Preliminary Mechanistic Studies --- p.39 / Chapter 2.9 --- Proposed C-F Activation Mechanism --- p.44 / Chapter 2.10 --- Proposed C-H Activation Mechanism --- p.48 / Chapter 2.11 --- Summary --- p.51 / Chapter Chapter 3 --- Experimental Section --- p.56 / References --- p.78 / Table of Content of Appendix --- p.83 / Appendix I Crystal Data and Processing Parameters --- p.85 / Appendix II Spectra --- p.91

ABSTRACT COMPARISON OF SORPTION CAPACITIES OF HYDROCARBONS ON DIFFERENT SAMPLES OF MCM-41 AYDOGDU, Birsu M. Sc., Department of Chemical Engineering Supervisor: Prof. Dr. Hayrettin Y&Uuml / CEL Co-Supervisor: Prof. Dr. G&uuml / rkan KARAKAS January 2013, 69 pages MCM-41(Mobil Composition Matter-41) is one of the three members of M41S family and has a highly ordered hexagonal honeycomb like structure with a narrow pore size distribution in mesopore range, high surface area, high pore volume and high thermal stability. These features make MCM-41 proper to use for adsorption, catalysis, ion exchange and separation processes. . In this study sorption capacities of C8 aromatics (o-, m-, p-xylene and ethylbenzene at 30 &deg / C, 50 &deg / C and 65 &deg / C) on a MCM-41 sample synthesized in our laboratory were determined gravimetrically by using a commercial automated electro balance system and compared with results obtained in a previous and similar MSc thesis study with a sample of different origin and characteristics / specifically low BET surface area (492 m2/g). MCM-41 sample was synthesized by hydrothermal synthesis method with cetyltrimethylammoniumbromide (CTAMBr as surfactant) and tetraethyl ortosilicate (TEOS as silica source) in basic conditions. This MCM-41 sample was calcined at 540 oC for 8 h and characterized by XRD, nitrogen adsorption at 77 K, TGA, TEM, SEM and SEM-EDX. According to XRD data, main characteristic peak for synthesized MCM-41 was obtained at 2&theta / =2.28&deg / . Three small reflection peaks can be seen at 2&theta / values of 2.59, 4.27&deg / and 4.5&deg / . XRD pattern of the MCM-41, indicated that the desired structure of MCM-41 was successfully synthesized. Surface area, pore volume and average pore diameter were obtained from the nitrogen adsorption data at 77 K as 1154 m2/g, 1.306 cm3/g and 2.75 nm respectively. TGA analysis showed that the 540 oC is proper for the calcination. SEM -EDX analysis gave an oxygen atomic concentration 66.40% and silicon atomic concentration 33.60%. These results showed that the chemical composition of the synthesize material was in almost pure SiO2 form. The adsorbed amount for all isomers at the same pressure decreased as the temperature of the adsorption isotherms increases as expected for physical adsorption. Nitrogen adsorption of MCM-41 in this study showed type IV isotherm with H2 type hysteresis loop according the IUPAC classification. However, for o-,m-, and p-xylene an approximately linear increase in the adsorbed amount as a function of relative pressure was observed from the adsorption isotherms. Except for adsorption isotherms of m-xylene and p-xylene at 65 oC all isotherms of xylenes showed hysteresis loops. Hysteresis loops narrowed down with increasing temperature. p-xylene and m-xylene adsorption isotherms at 65 oC were reversible and did not show any hysteresis loop. Ethylbenzene adsorption isotherms at 30 oC, 50 &deg / C and 65 oC also showed a linear increase in the adsorption amount as a function of relative pressure like xylenes. At 50 &deg / C and 65 oC adsorption isotherms of ethylbenzene were reversible without a hysteresis loop. For all adsorbates volume of adsorbed amounts were calculated on the assumption that they exist as saturated liquids at the isotherm temperature and found to be significantly lower than pore volume obtained from nitrogen adsorption isotherm at 77K. Sorption capacities of these hydrocarbons on MCM-41 were also very low when compared to values found in a previous study which involved a MCM-41 sample of significantly lower surface area ( 492 m2/g ). This may be attributed to structure degradation which requires further investigation.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1969. / Includes bibliographical references (p. 106-109).

Thesis (Ph. D.)--Materials Science and Engineering, Georgia Institute of Technology, 2009. / Committee Chair: Rina Tannenbaum; Committee Co-Chair: Rosario A. Gerhardt; Committee Member: E. Kent Barefield; Committee Member: Karl I. Jacob; Committee Member: Preet Singh; Committee Member: R. Bruce King. Part of the SMARTech Electronic Thesis and Dissertation Collection.