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No description available.

Ph. D.

Metal-organic frameworks (MOFs) are crystalline materials composed of metal clusters and organic ligands. MOFs that exhibit photoluminescence are promising materials for a broad range of applications. Due to their structural tunability and crystalline nature, luminescent MOFs also provide an excellent platform for studying structure–property relationships of materials. The photophysical properties of three anthracene-dicarboxylic acids – 1,4-anthracene dicarboxylic acid (1,4-ADCA), 2,6-anthracene dicarboxylic acid (2,6-ADCA) and 9,10-anthracene dicarboxylic acid (9,10-ADCA) – were studied in a series of polar aprotic solvents using steady-state absorption, steady-state emission spectroscopy and time-correlated single photon counting (TCSPC) emission lifetime spectroscopy. The addition of carboxylic acid functional groups on the anthracene ring alters photophysical properties to varying degrees depending on the location and protonation state. Density functional theory (DFT) calculations reveal that the lowest-energy ground-state structures of both 2,6-ADCA and 1,4-ADCA have dihedral angles between the carboxylic acids and aromatic planes of θ = 0°, while the same dihedral angle increases to θ = 56.6° for 9,10-ADCA. Time-dependent DFT calculations suggest that the carboxyl groups of 1,4-ADCA and 2,6-ADCA remain coplanar with the anthracene ring system in the excited state. In contrast, the calculations reveal significant changes between the ground and excited geometries for 9,10-ADCA and puckering of the anthracene moiety of is observed. The three anthracene dicarboxylic acids were then incorporated into zirconium-based MOFs. The MOF structures were characterized using powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). The steady-state absorption and emission spectra as well as the fluorescence lifetimes of the MOFs were compared to that of the corresponding ligand in solution. The MOFs comprising 9,10-ADCA and 2,6-ADCA formed highly crystalline octahedral shaped crystals and were found to be isostructural with the well-known UiO-66 and UiO-67 frameworks. However, incorporation of the 1,4-ADCA ligand resulted in large rod-shaped crystals. The absorption spectra of the MOFs are broadened and redshifted compared with that of the corresponding free ligands. The emission spectra of the MOFs constructed from 9,10-ADCA and 1,4-ADCA display emission bands that resemble that of the free ligand in acidic solutions, but are slightly broadened and redshifted in the MOF. Little difference is observed between that of 2,6-ADCA within the MOF and in acidic solution. The broadening and redshift observed in the absorption and emission is indicative of intermolecular interactions between anthracene units and/or with the Zr4+ clusters. The fluorescence lifetimes measured for the anthracene-based MOFs show a long component, comparable to the lifetime of the free ligand, along with shorter component. This may also suggest intermolecular interactions between chromophores in the MOFs. Altogether, derivatization of anthracene was shown to have specific effects on the photophysical properties of the parent anthracene molecule. These properties are further altered when the ligand is incorporated into a metal organic framework. Such systematic studies can provide a guide in designing luminescent MOFs with the excited-state properties desired for a given application. / Master of Science

The solubilities of benzene, naphthalene and anthracene were measured in five binary solvent systems. These systems consised of water and one of the following water miscible organic solvents: acetone, acetonitrile, methanol, ethanol, and isopropanol. The measurements were made at intervals of 0.1 volume fractions of the organic cosolvent. Solubility data were also collected for the above solutes in mixed cosolvents. solvent systems containing three In addition, the solubilities of and six five other aromatic solutes were measured in the binary solvent systems of methanol/water and acetone/water. The data was used to test the log-linear solubility model of Yalkowsky (1981). The model predicts a linear relationship between the solubility of a solute in a binary solvent system (S(m)) and the volume fraction of cosolvent present (f(c)) log S(m) = σf(c) + log S(w) Where S(w) is the solubility of the solute in water and σ is the proportionality constant and slope of the curve. The model is easily extended to multiple mixed solvents by combining the σ values from the binary solvent systems. log (S(m)/S(w)) = Σ₁ (σ₁£₁) A method was developed to estimate σ in a given binary solvent system from the octanol-water partition coefficient of the solute. Combining this method with the generalized solubility equation of Yalkowsky to estimate S(w), allows a priori estimates of solubility in mixed solvents. Maximum deviations in the binary solvent systems studied were related to maxima in excess density. In the alcoholic binary solvent systems the minima were related to minima in the heats of mixing of the two cosolvents. The herbicide atrazine deviated dramatically from the model. The system was examined for possible changes in the crystal structure of atrazine. It was found that some crystal modification occured in the presence of mixed solvents. The rate of the change appears to be dependant on the concentration of the cosolvent. A change or modification in the crystal violates one of the basic assumptions of the log-linear model. The assumption is that the crystal contributes equally to the solubility behavior irrespective of the solvent system. It was determined that atrazine undergoes a polymorphic transition in the systems studied. It is postulated that this polymorphism is responsible for the anomolous solubility behavior observed for atrazine.

This thesis describes the synthesis of a novel family of porphyrins fused to anthracenes, together with investigations into their optical and electrochemical properties, as well as exploring their potential for application in dye-sensitised solar cells. Chapter 1 gives an overview of the structure-property relationships of large planar pi- systems for organic electronic applications. Porphyrins are introduced as suitable building blocks for such systems, and approaches for extending the pi-conjugation of these macrocycles are presented. A literature review of porphyrins fused to aromatic units is presented in Chapter 2, with a focus on the influence of structure on the optoelectronic properties of such systems. The chapter concludes with a summary of my previous work on the synthesis of anthracene-fused porphyrins, and the aims of this project are stated. Chapter 3 describes the syntheses of fully and partially fused bis-anthracene porphyrin monomers and dimers. By varying peripheral substituents, it was possible to solve problems of aggregation encountered for these systems. Fusion of anthracene units to a porphyrin core was found to result in systems displaying strong absorption in the near-IR, small HOMO-LUMO gaps, and low oxidation potentials. Chapter 4 explores the synthesis, crystal structure and optoelectronic properties of a porphyrin fused to four anthracenes, revealing this system to exhibit the longest wavelength absorption of any porphyrin monomer. The synthesis of a liquid crystalline tetra-anthracene-fused porphyrin was proposed, and attempts to synthesise the necessary anthracene precursors were undertaken. Chapter 5 describes the molecular design and synthetic pathway to a mono-anthracene fused porphyrin, and its unfused analogue, for use in liquid electrolyte dye-sensitised solar cells. By varying the metal oxide layer or lithium ion concentration of the device, it was possible to achieve incident photon to current conversion efficiency (IPCE) responses at wavelengths beyond 1050 nm. Chapter 6 details the experimental synthetic procedures and characterisation data for all the compounds synthesised during this project.

Petroleum hydrocarbons are the most widespread contaminants in the environment. Interest in the biodegradation of polycyclic aromatic hydrocarbons and compounds (PAHs/PACs) is motivated by their ubiquitous distribution, their low bioavailability, high persistence in soils and their potentially deleterious effects to human health. Identifying the diversity of microorganisms that degrade PAHs/PACs can be utilised in the development of bioremediation techniques. Understanding the mechanisms of bacterial populations to adapt to the presence of pollutants and the extent that lateral transfer of key functional genes occurs, will allow the exploitation of microbial PAC/PAH-degradative capabilities and therefore enhance the successful application of bioremediation strategies. A key aim of this study was to isolate and identify PAC-degrading bacteria for potential use in future bioremediation programmes. A series of PAC enrichments were established under the same experimental conditions from a single sediment sample taken from a highly polluted estuarine site. Distinct microbial community shifts were directly attributable to enrichment with different PAC substrates. The findings of this study demonstrate that five divisions of the Proteobacteria and Actinobacteria can degrade PACs. By determining the precise identity of the PAC-degrading bacteria isolated, and by comparing these with previously published research, this study showed how bacteria with similar PAC degrading capabilities and 16S rRNA signatures are found in similarly polluted environments in geographically very distant locations e.g. China, Italy, Japan and Hawaii. Such a finding suggests that geographical barriers do not limit the distribution of key PAC-degrading bacteria. This is significant when considering the diversity and global distribution of microbes with PAC-degradative capabilities and the potential for utilising these microbial populations in future bioremediation strategies. In the laboratory, enrichment of bacteria able to utilise PAHs has commonly been performed in liquid media, with the PAH dissolved in a carrier solvent. This study found the presence of a carrier solvent significantly affects the resultant microbial population. Although the same sediment sample was used as the bacterial source in all enrichments, different bacterial strains were obtained depending upon the presence of the carrier solvent and the PAH. This is important when considering appropriate methodology for the isolation of PAH-degrading bacteria for future bioremediation programmes. Additionally, the species comprising the resultant population of the enrichment when a carrier solvent was present were similar to previously reported PAH-degrading species. Such a finding necessitates review of previously reported PAH-degrading bacterial species that have been isolated and identified from enrichments using a carrier solvent. Understanding how bacteria acclimatise to environmental pollutants is vital for exploiting these mechanisms within clear up strategies of contaminated sites. Two major lineages of the α subunit of PAH dioxygenases were identified: Actinobacteria and Proteobacteria. Comparison of the α subunit phylogeny with the 16S rRNA phylogeny implies that the PAH-dioxygenases evolved prior to the separation of these phyla or that lateral transfer occurred in the very distant past. No evidence for lateral transfer of the α subunit between the Actinobacteria and Proteobacteria was found in the phylogenetic analyses of this research. Multiple lateral transfer events were inferred between the species of the Actinobacteria and between the classes of the Proteobacteria. The clustering of the taxa within the α subunit phylogeny indicates that lateral transfer of the α subunit gene occurred after the separation of the classes of Proteobacteria and also after the speciation of the γ-Proteobacteria. These findings reveal how bacteria have acclimatised to PAH pollutants through multiple lateral transfer events of a key PAH-degradative gene. This knowledge of the transfer of genetic material will broaden our prospects of exploiting microbial populations.

Wong, Wing Yan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 76-79). / Abstracts in English and Chinese. / Contents --- p.i / Acknowledgments --- p.iii / Abstract --- p.iv / Abbreviations and Acronyms --- p.vii / Publications Originated from the Work of this Thesis --- p.ix / Chapter Part I: --- "Self-Assemblyy Stability Quantification, Controlled Molecular Switching, and Sensing Properties of an Anthracene-Containing Dynamic [2]Rotaxane" / Chapter Chapter 1 - --- Introduction / Chapter 1.1 --- Definition of Rotaxane --- p.2 / Chapter 1.2 --- Dynamic Covalent Chemistry in Rotaxane Synthesis --- p.5 / Chapter 1.3 --- Thermodynamic Template --- p.6 / Chapter 1.4 --- Molecular Sensing Properties in Rotaxane --- p.10 / Chapter 1.5 --- Examples --- p.13 / Chapter Chapter 2 - --- Anthracene-Containing Dynamic [2]Rotaxane / Chapter 2.1 --- Background --- p.17 / Chapter 2.2 --- Modification and Design of Dynamic [2]Rotaxane --- p.18 / Chapter 2.3 --- Self-Assembly of Rotaxane and Synthesis of Components --- p.19 / Chapter 2.4 --- Characterization / Chapter 2.4.1 --- 1H NMR Spectroscopy --- p.21 / Chapter 2.4.2 --- 13C NMR Spectroscopy --- p.23 / Chapter 2.4.3 --- Mass Spectrometry --- p.24 / Chapter 2.4.4 --- X-Ray Crystallography --- p.25 / Chapter 2.4.5 --- UV/Visible Absorption and Fluorescence Spectroscopies --- p.26 / Chapter 2.5 --- Effect of External Stimuli / Chapter 2.5.1 --- Addition of Water --- p.29 / Chapter 2.5.2 --- Addition of Acid --- p.33 / Chapter 2.5.3 --- Addition of Salts --- p.38 / Chapter 2.5.4 --- Addition of Amines --- p.40 / Chapter 2.6 --- Conclusions --- p.43 / Chapter Part II: --- Substituent Effect in Imine-Containing Molecular Tweezers / Chapter Chapter 3 - --- Molecular Tweezers / Chapter 3.1 --- Introduction --- p.46 / Chapter 3.2 --- Synthesis --- p.48 / Chapter 3.3 --- Characterization of Molecular Tweezers / Chapter 3.3.1 --- 1H NMR Spectroscopy --- p.49 / Chapter 3.3.2 --- Mass Spectrometry --- p.51 / Chapter 3.4 --- Characterization of Molecular Tweezers / Chapter 3.4.1 --- 1H NMR Spectroscopy --- p.51 / Chapter 3.4.2 --- X-Ray Crystallography --- p.59 / Chapter 3.4.3 --- Mass Spectrometry --- p.60 / Chapter 3.4.4 --- UV/Visible Absorption Spectroscopy --- p.61 / Chapter 3.5 --- Conclusions --- p.63 / Chapter Chapter 4 - --- Experimental Procedures / Chapter 4.1 --- General Information --- p.64 / Chapter 4.2 --- General Synthetic Procedures for Molecular Tweezers (34-40) --- p.65 / Chapter 4.3 --- Experimental Procedures --- p.65 / Chapter 4.4 --- Determination of Binding Constant K --- p.73 / References --- p.76 / Appendix / List of Spectra --- p.A-l / List of Crystal Data --- p.A-2

A dosimetria na radioterapia é realizada periodicamente como parte do controle de qualidade tanto dos equipamentos como dos tratamentos dos pacientes. O dosímetro convencional utilizado para essa finalidade é a câmara de ionização, no entanto, ela pode apresentar limitações quando se necessita de um dosímetro que possua resoluções espacial e temporal altas. Este trabalho tem como objetivo a caracterização do dosímetro de antraceno para radiação de fótons radioterápicos. O antraceno é um cristal orgânico cintilador com vantagens de ser praticamente equivalente à água e tecido mole em feixes radioterápicos e com possibilidade de possuir volume de detecção e tamanho pequenos, para utilizar em radiocirurgia e dosimetria in vivo. Neste trabalho, a caracterização do dosímetro de antraceno foi realizada obtendo-se o sinal de cintilação em função da sua granulosidade média, diâmetro da sua cápsula interna, dose absorvida, taxa de dose absorvida, energia do feixe de radiação e sua resolução espacial, sendo essa última realizada por três métodos diferentes relacionados e equivalentes: (função de espalhamento de borda (FEB), função de espalhamento linear (FEL) e função de transferência de modulação (MTF)). Os feixes de fótons utilizados para as irradiações do cintilador foram os de 60 Co (1,25 MeV), 137 Cs (0,661 MeV) e raios X (energias efetivas de 28,4; 46,5; 48,5; 94,0 e 106,0 keV). A instrumentação utilizada para a detecção do sinal do cintilador foi composta por uma fibra óptica, fotomultiplicadora, fonte de alta tensão, eletrômetro e multímetro. Dos dados obtidos, a contribuição da radiação Cerenkov, produzida na fibra óptica, foi subtraída, e as seguintes características dos sinais resultantes puderam ser inferidas: quanto maior a granulosidade maior o sinal de cintilação detectado; a dependência do sinal com o diâmetro interno da sua cápsula aumenta proporcionalmente com o cubo do diâmetro; dependência linear do sinal com a dose absorvida; independência com a taxa de dose absorvida; dependência linear para baixas energias e independência para altas energia do feixe. Além disso, das resoluções espaciais encontradas pelos três métodos diferentes, aquela calculada pelo método MTF é a que mais se aproximou das dimensões do detector (1,6 mm), tendo sido obtido um valor igual a 1,43+/-0,07 mm. Dos resultados foi possível caracterizar o dosímetro de antraceno de modo que sua utilização em trabalhos futuros seja mais adequada. / New radiotherapy techniques such as intensity-modulated radiation therapy and stereotactic radiosurgery have increased the need for dosimeters that can provide measurements in real time with high spatial resolution. Organic scintillation dosimeters are able to measure with accuracy small radiation fields and fields with high gradients, besides having advantages such as water and soft tissue equivalence and the possibility to be used in vivo. Anthracene is an organic scintillator crystal with the highest known scintillation efficiency among organic scintillation materials. The objective of this work is to characterize the antracene as a dosimeter under radiotherapic photons energies, analysing its signal against average granulosity, intern capsule diameter, absorbed dose, absorbed dose rate, photon energy and its spatial resolution; with the last one analysed under three methods (edge spread function, line spread function and modulation transfer function). The photons energies used were 1.25 MeV ( 60 Co), 0.661 MeV ( 137 Cs) and X-rays (effective energies of 28.4; 46.5; 48.5; 94.0 e 106.0 keV). The scintillation detection system consisted of an optical fiber with one end attached to the anthracene capsule and the other to a photomultiplier tube mantained by power supply followed by an electrometer. Once Cerenkov radiation occurs in the optical fiber, it was removed from the total scintillation signal trough the subtraction of the signal, taken irradiating the optical fiber without the anthracene attached to one of its extremity. From results obtained, one can infer that the dosimeter signal increases proportionally with average granulosity and intern capsule diameter. The signal is linearly dependent of absorbed dose, linearly dependent of low photons energies and independent for high photons energies, as well as independent of the absorbed dose rate. From the spatial resolution values obtained it was possible to infer that the one obtained through modulation transfer function, 1.43+/-0.07 mm, was the one that approximated the most to the actual dosimeter physical size (1.6 mm). From the characteristics obtained with this work, we think that future projects involving the anthracene will be carried out more properly.

Zhao, Wei. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Abstracts in English and Chinese. / Acknowledgements --- p.v / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2. --- H-bonded Acenes- An Approach to Self- assembled Organic Semiconductors --- p.16 / Chapter 2.1 --- Introduction --- p.16 / Chapter 2.2 --- Result and discussion --- p.17 / Chapter 2.3 --- Experiment --- p.23 / Chapter Chapter 3. --- Transistors from a Conjugated Macrocycle Molecule: Field and Photo Effects --- p.30 / Chapter 3.1 --- Introduction --- p.30 / Chapter 3.2 --- Result and discussion --- p.31 / Chapter 3.3 --- Conclusion --- p.37 / Chapter 3.4 --- Experiment --- p.37 / Chapter Chapter 4 --- Synthesis of Soluble and liquid crystalline Conjugated Macrocylces --- p.48 / Chapter 4.1 --- Introduction --- p.48 / Chapter 4.2 --- Result and Discussion --- p.49 / Chapter 4.3 --- Conclusion --- p.54 / Chapter 4.4 --- Experiment --- p.55 / Appendix --- p.65