Kam-Hung Low. / Thesis submitted in: December 2003. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of contents --- p.i. / Acknowledgements --- p.vi. / Abbreviations --- p.vii. / Abstract --- p.viii. / Abstract (Chinese) --- p.x. / Chapter Part I --- Synthesis and Characterization of Fluorene-Based Statistical Copolymers / Chapter Chapter I --- Introduction --- p.1 / Chapter 1. --- Background --- p.1 / Chapter 2. --- rinciple of Electroluminescence --- p.2 / Chapter 3. --- Electroluminescence from conjugatedolymers --- p.4 / Chapter 4. --- Device configurations --- p.6 / Chapter 4.1 --- Electrodes selection --- p.8 / Chapter 4.2 --- Charge injection and transporting layers --- p.9 / Chapter 5. --- Device characterizations --- p.12 / Chapter 6. --- Blue-light emittingolymers --- p.14 / Chapter 6.1 --- Fluorene homopolymers --- p.16 / Chapter 6.2 --- Fluorene copolymers --- p.19 / Chapter 6.3 --- Aggregation studies ofolyfluorenes --- p.22 / Chapter 7. --- Synthetic measures toward conjugatedolymers --- p.28 / Chapter Chapter II --- Results and discussion --- p.30 / Chapter 1. --- Synthesis --- p.30 / Chapter 1.1 --- olyfluorene synthesis --- p.30 / Chapter 1.2 --- Fluorene-based statistical copolymers --- p.34 / Chapter 1.2.1 --- Fluorene-biphenyl copolymers --- p.34 / Chapter 1.2.2 --- Fluorene-［2.2]paracyclophane copolymers --- p.37 / Chapter 2. --- Structural characterizations --- p.40 / Chapter 2.1 --- NMR spectroscopic data analyses --- p.40 / Chapter 2.2 --- Gelermeation chromatographic analyses --- p.44 / Chapter 2.3 --- Thermal analyses --- p.47 / Chapter 3. --- Opticalroperties characterizations --- p.50 / Chapter 3.1 --- UV-visible absorptions --- p.50 / Chapter 3.2 --- hotoluminescences --- p.53 / Chapter 3.2.1 --- hotoluminescences in solutions --- p.53 / Chapter 3.2.2 --- hotoluminescences in solid thin films --- p.59 / Chapter 4. --- Device fabrications --- p.61 / Chapter 5. --- I-V characterizations --- p.64 / Chapter 6. --- Electroluminescences --- p.66 / Chapter Chapter III --- Conclusion --- p.68 / Chapter Chapter IV --- Experimental --- p.70 / Reference --- p.77 / Appendix NMR spectra --- p.82 / Chapter Part II --- Regio-Specific Synthesis of Functionalized [2.2]PARACYCLOPHANES / Chapter Chapter I --- Introduction --- p.102 / Chapter 1. --- Background --- p.102 / Chapter 2. --- Synthetic Route to [2.2]Paracyclophane --- p.103 / Chapter 2.1 --- Macrocyclization via Wurtz coupling --- p.103 / Chapter 2.2 --- Extrusion of small gaseous molecules form macrocyclicrecursors --- p.106 / Chapter 2.3 --- Dimerization of/p-xylylene --- p.108 / Chapter 2.4 --- Miscellaneous methods --- p.110 / Chapter 3. --- Synthetic Routes to Substituted [2.2]Paracyclophanes --- p.111 / Chapter 3.1. --- Functionalization of [2.2]pracyclophane --- p.114 / Chapter 3.1.1 --- reparation of mono-substituted [2.2]paracyclophanes --- p.114 / Chapter 3.1.2 --- reparation of di-substituted [2.2]paracyclophanes --- p.117 / Chapter 3.1.3 --- reparation of tri-substituted [2.2]paracyclophanes --- p.120 / Chapter 3.1.4 --- reparation of tetra-substituted [2.2]paracyclophanes --- p.120 / Chapter 3.1.5 --- Functional group conversions in [2.2]paracyclophanes --- p.121 / Chapter Chapter II --- Syntheticlans --- p.124 / Chapter Chapter III --- Results and Discussion --- p.129 / Chapter 1. --- Effect ofolymerization inhibitor --- p.130 / Chapter 2. --- "Synthesis of 4,12-disbstituted [2.2]paracyclophanes" --- p.132 / Chapter 2.1 --- "Synthesis of 4,12-dibromo[2.2]paracyclophane" --- p.132 / Chapter 2.2 --- "Synthesis of 4,12-dichloro[2.2]paracyclophane" --- p.134 / Chapter 2.3 --- "Synthesis of 4,12-dimethyl[2.2]paracyclophane" --- p.135 / Chapter 3. --- "Synthesis of 4,7,13,16-tetrasubstituted [2.2]paracyclophanes" --- p.137 / Chapter 3.1 --- "Synthesis of 4,7,13,16-tetrabromo[2.2]paracyclophane" --- p.137 / Chapter 3.2 --- "Synthesis of 4,7,13,16-tetrabromo[2.2]paracyclophane" --- p.138 / Chapter 4. --- "Synthesis of 4,8,12,16-tetrasubstituted [2.2]paracyclophane" --- p.139 / Chapter 4.1 --- "Synthesis of 4,8,12,16-tetrabromo[2.2]paracyclophane" --- p.139 / Chapter 5. --- Summary --- p.141 / Chapter Chapter IV --- Conclusion --- p.145 / Chapter Chapter V --- Experimental --- p.146 / References --- p.160 / Appendix I X-ray crystallographic data --- p.162 / Appendix II NMR spectra --- p.183

The synthesis of amine end-functionalised polymers by controlled free radical techniques has been investigated with a focus on methods that provide primary amino end-functionalised polystyrene. The aim of these investigations was to provide precursors to block and graft polyolefins and polyesters by interchain coupling reactions. The approaches investigated involved developing strategies for the synthesis of phthalimido-functional polymers which can be quantitatively deprotected to yield the desired amino-functional polymers. Initially synthesis by atom transfer radical polymerisation (ATRP) was explored. A number of approaches based on ??-functionalisation (end-group substitution) and ??-functionalisation (functional initiator) were examined. A novel ATRP initiator, N-bromomethylphthalimide, provided the most promising results but still had limited applicability because of its low solubility in polymerisation media. The problems encountered with the ATRP approaches prompted an exploration of techniques based on reversible addition fragmentation chain transfer (RAFT) approach. Novel phthalimidomethyl RAFT agents (trithiocabonates, xanthates) were synthesized. The activity and scope of the new RAFT agents was investigated in polymerisations of styrene, n-butyl acrylate, Nisopropylacrylamide, N-vinylpyrrolidone (trithiocarbonate) and vinyl acetate (xanthate). The syntheses of ??-phthalimidomethylpolystyrene were successfully scaled up and hydrazinolysis afforded a range of ??- aminomethylpolystyrenes of low polydispersity and controlled molecular weight. The syntheses of primary amino-functional polymers using the pthalimidofunctional RAFT agents necessitated the development of a convenient method for conversion of trithiocarbonate groups to inert chain ends. Thermolysis proved a most simple and efficient method of achieving this for both polystyrene and poly(n-butyl acrylate). Thermolysis also provided a means of further characterising the mechanism of the RAFT process. A simple and efficient method for amino end-group analysis was developed that involved in-situ derivatisation with trichloroacetyl isocyanate followed by 1H NMR analysis. The method was shown to be a suitable method for determining a wide range protic end-groups (NH2, OH, COOH) in synthetic polymers. Finally, metallocene polyolefin based coupling trials largely with controlled amino-functional polystyrene were conducted as an initial investigation into the production of high value added grafted polyolefins (and polyester). The grafting trials were carried out on a small scale with a view to directing future experiments.

Abstract not available

Natural-synthetic hydrid biomaterials have been isolated from the growth of Alcaligenes latus and Pseudomonas oleovorans in the presence of diethylene glycol (DEG). A. latus could cometabolise DEG with 10 g/L glucose, while DEG was consumed by P. oleovorans with 20 mM sodium octanoate or octanoic acid. The presence of DEG in bioprocessing systems for the production of short chain length (scl-) and medium chain length (mcl-) PHAs consequently lowered cell viability and PHA yield. Cell morphology was slightly changed, but the PHA inclusion bodies apparently were not. DEG affected the composition of the mclPHA which was confirmed to be polyhydroxyoctanoate (PHO) with a significant increase in the C8 component. Gas chromatography-mass spectrometry (GC-MS) was used to quantitatively monitor DEG in the system and revealed its cellular adsorption. Intracellularly, the DEG significantly decreased the molar weight of the mclPHA and sclPHA. P1PH NMR, 2-D COSY and HSQC spectra confirmed that the polymer samples consisted of PHA chains terminated by DEG. Similar to the cultivation of P. oleovorans with DEG, the presence of PEG200 and PEG400 also had an effect on cell growth, PHO yield and cell viability. Furthermore, a hybrid copolymer of PHO-PEG200 was synthesised. The synthesis of these natural-synthetic hybrid copolymers could lead the way for a wide variety of PHA-PEG copolymers with a range of bioactive properties. All thermal properties of PHB were higher than those of PHB-DEG. This may be due to a combination of lower PHB molecular weight and termination of the chains by DEG, i.e. ???DEGylation???. However, PHB-DEG was more elastomeric when compared to PHB, showing properties similar to its copolymer with 20 mol% 3-hydroxyvalerate. Contact angles revealed that the PHB-DEG film was slightly more hydrophilic than PHB. Despite the large difference in their respective proportions, the comparatively small DEG component exerted an influence on chain confirmation, such that solvent casting under humid conditions apparently induced self-assembly and formed a disordered microporous film. DEGylation of PHO also had noticeable effects on the physiochemical properties of the biopolymer. A major decrease in molecular weight, together with the termination of hydrophobic PHO chains with hydrophilic end-groups resulted in changes to its thermal properties when compared to PHO. In comparison to PHO, solvent cast films of PHO-DEG were apparently less flexible, but more hydrophilic.

Thesis (Ph. D.)--University of Chicago, Dept. of Chemistry, June 1999. / Includes bibliographical references. Also available on the Internet.

The objective of this research is to investigate synthetic and polypeptide block copolymers, the structures they form, their response to various stimuli in solution and their capabilities for use in biomimicry. The self-assembled structures of both polymers will be used as a basis for the templating of hydrogels materials, both in the interior and on the surface of the vesicles. The resulting particles will be designed to show the structural and mechanical properties of living cells. The synthetic block copolymers are a polyethylene glycol and polybutadiene (PEO-b-PBd) copolymer and the polypeptide block copolymers are Lysine and Glysine (K-b-G) copolymers. Investigation of the structures synthetic block copolymers will focus on whether the polymer can form vesicles, how small of a vesicle structure can be made, and the formation of internal polymer networks. Subsequent investigations will look at the needed steps for biomimicry, using the synthetic block copolymers as a starting point and transitioning to a polypeptide block copolymer. The Lysine-Glysine copolymers are a new system of materials that form fluid vesicle structures. Therefore, we must characterize its assembly behavior and investigate how it responds to solution conditions, before we investigate how to make a cellular mimic from it. The size and mechanical behavior of the K-G vesicles will be measured to compare and contrast with the synthetic systems. The goals for creating a biomimic include a hollow sphere structure with a fluid bilayer, a vesicle that has controllable mechanical properties, and a vesicle with controllable surface chemistry. Overall, these experiments were a success; we showed that we can effectively control the size of vesicles created, the material properties of the vesicles, as well as the surface chemistry of the vesicles. Investigations into a novel polypeptide block copolymer were conducted and the block copolymer showed the ability to create vesicles that are responsive to changing salt and pH concentrations.

Thesis (Ph. D.)--Virginia Polytechnic Institute and State University, 1991. / Vita. Abstract. Includes bibliographical references (leaves 275-290). Also available via the Internet.

Thesis (Ph. D.)--Lehigh University, 2003. / Includes bibliographical references and vita.

Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references (leaves 132-136). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--University of Texas at Austin, 2002. / Vita. Includes bibliographical references. Available also from UMI Company.