The major objective of this research is a systematic experimental exploration of hydrophilic materials that can be applied as coating materials for conventional ultrafiltration (UF) membranes to improve their fouling resistance against organic components. This objective is achieved by developing new, fouling-reducing membrane coatings and applying these coatings to conventional UF membranes, which can provide unprecedented reduction in membrane fouling and marked improvements in membrane lifetime. Novel polymeric materials are synthesized via free-radical photopolymerization of mixtures containing poly(ethylene glycol) diacrylate (PEGDA), photoinitiator, and water. PEGDA chain length (n=10-45, where n is the average number of ethylene oxide units in the PEGDA molecule) and water content in the prepolymerization mixture (0-80 wt.%) were varied. Crosslinked PEGDA (XLPEGDA) exhibited high water permeability and good fouling resistance to oil/water mixtures. Water permeability increased strongly with increasing the water content in the prepolymerization mixture. Specifically, for XLPEGDA prepared with PEGDA (n=13), water permeability increased from 0.6 to 150 L um/(m2 h bar) as prepolymerization water content increased from 0 to 80 wt.%. Water permeability also increased with increasing PEGDA chain length. Moreover, water permeability exhibits a strong correlation with equilibrium water uptake. However, solute rejection, probed using poly(ethylene glycol)s of well defined molar mass, decreased with increasing prepolymerization water content and increasing PEGDA chain length. That is, there is a tradeoff between water permeability and separation properties: Materials with high water permeability typically exhibit low solute rejections, and vice versa. The fouling resistance of XLPEGDA materials was characterized via contact angle measurements and static protein adhesion experiments. From these results, XLPEGDA surfaces are more hydrophilic in samples prepared at higher prepolymerization water content or with longer PEGDA chains, and the more hydrophilic surfaces generally exhibit less BSA accumulation. These materials were applied to polysulfone (PSF) UF membranes to form coatings on the surface of the PSF membranes. Oil/water crossflow filtration experiments showed that the coated PSF membranes had water flux values 400% higher than that of an uncoated PSF membrane after 24 h of operation, and the coated membranes had higher organic rejection than the uncoated membranes. / text

The relaxation characteristics of rubbery poly(ethylene oxide) [PEO] networks have been investigated as a function of network composition and architecture via dynamic mechanical analysis and broadband dielectric spectroscopy. A series of model networks were prepared via UV photopolymerization using poly(ethylene glycol) diacrylate [PEGDA] as crosslinker: variations in crosslink density were achieved either by the introduction of water in the prepolymerization reaction mixture, or by the inclusion of mono-functional acrylate such as poly(ethylene glycol) methyl ether acrylate [PEGMEA] or poly(ethylene glycol) acrylate [PEGA]. Copolymerization with mono-functional acrylate led to the insertion of flexible branches along the network backbone, and the corresponding glass-rubber relaxation properties of the copolymers (i.e., Tg, relaxation breadth, fragility) were a sensitive function of network architecture and corresponding fractional free volume. Relatively subtle variations in network structure led to significant differences in relaxation characteristics, and a systematic series of studies was undertaken to examine the influence of branch length, branch end-group, and crosslinker flexibility on viscoelastic response. Dielectric spectroscopy was especially useful for the elucidation of localized, sub-glass relaxations in the polymer networks: the imposition of local constraint in the vicinity of the crosslink junctions led to the detection of a distinctive fast relaxation process in the networks that was similar to a comparable sub-glass relaxation observed in crystalline PEO and in the confined regions of PEO nanocomposites. Gas permeation studies on the model PEGDA networks confirmed their utility as highly-permeable, reverse-selective membrane materials, and strategic control of the network architecture could be used to optimize gas separation performance. Dynamic mechanical and dielectric measurements have also been performed on a semicrystalline polyester, poly(trimethylene terephthalate) [PTT], in order to assess the influence of processing history on the resultant morphology and corresponding viscoelastic relaxation characteristics. Studies on both quenched and annealed PTT revealed the presence of a substantial fraction of rigid amorphous phase (RAP) material in the crystalline samples: dielectric measurements showed a strong increase in relaxation intensity above the glass transition indicating a progressive mobilization of the rigid amorphous phase with increasing temperature prior to crystalline melting.

Twelve lactating Holstein dairy cows were randomly divided into four groups of three animals each. Group A served as the control, group B was dosed at 0.05ppm/day of DDE (2,2-bis(P-chlorophenyl-1, 1-dichloroethylene), cows in group C were dosed at 0.1ppm DDE/day, while group D cows were dosed at 1.0ppm DDE/day. DDE was administered in a residue free peanut oil solution for 32-consecutive days. Milk samples were taken daily during the 32 day dosing period and for an additional 32 days after the dosing period. Quantitative analysis of DDE residue in milk fat was determined by using a Tracor MT-220 gas chromatograph with a Tritium electron capture detector. The average increase in DDE milk fat concentration during the dosing period was directly related to intake levels. DDE was the only organochlorine compound detected in the milk fat. The general slope and shape of the curves of milk fat DDE levels were similar for all treatments. The levels of DDE increased rapidly after the onset of dosing. After 15 days of dosing and throughout the remaining 17 days of the dosing period, milk fat DDE increased at a relatively slow rate. The level of milk fat DDE declined rapidly as soon as the DDE residue source was withdrawn. At the end of the 32-day post-dosing period, one cow from each group was slaughtered and samples were taken from muscles, brain, lung, lymph, spleen, kidney fat, heart, gonad, placenta, udder, and kidney for DDE analysis. Considerable DDE was found in the muscle, lymph, kidney fat, and udder tissues.

Catalytic ethylene oligomerization is a well understood industrially viable process. The large majority of scientific literature and patents concerning this process has been developed with the use of chromium catalysts. Commercial systems producing selective tri/tetramerization, non-selective oligomerization and polymerization are all based on this metal with the exception of a few systems based on other transition metals (Zr, Ti, Ni etc.). This versatility raises interesting questions about chromium’s unique behaviour. Essentially, selective or non-selective oligomerization and polymerization processes could be regarded as belonging to the same category of C-C bond forming reactions, though different mechanisms are involved. The first part of this thesis explores a variety of chromium complexes for ethylene oligomerization purposes. In order to gather further information about the unique behaviour of chromium, we have explored a variety of nitrogen and phosphorus containing ligands. We started with a simple bi-dentate anionic amidophosphine (NP) ligand and assessed the role of the ligand’s negative charge and number of donor atoms in determining the type of catalytic behaviour in relation to the metal oxidation state. This ligand proved capable of generating a series of chromium dimeric, tetrameric or polymeric and even heterobimetallic chromium-aluminate complexes in different valence states. This allowed us to isolate a “single component” self activating Cr(II) complex as well as a rare example of mixed valence Cr(I)/Cr(II) species. Additionally, each of these species acted as switchable catalyst depending on the type of co-catalyst

Cell adhesion is the first step of cell response to materials and the extracellular matrix (ECM), and is essential to all cell behaviours such as cell proliferation, differentiation, migration and apoptosis for anchor-dependent cells. Therefore, studies of cell attachment have important implications to control and study cell behaviours. During many developed techniques for cell attachment, the manipulation of surface chemistry is a very important method to control initial cell attachment. To control cell adhesion on a two-dimensional surface is a simple model to study cell behaviours, and is a fundamental topic for cell biology, tissue engineering, and the development of biosensors. From the engineering point of view, the preparation of a material with controllable surface chemistry can help studies of cell behaviours and help scientists understand how surface features and chemistry influence cell behaviours. During the fabrication, the challenge is to create a surface with heterogeneous surface properties in the micro scale and subsequently to guide cell initial adhesion. In order to control cell adhesion in a spatial and temporal manner, a photochemical method to control surface chemistry was employed to control the surface property for cell adhesion in this project. Two photocleavable derivatives of the nitrobenzyl group were tried on two types of surfaces: a model self-assembled monolayer (SAM) with alkanethiol-gold surface and biodegradable chitosan. Reactive functional groups on two different surfaces can be inactivated by covalent binding with these photocleavable molecules, and light can be further introduced into the system as a stimulus to recover their reactivity. By simply applying a photomask with diffe

Heartwood is the dead, inner layers of wood in the tree which no longer transport water. It is usually dark in colour and has increased decay-resistance compared to the sapwood. Heartwood forms in the transition zone when the ray cells die and deposit chemical extractives in the surrounding xylem. These chemicals convey natural durability which is of value to the forest and timber industry. Despite its value the formation of heartwood is poorly understood. The objective of this PhD is to improve our understanding of heartwood formation in Sitka spruce and Scots pine, the most widely planted species in Britain. Separating heartwood and sapwood at the sawmill can increase timber value due to differences in wood properties. The amount of heartwood varies both with height within, and between trees. Empirical models were developed to describe heartwood and sapwood distribution by diameter, area and ring number 1) within any wood disc 2) with height in the standing tree using taper functions, and 3) its variation between trees. Models will be incorporated into wood quality models to optimise heartwood utilisation. According to pipe theory a certain area of sapwood sustains a volume of canopy, with redundant sapwood converted to heartwood. Sap flux was examined across the sapwood and transition zone in Sitka spruce to understand water transport in relation to heartwood formation and identify seasonal change in transport in the transition zone. Results suggest that the transition zone ceases water transport around dormancy and the amount of heartwood formed may be driven by new wood formation, maintaining sapwood depth. Heartwood formation is a seasonal process, however this has not been confirmed in Sitka spruce or Scots pine, or under UK climatic conditions. Seasonal variation in carbon dioxide and ethylene production by the transition zone were measured to identify the time of heartwood formation, which was late summer through dormancy, consistent with published literature. The role of ethylene in heartwood formation is confirmed. Heartwood formation is an active developmental process, a form of programmed cell death, and as such must be carefully regulated temporally and spatially. Regulation by phytohormones has been proposed but not confirmed. Screening for a broad range of phytohormones during the proposed season of heartwood formation identified an increase in abscisic acid and a decrease in auxin concentration in the transition zone. Abscisic acid, auxin and ethylene also regulate xylogenesis, therefore the same signals that initiate cambial dormancy may also provide the temporal regulation of heartwood formation. The results of this PhD will optimise the use of heartwood in Sitka spruce and Scots pine in the UK and contribute towards selective tree breeding for increased heartwood volume worldwide.

Mitogen-activated protein kinases are part of an evolutionarily conserved protein phosphorylation cascade which serves essential regulatory functions in eukaryotic organisms. Although the role of MAPKs in the regulation of a plant’s response to environmental stress and plant defense has been well established, very little is known about their role in the regulation of plant developmental processes. In order to examine the role of MAPKs in plant growth and development, a strong mammalian MAPK phosphatase (MKP-1), which is known to inactivate MAPKs in plants, was introduced into tobacco plants. In tobacco plants, MKP-1 overexpression altered plant responses to the phytohormones, ethylene and cytokinin. Tobacco plants expressing MKP-1 flowered earlier and senesced later than wild-type. Additionally, these plants exhibited similar floral morphology as flowers from ethylene-insensitive tobacco plants. These observed phenotypes seem to depend on the protein phosphatase activity, as transgenic lines expressing an inactive form of MKP-1 (MKPCS) did not show the same phenotypes. Furthermore, both tobacco and Arabidopsis MKP-1 transgenic plants exhibited increased shoot regeneration when compared to wild-type plants, suggesting increased cytokinin sensitivity. In an attempt to elucidate the mechanism by which MKP-1 affects plant growth and development, expression of selected genes were analyzed using RT-PCR. MKP-1 transformed tobacco plants exhibited downregulated expression of an ethylene biosynthesis gene (NtACO) and upregulated expression of a pathogenesis-related gene (PR-1b), similar to gene expression studies previously conducted in plants with increased production of cytokinin. The same MKP-1 transgenic plants also exhibited upregulated expression of the flowering time gene, FT. Results from this study indicate that constitutive expression of MKP-1 may interfere with ethylene-related MAPK pathways, which normally serves to restrict plant growth during times of environmental stress. The reduced responses to ethylene resulted in elevated sensitivity to cytokinin, promoting an enhanced shoot regeneration phenotype.

Ph.D. / This work presents a detailed study of the synthesis of carbon nanotubes and nanospheres by nebulised spray pyrolysis. This method has been used by other workers mainly for preparation of sub-micron particles and the deposition of thin films on various substrates. The effect of various synthesis parameters including the temperature, choice of the carbon source and the metal precursor as well as the carrier gas flow rate on the selectivity of the reaction and the properties of the carbon nanotubes produced was investigated. A major part of this work was devoted to a study of the effects of the addition of small quantities of oxygencontaining compounds (alcohols, esters and aldehydes) to the reaction mixture. The products were analysed using various methods including TEM, SEM, Laser- Raman spectroscopy and HRTEM. Furthermore, the possible use of carbon nanotubes and carbon nanospheres as supports for palladium in the hydrogenation of ethylene was investigated. Nebulised spray pyrolysis proved to be a suitable technique for the synthesis of well graphitized carbon nanotubes and carbon nanospheres with uniform diameters and it was demonstrated that good control of the carbon nanotube properties could be achieved by controlling the synthesis parameters. Better graphitization of the carbon nanotubes was observed at higher temperatures. Ferrocene, iron pentacarbonyl, nickelocene and cobaltocene were successfully used in carbon nanotube synthesis with the last two producing carbon nanotubes with diameters close to those on single-walled carbon nanotubes. Toluene (with and without acetylene as a supplementary carbon source), benzene, mesitylene, xylene and nhexane were successfully used to produce carbon nanotubes with a high degree of alignment while no success was achieved with ethanol. The poor yields obtained with ethanol appear to be a consequence of chemical changes in the ethanol induced by exposure to ultrasound irradiation. On the other hand, low concentrations of methyl acetate and ethyl acetate appear to enhance the production of carbon nanotubes. It was demonstrated that carbon nanotubes and nanospheres are suitable for use as supports for palladium in the hydrogenation of ethylene. Pd particles of uniform size were obtained and the conversion rates were slightly higher when the carbon nanotubes were pre-treated with a mixture of sulphuric acid and nitric acid.

β-sitosterol/poly(ethylene glycol)-block-poly(lactic acid) (PLA-b-PEG) complexes were prepared by solution blending in purified water and ethanol. The mixture of water and ethanol is a suitable solvent system for the two components. The complex was studied by using Nuclear Magnetic Resonance (NMR) spectroscopy and Differential Scanning Calorimetry (DSC). β-sitosterol is a drug that may reduce the swelling of benign prostatic hyperplasia (BPH) and diminishing inflammation. However, it is hydrophobic and difficult to deliver in aqueous solution. Since PLA-b-PEG has amphiphilic properties, the complex described here may enhance delivery of this drug for treatment of BPH. Proton NMR (1HNMR) of the complexes shows that the methylene (CH2) protons of the PEG, the (-O-CH-) of PLA, and (CH3) of PLA are slightly shifted because of its non-covalent interaction with β-sitosterol. The complex formation was supported by 2-D NMR (NOESY) spectroscopy. NOESY spectra show cross peaks, indicating the interaction between the two components. DSC of the complexes shows thermal characteristics that are different from the individual components. In particular, the PEG in the complex shows a lower melting point and decreased crystallinity compared to the pure PEG. The melting point is lowered from 57°C to 55.3 °C for the PEG-b-PLA/β-sitosterol (5%) complex. Under the same condition, the melting point of PLA dropped from 170 °C to 130 °C. Atomic force microscopy shows changes in the surface morphology of the copolymer from crystalline to amorphous when incorporated with the drug. NMR, DSC, AFM, and MTT assay studies suggest the formation of a relatively stable β-sitosterol/poly(lactic acid)-block-poly(ethylene glycol) complex. The cell proliferation assay (MTT assay) suggests significant inhibition of the stimulation of growth of prostate cancer cells upon addition the complex.

Ce travail porte sur l’étude de revêtements polysilazane (PSZ) élaborés dans le but d’inhiber l’adhésion des bactéries marines. Deux stratégies ont été étudiées : le greffage de chaînes poly(oxyde d’éthylène) (POE) (350, 750 ou 2000 g/mol) sur les chaînes PSZ par réactions d’hydrosilylation d’une part, et l’incorporation de composés du cuivre dans un film céramique issu de la pyrolyse d’un précurseur PSZ, d’autre part. Les conditions optimales de synthèse des PSZ greffés POE ont été définies afin de limiter notamment la réaction d’isomérisation de l’allyl-POE. La réticulation des PSZ greffés POE est alors effectuée par voie humide à température ambiante et procède par hydrolyse-condensation des fonctions alcoxysilane, SiH et SiN du précurseur PSZ. La prédominance des Si de type T3 (RSi(OSi)3) a été mise évidence par spectrométrie RMN du 29Si à l’état solide. La cristallisation des chaînes courtes de POE (350 g/mol) est totalement inhibée alors que l’aptitude des chaînes longues POE (750 et 2000 g/mol) à cristalliser est préservée. Le caractère hydrophile-hydrophobe et la capacité des films à inhiber l’adhésion bactérienne a été étudiée sur des revêtements à densités de greffons et à longueur de chaînes POE différentes. Les PSZs greffés POE 350g/mol avec un taux de greffage maximal conduisent à l’activité bactérienne la plus élevée de l’ensemble des revêtements étudiés.Les films céramiques incorporant du cuivre ont été préparés par pyrolyse d’un oligovinylsilazane en présence d’acétylacétonate de cuivre II sous atmosphère oxydante ou non oxydante. L’identification des phases des composés du cuivre a été effectuée par analyse DRX. L’environnement réducteur généré lors de la pyrolyse du PSZ favorise la formation d’espèces de cuivre (0) et cuivre (I) au détriment de cuivre (II). Les études bactériennes suggèrent que les cristaux CuO et Cu2O sont plus efficaces que le cuivre métal pour lutter contre l’adhésion bactérienne. / The objective of this work was to develop new polysilazane (PSZ) coatings which can inhibit the adhesion of marine bacteria. Two chemical strategies have been investigated: the grafting of poly(ethylene oxide) (POE) (350, 750, 2000 g/mol) on PSZ chains by hydrosilylation and the association of copper compounds with a pyrolized vinylsilazane matrix. The optimum conditions for grafting POE were defined to have a high selectivity toward olefin hydrosilylation. Crosslinking of POE-graft-PSZ was performed by moisture curing at room temperature. The main reactions occuring during curing are hydrolysis-condensation reactions of alkoxysilane, Si-H and Si-N functionalities. 29Si NMR in the solid state revealed the formation of a large amount of T3 Si [(RSi(OSi)3)]. The crystallization of short POE chains (350 g/mol) was found to be totally inhibited whereas long POE grafts (750 and 2000 g/mol) are still able to crystallize. The hydrophilic-hydrophobic properties and the antibactericidal activity of films with different graft density and POE chain length were studied. The POE (350 g/mol)-graft-PSZ with the greatest graft density were found to have the best antibactericidal activity. The incorporation of copper compounds in a pyrolized oligovinylsilazane was performed using copper acetylacetonate as a copper source. Pyrolysis was conducted in air or in Argon atmosphere. Identification of the copper phases was performed by XRD analysis. The reductive environment during thermal degradation of PSZ was found to favour the formation of copper (0) and copper (I) species relative to copper (II) species. The study of bacterial adhesion suggested that CuO and Cu2O crystals were more effective against bacterial adhesion than copper metal.