The synthesis and application of novel profluorescent nitroxides as probes for polymer degradation

This PhD project has expanded the knowledge in the area of profluorescent nitroxides with regard to the synthesis and characterisations of novel profluorescent nitroxide probes as well as physical characterisation of the probe molecules in various polymer/physical environments. The synthesis of the first example of an azaphenalene-based fused aromatic nitroxide TMAO, [1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl, was described. This novel nitroxide possesses some of the structural rigidity of the isoindoline class of nitroxides, as well as some properties akin to TEMPO nitroxides. Additionally, the integral aromatic ring imparts fluorescence that is switched on by radical scavenging reactions of the nitroxide, which makes it a sensitive probe for polymer degradation. In addition to the parent TMAO, 5 other azaphenalene derivatives were successfully synthesised. This new class of nitroxide was expected to have interesting redox properties when the structure was investigated by high-level ab initio molecular orbitals theory. This was expected to have implications with biological relevance as the calculated redox potentials for the azaphenalene ring class would make them potent antioxidant compounds. The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrroline, piperidine, isoindoline and azaphenalene) were determined by cyclic voltammetry in acetonitrile. It was shown that potentials related to the one electron processes of the nitroxide were influenced by the type of ring system, ring substituents or groups surrounding the moiety. Favourable comparisons were found between theoretical and experimental potentials for pyrroline, piperidine and isoindoline ring classes. Substitution of these ring classes, were correctly calculated to have a small yet predictable effect on the potentials. The redox potentials of the azaphenalene ring class were underestimated by the calculations in all cases by at least a factor of two. This is believed to be due to another process influencing the redox potentials of the azaphenalene ring class which is not taken into account by the theoretical model. It was also possible to demonstrate the use of both azaphenalene and isoindoline nitroxides as additives for monitoring radical mediated damage that occurs in polypropylene as well as in more commercially relevant polyester resins. Polymer sample doped with nitroxide were exposed to both thermo-and photo-oxidative conditions with all nitroxides showing a protective effect. It was found that isoindoline nitroxides were able to indicate radical formation in polypropylene aged at elevated temperatures via fluorescence build-up. The azaphenalene nitroxide TMAO showed no such build-up of fluorescence. This was believed to be due to the more labile bond between the nitroxide and macromolecule and the protection may occur through a classical Denisov cycle, as is expected for commercially available HAS units. Finally, A new profluorescent dinitroxide, BTMIOA (9,10-bis(1,1,3,3- tetramethylisoindolin-2-yloxyl-5-yl)anthracene), was synthesised and shown to be a powerful probe for detecting changes during the initial stages of thermo-oxidative degradation of polypropylene. This probe, which contains a 9,10-diphenylanthracene core linked to two nitroxides, possesses strongly suppressed fluorescence due to quenching by the two nitroxide groups. This molecule also showed the greatest protective effect on thermo-oxidativly aged polypropylene. Most importantly, BTMIOA was found to be a valuable tool for imaging and mapping free-radical generation in polypropylene using fluorescence microscopy.

Attention and memory bias for body image and health related information using an Emotional Stroop task in a non-clinical sample

It has been proposed that body image disturbance is a form of cognitive bias wherein schemas for self-relevant information guide the selective processing of appearancerelated information in the environment. This threatening information receives disproportionately more attention and memory, as measured by an Emotional Stroop and incidental recall task. The aim of this thesis was to expand the literature on cognitive processing biases in non-clinical males and females by incorporating a number of significant methodological refinements. To achieve this aim, three phases of research were conducted. The initial two phases of research provided preliminary data to inform the development of the main study. Phase One was a qualitative exploration of body image concerns amongst males and females recruited through the general community and from a university. Seventeen participants (eight male; nine female) provided information on their body image and what factors they saw as positively and negatively impacting on their self evaluations. The importance of self esteem, mood, health and fitness, and recognition of the social ideal were identified as key themes. These themes were incorporated as psycho-social measures and Stroop word stimuli in subsequent phases of the research. Phase Two involved the selection and testing of stimuli to be used in the Emotional Stroop task. Six experimental categories of words were developed that reflected a broad range of health and body image concerns for males and females. These categories were high and low calorie food words, positive and negative appearance words, negative emotion words, and physical activity words. Phase Three addressed the central aim of the project by examining cognitive biases for body image information in empirically defined sub-groups. A National sample of males (N = 55) and females (N = 144), recruited from the general community and universities, completed an Emotional Stroop task, incidental memory test, and a collection of psycho-social questionnaires. Sub-groups of body image disturbance were sought using a cluster analysis, which identified three sub-groups in males (Normal, Dissatisfied, and Athletic) and four sub-groups in females (Normal, Health Conscious, Dissatisfied, and Symptomatic). No differences were noted between the groups in selective attention, although time taken to colour name the words was associated with some of the psycho-social variables. Memory biases found across the whole sample for negative emotion, low calorie food, and negative appearance words were interpreted as reflecting the current focus on health and stigma against being unattractive. Collectively these results have expanded our understanding of processing biases in the general community by demonstrating that the processing biases are found within non-clinical samples and that not all processing biases are associated with negative functionality

Synthesis and Raman spectroscopic study of Mg/Al,Fe hydrotalcites with variable cationic ratios

Hydrotalcites of formula Mg6 (Fe,Al)2(OH)16(CO3).4H2O formed by intercalation with the carbonate anion as a function of divalent/trivalent cationic ratio have been successfully synthesised. The XRD patterns show variation in the d-spacing attributed to the size of the cation. Raman and infrared bands in the OH stretching region are assigned to (a) brucite layer OH stretching vibrations (b) water stretching bands and (c) water strongly hydrogen bonded to the carbonate anion. Multiple (CO3)2- symmetric stretching bands suggest that different types of (CO3)2- exist in the hydrotalcite interlayer. Increasing the cation ratio (Mg/Al,Fe) resulted in an increase in the combined intensity of the 2 Raman bands at around 3600 cm-1, attributed to Mg-OH stretching modes, and a shift of the overall band profile to higher wavenumbers. These observations are believed to be a result of the increase in magnesium in the structure. Raman spectroscopy shows a reduction in the symmetry of the carbonate, leading to the conclusion that the anions are bonded to the brucite-like hydroxyl surface and to the water in the interlayer. Water bending modes are identified in the infrared spectra at positions greater than 1630 cm-1, indicating the water is strongly hydrogen bonded to both the interlayer anions and the brucite-like surface.

Generation of a 3D proximal femur shape from a single projection 2D radiographic image.

Summary Generalized Procrustes analysis and thin plate splines were employed to create an average 3D shape template of the proximal femur that was warped to the size and shape of a single 2D radiographic image of a subject. Mean absolute depth errors are comparable with previous approaches utilising multiple 2D input projections. Introduction Several approaches have been adopted to derive volumetric density (g cm-3) from a conventional 2D representation of areal bone mineral density (BMD, g cm-2). Such approaches have generally aimed at deriving an average depth across the areal projection rather than creating a formal 3D shape of the bone. Methods Generalized Procrustes analysis and thin plate splines were employed to create an average 3D shape template of the proximal femur that was subsequently warped to suit the size and shape of a single 2D radiographic image of a subject. CT scans of excised human femora, 18 and 24 scanned at pixel resolutions of 1.08 mm and 0.674 mm, respectively, were equally split into training (created 3D shape template) and test cohorts. Results The mean absolute depth errors of 3.4 mm and 1.73 mm, respectively, for the two CT pixel sizes are comparable with previous approaches based upon multiple 2D input projections. Conclusions This technique has the potential to derive volumetric density from BMD and to facilitate 3D finite element analysis for prediction of the mechanical integrity of the proximal femur. It may further be applied to other anatomical bone sites such as the distal radius and lumbar spine.

Synthesis of a heparan sulfate mimetic disaccharide with a conformationally locked residue from a common intermediate

A simple mimetic of a heparan sulfate disaccharide sequence that binds to the growth factors FGF-1 and FGF-2 was synthesized by coupling a 2-azido-2-deoxy-D-glucosyl trichloroacetimidate donor with a 1,6-anhydro-2-azido-2-deoxy--D-glucose acceptor. Both the donor and acceptor were obtained from a common intermediate readily obtained from D-glucal. Molecular docking calculations showed that the predicted locations of the disaccharide sulfo groups in the binding site of FGF-1 and FGF-2 are similar to the positions observed for co-crystallized heparin-derived oligosaccharides obtained from published crystal structures.

Mid-level concept learning with visual contextual ontologies and probabilistic inference for image annotation

To date, automatic recognition of semantic information such as salient objects and mid-level concepts from images is a challenging task. Since real-world objects tend to exist in a context within their environment, the computer vision researchers have increasingly incorporated contextual information for improving object recognition. In this paper, we present a method to build a visual contextual ontology from salient objects descriptions for image annotation. The ontologies include not only partOf/kindOf relations, but also spatial and co-occurrence relations. A two-step image annotation algorithm is also proposed based on ontology relations and probabilistic inference. Different from most of the existing work, we specially exploit how to combine representation of ontology, contextual knowledge and probabilistic inference. The experiments show that image annotation results are improved in the LabelMe dataset.

Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption

In this work, natural palygorskite impregnated with zero-valent iron (ZVI) was prepared and characterised. The combination of ZVI particles on surface of fibrous palygorskite can help to overcome the disadvantage of ultra-fine powders which may have strong tendency to agglomerate into larger particles, resulting in an adverse effect on both effective surface area and catalyst performance. There is a significant increase of methylene blue (MB) decolourized efficiency on acid treated palygorskite with ZVI grafted, within 5 mins, the concentration of MB in the solution was decreased from 94 mg/L to around 20 mg/L and the equilibration was reached at about 30 to 60 mins with only around 10 mg/L MB remained in solution. Changes in the surface and structure of prepared materials were characterized using X-ray diffraction (XRD), infrared (IR) spectroscopy, surface analysing and scanning electron microscopy (SEM) with element analysis and mapping. Comparing with zero-valent iron and palygorskite, the presence of zero-valent iron reactive species on the palygorskite surface strongly increases the decolourization capacity for methylene blue, and it is significant for providing novel modified clay catalyst materials for the removal of organic contaminants from waste water.

Synthesis and characterization of boehmite nanofibers

Boehmite nanofibers of high quality were synthesized through a wet-gel conversion process without the use of a surfactant. The long nanofibers of boehmite with clear-cut edges were obtained by steaming the wet-gel precipitate at 170 ºC for 2 days under a pH 5. Hydrothermal treatment of the boehmite gels enabled self-assembly through directed crystal growth. Detailed characterization using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Infrared Emission Spectroscopy (IES) and Raman Spectroscopy is presented.

Synthesis of 4-arm star poly(L-Lactide) oligomers using an in situ-generated calcium-based initiator

Using an in situ-generated calcium-based initiating species derived from pentaerythritol, the bulk synthesis of well-defined 4-arm star poly(L-lactide) oligomers has been studied in detail. The substitution of the traditional initiator, stannous octoate with calcium hydride allowed the synthesis of oligomers that had both low PDIs and a comparable number of polymeric arms (3.7 – 3.9) to oligomers of similar molecular weight. Investigations into the degree of control observed during the course of the polymerization found that the insolubility of pentaerythritol in molten L-lactide resulted in an uncontrolled polymerization only when the feed mole ratio of L-lactide to pentaerythritol was 13. At feed ratios of 40 and greater, a pseudo-living polymerization was observed. As part of this study, in situ FT-Raman spectroscopy was demonstrated to be a suitable method to monitor the kinetics of the ring-opening polymerization (ROP) of lactide. The advantages of using this technique rather than FT-IR-ATR and 1H NMR for monitoring L-lactide consumption during polymerization are discussed.