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.

Review of strengthening techniques using externally bonded fiber reinforced polymer composites

This report reviews the selection, design, and installation of fiber reinforced polymer systems for strengthening of reinforced concrete or pre-stressed concrete bridges and other structures. The report is prepared based on the knowledge gained from worldwide experimental research, analytical work, and field applications of FRP systems used to strengthen concrete structures. Information on material properties, design and installation methods of FRP systems used as external reinforcement are presented. This information can be used to select an FRP system for increasing the strength and stiffness of reinforced concrete beams or the ductility of columns, and other applications. Based on the available research, the design considerations and concepts are covered in this report. In the next stage of the project, these will be further developed as design tools. It is important to note, however, that the design concepts proposed in literature have not in many cases been thoroughly developed and proven. Therefore, a considerable amount of research work will be required prior to development of the design concepts into practical design tools, which is a major goal of the current research project. The durability and long-term performance of FRP materials has been the subject of much research, which still are on going. Long-term field data are not currently available, and it is still difficult to accurately predict the life of FRP strengthening systems. The report briefly addresses environmental degradation and long-term durability issues as well. A general overview of using FRP bars as primary reinforcement of concrete structures is presented in Chapter 8. In Chapter 9, a summary of strengthening techniques identified as part of this initial stage of the research project and the issues which require careful consideration prior to practical implementation of these identified techniques are presented.

User friendly guide for rehabilitation or strengthening of bridge structures using fiber reinforced polymer composites

A worldwide interest is being generated in the use of fibre reinforced polymer composites (FRP) in rehabilitation of reinforced concrete structures. As a replacement for the traditional steel plates or external post-tensioning in strengthening applications, various types of FRP plates, with their high strength to weight ratio and good resistance to corrosion, represent a class of ideal material in external retrofitting. Within the last ten years, many design guidelines have been published to provide guidance for the selection, design and installation of FRP systems for external strengthening of concrete structures. Use of these guidelines requires understanding of a number of issues pertaining to different properties and structural failure modes specific to these materials. A research initiative funded by the CRC for Construction Innovation was undertaken (primarily at RMIT) to develop a decision support tool and a user friendly guide for use of fibre reinforced polymer composites in rehabilitation of concrete structures. The user guidelines presented in this report were developed after industry consultation and a comprehensive review of the state of the art technology. The scope of the guide was mainly developed based on outcomes of two workshops with Queensland Department of Main Roads (QDMR). The document covers material properties, recommended construction requirements, design philosophy, flexural, shear and torsional strengthening of beams and strengthening of columns. In developing this document, the guidelines published on FIB Bulletin 14 (2002), Task group 9.3, International Federation of Structural Concrete (FIB) and American Concrete Institute Committee 440 report (2002) were consulted in conjunction with provisions of the Austroads Bridge design code (1992) and Australian Concrete Structures code AS3600 (2002). In conclusion, the user guide presents design examples covering typical strengthening scenarios.

Sodium 2-nitrocinnamate dihydrate: a one-dimensional hydrogen-bonded coordination polymer

The title compound catena-poly[aqua-mu3-2-nitrocinnamato], [Na(C9H6NO4)(H2O)2]n, the sodium salt of trans-2-nitrocinnamic acid, is a one-dimensional coordination polymer based on six-coordinate octahedral NaO6 centres comprising three facially-related monodentate carboxylate O-atom donors from separate ligands (all bridging)[Na-O, 2.4370(13)-2.5046(13)A] and three water molecules (two bridging, one monodentate) [Na-O, 2.3782(13)-2.4404(17)A]. The structure is also stabilized by intra-chain water-O-H...O(carboxylate) and O-H...O(nitro) hydrogen bonds.

Processing of polycaprolactone and polycaprolactone-based copolymers into 3D scaffolds and their cellular responses

Synthetic polymers have attracted much attention in tissue engineering due to their ability to modulate biomechanical properties. This study investigated the feasibility of processing poly(varepsilon-caprolactone) (PCL) homopolymer, PCL-poly(ethylene glycol) (PEG) diblock, and PCL-PEG-PCL triblock copolymers into three-dimensional porous scaffolds. Properties of the various polymers were investigated by dynamic thermal analysis. The scaffolds were manufactured using the desktop robot-based rapid prototyping technique. Gross morphology and internal three-dimensional structure of scaffolds were identified by scanning electron microscopy and micro-computed tomography, which showed excellent fusion at the filament junctions, high uniformity, and complete interconnectivity of pore networks. The influences of process parameters on scaffolds' morphological and mechanical characteristics were studied. Data confirmed that the process parameters directly influenced the pore size, porosity, and, consequently, the mechanical properties of the scaffolds. The in vitro cell culture study was performed to investigate the influence of polymer nature and scaffold architecture on the adhesion of the cells onto the scaffolds using rabbit smooth muscle cells. Light, scanning electron, and confocal laser microscopy showed cell adhesion, proliferation, and extracellular matrix formation on the surface as well as inside the structure of both scaffold groups. The completely interconnected and highly regular honeycomb-like pore morphology supported bridging of the pores via cell-to-cell contact as well as production of extracellular matrix at later time points. The results indicated that the incorporation of hydrophilic PEG into hydrophobic PCL enhanced the overall hydrophilicity and cell culture performance of PCL-PEG copolymer. However, the scaffold architecture did not significantly influence the cell culture performance in this study.

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.

Tear film surface quality with soft contact lenses using dynamic-area high-speed videokeratoscopy

Objectives. To evaluate the performance of the dynamic-area high-speed videokeratoscopy technique in the assessment of tear film surface quality with and without the presence of soft contact lenses on eye. Methods. Retrospective data from a tear film study using basic high-speed videokeratoscopy, captured at 25 frames per second, (Kopf et al., 2008, J Optom) were used. Eleven subjects had tear film analysis conducted in the morning, midday and evening on the first and seventh day of one week of no lens wear. Five of the eleven subjects then completed an extra week of hydrogel lens wear followed by a week of silicone hydrogel lens wear. Analysis was performed on a 6 second period of the inter-blink recording. The dynamic-area high-speed videokeratoscopy technique uses the maximum available area of Placido ring pattern reflected from the tear interface and eliminates regions of disturbance due to shadows from the eyelashes. A value of tear film surface quality was derived using image rocessing techniques, based on the quality of the reflected ring pattern orientation. Results. The group mean tear film surface quality and the standard deviations for each of the conditions (bare eye, hydrogel lens, and silicone hydrogel lens) showed a much lower coefficient of variation than previous methods (average reduction of about 92%). Bare eye measurements from the right and left eyes of eleven individuals showed high correlation values (Pearson’s correlation r = 0.73, p < 0.05). Repeated measures ANOVA across the 6 second period of measurement in the normal inter-blink period for the bare eye condition showed no statistically significant changes. However, across the 6 second inter-blink period with both contact lenses, statistically significant changes were observed (p < 0.001) for both types of contact lens material. Overall, wearing hydrogel and silicone hydrogel lenses caused the tear film surface quality to worsen compared with the bare eye condition (repeated measures ANOVA, p < 0.0001 for both hydrogel and silicone hydrogel). Conclusions. The results suggest that the dynamic-area method of high-speed videokeratoscopy was able to distinguish and quantify the subtle, but systematic worsening of tear film surface quality in the inter-blink interval in contact lens wear. It was also able to clearly show a difference between bare eye and contact lens wearing conditions.

Assessment of tear film surface quality using dynamic-area high-speed videokeratoscopy

A new method for noninvasive assessment of tear film surface quality (TFSQ) is proposed. The method is based on high-speed videokeratoscopy in which the corneal area for the analysis is dynamically estimated in a manner that removes videokeratoscopy interference from the shadows of eyelashes but not that related to the poor quality of the precorneal tear film that is of interest. The separation between the two types of seemingly similar videokeratoscopy interference is achieved by region-based classification in which the overall noise is first separated from the useful signal (unaltered videokeratoscopy pattern), followed by a dedicated interference classification algorithm that distinguishes between the two considered interferences. The proposed technique provides a much wider corneal area for the analysis of TFSQ than the previously reported techniques. A preliminary study with the proposed technique, carried out for a range of anterior eye conditions, showed an effective behavior in terms of noise to signal separation, interference classification, as well as consistent TFSQ results. Subsequently, the method proved to be able to not only discriminate between the bare eye and the lens on eye conditions but also to have the potential to discriminate between the two types of contact lenses.

Carbodiimide-mediated synthesis of poly(L-lactide)-based networks

Poly(L-lactide-co-succinic anhydride) networks were synthesised via the carbodiimide-mediated coupling of poly(L-lactide) (PLLA) star polymers. When 4-(dimethylamino)pyridine (DMAP) alone was used as the catalyst gelation did not occur. However, when 4-(dimethylamino)pyridinium p-toluenesulfonate (DPTS), the salt of DMAP and p-toluenesulfonic acid (PTSA), was the catalyst, the networks obtained had gel fractions comparable to those which were reported for networks synthesised by conventional methods. Greater gel fractions and conversion of the prepolymer terminal hydroxyl groups were observed when the hydroxyl-terminated star prepolymers reacted with succinic anhydride in a one-pot procedure than when the hydroxyl-terminated star prepolymers reacted with presynthesised succinic-terminated star prepolymers. The thermal properties of the networks, glass transition temperature (Tg), melting temperature (Tm) and crystallinity (Xc) were all strongly influenced by the average molecular weights between the crosslinks ((M_c). The network with the smallest (M_c )(1400 g/mol) was amorphous and had a Tg of 59 °C while the network with the largest (M_c ) (7800 g/mol) was 15 % crystalline and had a Tg of 56 °C.

Effect of simulated space environments on piezoelectric vinylidene flouride-based polymers

Piezoelectric polymers based on polyvinylidene flouride (PVDF) are of interest as adaptive materials for large aperture space-based telescopes. In this study, two piezoelectric polymers, PVDF and P(VDF-TrFE), were exposed to conditions simulating the thermal, radiative and atomic oxygen conditions of low Earth orbit. The degradation pathways were governed by a combination of chemical and physical degradation processes with the molecular changes primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure, as evident from depoling, loss of orientation and surface erosion. The piezoelectric responsiveness of each polymer was strongly dependent on exposure temperature. Radiation and atomic oxygen exposure caused physical and chemical degradation, which would ultimately cause terminal damage of thin films, but did not adversely affect the piezoelectric properties.

Nitrogen and phosphorus transformations in fixed-film biofilters subjected to aeration/no-aeration cycles

Despite recent developments in fixed-film combined biological nutrients removal (BNR) technology; fixed-film systems (i.e., biofilters), are still at the early stages of development and their application has been limited to a few laboratory-scale experiments. Achieving enhanced biological phosphorus removal in fixed-film systems requires exposing the micro-organisms and the waste stream to alternating anaerobic/aerobic or anaerobic/anoxic conditions in cycles. The concept of cycle duration (CD) as a process control parameter is unique to fixed-film BNR systems, has not been previously investigated, and can be used to optimise the performance of such systems. The CD refers to the elapsed time before the biomass is re-exposed to the same environmental conditions in cycles. Fixed-film systems offer many advantages over suspended growth systems such as reduced operating costs, simplicity of operation, absence of sludge recycling problems, and compactness. The control of nutrient discharges to water bodies, improves water quality, fish production, and allow water reuse. The main objective of this study was to develop a fundamental understanding of the effect of CD on the transformations of nutrients in fixed-film biofilter systems subjected to alternating aeration I no-aeration cycles A fixed-film biofilter system consisting of three up-flow biofilters connected in series was developed and tested. The first and third biofilters were operated in a cyclic mode in which the biomass was subjected to aeration/no-aeration cycles. The influent wastewater was simulated aquaculture whose composition was based on actual water quality parameters of aquacuture wastewater from a prawn grow-out facility. The influent contained 8.5 - 9:3 mg!L a111monia-N, 8.5- 8.7 mg/L phosphate-P, and 45- 50 mg!L acetate. Two independent studies were conducted at two biofiltration rates to evaluate and confirm the effect of CD on nutrient transformations in the biofilter system for application in aquaculture: A third study was conducted to enhance denitrification in the system using an external carbon- source at a rate varying from 0-24 ml/min. The CD was varied in the range of0.25- 120 hours for the first two studies and fixed at 12 hours for the third study. This study identified the CD as an important process control parameter that can be used to optimise the performance of full-scale fixed-film systems for BNR which represents a novel contribution in this field of research. The CD resulted in environmental conditions that inhibited or enhanced nutrient transformations. The effect of CD on BNR in fixed-film systems in terms of phosphorus biomass saturation and depletion has been established. Short CDs did not permit the establishment of anaerobic activity in the un-aerated biofilter and, thus, inhibited phosphorus release. Long CDs resulted in extended anaerobic activity and, thus, resulted in active phosphorus release. Long CDs, however, resulted in depleting the biomass phosphorus reservoir in the releasing biofilter and saturating the biomass phosphorus reservoir in the up-taking biofilter in the cycle. This phosphorus biomass saturation/depletion phenomenon imposes a practical limit on how short or long the CD can be. The length of the CD should be somewhere just before saturation or depletion occur and for the system tested, the optimal CD was 12 hours for the biofiltration rates tested. The system achieved limited net phosphorus removal due to the limited sludge wasting and lack of external carbon supply during phosphorus uptake. The phosphorus saturation and depletion reflected the need to extract phosphorus from the phosphorus-rich micro-organisms, for example, through back-washing. The major challenges of achieving phosphorus removal in the system included: (I) overcoming the deterioration in the performance of the system during the transition period following the start of each new cycle; and (2) wasting excess phosphorus-saturated biomass following the aeration cycle. Denitrification occurred in poorly aerated sections of the third biofilter and generally declined as the CD increased and as the time progressed in the individual cycle. Denitrification and phosphorus uptake were supplied by an internal organic carbon source, and the addition of an external carbon source (acetate) to the third biofilter resulted in improved denitrification efficiency in the system from 18.4 without supplemental carbon to 88.7% when the carbon dose reached 24 mL/min The removal of TOC and nitrification improved as the CD increased, as a result of the reduction in the frequency of transition periods between the cycles. A conceptual design of an effective fixed-film BNR biofilter system for the treatment of the influent simulated aquaculture wastewater was proposed based on the findings of the study.

In vivo evaluation of an ultra-thin polycaprolactone film as a wound dressing

The use of ultra-thin films as dressings for cutaneous wounds could prove advantageous in terms of better conformity to wound topography and improved vapour transmission. For this purpose, ultra-thin poly(epsilon-caprolactone) (PCL) films of 5-15 microm thickness were fabricated via a biaxial stretching technique. To evaluate their in vivo biocompatibility and feasibility as an external wound dressing, PCL films were applied over full and partial-thickness wounds in rat and pig models. Different groups of PCL films were used: untreated, NaOH-treated, untreated with fibrin, NaOH-treated with perforations, and NaOH-treated with fibrin and S-nitrosoglutathione. Wounds with no external dressings were used as controls. Wound contraction rate, histology and biomechanical analyses were carried out. Wounds re-epithelialized completely at a comparable rate. Formation of a neo-dermal layer and re-epithelialization were observed in all the wounds. A lower level of fibrosis was observed when PCL films were used, compared to the control wounds. Ultimate tensile strength of the regenerated tissue in rats reached 50-60% of that in native rat skin. Results indicated that biaxially-stretched PCL films did not induce inflammatory reactions when used in vivo as a wound dressing and supported the normal wound healing process in full and partial-thickness wounds.