Anti-staphylococcal activity of C-methyl flavanones from propolis of Australian stingless bees (Tetragonula carbonaria) and fruit resins of Corymbia torelliana (Myrtaceae)

Propolis of Australian stingless bees (Tetragonula carbonaria, Meliponini) originating from Corymbia torelliana (Myrtaceae) fruit resins was tested for its antimicrobial activities as well as its flavonoid contents. This study aimed at the isolation, structural elucidation and antibacterial testing of flavanones of C. torelliana fruit resins that are incorporated into stingless bee propolis. Flavanones of this study were elucidated by spectroscopic and spectrometric methods including UV, 1D and 2D NMR, EI-MS, ESI-MS and HR-MS. The results indicated known C-methylated flavanones namely, 1 (2S)-cryptostrobin, its regioisomer 2 (2S)- stroboponin, 3 (2S)- cryptostrobin 7-methyl ether, and 6 (2S)- desmethoxymatteucinol, and known flavanones 4 (2S)- pinostrobin and 5 (2S)- pinocembrin as markers for C. torelliana fruit resins and one propolis type. Ethanolic preparations of propolis were shown to be active against Staphylococcus aureus (ATCC 25923) and to a lesser extent against Pseudomonas aeruginosa (ATCC 27853). C. torelliana flavanones inhibited the growth of S. aureus therefore contributing to the antibacterial effects observed for Australian stingless bee propolis extracts.

Ion exchange of sodium chloride and sodium bicarbonate solutions using strong acid cation resins in relation to coal seam water treatment

Coal seam gas production has resulted in the production of large volumes of associated water which contains dissolved salts dominated by sodium chloride and sodium bicarbonate. Ion exchange using synthetic resins has been proposed as a method for desalination of coal seam water to make it suitable for various beneficial reuse options. This study investigated the behaviour of solutions of sodium chloride and sodium bicarbonate with respect to exchange with Lanxess S108H strong acid cation (SAC) resin. Equilibrium isotherms were created for solutions of NaCl and NaHCO3 and an actual sample of coal seam water from the Surat Basin in southern Queensland. The exchange of sodium ions arising from sodium bicarbonate was found to be considerably more favourable than exchange of sodium ions from sodium chloride solutions. This latter behaviour was attributed to the secondary decomposition of bicarbonate species under acidic conditions which resulted in the evolution of carbon dioxide and formation of water. The isotherm profiles could not be satisfactorily fitted by a single isotherm model such as the Langmuir expression. Instead, two Langmuir equations had to be simultaneously applied in order to fit the sections of the isotherm attributable to sodium ion exchange from sodium bicarbonate and sodium chloride. The shape of the isotherm profile was dependent upon the ratio of sodium chloride to sodium bicarbonate in solution and there was a high degree of correlation between simulated and actual coal seam water solutions.

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.

Methacrylate-functionalized oligomers based on lactide, E-caprolactone and trimethylene carbonate for application in stereo-lithography

Photo-curable biodegradable macromers were prepared by ring opening polymerization of D,L-lactide (DLLA), (similar to)-caprolactone (CL) and 1,3-trimethylene carbonate (TMC) in the presence of glycerol or sorbitol as initiator and stannous octoate as catalyst, and subsequent methacrylation of the terminal hydroxyl groups. These methacrylated macromers, ranging in molecular weight from approximately 700 to 6000 g/mol, were cross-linked using ultraviolet (UV) light to form biodegradable networks. Homogeneous networks with high gel contents were prepared. One of the resins based on PTMC was used to prepare three-dimensional structures by stereo-lithography using a commercially available apparatus.

Methacrylate-functionalized oligomers based on lactide, ε- caprolactone and trimethylene carbonate for application in stereo-lithography

Photo-curable biodegradable macromers were prepared by ring opening polymerization of D,L-lactide (DLLA), ε-caprolactone (CL) and 1,3-trimethylene carbonate (TMC) in the presence of glycerol or sorbitol as initiator and stannous octoate as catalyst, and subsequent methacrylation of the terminal hydroxyl groups. These methacrylated macromers, ranging in molecular weight from approximately 700 to 6000 g/mol, were cross-linked using ultraviolet (UV) light to form biodegradable networks. Homogeneous networks with high gel contents were prepared. One of the resins based on PTMC was used to prepare three-dimensional structures by stereo-lithography using a commercially available apparatus.

Photo-crosslinking of functionalised lactide oligomers for the fabrication of osteochondral tissue engineering scaffolds

In the fabrication of osteochondral tissue engineering scaffolds, the two distinct tissues impose different requirements on the architecture. Stereo-lithography is a rapid prototyping method that can be utilised to make 3D constructs with high spatial control by radical photopolymerization. In this study, biodegradable resins are developed that can be applied in stereo-lithography. Photo-crosslinked poly(lactide) networks with varying physical properties were synthesised, and by photo polymerizing in the presence of leachable particles porous scaffolds could be prepared as well.

Development of a PDLLA-based stereolithography resin for making tissue engineering scaffolds

The use of porous structures as tissue engineering scaffolds imposes high demands on the pore architecture. Stereolithography is a rapid prototyping method based on photo-polymerisation, that can be utilised to make 3D constructs with high spatial control. In this study, biodegradable resins were developed that can find application in stereolithography. Poly(D,L-lactide) (PDLLA) oligomers were synthesised and functionalised with methacrylate end-groups. By mixing the resulting macromers with a diluent, photo-initiator and inhibitor, lowviscosity resins were obtained that were photocrosslinked to yield stiff and strong degradable poly(lactide) networks. Also, porous scaffolds were fabricated on a stereolithography apparatus (SLA) from a nondegradable resin.

Temperature dependent electrical resistivity in expoxy : multiwall carbon nanotube nanocomposites

Thin films of expoxy nanocomposites modified by multiwall carbon nanotubes (MWCNTs) were prepared by shear mixing and spin casting. The electrical behaviour and its dependence with temperature between 243 and 353 degrees Kelvin were characterized by measuring the direct current (DC) conductivity. Depending on the fabrication process, both linear and non-linear relationships between conductivity and temperature were observed. In addition, the thermal history also played a role in dictating the conductivity. The implications of these observations for potential application of these files as strain sensors are discussed.

Sandwiched carbon nanotube film as strain sensor

Two types of carbon nanotube nanocomposite strain sensors were prepared by mixing carbon nanotubes with epoxy (nanocomposite sensor) and sandwiching a carbon nanotube film between two epoxy layers (sandwich sensor). The conductivity, response and sensitivity to static and dynamic mechanical strains in these sensors were investigated. The nanocomposite sensor with 2-3 wt.% carbon nanotube demonstrated high sensitivity to mechanical strain and environmental temperature, with gauge factors of 5-8. On the other hand, a linear relationship between conductivity and dynamic mechanical strain was observed in the sandwich sensor. The sandwich sensor was also not sensitive to temperature although its strain sensitivity (gauge factor of about 3) was lower as compared with the nanocomposite sensor. Both sensors have excellent response to static and dynamic strains, thereby having great potential for strain sensing applications.

Characterisation of multi wall carbon nanotube–polymer composites for strain sensing applications

Carbon nanotubes (CNTs) have excellent electrical, mechanical and electromechanical properties. When CNTs are incorporated into polymers, electrically conductive composites with high electrical conductivity at very low CNT content (often below 1% wt CNT) result. Due to the change in electrical properties under mechanical load, carbon nanotube/polymer composites have attracted significant research interest especially due to their potential for application in in-situ monitoring of stress distribution and active control of strain sensing in composite structures or as strain sensors. To sucessfully develop novel devices for such applications, some of the major challenges that need to be overcome include; in-depth understanding of structure-electrical conductivity relationships, response of the composites under changing environmental conditions and piezoresistivity of different types of carbon nanotube/polymer sensing devices. In this thesis, direct current (DC) and alternating current (AC) conductivity of CNT-epoxy composites was investigated. Details of microstructure obtained by scanning electron microscopy were used to link observed electrical properties with structure using equivalent circuit modeling. The role of polymer coatings on macro and micro level electrical conductivity was investigated using atomic force microscopy. Thermal analysis and Raman spectroscopy were used to evaluate the heat flow and deformation of carbon nanotubes embedded in the epoxy, respectively, and related to temperature induced resistivity changes. A comparative assessment of piezoresistivity was conducted using randomly mixed carbon nanotube/epoxy composites, and new concept epoxy- and polyurethane-coated carbon nanotube films. The results indicate that equivalent circuit modelling is a reliable technique for estimating values of the resistance and capacitive components in linear, low aspect ratio-epoxy composites. Using this approach, the dominant role of tunneling resistance in determining the electrical conductivity was confirmed, a result further verified using conductive-atomic force microscopy analysis. Randomly mixed CNT-epoxy composites were found to be highly sensitive to mechanical strain and temperature variation compared to polymer-coated CNT films. In the vicinity of the glass transition temperature, the CNT-epoxy composites exhibited pronounced resistivity peaks. Thermal and Raman spectroscopy analyses indicated that this phenomenon can be attributed to physical aging of the epoxy matrix phase and structural rearrangement of the conductive network induced by matrix expansion. The resistivity of polymercoated CNT composites was mainly dominated by the intrinsic resistivity of CNTs and the CNT junctions, and their linear, weakly temperature sensitive response can be described by a modified Luttinger liquid model. Piezoresistivity of the polymer coated sensors was dominated by break up of the conducting carbon nanotube network and the consequent degradation of nanotube-nanotube contacts while that of the randomly mixed CNT-epoxy composites was determined by tunnelling resistance between neighbouring CNTs. This thesis has demonstrated that it is possible to use microstructure information to develop equivalent circuit models that are capable of representing the electrical conductivity of CNT/epoxy composites accurately. New designs of carbon nanotube based sensing devices, utilising carbon nanotube films as the key functional element, can be used to overcome the high temperature sensitivity of randomly mixed CNT/polymer composites without compromising on desired high strain sensitivity. This concept can be extended to develop large area intelligent CNT based coatings and targeted weak-point specific strain sensors for use in structural health monitoring.

Electron petrography of fine-grained matrix in the Karoonda C4 carbonaceous chondrite

The study of matrices of rare Type 4 carbonaceous chondrites can reveal important information on parent body rnetamorp~ic processes and provide a comparison with processes on parent bodies of ordinary chc-idrites. Reflectance spectra (Tholen, 1984) from the two largest asteroids in the asteroid belt, Ceres and Pallas, suggest that they may be metamorphosed carbonaceous chondrites. These two asteroids constitute - onethird of the mass in the asteroid belt implying that type 4-6 carbonaceous chondrites are poorly represented in the meteorite collection and may be of considerable importance. The matrix of the C4 chondrite Karoonda has been investigated using a JEOL 2000FX analytical electron microscope (AEM) with an attached Tracor-Northem TN5500 energy dispersive spectrometer (EDS). In previous studies (Scott and Taylor, 1985; Fitzgerald, 1979; Van Schmus, 1969), the petrography of the Karoonda matrix has been described as consisting largely of coarse-grained (50-200 urn in size) olivine and plagioclase (20-100 um in size), associated with micrometer sized magnetite and rare sulphides. AEM observations on matrix show that in addition to these large grains, there is a significant fraction (10 vol%) of interstitial fine grained phases « 5 urn). The mineralogy of these fine-grained phases differs in some respects from that of the coarser-grained matrix identified by optical and SEM techniques (Scott and Taylor, 1985; Fitzgerald, 1979; Van Schmus, 1969). I~ particular crystals of two compositionally distinct pyroxenes « 2 urn in size) have been identified which have not been previously observed in Karoonda by other analytical techniques. Thin film microanalyses (Mackinnon et al., 1986) of these two pyroxenes indicate compositions consistent with augite and low-Ca pyroxene (- Fs27). Fine-grained anhedral olivine « 2 urn size) is the most abundant phase with composition -Fa29' This composition is essentially indistinguishable from that determined for coarser-grained matrix olivines using an electron microprobe (Scott and Taylor, 1985; Fitzgerald, 1979; Van Schmus, 1969). All olivines are associated with subhedral magnetites « 1 urn size) which contain significant Cr (- 2%) and Al (- 1%) as was also noted for larger sized Karoonda magnetites by Delaney et al. (1985). It has recently been suggested (Burgess et al., 1987) on the basis of sulphur release profiles for S-isotope analyses of Karoonda that CaS04 (anhydrite) may be present. However, no sulphate phase has, as yet, been identified in the matrix of Karoonda. Low magnification contrast images suggest that Karoonda may have a significant porosity within the fine-grained matrix fraction. Most crystals are anhedral and do not show evidence for significant compaction. Individual grains often show single point contact with other grains which result in abundant intergranular voids. These voids frequently contain epoxy which was used as part of the specimen preparation procedure due to the friable nature of the bulk sample.

Porosity of serially sectioned interplanetary dust particles

The application of epoxy embedding and microtomy to individual chondritic interplanetary dust particles (lOP's)(Bradley and Brownlee, 1986a) provides not only higher precision in thin-film elemental analyses (Bradley and Brownlee, 19861:1), but also allows a wealth of other important techniques for the micro-characterization of these primitive extraterrestrial materials. For example, individual sections (e.g. 100 nm thick) or a series of sections, can be examined using image analysis techniques which utilize either transmitted or scanned secondary electron images, or alternatively, secondary X-ray spectra collected concurrently from a given region of sample. Individual particles, or groups of particles with similar image characteristics can then be rapidly identified using conventional grey-scale/particle recognition techniques for each microtomed section of lOP. This type of image analysis provides a suitable method for determination of particle size and shape distribution as well as porosity throughout the aggregate.

Superior piezoelectric composite films : taking advantage of carbon nanomaterials

Piezoelectric composites comprising an active phase of ferroelectric ceramic and a polymer matrix have recently attracted numerous sensory applications. However, it remains a major challenge to further improve their electromechanical response for advanced applications such as precision control and monitoring systems. We hereby investigated the incorporation of graphene platelets (GnPs) and multi-walled carbon nanotubes (MWNTs), each with various weight fractions, into PZT (lead zirconate titanate)/epoxy composites to produce three-phase nanocomposites. The nanocomposite films show markedly improved piezoelectric coefficients and electromechanical responses (50%) besides an enhancement of ~200% in stiffness. Carbon nanomaterials strengthened the impact of electric field on the PZT particles by appropriately raising the electrical conductivity of epoxy. GnPs have been proved far more promising in improving the poling behavior and dynamic response than MWNTs. The superior dynamic sensitivity of GnP-reinforced composite may be caused by GnPs’ high load transfer efficiency arising from their two-dimensional geometry and good compatibility with the matrix. Reduced acoustic impedance mismatch resulted from the improved thermal conductance may also contribute to the higher sensitivity of GnP-reinforced composite. This research pointed out the potential of employing GnPs to develop highly sensitive piezoelectric composites for sensing applications.

Effects of cold weather on durability of CFRP strengthened circular hollow steel members

Tubular members have become progressively more popular due to excellent structural properties, aesthetic appearance, corrosion and fire protection capability. However, a large number of such structures are found structurally deficient due to reduction of strength when they expose to severe environmental conditions such as marine environment, cold and hot weather. Hence strengthening and retrofitting of structural members are in high demands. In recent times Carbon Fibre Reinforced Polymers (CFRP) composites appears to be an excellent solution to enhance the load carrying capacity and serviceability of steel structures because of its superior physical and mechanical properties. However, the durability of such strengthening system under cold environmental condition has not yet been well documented to guide the engineers. This paper presents the findings of a study conducted to enhance the bond durability of CFRP strengthened steel tubular members by treating steel surface using epoxy based adhesion promoter under cold weather subjected to bending. The experimental program consisted of six number of CFRP strengthened specimens and one bare specimen. The sand blasted surface of the three specimens to be strengthened was pre-treated with MBrace primer and other three were remained untreated and then cured under ambient temperature and cold weather (3oC) for three and six months period of time. The beams were then loaded to failure under four point bending. The structural response of each specimen was predicted in terms of failure mode, failure load and mid-span deflection. The research findings show that the cold weather immersion had an adverse effect on durability of CFRP strengthened structures. Moreover, the epoxy based adhesion promoter was found to enhance the bond durability in elastic range.