Enhancing the health-status of processed meats through ingredient manipulation and its effects on sensory and physiochemical product attributes

An important component of this Ph.D. thesis was to determine the European consumers’ views on processed meats and bioactive compounds. Thus a survey gathered information form over 500 respondents and explored their perceptions on the healthiness and purchase-ability for both traditional and functional processed meats. This study found that the consumer was distrustful towards processed meat, especially high salt and fat content. Consumers were found to be very pro-bioactive compounds in yogurt style products but unsure of their feelings on the idea of them in meat based products, which is likely due to the lack of familiarity to these products. The work in this thesis also centred on the applied acceptable reduction of salt and fat in terms of consumer sensory analysis. The products chosen ranged in the degree of comminution, from a coarse beef patty to a more fine emulsion style breakfast sausage and frankfurter. A full factorial design was implemented which saw the production of twenty beef patties with varying concentrations of fat (30%, 40%, 50%, 60% w/w) and salt (0.5%, 0.75%, 1.0%, 1.25%, 1.5% w/w). Twenty eight sausage were also produced with varying concentrations of fat (22.5%, 27.5%, 32.5%, 37.5% w/w) and salt (0.8%, 1%, 1.2%, 1.4%, 1.6%, 2%, 2.4% w/w). Finally, twenty different frankfurters formulations were produced with varying concentrations of fat (10%, 15%, 20%, 25% w/w) and salt (1%, 1.5%, 2%, 2.5%, 3% w/w). From these products it was found that the most consumer acceptable beef patty was that containing 40% fat with a salt level of 1%. This is a 20% decrease in fat and a 50% decrease in salt levels when compared to commercial patty available in Ireland and the UK. For sausages, salt reduced products were rated by the consumers as paler in colour, more tender and with greater meat flavour than higher salt containing products. The sausages containing 1.4 % and 1.0 % salt were significantly (P<0.01) found to be more acceptable to consumers than other salt levels. Frankfurter salt levels below 1.5% were shown to have a negative effect on consumer acceptability, with 2.5% salt concentration being the most accepted (P<0.001) by consumers. Samples containing less fat and salt were found to be tougher, less juicy and had greater cooking losses. Thus salt perception is very important for consumer acceptability, but fat levels can be potentially reduced without significantly affecting overall acceptability. Overall it can be summarised that the consumer acceptability of salt and fat reduced processed meats depends very much on the product and generalisations cannot be assumed. The study of bio-actives in processed meat products found that the reduced salt/fat patties fortified with CoQ10 were rated as more acceptable than commercially available products for beef patties. The reduced fat and salt, as well as the CoQ10 fortified, sausages were found to compare quite well to their commercial counterparts for overall acceptability, whereas commercial frankfurters were found to be the more favoured in comparison to reduced fat and CoQ10 fortified Frankfurters.

Optical micro- and nanofibres: Higher mode generation and particle manipulation studies

This thesis is centred on two experimental fields of optical micro- and nanofibre research; higher mode generation/excitation and evanescent field optical manipulation. Standard, commercial, single-mode silica fibre is used throughout most of the experiments; this generally produces high-quality, single-mode, micro- or nanofibres when tapered in a flame-heated, pulling rig in the laboratory. Single mode fibre can also support higher transverse modes, when transmitting wavelengths below that of their defined single-mode regime cut-off. To investigate this, a first-order Laguerre-Gaussian beam, LG01 of 1064 nm wavelength and doughnut-shaped intensity profile is generated free space via spatial light modulation. This technique facilitates coupling to the LP11 fibre mode in two-mode fibre, and convenient, fast switching to the fundamental mode via computer-generated hologram modulation. Following LP11 mode loss when exponentially tapering 125μm diameter fibre, two mode fibre with a cladding diameter of 80μm is selected fir testing since it is more suitable for satisfying the adiabatic criteria for fibre tapering. Proving a fruitful endeavour, experiments show a transmission of 55% of the original LP11 mode set (comprising TE01, TM01, HE21e,o true modes) in submicron fibres. Furthermore, by observing pulling dynamics and progressive mode-lass behaviour, it is possible to produce a nanofibre which supports only the TE01 and TM01 modes, while suppressing the HE21e,o elements of the LP11 group. This result provides a basis for experimental studies of atom trapping via mode-interference, and offers a new set of evanescent field geometries for sensing and particle manipulation applications. The thesis highlights the experimental results of the research unit’s Cold Atom subgroup, who successfully integrated one such higher-mode nanofibre into a cloud of cold Rubidium atoms. This led to the detection of stronger signals of resonance fluorescence coupling into the nanofibre and for light absorption by the atoms due to the presence of higher guided modes within the fibre. Theoretical work on the impact of the curved nanofibre surface on the atomic-surface van der Waals interaction is also presented, showing a clear deviation of the potential from the commonly-used flat-surface approximation. Optical micro- and nanofibres are also useful tools for evanescent-field mediated optical manipulation – this includes propulsion, defect-induced trapping, mass migration and size-sorting of micron-scale particles in dispersion. Similar early trapping experiments are described in this thesis, and resulting motivations for developing a targeted, site-specific particle induction method are given. The integration of optical nanofibres into an optical tweezers is presented, facilitating individual and group isolation of selected particles, and their controlled positioning and conveyance in the evanescent field. The effects of particle size and nanofibre diameter on pronounced scattering is experimentally investigated in this systems, as are optical binding effects between adjacent particles in the evanescent field. Such inter-particle interactions lead to regulated self-positioning and particle-chain speed enhancements.

Photonic integrated circuit for the manipulation of coherent optical combs

Photonic integration has become an important research topic in research for applications in the telecommunications industry. Current optical internet infrastructure has reached capacity with current generation dense wavelength division multiplexing (DWDM) systems fully occupying the low absorption region of optical fibre from 1530 nm to 1625 nm (the C and L bands). This is both due to an increase in the number of users worldwide and existing users demanding more bandwidth. Therefore, current research is focussed on using the available telecommunication spectrum more efficiently. To this end, coherent communication systems are being developed. Advanced coherent modulation schemes can be quite complex in terms of the number and array of devices required for implementation. In order to make these systems viable both logistically and commercially, photonic integration is required. In traditional DWDM systems, arrayed waveguide gratings (AWG) are used to both multiplex and demultiplex the multi-wavelength signal involved. AWGs are used widely as they allow filtering of the many DWDM wavelengths simultaneously. However, when moving to coherent telecommunication systems such as coherent optical frequency division multiplexing (OFDM) smaller FSR ranges are required from the AWG. This increases the size of the device which is counter to the miniaturisation which integration is trying to achieve. Much work was done with active filters during the 1980s. This involved using a laser device (usually below threshold) to allow selective wavelength filtering of input signals. By using more complicated cavity geometry devices such as distributed feedback (DFB) and sampled grating distributed Bragg gratings (SG-DBR) narrowband filtering is achievable with high suppression (>30 dB) of spurious wavelengths. The active nature of the devices also means that, through carrier injection, the index can be altered resulting in tunability of the filter. Used above threshold, active filters become useful in filtering coherent combs. Through injection locking, the coherence of the filtered wavelengths with the original comb source is retained. This gives active filters potential application in coherent communication system as demultiplexers. This work will focus on the use of slotted Fabry-Pérot (SFP) semiconductor lasers as active filters. Experiments were carried out to ensure that SFP lasers were useful as tunable active filters. In all experiments in this work the SFP lasers were operated above threshold and so injection locking was the mechanic by which the filters operated. Performance of the lasers under injection locking was examined using both single wavelength and coherent comb injection. In another experiment two discrete SFP lasers were used simultaneously to demultiplex a two-line coherent comb. The relative coherence of the comb lines was retained after demultiplexing. After showing that SFP lasers could be used to successfully demultiplex coherent combs a photonic integrated circuit was designed and fabricated. This involved monolithic integration of a MMI power splitter with an array of single facet SFP lasers. This device was tested much in the same way as the discrete devices. The integrated device was used to successfully demultiplex a two line coherent comb signal whilst retaining the relative coherence between the filtered comb lines. A series of modelling systems were then employed in order to understand the resonance characteristics of the fabricated devices, and to understand their performance under injection locking. Using this information, alterations to the SFP laser designs were made which were theoretically shown to provide improved performance and suitability for use in filtering coherent comb signals.

Manipulation of magnetic anisotropy in nanostructures

Of late, the magnetic properties of micro/nano-structures have attracted intense research interest both fundamentally and technologically particularly to address the question that how the manipulation in the different layers of nanostructures, geometry of a patterned structure can affect the overall magnetic properties, while generating novel applications such as in magnetic sensors, storage devices, integrated inductive components and spintronic devices. Depending on the applications, materials with high, medium or low magnetic anisotropy and their possible manipulation are required. The most dramatic manifestation in this respect is the chance to manipulate the magnetic anisotropy over the intrinsic preferential direction of the magnetization, which can open up more functionality particularly for device applications. Types of magnetic anisotropies of different nanostructured materials and their manipulation techniques are investigated in this work. Detail experimental methods for the quantitative determination of magnetic anisotropy in nanomodulated Ni45Fe55 thin film are studied. Magnetic field induced in-plane rotations within the nanomodulated Ni45Fe55 continuous films revealed various rotational symmetries of magnetic anisotropy due to dipolar interactions showing a crossover from lower to higher fold of symmetry as a function of modulation geometry. In a second approach, the control of exchange anisotropy at ferromagnetic (FM) – aniferomagnetic (AFM) interface in multifferoic nanocomposite materials, where two different phase/types of materials were simultaneously synthesized, was investigated. The third part of this work was to study the electroplated thin films of metal alloy nanocomposite for enhanced exchange anisotropy. In this work a unique observation of an anti-clock wise as well as a clock wise hysteresis loop formation in the Ni,Fe solid solution with very low coercivity and large positive exchange anisotropy/exchange bias have been investigated. Hence, controllable positive and negative exchange anisotropy has been observed for the first time which has high potential applications such as in MRAM devices.

Systematic delay-driven power optimisation and power-driven delay optimisation of combinational circuits

With the proliferation of mobile wireless communication and embedded systems, the energy efficiency becomes a major design constraint. The dissipated energy is often referred as the product of power dissipation and the input-output delay. Most of electronic design automation techniques focus on optimising only one of these parameters either power or delay. Industry standard design flows integrate systematic methods of optimising either area or timing while for power consumption optimisation one often employs heuristics which are characteristic to a specific design. In this work we answer three questions in our quest to provide a systematic approach to joint power and delay Optimisation. The first question of our research is: How to build a design flow which incorporates academic and industry standard design flows for power optimisation? To address this question, we use a reference design flow provided by Synopsys and integrate in this flow academic tools and methodologies. The proposed design flow is used as a platform for analysing some novel algorithms and methodologies for optimisation in the context of digital circuits. The second question we answer is: Is possible to apply a systematic approach for power optimisation in the context of combinational digital circuits? The starting point is a selection of a suitable data structure which can easily incorporate information about delay, power, area and which then allows optimisation algorithms to be applied. In particular we address the implications of a systematic power optimisation methodologies and the potential degradation of other (often conflicting) parameters such as area or the delay of implementation. Finally, the third question which this thesis attempts to answer is: Is there a systematic approach for multi-objective optimisation of delay and power? A delay-driven power and power-driven delay optimisation is proposed in order to have balanced delay and power values. This implies that each power optimisation step is not only constrained by the decrease in power but also the increase in delay. Similarly, each delay optimisation step is not only governed with the decrease in delay but also the increase in power. The goal is to obtain multi-objective optimisation of digital circuits where the two conflicting objectives are power and delay. The logic synthesis and optimisation methodology is based on AND-Inverter Graphs (AIGs) which represent the functionality of the circuit. The switching activities and arrival times of circuit nodes are annotated onto an AND-Inverter Graph under the zero and a non-zero-delay model. We introduce then several reordering rules which are applied on the AIG nodes to minimise switching power or longest path delay of the circuit at the pre-technology mapping level. The academic Electronic Design Automation (EDA) tool ABC is used for the manipulation of AND-Inverter Graphs. We have implemented various combinatorial optimisation algorithms often used in Electronic Design Automation such as Simulated Annealing and Uniform Cost Search Algorithm. Simulated Annealing (SMA) is a probabilistic meta heuristic for the global optimization problem of locating a good approximation to the global optimum of a given function in a large search space. We used SMA to probabilistically decide between moving from one optimised solution to another such that the dynamic power is optimised under given delay constraints and the delay is optimised under given power constraints. A good approximation to the global optimum solution of energy constraint is obtained. Uniform Cost Search (UCS) is a tree search algorithm used for traversing or searching a weighted tree, tree structure, or graph. We have used Uniform Cost Search Algorithm to search within the AIG network, a specific AIG node order for the reordering rules application. After the reordering rules application, the AIG network is mapped to an AIG netlist using specific library cells. Our approach combines network re-structuring, AIG nodes reordering, dynamic power and longest path delay estimation and optimisation and finally technology mapping to an AIG netlist. A set of MCNC Benchmark circuits and large combinational circuits up to 100,000 gates have been used to validate our methodology. Comparisons for power and delay optimisation are made with the best synthesis scripts used in ABC. Reduction of 23% in power and 15% in delay with minimal overhead is achieved, compared to the best known ABC results. Also, our approach is also implemented on a number of processors with combinational and sequential components and significant savings are achieved.

A knowledge management system to optimise comfort throughout the building life-cycle

Comfort is, in essence, satisfaction with the environment, and with respect to the indoor environment it is primarily satisfaction with the thermal conditions and air quality. Improving comfort has social, health and economic benefits, and is more financially significant than any other building cost. Despite this, comfort is not strictly managed throughout the building lifecycle. This is mainly due to the lack of an appropriate system to adequately manage comfort knowledge through the construction process into operation. Previous proposals to improve knowledge management have not been successfully adopted by the construction industry. To address this, the BabySteps approach was devised. BabySteps is an approach, proposed by this research, which states that for an innovation to be adopted into the industry it must be implementable through a number of small changes. This research proposes that improving the management of comfort knowledge will improve comfort. ComMet is a new methodology proposed by this research that manages comfort knowledge. It enables comfort knowledge to be captured, stored and accessed throughout the building life-cycle and so allowing it to be re-used in future stages of the building project and in future projects. It does this using the following: Comfort Performances – These are simplified numerical representations of the comfort of the indoor environment. Comfort Performances quantify the comfort at each stage of the building life-cycle using standard comfort metrics. Comfort Ratings - These are a means of classifying the comfort conditions of the indoor environment according to an appropriate standard. Comfort Ratings are generated by comparing different Comfort Performances. Comfort Ratings provide additional information relating to the comfort conditions of the indoor environment, which is not readily determined from the individual Comfort Performances. Comfort History – This is a continuous descriptive record of the comfort throughout the project, with a focus on documenting the items and activities, proposed and implemented, which could potentially affect comfort. Each aspect of the Comfort History is linked to the relevant comfort entity it references. These three components create a comprehensive record of the comfort throughout the building lifecycle. They are then stored and made available in a common format in a central location which allows them to be re-used ad infinitum. The LCMS System was developed to implement the ComMet methodology. It uses current and emerging technologies to capture, store and allow easy access to comfort knowledge as specified by ComMet. LCMS is an IT system that is a combination of the following six components: Building Standards; Modelling & Simulation; Physical Measurement through the specially developed Egg-Whisk (Wireless Sensor) Network; Data Manipulation; Information Recording; Knowledge Storage and Access.Results from a test case application of the LCMS system - an existing office room at a research facility - highlighted that while some aspects of comfort were being maintained, the building’s environment was not in compliance with the acceptable levels as stipulated by the relevant building standards. The implementation of ComMet, through LCMS, demonstrates how comfort, typically only considered during early design, can be measured and managed appropriately through systematic application of the methodology as means of ensuring a healthy internal environment in the building.

Fabrication and characterisation of semiconductor nanowires and metal interconnects

One-dimensional semiconductor nanowires are considered to be promising materials for future nanoelectronic applications. However, before these nanowires can be integrated into such applications, a thorough understanding of their growth behaviour is necessary. In particular, methods that allow the control over nanowire growth are deemed especially important as it is these methods that will enable the control of nanowire dimensions such as length and diameter (high aspect ratios). The production of nanowires with high-aspect ratios is vital in order to take advantage of the unique properties experienced at the nanoscale, thus allowing us to maximise their use in devices. Additionally, the development of low-resistivity interconnects is desirable in order to connect such nanowires in multi-nanowire components. Consequently, this thesis aims to discuss the synthesis and characterisation of germanium (Ge) nanowires and platinum (Pt) interconnects. Particular emphasis is placed on manipulating the nanowire growth kinetics to produce high aspect ratio structures. The discussion of Pt interconnects focuses on the development of low-resistivity devices and the electrical and structural analysis of those devices. Chapter 1 reviews the most critical aspects of Ge nanowire growth which must be understood before they can be integrated into future nanodevices. These features include the synthetic methods employed to grow Ge nanowires, the kinetic and thermodynamic aspects of their growth and nanowire morphology control. Chapter 2 outlines the experimental methods used to synthesise and characterise Ge nanowires as well as the methods used to fabricate and analyse Pt interconnects. Chapter 3 discusses the control of Ge nanowire growth kinetics via the manipulation of the supersaturation of Ge in the Au/Ge binary alloy system. This is accomplished through the use of bi-layer films, which pre-form Au/Ge alloy catalysts before the introduction of the Ge precursor. The growth from these catalysts is then compared with Ge nanowire growth from standard elemental Au seeds. Nanowires grown from pre-formed Au/Ge alloy seeds demonstrate longer lengths and higher growth rates than those grown from standard Au seeds. In-situ TEM heating on the Au/Ge bi-layer films is used to support the growth characteristics observed. Chapter 4 extends the work of chapter 3 by utilising Au/Ag/Ge tri-layer films to enhance the growth rates and lengths of Ge nanowires. These nanowires are grown from Au/Ag/Ge ternary alloy catalysts. Once again, the supersaturation is influenced, only this time it is through the simultaneous manipulation of both the solute concentration and equilibrium concentration of Ge in the Au/Ag/Ge ternary alloy system. The introduction of Ag to the Au/Ge binary alloy lowers the equilibrium concentration, thus increasing the nanowire growth rate and length. Nanowires with uniform diameters were obtained via synthesis from AuxAg1-x alloy nanoparticles. Manifestation of the Gibbs-Thomson effect, resulting from the dependence of the mean nanowire length as a function of diameter, was observed for all of the nanowires grown from the AuxAg1-x nanoparticles. Finally, in-situ TEM heating was used to support the nanowire growth characteristics. Chapter 5 details the fabrication and characterisation of Pt interconnects deposited by electron beam induced deposition of two different precursors. The fabrication is conducted inside a dual beam FIB. The electrical and structural characteristics of interconnects deposited from a standard organometallic precursor and a novel carbon-free precursor are compared. The electrical performance of the carbon-free interconnects is shown to be superior to that of the organometallic devices and this is correlated to the structural composition of both interconnects via in-situ TEM heating and HAADF-STEM analysis. Annealing of the interconnects is carried out under two different atmospheres in order to reduce the electrical resistivity even further. Finally, chapter 6 presents some important conclusions and summarises each of the previous chapters.

Pyramidal quantum dots: single and entangled photon sources and correlation studies

Practical realisation of quantum information science is a challenge being addressed by researchers employing various technologies. One of them is based on quantum dots (QD), usually referred to as artificial atoms. Being capable to emit single and polarization entangled photons, they are attractive as sources of quantum bits (qubits) which can be relatively easily integrated into photonic circuits using conventional semiconductor technologies. However, the dominant self-assembled QD systems suffer from asymmetry related problems which modify the energetic structure. The main issue is the degeneracy lifting (the fine-structure splitting, FSS) of an optically allowed neutral exciton state which participates in a polarization-entanglement realisation scheme. The FSS complicates polarization-entanglement detection unless a particular FSS manipulation technique is utilized to reduce it to vanishing values, or a careful selection of intrinsically good candidates from the vast number of QDs is carried out, preventing the possibility of constructing vast arrays of emitters on the same sample. In this work, site-controlled InGaAs QDs grown on (111)B oriented GaAs substrates prepatterned with 7.5 μm pitch tetrahedrons were studied in order to overcome QD asymmetry related problems. By exploiting an intrinsically high rotational symmetry, pyramidal QDs were shown as polarization-entangled photon sources emitting photons with the fidelity of the expected maximally entangled state as high as 0.721. It is the first site-controlled QD system of entangled photon emitters. Moreover, the density of such emitters was found to be as high as 15% in some areas: the density much higher than in any other QD system. The associated physical phenomena (e.g., carrier dynamic, QD energetic structure) were studied, as well, by different techniques: photon correlation spectroscopy, polarization-resolved microphotoluminescence and magneto-photoluminescence.

Stress-induced visceral pain in rodents: neurochemical, hormonal, immune and epigenetic mechanisms

Visceral pain is a debilitating disorder which affects up to 25% of the population at any one time. It is a global term used to describe pain originating from the internal organs, which is distinct from somatic pain. Currently the treatment strategies are unsatisfactory, with development of novel therapeutics hindered by a lack of detailed knowledge of the underlying mechanisms. The work presented in this thesis aimed to redress this issue and look in more detail at the molecular mechanisms of visceral pain in preclinical models. Stress has long been implicated in the pathophysiology of visceral pain in both preclinical and clinical studies. Here a mouse model of early-life stress-induced visceral hypersensitivity was validated. Moreover, mouse strain differences were also apparent in visceral sensitivity suggesting a possible genetic component to the underlying pathophysiology. Furthermore, gender and sex hormones were also implicated in stress sensitivity and visceral pain. Using the rat model of maternal separation, some of the epigenetic mechanisms underpinning visceral hypersensitivity, specifically the contribution of histone acetylation were unravelled. Glutamate has been well established in somatic pain processing, however, its contribution to visceral pain has not been extensively characterised. It was found that glutamate uptake is impaired in viscerally hypersensitive animals, an effect which could be reversed by treatment with riluzole, a glutamate uptake activator. Moreover, negative modulation of the metabotropic glutamate (mGlu) receptor 7 was sufficient to reverse visceral hypersensitivity in a stress sensitive rat strain, the Wistar Kyoto rat. Furthermore, toll-like receptor 4 (TLR4) was implicated in chronic stress-induced visceral hypersensitivity. Taken together, these findings have furthered our knowledge of the pathophysiology of visceral pain. In addition, we have identified glutamate transporters, mGlu7 receptor, histone acetylation and TLR4 as novel targets, amenable to pharmacological manipulation for the specific treatment of visceral pain.

Studies on factors relating to the development of defects in commercial cheese

Defects in commercial cheese result in a downgrading of the final cheese and a consequential economic loss to the cheese producer. Developments of defects in cheese are often not fully understood and therefore not controllable by the producer. This research investigated the underlying factors in the development of split and secondary fermentation defect and of pinking defects in commercial Irish cheeses. Split defect in Swiss-type cheese is a common defect associated with eye formation and manifests as slits and cracks visible in the cut cheese loaf (Reinbold, 1972; Daly et al., 2010). No consensus exists as to the definitive causes of the defect and possible factors which may contribute to the defect were reviewed. Models were derived to describe the relationship between moisture, pH, and salt levels and the distance from sample location to the closest external block surface during cheese ripening. Significant gradients within the cheese blocks were observed for all measured parameters in cheeses at 7 day post/after manufacture. No significant pH gradient was found within the blocks on exit from hot-room ripening and at three months post exit from the hot-room. Moisture content reached equilibrium within the blocks between exit from hot-room and 3 months after exit from hot-room while salt and salt-to-moisture levels had not reached equilibrium within the cheese blocks even at three months after exit from hot-room ripening. A characterisation of Swiss-type cheeses produced from a seasonal milk supply was undertaken. Cheeses were sampled on two days per month of the production year, at three different times during the manufacturing day, at internal and external regions of the cheese block and at four ripening time points (7 days post manufacture, post hot-room, 14 days post hot-room and 3 months in a cold room after exit from hot-room). Compositional, biochemical and microbial indices were determined, and the results were analysed as a splitplot with a factorial arrangement of treatments (season, time of day, area) on the main plot and ripening time on the sub-plot. Season (and interactions) had a significant effect on pH and salt-in-moisture levels (SM), mean viable counts of L. helveticus, propionic acid and non-starter lactic acid bacteria, levels of primary and secondary proteolysis and cheese firmness. Levels of proteolysis increased significantly during hot-room ripening but also during cold room storage, signifying continued development of cheese ripening during cold storage (> 8°C). Rheological parameters (e.g. springiness and cohesiveness) were significantly affected by interactions between ripening and location within cheese blocks. Time of day of manufacture significantly affected mean cheese calcium levels at 7 days post manufacture and mean levels of arginine and mean viable counts of NSLAB. Cheeses produced during the middle of the production day had the best grading scores and were more consistent compared to cheeses produced early or late during day of manufacture. Cheeses with low levels of S/M and low values of resilience were associated with poor grades at 7 days post manufacture. Chesses which had high elastic index values and low values of springiness in the external areas after exit from hot-room ripening also obtained good commercial grades. Development of a pink colour defect is an intermittent defect in ripened cheese which may or may not contain an added colourant, e.g., annatto. Factors associated with the defect were reviewed. Attempts at extraction and identification of the pink discolouration were unsuccessful. The pink colour partitioned with the water insoluble protein fraction. No significant difference was observed between ripened control and defect cheese for oxygen levels and redox potential or for the results of elemental analysis. A possible relationship between starter activity and defect development was established in cheeses with added coulourant, as lower levels of residual galactose and lactose were observed in defective cheese compared to control cheese free of the defect. Swiss-type cheese without added colourant had significantly higher levels of arginine and significantly lower lactate levels. Flow cell cytometry indicated that levels of bacterial cell viability and metabolic state differed between control and defect cheeses (without added colourant). Pyrosequencing analysis of cheese samples with and without the defect detected the previously unreported bacteria in cheese, Deinococcus thermus (a potential carotenoid producer). Defective Swiss-type cheeses had elevated levels of Deinococcus thermus compared to control cheeses, however the direct cause of pink was not linked to this bacterium alone. Overall, research was undertaken on underlying factors associated with the development of specific defects in commercial cheese, but also characterised the dynamic changes in key microbial and physicochemical parameters during cheese ripening and storage. This will enable the development of processing technologies to enable seasonal manipulation of manufacture protocols to minimise compositional and biochemical variability and to reduce and inhibit the occurrence of specific quality defects.

Towards the enantioselective synthesis of Plakortide P and its application to the development of drugs for the treatment of Chagas disease

The primary focus of this thesis was the asymmetric peroxidation of α,β-unsaturated aldehydes and the development of this methodology to include the synthesis of bioactive chiral 1,2-dioxane and 1,2-dioxalane rings. In Chapter 1 a review detailing the new and improved methods for the acyclic introduction of peroxide functionality to substrates over the last decade was discussed. These include a detailed examination of metal-mediated transformations, chiral peroxidation using organocatalytic means and the improvements in methodology of well-established peroxidation pathways. The second chapter discusses the method by which peroxidation of our various substrates was attempted and the optimisation studies associated with these reactions. The method by which the enantioselectivity of our β-peroxyaldehydes was determined is also reviewed. Chapters 3 and 4 focus on improving the enantioselectivity associated with our asymmetric peroxidation reaction. A comprehensive analysis exploring the effect of solvent, concentration and temperature on enantioselectivity was examined. The effect that different catalytic systems have on enantioselectivity and reactivity was also investigated in depth. Chapter 5 details the various transformations that β-peroxyaldehydes can undergo and the manipulation of these transformations towards the establishment of several routes for the formation of chiral 1,2-dioxane and 1,2-dioxalane rings. Chapter 6 details the full experimental procedures, including spectroscopic and analytical data for the compounds prepared during this research.

Development of large-scale colloidal crystallisation methods for the production of photonic crystals

Colloidal photonic crystals have potential light manipulation applications including; fabrication of efficient lasers and LEDs, improved optical sensors and interconnects, and improving photovoltaic efficiencies. One road-block of colloidal selfassembly is their inherent defects; however, they can be manufactured cost effectively into large area films compared to micro-fabrication methods. This thesis investigates production of ‘large-area’ colloidal photonic crystals by sonication, under oil co-crystallization and controlled evaporation, with a view to reducing cracking and other defects. A simple monotonic Stöber particle synthesis method was developed producing silica particles in the range of 80 to 600nm in a single step. An analytical method assesses the quality of surface particle ordering in a semiquantitative manner was developed. Using fast Fourier transform (FFT) spot intensities, a grey scale symmetry area method, has been used to quantify the FFT profiles. Adding ultrasonic vibrations during film formation demonstrated large areas could be assembled rapidly, however film ordering suffered as a result. Under oil cocrystallisation results in the particles being bound together during film formation. While having potential to form large areas, it requires further refinement to be established as a production technique. Achieving high quality photonic crystals bonded with low concentrations (<5%) of polymeric adhesives while maintaining refractive index contrast, proved difficult and degraded the film’s uniformity. A controlled evaporation method, using a mixed solvent suspension, represents the most promising method to produce high quality films over large areas, 75mm x 25mm. During this mixed solvent approach, the film is kept in the wet state longer, thus reducing cracks developing during the drying stage. These films are crack-free up to a critical thickness, and show very large domains, which are visible in low magnification SEM images as Moiré fringe patterns. Higher magnification reveals separation between alternate fringe patterns are domain boundaries between individual crystalline growth fronts.

Formation and characterisation of ordered porous vanadium oxide inverse opal materials for Li-ion batteries

This thesis presents several routes towards achieving artificial opal templates by colloidal self-assembly of polystyrene (PS) or poly(methyl methacrylate) (PMMA) spheres and the use of these template for the fabrication of V2O5 inverse opals as cathode materials for lithium ion battery applications. First, through the manipulation of different experimental factors, several methods of affecting or directing opal growth towards realizing different structures, improving order and/or achieving faster formation on a variety of substrates are presented. The addition of the surfactant sodium dodecyl sulphate (SDS) at a concentration above the critical micelle concentration for SDS to a 5 wt% solution of PMMA spheres before dip-coating is presented as a method of achieving ordered 2D PhC monolayers on hydrophobic Au-coated silicon substrates at fast and slow rates of withdrawal. The effect that the degree of hydrophilicity of glass substrates has on the ordering of PMMA spheres is next investigated for a slow rate of withdrawal under noise agitation. Heating of the colloidal solution is also presented as a means of affecting order and thickness of opal deposits formed using fast rate dip coating. E-beam patterned substrates are shown as a means of altering the thermodynamically favoured FCC ordering of polystyrene spheres (PS) when dip coated at slow rate. Facile routes toward the synthesis of ordered V2O5 inverse opals are presented with direct infiltration of polymer sphere templates using liquid precursor. The use of different opal templates, both 2D and 3D partially ordered templates, is compared and the composition and arrangement of the subsequent IO structures post infiltration and calcination for various procedures is characterised. V2O5 IOs are also synthesised by electrodeposition from an aqueous VOSO4 solution at constant voltage. Electrochemical characterisation of these structures as cathode material for Li-ion batteries is assessed in a half cell arrangement for samples deposited on stainless steel foil substrates. Improved rate capabilities are demonstrated for these materials over bulk V2O5, with the improvement attributed to the shorter Li ion diffusion distances and increased electrolyte infiltration provided by the IO structure.