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.

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.

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.

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.