Low-dimensional, hinged bar-code metal oxide layers and free-standing, ordered organic nanostructures from turbostratic vanadium oxide

Both low-dimensional bar-coded metal oxide layers, which exhibit molecular hinging, and free-standing organic nanostructures can be obtained from unique nanofibers of vanadium oxide (VOx). The nanofibers are successfully synthesized by a simple chemical route using an ethanolic solution of vanadium pentoxide xerogel and dodecanethiol resulting in a double bilayered laminar turbostratic structure. The formation of vanadium oxide nanofibers is observed after hydrothermal treatment of the thiol-intercalated xerogel, resulting in typical lengths in the range 2–6 µm and widths of about 50–500 nm. We observe concomitant hinging of the flexible nanofiber lamina at periodic hinge points in the final product on both the nanoscale and molecular level. Bar-coded nanofibers comprise alternating segments of organic–inorganic (thiols–VOx) material and are amenable to segmented, localized metal nanoparticle docking. Under certain conditions free-standing bilayered organic nanostructures are realized.

Accommodating curvature in a highly ordered functionalized metal oxide nanofiber: synthesis, characterization and multi-scale modeling of layered nanosheets

A key element in the rational design of hybrid organic-inorganic nanostructures, is control of surfactant packing and adsorption onto the inorganic phase in crystal growth and assembly. In layered single crystal nanofibers and bilayered 2D nanosheets of vanadium oxide, we show how the chemisorption of preferred densities of surfactant molecules can direct formation of ordered, curved layers. The atom-scale features of the structures are described using molecular dynamics simulations that quantify surfactant packing effects and confirm the preference for a density of 5 dodecanethiol molecules per 8 vanadium attachment sites in the synthesised structures. This assembly maintains a remarkably well ordered interlayer spacing, even when curved. The assemblies of interdigitated organic bilayers on V2O5 are shown to be sufficiently flexible to tolerate curvature while maintaining a constant interlayer distance without rupture, delamination or cleavage. The accommodation of curvature and invariant structural integrity points to a beneficial role for oxide-directed organic film packing effects in layered architectures such as stacked nanofibers and hybrid 2D nanosheet systems.

The double bind for non-traditional families in post-primary settings; to tell or not to tell their family identity

This thesis involved researching normative family discourses which are mediated through educational settings. The traditional family, consisting of father, mother and children all living together in one house is no longer reflective of the home situation of many Irish students (Lunn and Fahey, 2011). My study problematizes the dominant discourses which reflect how family differences are managed and recognised in schools. A framework using Foucauldian post structural critical analysis traces family stratification through the organisation of institutional and interpersonal relations at micro level in four post-primary schools. Standardising procedures such as the suppression of intimate relations between and among teacher and student, as well as the linear ordering of intergenerational relations, such as teacher/student and adult/child are critiqued. Normalising discourses operate in practices such as notes home which presume two parents together. Teacher assumptions about heterosexual two-parent families make it difficult for students to be open about a family setup that is constructed as different to the rest of the schools'. The management of family difference and deficit through pastoral care structures suggests a school-based politics of family adjustment. These practices beg the question whether families are better off not telling the school about their family identity. My thesis will be of interest to educational research and educational policy because it highlights how changing demographics such as family compositions are mis-conceptualised in schools, as well as revealing the changing forms of family governance through regimes such as pastoral care. This analysis allows for the existence of, and a valuing for, alternative modes of family existence, so that future curricular and legal discourses can be challenged in the interest of equity and social justice.

Reasoning with sorted-pareto dominance and other qualitative and partially ordered preferences in soft constraints

In decision making problems where we need to choose a particular decision or alternative from a set of possible choices, we often have some preferences which determine if we prefer one decision over another. When these preferences give us an ordering on the decisions that is complete, then it is easy to choose the best or one of the best decisions. However it often occurs that the preferences relation is partially ordered, and we have no best decision. In this thesis, we look at what happens when we have such a partial order over a set of decisions, in particular when we have multiple orderings on a set of decisions, and we present a framework for qualitative decision making. We look at the different natural notions of optimal decision that occur in this framework, which gives us different optimality classes, and we examine the relationships between these classes. We then look in particular at a qualitative preference relation called Sorted-Pareto Dominance, which is an extension of Pareto Dominance, and we give a semantics for this relation as one that is compatible with any order-preserving mapping of an ordinal preference scale to a numerical one. We apply Sorted-Pareto dominance to a Soft Constraints setting, where we solve problems in which the soft constraints associate qualitative preferences to decisions in a decision problem. We also examine the Sorted-Pareto dominance relation in the context of our qualitative decision making framework, looking at the relevant optimality classes for the Sorted-Pareto case, which gives us classes of decisions that are necessarily optimal, and optimal for some choice of mapping of an ordinal scale to a quantitative one. We provide some empirical analysis of Sorted-Pareto constraints problems and examine the optimality classes that result.

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.

A critical realist examination of the inhibitors of double loop learning in an agile adoption

The original solution to the high failure rate of software development projects was the imposition of an engineering approach to software development, with processes aimed at providing a repeatable structure to maintain a consistency in the ‘production process’. Despite these attempts at addressing the crisis in software development, others have argued that the rigid processes of an engineering approach did not provide the solution. The Agile approach to software development strives to change how software is developed. It does this primarily by relying on empowered teams of developers who are trusted to manage the necessary tasks, and who accept that change is a necessary part of a development project. The use of, and interest in, Agile methods in software development projects has expanded greatly, yet this has been predominantly practitioner driven. There is a paucity of scientific research on Agile methods and how they are adopted and managed. This study aims at addressing this paucity by examining the adoption of Agile through a theoretical lens. The lens used in this research is that of double loop learning theory. The behaviours required in an Agile team are the same behaviours required in double loop learning; therefore, a transition to double loop learning is required for a successful Agile adoption. The theory of triple loop learning highlights that power factors (or power mechanisms in this research) can inhibit the attainment of double loop learning. This study identifies the negative behaviours - potential power mechanisms - that can inhibit the double loop learning inherent in an Agile adoption, to determine how the Agile processes and behaviours can create these power mechanisms, and how these power mechanisms impact on double loop learning and the Agile adoption. This is a critical realist study, which acknowledges that the real world is a complex one, hierarchically structured into layers. An a priori framework is created to represent these layers, which are categorised as: the Agile context, the power mechanisms, and double loop learning. The aim of the framework is to explain how the Agile processes and behaviours, through the teams of developers and project managers, can ultimately impact on the double loop learning behaviours required in an Agile adoption. Four case studies provide further refinement to the framework, with changes required due to observations which were often different to what existing literature would have predicted. The study concludes by explaining how the teams of developers, the individual developers, and the project managers, working with the Agile processes and required behaviours, can inhibit the double loop learning required in an Agile adoption. A solution is then proposed to mitigate these negative impacts. Additionally, two new research processes are introduced to add to the Information Systems research toolkit.

Micro and nanostructured impedance sensors for biological and biomedical applications

This thesis work covered the fabrication and characterisation of impedance sensors for biological applications aiming in particular to the cytotoxicity monitoring of cultured cells exposed to different kind of chemical compounds and drugs and to the identification of different types of biological tissue (fat, muscles, nerves) using a sensor fabricated on the tip of a commercially available needle during peripheral nerve block procedures. Gold impedance electrodes have been successfully fabricated for impedance measurement on cells cultured on the electrode surface which was modified with the fabrication of gold nanopillars. These nanostructures have a height of 60nm or 100nm and they have highly ordered layout as they are fabricated through the e-beam technique. The fabrication of the threedimensional structures on the interdigitated electrodes was supposed to improve the sensitivity of the ECIS (electric cell-substrate impedance sensing) measurement while monitoring the cytotoxicity effects of two different drugs (Antrodia Camphorata extract and Nicotine) on three different cell lines (HeLa, A549 and BALBc 3T3) cultured on the impedance devices and change the morphology of the cells growing on the nanostructured electrodes. The fabrication of the nanostructures was achieved combining techniques like UV lithography, metal lift-off, evaporation and e-beam lithography techniques. The electrodes were packaged using a pressure sensitive, medical grade adhesive double-sided tape. The electrodes were then characterised with the aid of AFM and SEM imaging which confirmed the success of the fabrication processes showing the nanopillars fabricated with the right layout and dimensions figures. The introduction of nanopillars on the impedance electrodes, however, did not improve much the sensitivity of the assay with the exception of tests carried out with Nicotine. HeLa and A549 cells appeared to grow in a different way on the two surfaces, while no differences where noticed on the BALBc 3T3 cells. Impedance measurements obtained with the dead cells on the negative control electrodes or the test electrodes with the drugs can be compared to those done on the electrodes containing just media in the tested volume (as no cells are attached and cover the electrode surface). The impedance figures recorded using these electrodes were between 1.5kΩ and 2.5 kΩ, while the figures recorded on confluent cell layers range between 4kΩ and 5.5kΩ with peaks of almost 7 kΩ if there was more than one layer of cells growing on each other. There was then a very clear separation between the values of living cell compared to the dead ones which was almost 2.5 - 3kΩ. In this way it was very easy to determine whether the drugs affected the cells normal life cycle on not. However, little or no differences were noticed in the impedance analysis carried out on the two different kinds of electrodes using cultured cells. An increase of sensitivity was noticed only in a couple of experiments carried out on A549 cells growing on the nanostructured electrodes and exposed to different concentration of a solution containing Nicotine. More experiments to achieve a higher number of statistical evidences will be needed to prove these findings with an absolute confidence. The smart needle project aimed to reduce the limitations of the Electrical Nerve Stimulation (ENS) and the Ultra Sound Guided peripheral nerve block techniques giving the clinicians an additional tool for performing correctly the peripheral nerve block. Bioimpedance, as measured at the needle tip, provides additional information on needle tip location, thereby facilitating detection of intraneural needle placement. Using the needle as a precision instrument and guidance tool may provide additional information as to needle tip location and enhance safety in regional anaesthesia. In the time analysis, with the frequency fixed at 10kHz and the samples kept at 12°C, the approximate range for muscle bioimpedance was 203 – 616 Ω, the approximate bioimpedance range for fat was 5.02 - 17.8 kΩ and the approximate range for connective tissue was 790 Ω – 1.55 kΩ. While when the samples were heated at 37°C and measured again at 10kHz, the approximate bioimpedance range for muscle was 100-175Ω. The approximate bioimpedance range of fat was 627 Ω - 3.2 kΩ and the range for connective tissue was 221-540Ω. In the experiments done on the fresh slaughtered lamb carcass, replicating a scenario close to the real application, the impedance values recorded for fat were around 17 kΩ, for muscle and lean tissue around 1.3 kΩ while the nervous structures had an impedance value of 2.9 kΩ. With the data collected during this research, it was possible to conclude that measurements of bioimpedance at the needle tip location can give valuable information to the clinicians performing a peripheral nerve block procedure as the separation (in terms of impedance figures) was very marked between the different type of tissues. It is then feasible to use an impedance electrode fabricated on the needle tip to differentiate several tissues from the nerve tissue. Currently, several different methods are being studied to fabricate an impedance electrode on the surface of a commercially available needle used for the peripheral nerve block procedure.