13 resultados para Attached gingiva

em CORA - Cork Open Research Archive - University College Cork - Ireland


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This work presents the design and evaluation of the REAM (Remote Electricity Actuation and Monitoring) node based around the modular Tyndall Mote platform. The REAM node enables the user to remotely actuate power to a mains power extension board while sampling the current, voltage, power and power factor of the attached load. The node contains a current transformer interfaced to an Energy Metering IC which continuously samples current and voltage. These values are periodically read from the part by a PIC24 microcontroller, which calculates the RMS current and voltage, power factor and overall power. The resultant values can then be queried wirelessly employing the Tyndall 802.15.4 compliant wireless module.

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In this work, we investigate tennis stroke recognition using a single inertial measuring unit attached to a player’s forearm during a competitive match. This paper evaluates the best approach for stroke detection using either accelerometers, gyroscopes or magnetometers, which are embedded into the inertial measuring unit. This work concludes what is the optimal training data set for stroke classification and proves that classifiers can perform well when tested on players who were not used to train the classifier. This work provides a significant step forward for our overall goal, which is to develop next generation sports coaching tools using both inertial and visual sensors in an instrumented indoor sporting environment.

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This thesis describes the optimisation of chemoenzymatic methods in asymmetric synthesis. Modern synthetic organic chemistry has experienced an enormous growth in biocatalytic methodologies; enzymatic transformations and whole cell bioconversions have become generally accepted synthetic tools for asymmetric synthesis. Biocatalysts are exceptional catalysts, combining broad substrate scope with high regio-, enantio- and chemoselectivities enabling the resolution of organic substrates with superb efficiency and selectivity. In this study three biocatalytic applications in enantioselective synthesis were explored and perhaps the most significant outcome of this work is the excellent enantioselectivity achieved through optimisation of reaction conditions improving the synthetic utility of the biotransformations. In the first chapter a summary of literature discussing the stereochemical control of baker’s yeast (Saccharomyces Cerevisae) mediated reduction of ketones by the introduction of sulfur moieties is presented, and sets the work of Chapter 2 in context. The focus of the second chapter was the synthesis and biocatalytic resolution of (±)-trans-2-benzenesulfonyl-3-n-butylcyclopentanone. For the first time the practical limitations of this resolution have been addressed providing synthetically useful quantities of enantiopure synthons for application in the total synthesis of both enantiomers of 4-methyloctanoic acid, the aggregation pheromone of the rhinoceros beetles of the genus Oryctes. The unique aspect of this enantioselective synthesis was the overall regio- and enantioselective introduction of the methyl group to the octanoic acid chain. This work is part of an ongoing research programme in our group focussed on baker’s yeast mediated kinetic resolution of 2-keto sulfones. The third chapter describes hydrolase-catalysed kinetic resolutions leading to a series of 3-aryl alkanoic acids. Hydrolysis of the ethyl esters with a series of hydrolases was undertaken to identify biocatalysts that yield the corresponding acids in highly enantioenriched form. Contrary to literature reports where a complete disappearance of efficiency and, accordingly enantioselection, was described upon kinetic resolution of sterically demanding 3-arylalkanoic acids, the highest reported enantiopurities of these acids was achieved (up to >98% ee) in this study through optimisation of reaction conditions. Steric and electronic effects on the efficiency and enantioselectivity of the biocatalytic transformation were also explored. Furthermore, a novel approach to determine the absolute stereochemistry of the enantiopure 3-aryl alkanoic acids was investigated through combination of co-crystallisation and X-ray diffraction linked with chiral HPLC analysis. The fourth chapter was focused on the development of a biocatalytic protocol for the asymmetric Henry reaction. Efficient kinetic resolution in hydrolase-mediated transesterification of cis- and trans- β-nitrocyclohexanol derivatives was achieved. Combination of a base-catalysed intramolecular Henry reaction coupled with the hydrolase-mediated kinetic resolution with the view to selective acetylation of a single stereoisomer was investigated. While dynamic kinetic resolution in the intramolecular Henry was not achieved, significant progress in each of the individual elements was made and significantly the feasibility of this process has been demonstrated. The final chapter contains the full experimental details, including spectroscopic and analytical data of all compounds synthesised in this project, while details of chiral HPLC analysis are included in the appendix. The data for the crystal structures are contained in the attached CD.

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There are a number of reasons why this researcher has decided to undertake this study into the differences in the social competence of children who attend integrated Junior Infant classes and children who attend segregated learning environments. Theses reasons are both personal and professional. My personal reasons stem from having grown up in a family which included both an aunt who presented with Down Syndrome and an uncle who presented with hearing impairment. Both of these relatives' experiences in our education system are interesting. My aunt was considered ineducable while her brother - my uncle - was sent to Dublin (from Cork) at six years of age to be educated by a religious order. My professional reasons, on the other hand, stemmed from my teaching experience. Having taught in both special and integrated classrooms it became evident to me that there was somewhat 'suspicion' attached to integration. Parents of children without disabilities questioned whether this process would have a negative impact on their children's education. While parents of children with disabilities debated whether integrated settings met the specific needs of their children. On the other hand, I always questioned whether integration and inclusiveness meant the same thing. My research has enabled me to find many answers. Increasingly, children with special educational needs (SEN) are attending a variety of integrated and inclusive childcare and education settings. This contemporary practice of educating children who present with disabilities in mainstream classrooms has stimulated vast interest on the impact of such practices on children with identified disabilities. Indeed, children who present with disabilities "fare far better in mainstream education than in special schools" (Buckley, cited in Siggins, 2001,p.25). However, educators and practitioners in the field of early years education and care are concerned with meeting the needs of all children in their learning environments, while also upholding high academic standards (Putman, 1993). Fundamentally, therefore, integrated education must also produce questions about the impact of this practice on children without identified special educational needs. While these questions can be addressed from the various areas of child development (i.e. cognitive, physical, linguistic, emotional, moral, spiritual and creative), this research focused on the social domain. It investigates the development of social competence in junior infant class children without identified disabilities as they experience different educational settings.

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Plant galls constitute a branch of study and research which has been to me a subject of much interest for some time. At the start of this work, it was intended to include Plant galls in general, but after some months this was found to be too comprehensive a field and would in fact take a great many years to study fully. Even leaf galls alone, both of herbs and trees provide so large a field of investigation that ultimately I decided to confine my attention to those or our native trees and shrubs. Upon looking up the literature on this subject, it will be found that in nearly all cases, either the gall is described fully and mere mention made or the agent concerned in its production, or vice versa. This state of things is most unsatisfactory, as in studying galls, both the gall-maker and the gall formation must be examined in detail before it is safe to apply nomenclature. This work, therefore, sets out to give accurate and scientific descriptions of both galls and gall-makers. The difficulties encountered are manifold; firstly, our trees are all deciduous, hence, the collecting period is necessarily restricted to that time of the year between the appearance of the buds and the fall of the leaf. Secondly, the rearing of imagines is always difficult, especially in the case or the autumn gall; more will be said on this matter later. Lastly, due to war-time conditions much trouble was experienced in obtaining suitable literature and many invaluable books on this subject were unprocurable. The Plates at the back have all been copied from original material except in the case or the Phytoptid mites which have been sketched with the help of illustrations, the reason for this being the difficulty of making suitable mounts of these minute creatures, Where possible all stages or at least larva and imago have been sketched, together with the host plant and the type of gall-formation produced. Slides have also been made of most larvae and the imagines attached to cards and pinned on to pith or cork in the usual manner.

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The research described in this thesis focuses on the design and synthesis of stable α-diazosulfoxides and investigation of their reactivity under a variety of conditions (transition-metal catalysis, thermal, photochemical and microwave) with a particular emphasis on the synthesis of novel heterocyclic compounds with potential biological activity. The exclusive reaction pathway for these α-diazosulfoxides was found to be hetero-Wolff rearrangement to give α-oxosulfine intermediates. In the first chapter, a literature review of sulfines is presented, including a discussion of naturally occurring sulfines, and an overview of the synthesis and reactivity of sulfines. The potential of sulfines in organic synthesis and recent developments in particular are highlighted. The second chapter discusses the synthesis and reactivity of α-diazosulfoxides, building on earlier results in this research group. The synthesis of lactone-based α-diazosulfoxides and, for the first time, ketone-based benzofused and monocyclic α-diazosulfoxides is described. The reactivity of these α-diazosulfoxides is then explored under a variety of conditions, such as transition-metal catalysis, photochemical and microwave, generating labile α-oxosulfine intermediates, which are trapped using amines and dienes, in addition to the spontaneous reaction pathways which occur with α-oxosulfines in the absence of a trap. A new reaction pathway was explored with the lactone based α-oxosulfines, involving reaction with amines to generate novel 3-aminofuran-2(5H)-ones via carbophilic attack, in very good yields. The reactivity of ketone-based α-diazosulfoxides was explored for the first time, and once again, pseudo-Wolff rearrangement to the α-oxosulfines was the exclusive reaction pathway observed. The intermediacy of the α-oxosulfines was confirmed by trapping as cycloadducts, with the stereochemical features dependant on the reaction conditions. In the absence of a diene trap, a number of reaction fates from the α-oxosulfines were observed, including complete sulfinyl extrusion to give indanones, sulfur extrusion to give indanediones, and, to a lesser extent, dimerisation. The indanediones were characterised by trapping as quinoxalines, to enable full characterisation. One of the overriding outcomes of this thesis was the provision of new insights into the behaviour of α-oxosulfines with different transition metal catalysts, and under thermal, microwave and photolysis conditions. A series of 3-aminofuran-2(5H)-ones and benzofused dihydro-2H-thiopyran S-oxides were submitted for anticancer screening at the U.S. National Cancer Institute. A number of these derivatives were identified as hit compounds, with excellent cell growth inhibition. One 3-aminofuran-2(5H)-one derivative has been chosen for further screening. The third chapter details the full experimental procedures, including spectroscopic and analytical data for the compounds prepared during this research. The data for the crystal structures are contained in the attached CD.

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The overall objective of this thesis is to integrate a number of micro/nanotechnologies into integrated cartridge type systems to implement such biochemical protocols. Instrumentation and systems were developed to interface such cartridge systems: (i) implementing microfluidic handling, (ii) executing thermal control during biochemical protocols and (iii) detection of biomolecules associated with inherited or infectious disease. This system implements biochemical protocols for DNA extraction, amplification and detection. A digital microfluidic chip (ElectroWetting on Dielectric) manipulated droplets of sample and reagent implementing sample preparation protocols. The cartridge system also integrated a planar magnetic microcoil device to generate local magnetic field gradients, manipulating magnetic beads. For hybridisation detection a fluorescence microarray, screening for mutations associated with CFTR gene is printed on a waveguide surface and integrated within the cartridge. A second cartridge system was developed to implement amplification and detection screening for DNA associated with disease-causing pathogens e.g. Escherichia coli. This system incorporates (i) elastomeric pinch valves isolating liquids during biochemical protocols and (ii) a silver nanoparticle microarray for fluorescent signal enhancement, using localized surface plasmon resonance. The microfluidic structures facilitated the sample and reagent to be loaded and moved between chambers with external heaters implementing thermal steps for nucleic acid amplification and detection. In a technique allowing probe DNA to be immobilised within a microfluidic system using (3D) hydrogel structures a prepolymer solution containing probe DNA was formulated and introduced into the microfluidic channel. Photo-polymerisation was undertaken forming 3D hydrogel structures attached to the microfluidic channel surface. The prepolymer material, poly-ethyleneglycol (PEG), was used to form hydrogel structures containing probe DNA. This hydrogel formulation process was fast compared to conventional biomolecule immobilization techniques and was also biocompatible with the immobilised biomolecules, as verified by on-chip hybridisation assays. This process allowed control over hydrogel height growth at the micron scale.

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The bottom-up colloidal synthesis of photonic crystals has attracted interest over top-down approaches due to their relatively simplicity, the potential to produce large areas, and the low-costs with this approach in fabricating complex 3-dimensional structures. This thesis focuses on the bottom-up approach in the fabrication of polymeric colloidal photonic crystals and their subsequent modification. Poly(methyl methacrylate) sub-micron spheres were used to produce opals, inverse opals and 3D metallodielectric photonic crystal (MDPC) structures. The fabrication of MDPCs with Au nanoparticles attached to the PMMA spheres core–shell particles is described. Various alternative procedures for the fabrication of photonic crystals and MDPCs are described and preliminary results on the use of an Au-based MDPC for surface-enhanced Raman scattering (SERS) are presented. These preliminary results suggest a threefold increase of the Raman signal with the MDPC as compared to PMMA photonic crystals. The fabrication of PMMA-gold and PMMA-nickel MDPC structures via an optimised electrodeposition process is described. This process results in the formation of a continuous dielectric-metal interface throughout a 3D inverted photonic crystal structure, which are shown to possess interesting optical properties. The fabrication of a robust 3D silica inverted structure with embedded Au nanoparticles is described by a novel co-crystallisation method which is capable of creating a SiO2/Au NP composite structure in a single step process. Although this work focuses on the creation of photonic crystals, this co-crystallisation approach has potential for the creation of other functional materials. A method for the fabrication of inverted opals containing silicon nanoparticles using aerosol assisted chemical vapour deposition is described. Silicon is a high dielectric material and nanoparticles of silicon can improve the band gap and absorption properties of the resulting structure, and therefore have the potential to be exploited in photovoltaics.

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Group IV materials such as silicon nanocrystals (Si NCs) and carbon quantum dots (CQDs) have received great attention as new functional materials with unique physical/chemical properties that are not found in the bulk material. This thesis reports the synthesis and characterisation of both types of nanocrystal and their application as fluorescence probes for the detection of metal ions. In chapter 2, a simple method is described for the size controlled synthesis of Si NCs within inverse micelles having well defined core diameters ranging from 2 to 6 nm using inert atmospheric synthetic methods. In addition, ligands with different molecular structures were utilised to reduce inter-nanocrystal attraction forces and improve the stability of the NC dispersions in water and a variety of organic solvents. Regulation of the Si NCs size is achieved by variation of the surfactants and addition rates, resulting high quality NCs with standard deviations (σ = Δd/d) of less than 10 %. Large scale production of highly mondisperse Si NC was also successfully demonstrated. In chapter 3, a simple solution phase synthesis of size monodisperse carbon quantum dots (CQDs) using a room temperature microemulsion strategy is demonstrated. The CQDs are synthesized in reverse micelles via the reduction of carbon tetrachloride using a hydride reducing agent. CQDs may be functionalised with covalently attached alkyl or amine monolayers, rendering the CQDs dispersible in wide range of polar or non-polar solvents. Regulation of the CQDs size was achieved by utilizing hydride reducing agents of different strengths. The CQDs possess a high photoluminescence quantum yield in the visible region and exhibit excellent photostability. In chapter 4, a simple and rapid assay for detection of Fe3+ ions was developed, based on quenching of the strong blue-green Si NC photoluminescence. The detection method showed a high selectivity, with only Fe3+ resulting in strong quenching of the fluorescence signal. No quenching of the fluorescence signal was induced by Fe2+ ions, allowing for solution phase discrimination between the same ion in different charge states. The optimised sensor system showed a sensitive detection range from 25- 900 μM and a limit of detection of 20.8 μM

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Go príomha, is tráchtas é seo a dhéanann staidéar ar ghné de litríocht iar-chlasaiceach na Gaeilge. Baineann sé go háirithe leis an sraith chaointe nó marbhnaí i bhfoirm véarsaíochta a cumadh do Shéamas Óg Mac Coitir (1689-1720), duine uasal Caitliceach ó Charraig Tuathail, Co. Chorcaí, nuair a ciontaíodh é in éigniú Elizabeth Squibb, bean de Chumann na gCarad; nuair a cuireadh pionós an bháis air; agus nuair a crochadh é i gCathair Chorcaí an 7 Bealtaine, 1720. Ó thaobh na staire de, scrúdaítear Clann Choitir mar shampla de theaghlach nár cheil a ndílseacht do chúis pholaitiúil na Stíobhartach agus a sheas an fód go cróga faoi mar a bhí a ngreim polaitiúil á dhaingniú ag an gCinsealacht Phrotastúnach ó dheireadh an 17ú haois amach. Tagraítear do sheicteachas na sochaí comhaimseartha agus don teannas idir an pobal Caitliceach agus an pobal Protastúnach ag an am. Déantar scagadh ar an véarsaíocht mar fhoinse luachmhar do dhearcadh míshásta an mhóraimh Chaitlicigh ar struchtúr polaitiúil chontae Chorcaí (agus na hÉireann) i dtosach an 18ú haois. Is feiniméan liteartha an dlús véarsaíochta seo a bhaineann go háirithe le traidisiún liteartha Chorcaí. Tá na dánta curtha in eagar agus aistriúchán go Béarla curtha ar fáil: is é seo croí an tráchtais. Tá an t-eagrán bunaithe ar scrúdú cuimsitheach ar thraidisiún na lsí; pléitear modheolaíocht na heagarthóireachta. Déantar iarracht ar na dánta a shuíomh sa traidisiún casta liteartha sa tráchtaireacht tosaigh; sa chuid eile den bhfearas scoláiriúil, scrúdaítear ceisteanna a bhaineann le cúrsaí teanga, foclóra, meadarachta agus stíle. Tá innéacsanna agus liosta foinsí le fáil i ndeireadh an tráchtais.

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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.

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This thesis examines important issues of Irish vernacular Catholicism, Irish religious and cultural identities, the impacts of modernity plus socio-religious and economic change on traditional religiosity, sacred landscape and topophilia, religious material culture, folk and individual creativity, gender roles and expectations, and devotional subcultures through the vehicle of Marian apparitions and their aftermath in the Republic of Ireland in the late 20th and early 21st centuries. This thesis examines in detail five Irish Marian shrines as case studies; Knock shrine (Co. Mayo), Ballinspittle and Mitchelstown grottoes (Co. Cork), Mount Melleray grotto (Co. Waterford) and the Marian shrines of Inchigeela in West Cork and the attached houses of prayer. Key themes include; vernacular religious theory; the nature of Irish indigenous Catholicism; local, global and transnational trends in contemporary Irish devotional life; areas of individual creativity, fluidity and agency in Marian devotion; and the vital role and influence of material culture in and on local and individual religiosity.

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This portfolio of exploration explores the role of transformative thinking and practice in a property entrepreneur’s response to the financial crisis which swept over Ireland from 2008. The complexity of this challenge and the mental capacity to meet its demands is at the core of the exploration. This inquiry emerged from the challenges the financial crisis presented to my values, beliefs, assumptions, and theories, i.e. the interpretive lens through which I make meaning of my experiences. Given the issue identified, this inquiry is grounded in aspects of theories of constructive developmental psychology, applied developmental science, and philosophy. Integrating and linking these elements to business practice is the applied element of the Portfolio. As the 2008 crisis unfolded I realised I was at the limits of my way of knowing. I came to understand that the underlying structure of a way of knowing is the ‘subject-object relationship’ i.e. what a way of knowing can reflect upon, look at, have perspective on, in other words, make object, as against what is it embedded in, attached to, identified within, or subject to. My goal became enhancing my awareness of how I made meaning and how new insights, which would transform a way of knowing, are created. The focus was on enhancing my practice. This Portfolio is structured into three essays. Essay One reported on my self-reflection and external evaluation out of which emerged my developmental goals. In Essay Two I undertake a reading for change programme in which different meaning making systems were confronted in order to challenge me as a meaning maker. Essay Three reported on my experiment which concerned the question whether it was possible for me as a property entrepreneur, and for others alike, to retain bank finance in the face of the overwhelming objective of the bank to deleverage their balance sheet of property loans. The output of my research can be grouped into General Developmental and Specific Business Implications. Firstly I address those who are interested in a transformational-based response to the challenges of operating in the property sector in Ireland during a crisis. I outline the apparatus of thought that I used to create insight, and thus transform how I thought, these are Awareness, Subject-object separation, Exploring other’s perspectives from the position of incompleteness, Dialectical thinking and Collingwood’s Questioning activity. Secondly I set out my learnings from the crisis and their impact on entrepreneurial behaviour and the business of property development. I identify ten key insights that have emerged from leading a property company through the crisis. Many of these are grounded in common sense, however, in my experience these were, to borrow Shakespeare’s words, “More honor'd in the breach than the observance” in pre Crisis Ireland. Finally I set out a four-step approach for forging a strategy. This requires my peer practitioners to identify (i) what they are subject to, (ii) Assess the Opportunity or challenge in a Systemic Context, (iii) Explore Multiple Perspectives on the opportunity or Challenge with an Orientation to change how you know and (iv) Using the Questioning Activity to create Knowledge. Based on my experience I conclude that transformative thinking and practice is a key enabler for a property entrepreneur, in responding to a major collapse of traditional (bank debt) funding.