973 resultados para Disorganized attachment


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Wydział Studiów Edukacyjnych: Zakład Teoretycznych Podstaw Edukacji

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The present work examines the beginnings of ancient hermeneutics. More specifically, it discusses the connection between the rise of the practice of allegoresis, on the one hand, and the emergence of the first theory of figurative language, on the other. Thus, this book investigates the specific historical and cultural circumstances that enabled the ancient Greeks not only to discover the possibility of allegorical interpretation, but also to treat figurative language as a philosophical problem. By posing difficulties in understanding the enigmatic sense of various esoteric doctrines, poems, oracles and riddles, figurative language created the context for theoretical reflection on the meaning of these “messages”. Hence, ancient interpreters began to ponder over the nature and functions of figurative (“enigmatic”) language as well as over the techniques of its proper use and interpretation. Although the practice of allegorical interpretation was closely linked to the development of the whole of ancient philosophy, the present work covers only the period from the 6th to the 4th century B.C. It concentrates, then, on the philosophical and cultural consequences of allegoresis in the classical age. The main thesis advocated here has it that the ancient Greeks were in-clined to regard allegory as a cognitive problem rather than merely as a stylistic or a literary one. When searching for the hidden meanings of various esoteric doc-trines, poems, oracles and riddles, ancient interpreters of these “messages” assumed allegory to be the only tool suitable for articulating certain matters. In other words, it was their belief that the use of figurative language resulted from the necessity of expressing things that were otherwise inexpressible. The present work has been organized in the following manner. The first part contains historical and philological discussions that provide the point of departure for more philosophical considerations. This part consists of two introductory chapters. Chapter one situates the practice of allegorical interpretation at the borderline of two different traditions: the rhetorical-grammatical and the hermeneutical. In order to clearly differentiate between the two, chapter one distinguishes between allegory and allegoresis, on the one hand, and allegoresis and exegesis, on the other. While pointing to the conventionality (and even arbitrariness) of such distinctions, the chapter argues, nevertheless, for their heuristic usefulness. The remaining part of chapter one focuses on a historical and philological reconstruction of the most important conceptual tools of ancient hermeneutics. Discussing the semantics of such terms as allēgoría, hypónoia, ainigma and symbolon proves important for at least two crucial reasons. Firstly, it reveals the mutual affinity between allegoresis and divination, i.e., practices that are inherently connected with the need to discover the latent meaning of the “message” in question (whether poem or oracle). Secondly, these philological analyses bring to light the specificity of the ancient understanding of such concepts as allegory or symbol. It goes without saying that antiquity employed these terms in a manner quite disparate from modernity. Chapter one concludes with a discussion of ancient views on the cognitive value of figurative (“enigmatic”) language. Chapter two focuses on the role that allegoresis played in the process of transforming mythos into logos. It is suggested here that it was the practice of allegorical interpretation that made it possible to preserve the traditional myths as an important point of reference for the whole of ancient philosophy. Thus, chapter two argues that the existence of a clear opposition between mythos into logos in Preplatonic philosophy is highly questionable in light of the indisputable fact that the Presocratics, Sophists and Cynics were profoundly convinced about the cognitive value of mythos (this conviction was also shared by Plato and Aristotle, but their attitude towards myth was more complex). Consequently, chapter two argues that in Preplatonic philosophy, myth played a function analogous to the concepts discussed in chapter one (i.e., hidden meanings, enigmas and symbols), for in all these cases, ancient interpreters found tools for conveying issues that were otherwise difficult to convey. Chapter two concludes with a classification of various types of allegoresis. Whilst chapters one and two serve as a historical and philological introduction, the second part of this book concentrates on the close relationship between the development of allegoresis, on the one hand, and the flowering of philosophy, on the other. Thus, chapter three discusses the crucial role that allegorical interpretation came to play in Preplatonic philosophy, chapter four deals with Plato’s highly complex and ambivalent attitude to allegoresis, and chapter five has been devoted to Aristotle’s original approach to the practice of allegorical interpretation. It is evident that allegoresis was of paramount importance for the ancient thinkers, irrespective of whether they would value it positively (Preplatonic philosophers and Aristotle) or negatively (Plato). Beginning with the 6th century B.C., the ancient practice of allegorical interpretation is motivated by two distinct interests. On the one hand, the practice of allegorical interpretation reflects the more or less “conservative” attachment to the authority of the poet (whether Homer, Hesiod or Orpheus). The purpose of this apologetic allegoresis is to exonerate poetry from the charges leveled at it by the first philosophers and, though to a lesser degree, historians. Generally, these allegorists seek to save the traditional paideia that builds on the works of the poets. On the other hand, the practice of allegorical interpretation reflects also the more or less “progressive” desire to make original use of the authority of the poet (whether Homer, Hesiod or Orpheus) so as to promote a given philosophical doctrine. The objective of this instrumental allegoresis is to exculpate philosophy from the accusations brought against it by the more conservative circles. Needless to say, these allegorists significantly contribute to the process of the gradual replacing of the mythical view of the world with its more philosophical explanation. The present book suggests that it is the philosophy of Aristotle that should be regarded as a sort of acme in the development of ancient hermeneutics. The reasons for this are twofold. On the one hand, the Stagirite positively values the practice of allegoresis, rehabilitating, thus, the tradition of Preplatonic philosophy against Plato. And, on the other hand, Aristotle initiates the theoretical reflection on figurative (“enigmatic”) language. Hence, in Aristotle we encounter not only the practice of allegoresis, but also the theory of allegory (although the philosopher does not use the term allēgoría). With the situation being as it is, the significance of Aristotle’s work cannot be overestimated. First of all, the Stagirite introduces the concept of metaphor into the then philosophical considerations. From that moment onwards, the phenomenon of figurative language becomes an important philosophical issue. After Aristo-tle, the preponderance of thinkers would feel obliged to specify the rules for the appropriate use of figurative language and the techniques of its correct interpretation. Furthermore, Aristotle ascribes to metaphor (and to various other “excellent” sayings) the function of increasing and enhancing our knowledge. Thus, according to the Stagirite, figurative language is not only an ornamental device, but it can also have a significant explanatory power. Finally, Aristotle observes that figurative expressions cause words to become ambiguous. In this context, the philosopher notices that ambiguity can enrich the language of a poet, but it can also hinder a dialectical discussion. Accordingly, Aristotle is inclined to value polysemy either positively or negatively. Importantly, however, the Stagirite is perfectly aware of the fact that in natural languages ambiguity is unavoidable. This is why Aristotle initiates a syste-matic reflection on the phenomenon of ambiguity and distinguishes its various kinds. In Aristotle, ambiguity is, then, both a problem that needs to be identified and a tool that can help in elucidating intricate philosophical issues. This unique approach to ambiguity and figurative (“enigmatic”) language enabled Aristotle to formulate invaluable intuitions that still await appropriate recognition.

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Dissertação de Mestrado apresentada à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Psicologia, especialização em Psicologia da Educação e Intervenção Comunitária.

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Tese de Doutoramento apresentada à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Doutor em Ciências Sociais.

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Dissertação apresentada à Universidade Fernando Pessoa como parte dos requisitos para a obtenção do grau de Mestre em Psicologia, ramo de Psicologia Clínica e da Saúde

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Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

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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.

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The focus of this thesis is the preparation of enantiopure sulfoxides by means of copper-catalysed asymmetric sulfoxidation, with particular emphasis on the synthesis of aryl benzyl and aryl alkyl sulfoxides. Chapter 1 contains a review of the methods employed for the asymmetric synthesis of sulfoxides, compounds with many applications in stereoselective synthesis and in some cases with pharmaceutical application. Chapter 1 describes asymmetric oxidation, including metal-catalysed, non metal-catalysed and enzyme-catalysed, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Kinetic resolution in oxidation of sulfoxides to the analogous sulfones is also discussed; in certain cases, access to enantioenriched sulfoxides can be achieved via a combination of asymmetric sulfoxidation and complementary kinetic resolution. The design and synthesis of a series of sulfides to enable exploration of the substituent effects of the copper-mediated oxidation was undertaken, and oxidation to the racemic sulfoxides and sulfones to provide reference samples was conducted. Oxidation of the sulfides using copper-Schiff base catalysis was undertaken leading to enantioenriched sulfoxides. The procedure employed is clean, inexpensive, not air-sensitive and utilises aqueous hydrogen peroxide as oxidant. Extensive investigation of the influence of the reaction conditions such as solvent, temperature, copper salt and ligand was undertaken to lead to the optimised conditions. While the direct attachment of one aryl substituent to the sulfide is essential for efficient enantiocontrol, in the case of the second substituent the enantiocontol is dependent on the steric rather than electronic features of the substituent. Significantly, use of naphthyl-substituted sulfides results in excellent enantiocontrol; notably 97% ee, obtained in the oxidation of 2-naphthyl benzyl sulfide, represents the highest enantioselectivity reported to date for a copper-mediated sulfur oxidation. Some insight into the mechanistic features of the copper-mediated sulfur oxidation has been developed based on this work, although further investigation is required to establish the precise nature of the catalytic species responsible for asymmetric sulfur oxidation. Full experimental details, describing the synthesis and structural characterisation, and determination of enantiopurity are included in chapter 3.

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Starches are a source of digestible carbohydrate and are frequently used in formulated food products in the presence of other carbohydrates, proteins and fat. This thesis explored the effect of addition of neutral (Konjac glucomannan) or charged (milk proteins) polymers on the physical characteristics and digestion kinetics of waxy maize starch. The aim was to identify mechanisms to modulate the pasting properties and subsequent susceptibility to amylolytic digestion. Addition of αs- or β-caseinate protein fractions to waxy maize starch restricted granular swelling during gelatinisation, increasing granule integrity. It was shown that, while β-caseinate can adsorb to starch granules during pasting, αscaseinate can be absorbed into maize starch granules. The resultant effect was a reduction in granule size after heating, more intact granules and a subsequent decrease in starch digestion in vitro as determined by analysis of reducing sugars. The ability of αs-caseinate to reduce the level of amylolytic digestion was confirmed through in vivo pig (Teagasc, Moorepark) and human (University of Surrey, UK) trials. The scope of the thesis extended to the development of a new automated cell for attachment to a rheometer to measure digestion kinetics of starch-protein mixtures. In conclusion, the thesis offers new approaches to modulation of the physical characteristics of unmodified starch during gelatinisation and suggests that the type of protein and/or polysaccharide used in starch-based food systems may influence the ability of the food to modulate glycemia. This is an important consideration in the design of foods with positive health benefits.

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The objective of my Portfolio is to explore the working hypothesis that the organic growth of a firm is governed by the perspectives of individuals and such perspectives are governed by their meaning-making. The Portfolio presents explorations of the transformation of my meaning making and in adopting new practices to support the organic growth of a firm. I use the work of other theorists to transition my understanding of how the world works. This transition process is an essential tool to engage with and understand the perspectives of others and develop a mental capacity to “train one’s imagination to go visiting” (Arendt, 1982; p.43). The Portfolio, therefore, is primarily located in reflective research. Using Kegan’s (1994) approach to Adult Mental Development, and Sowell’s (2007) understanding of the visions which silently shape our thoughts I organise the developments of my meaning making around three transformation pillars of change. In pillar one I seek to transform an unthinking respect for authority and break down a blind pervasiveness of thought within my reasoning process arising from an instinct for attachment and support from others whom I trust. In pillar two I seek to discontinue using autocratic leadership and learn to use the thoughts and contributions of a wider team to make improved choices about uncertain future events. In pillar three I explore the use of a more reflective thinking framework to test the accuracy of my perceptions and apply a high level of integrity in my reasoning process. The transformation of my meaning making has changed my perspectives and in turn my preferred practices to support the organic growth of a firm. I identify from practice that a transformative form of leadership is far more effective that a transactional form of leadership to stimulate the trust and teamwork required to sustain the growth a firm. Creating an environment where one feels free to share thoughts and feelings with others is an essential tool to build a team to critique the thoughts of one other. Furthermore, the entrepreneurial wisdom to grow a firm must come from a wider team, located both inside and outside the boundaries of a firm. No individual or small team has the mental capacity to provide the entrepreneurship required to drive the organic growth of a firm. I address my Portfolio to leaders in organisations who have no considered framework on the best practices required to lead a social organisation. These individuals may have no sense of what they implicitly believe drives social causation and they may have no understanding if their meaning making supports or curtails the practices required to grow a firm. They may have a very limited capacity to think in a logical manner, with the result they are using guesses from their ‘gut’ to make poor judgements in the management of a firm.

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Nanostructured materials are central to the evolution of future electronics and biomedical applications amongst other applications. This thesis is focused on developing novel methods to prepare a number of nanostructured metal oxide particles and films by a number of different routes. Part of the aim was to see how techniques used in nanoparticle science could be applied to thin film methods to develop functional surfaces. Wet-chemical methods were employed to synthesize and modify the metal oxide nanostructures (CeO2 and SiO2) and their structural properties were characterized through advanced X-ray diffraction, electron microscopy, photoelectron spectroscopy and other techniques. Whilst particulates have uses in many applications, their attachment to surfaces is of importance and this is frequently challenging. We examined the use of block copolymer methods to form very well defined metal oxide particulate-like structures on the surface of a number of substrates. Chapter 2 describes a robust method to synthesize various sized silica nanoparticles. As-synthesized silica nanoparticles were further functionalized with IR-820 and FITC dyes. The ability to create size controlled nanoparticles with associated (optical) functionality may have significant importance in bio-medical imaging. Thesis further describes how non-organic modified fluorescent particles might be prepared using inorganic oxides. A study of the concentrations and distributions of europium dopants within the CeO2 nanoparticles was undertaken and investigated by different microscopic and spectroscopic techniques. The luminescent properties were enhanced by doping and detailed explanations are reported. Additionally, the morphological and structural evolution and optical properties were correlated as a function of concentrations of europium doping as well as with further annealing. Further work using positron annihilation spectroscopy allowed the study of vacancy type defects formed due to europium doping in CeO2 crystallites and this was supported by complimentary UV-Vis spectra and XRD work. During the last few years the interest in mesoporous silica materials has increased due to their typical characteristics such as potential ultra-low dielectric constant materials, large surface area and pore volume, well-ordered and uniform pores with adjustable pores between 2 and 50 nm. A simple, generic and cost-effective route was used to demonstrate the synthesis of 2D mesoporous silica thin films over wafer scale dimensions in chapter 5. Lithographic resist and in situ hard mask block copolymer followed by ICP dry etching were used to fabricate mesoporous silica nanostructures. The width of mesoporous silica channels can be varied by using a variety of commercially available lithographic resists whereas depth of the mesoporous silica channels can be varied by altering the etch time. The crystal structure, morphology, pore arrangement, pore diameters, thickness of films and channels were determined by XRD, SEM, ellipsometry and the results reported. This project also extended work towards the study of the antimicrobial study of nanopatterned silver nanodot arrays formed using the block copolymer approach defined above. Silver nanodot arrays were successfully tested for antimicrobial activity over S. aureus and P. aeruginosa biofilms and results shows silver nanodots has good antimicrobial activity for both S. aureus and P. aeruginosa biofilms. Thus, these silver nanodot arrays shows a potential to be used as a substitute for the resolution of infection complications in many areas.

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The bifunctional Ru(II) complex [Ru(BPY)2POQ-Nmet]2+ (1), in which the metallic unit is tethered by an aliphatic chain to an organic DNA binder, was designed in order to increase the affinity toward nucleic acids. The interaction of 1 with DNA was characterised from luminescence and absorption data and compared with the binding of its monofunctional metallic and organic analogues, [Ru(BPY)2(ac)phen]2+ (2) and Nmet-quinoline (3). The bifunctional complex has a binding affinity one order of magnitude higher than that of each of its separated moieties. Absorption changes induced upon addition of DNA at different pH indicate protonation of the organic sub-unit upon interaction with DNA under neutral conditions. The combination of the luminescence data under steady-state and time-resolved conditions shows that the attachment of the organic unit in 1 induces modifications of the association modes of the metallic unit, owing to the presence of the aliphatic chain which probably hinders the metallic moiety binding. The salt dependence of the binding constants was analysed in order to compare the thermodynamic parameters describing the association with DNA for each complex. This study demonstrates the interest of the derivatisation of a Ru(II) complex with an organic moiety (ia the bifunctional ligand POQ-Nmet) for the development of high affinity DNA probes or photoreactive agents.

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The transport of uncoated silver nanoparticles (AgNPs) in a porous medium composed of silica glass beads modified with a partial coverage of iron oxide (hematite) was studied and compared to that in a porous medium composed of unmodified glass beads (GB). At a pH lower than the point of zero charge (PZC) of hematite, the affinity of AgNPs for a hematite-coated glass bead (FeO-GB) surface was significantly higher than that for an uncoated surface. There was a linear correlation between the average nanoparticle affinity for media composed of mixtures of FeO-GB and GB collectors and the relative composition of those media as quantified by the attachment efficiency over a range of mixing mass ratios of the two types of collectors, so that the average AgNPs affinity for these media is readily predicted from the mass (or surface) weighted average of affinities for each of the surface types. X-ray photoelectron spectroscopy (XPS) was used to quantify the composition of the collector surface as a basis for predicting the affinity between the nanoparticles for a heterogeneous collector surface. A correlation was also observed between the local abundances of AgNPs and FeO on the collector surface.

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"Push-pull" chromophores based on extended pi-electron systems have been designed to exhibit exceptionally large molecular hyperpolarizabilities. We have engineered an amphiphilic four-helix bundle peptide to vectorially incorporate such hyperpolarizable chromophores having a metalloporphyrin moiety, with high specificity into the interior core of the bundle. The amphiphilic exterior of the bundle facilitates the formation of densely packed monolayer ensembles of the vectorially oriented peptide-chromophore complexes at the liquid-gas interface. Chemical specificity designed into the ends of the bundle facilitates the subsequent covalent attachment of these monolayer ensembles onto the surface of an inorganic substrate. In this article, we describe the structural characterization of these monolayer ensembles at each stage of their fabrication for one such peptide-chromophore complex designated as AP0-RuPZn. In the accompanying article, we describe the characterization of their macroscopic nonlinear optical properties.

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BACKGROUND: Myosin VIIA (MyoVIIA) is an unconventional myosin necessary for vertebrate audition [1]-[5]. Human auditory transduction occurs in sensory hair cells with a staircase-like arrangement of apical protrusions called stereocilia. In these hair cells, MyoVIIA maintains stereocilia organization [6]. Severe mutations in the Drosophila MyoVIIA orthologue, crinkled (ck), are semi-lethal [7] and lead to deafness by disrupting antennal auditory organ (Johnston's Organ, JO) organization [8]. ck/MyoVIIA mutations result in apical detachment of auditory transduction units (scolopidia) from the cuticle that transmits antennal vibrations as mechanical stimuli to JO. PRINCIPAL FINDINGS: Using flies expressing GFP-tagged NompA, a protein required for auditory organ organization in Drosophila, we examined the role of ck/MyoVIIA in JO development and maintenance through confocal microscopy and extracellular electrophysiology. Here we show that ck/MyoVIIA is necessary early in the developing antenna for initial apical attachment of the scolopidia to the articulating joint. ck/MyoVIIA is also necessary to maintain scolopidial attachment throughout adulthood. Moreover, in the adult JO, ck/MyoVIIA genetically interacts with the non-muscle myosin II (through its regulatory light chain protein and the myosin binding subunit of myosin II phosphatase). Such genetic interactions have not previously been observed in scolopidia. These factors are therefore candidates for modulating MyoVIIA activity in vertebrates. CONCLUSIONS: Our findings indicate that MyoVIIA plays evolutionarily conserved roles in auditory organ development and maintenance in invertebrates and vertebrates, enhancing our understanding of auditory organ development and function, as well as providing significant clues for future research.