Orientador: Eduardo Bresciani / Banca: Rebeca Di Nicoló / Banca: Taciana Marco Ferraz Caneppele / Banca: Luciana Fávaro Francisconi dos Rios / Banca: Flávio Henrique Baggio Aguiar / Resumo: Este estudo foi composto por um estudo in vitro, um estudo clínico randomizado, controlado e duplo cego e uma revisão sistemática, com objetivo de compreender e avaliar a aplicabilidade da técnica da dentina úmida por etanol (EWBT) em procedimentos restauradores. Estudo laboratorial: 48 incisivos bovinos foram divididos em 2 grupos, com a utilização ou não de etanol anterior ao sistema adesivo universal (Single Bond Universal) no modo autocondicionante. Em seguida blocos de resina composta (Filtek Z350 xt) foram confeccionados. A interface adesiva foi analisada, antes e após envelhecimento por 6 meses em água, com relação à nanodureza e módulo de elasticidade e em microscopia eletrônica de varredura (MEV) após a realização de nanoinfiltração com nitrato de prata. Os dados de nanodureza e módulo de elasticidade foram analisados estatisticamente com ANOVA e teste de Tukey (α=5%). Houve diferença estatística para as áreas avaliadas (p<0.001) e também para a aplicação do etanol (p<0.001). A dentina apresentou valores maiores de nanodureza quando comparado com a camada híbrida. EWBT foi capaz de manter as propriedades da interface adesiva mesmo após envelhecimento. Estudo clínico randomizado: Os voluntários receberam restaurações em cavidades do tipo classe V, provenientes de lesões cervicais não cariosas, com extensão e profundidade de no mínimo 1 mm. As restaurações foram realizadas aleatoriamente, de acordo com a divisão dos grupos, sendo o grupo controle sem pré-tratamento den... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study was composed by an in vitro study, a randomized, controlled and double blind clinical trial, and a systematic review, aiming to understand and evaluate the applicability of ethanol-wet-bonding technique (EWBT) in restorative procedures. Laboratory study: 48 bovine incisors were divided into 2 groups, according to EWBT use prior to the universal adhesive system (Single Bond Universal) in the self-etch mode. Blocks of composite resin (Filtek Z350 xt) were made. The adhesive interface was analyzed, on baseline and 6 months of water aging, by scanning electron microscopy (SEM) after nanoleakage with silver nitrate, besides the nanohardness and elastic modulus. The data of nanohardness and elastic modulus were statistically analyzed with ANOVA and Tukey test (α=5%). There was a statistically significant difference for the areas evaluated, in which dentin presented higher values, for nanohardness, than the hybrid layer (p<0.001) and for the use of ethanol (p<0.001). The use of ethanol was able to maintain the properties of the adhesive layer even after aging. Randomized clinical trial: The volunteers received restorations in class V cavities from non-carious cervical lesions (NCCL), with cavity extension and depth of at least 1 mm. The restorations were randomly performed according to group division: no ethanol dentin pretreatment (SE), with ethanol dentin pretreatment in association with 3-step (E) or 2-step (EU) or adhesive, or hydrophobic adhesive (EB). The restoratio... (Complete abstract click electronic access below) / Doutor

Analysis of calcium and oxygen atom arrays of known cement minerals and the structures of cellulose polymorphs were performed to see if it was possible to arrange a cellulose fibre on a cement mineral face such that the fibre is bonded by a repeating array of hydrogen or hydroxide coordination bonds for the full length of the attachment. Of the sixteen important cement minerals modelled, xonotlite, foshagite, tricalcium aluminate hydrate, chondronite and rosenhahnite could form such bonds to modified cellulose fibre. However, this was not the case for other cement minerals, especially tobermorite. Alumium hydroxide, when added to cement-quartz pastes and autoclaved at 180 degrees C, was found to improve the cement's ability to resist carbonation. / Doctor of Philosophy (PhD)

This thesis brings together a series of existing and ongoing pieces of research, conducted over a period of some years. There are five primary aims. The first is to construct a coherent empirical picture of the social organisation of space in rural South Australia by the early 1980s, at the outset of a period of turmoil and rapid change. The second is to bring together two relevant but disparate levels of theory (globalisation/structural change and localism/place attachment), to understand the impact of the rural crisis of 1984-94 on rural communities, families and individuals. The third is to trace the context and development of the crisis itself, the resultant poverty, demographic change, and reduced socio-economic viability of communities. Fourthly, the theoretical and empirical findings are applied to the search for an altered accommodation between society and space, through which a modified and regrouped but still essentially intact rural society can survive beyond the crisis. Finally, I reflect on the methodological contribution and limitations of the thesis, and also on the ethical concerns and values confronting an academic researcher reporting on a local- or micro-level social tragedy, concealed and rationalised by national macro-level success. Chapter 1 deals with fundamental concepts and epistemology. Chapter 2 sketches the evolution of the South Australian rural habitat up to the 1980s. Chapter 3 examines macro-level theory on globalisation in the structuralist and political economy traditions, which seek to explain the forces changing the politico-economic ground rules within which rural communities have to operate. Chapter 4 examines theory relating to the world of the individual person and his/her most immediate social reference groups - family, neighbourhood and community. It presents a model of place-making, and evaluates the contributions of various disciplines towards understanding specific aspects of this process, particularly rural sociology, social and humanistic geography, structuration theory and theory relating to human territoriality. Chapter 5 reveals how individuals and local social groups actually occupied space and developed place-attachment in rural South Australia in the early 1980s. It draws on field studies carried out between 1979 and 1986, and on a 1982-83 postal sample survey of 2000 rural households. Chapter 6 traces the course of a decade of almost continuous rural crisis, from about 1984. It shows how the global economy and political decisions (international, national and State) flowed through to rural people and places. Demographic and economic impacts are examined at State level, with a regional example. Chapters 7 (quantitative) and 8 (qualitative) examine the changes wrought by the crisis on rural society and the social organisation of space. They draw on a 1992/93 replication of the previous postal survey to demonstrate the persistence and continuity of major features of the rural society, but also the fragility of the current spatial organisation. The widespread rural poverty in the early 1990s and its impact on the state of rural morale are demonstrated, along with perceived changes in key community characteristics, and divergence of the economic from the social organisation of rural space. Chapter 9 assesses requirements for a socially sustainable rural Australia, in the light of the last ten years� developments in rural research. It argues the need for the focus of localism to be re-defined upwards from individual community to regional level Finally in Chapter 10, I reflect on the contribution and limitations of the thesis, and on the wider problem of the role academics could, should and do play in relation to the deeply meaningful social transformations we purport to study.

The aim to provide preventive healthcare and high quality medical diagnostics and treatment to an increasingly ageing population caused a rapidly increasing demand for point-of-care diagnostic devices. Disposables have an advantage over re-usable units as cross-contamination is avoided, no cleaning and sterilising of equipment is required and devices can be used out of centralised laboratories. To remain cost-effective, costs for disposables should be kept low. This makes polymer materials an obvious choice. One method for the realisation of fluidic micro devices is the stacking of several layers of microstructured polymer films. Reel-to-reel manufacturing is a promising technique for high-volume manufacturing of disposable polymer bio-analytical devices. Polyethylene terephthalate (PET) and cycloolefin copolymer (COC) were selected as suitable polymer substrate materials and polydimethyl siloxane (PDMS) as membrane layer. Bonding of polymer films with the help of adhesives carries the risk of channel blocking. Despite this drawback, no other method of bonding PDMS to a structural layer could be identified. Bonding with solvents avoids channel blocking issues, but adversely affects biocompatibility. Thermal diffusion processes enable bonding of COC and PET without the use of any auxiliary material. The extensive process times requires for thermal diffusion bonding can be considerably shortened by pre-treating the material with plasma or UV exposure. Welding with the use of a laser energy absorbing dye was demonstrated to be particularly suitable for selective bonding around channels and reservoirs. None of the assessed bonding methods provide a generic solution to all bonding applications. Instead, the selection of an appropriate technique depends on the intended application and the required level of biocompatibility. Since this selection has implications on the feasibility and reliability of microfluidic structures on the device, design rules which ensure design for production have to be established and followed.

This thesis employs experimental and theoretical methods to characterise carbon nitride solids and proposes a generalstructural model for amorphous carbon nitride (a-C:N). It finds that a-C:N deposited by several methods is essentially identical, with similar bonding environments for carbon and nitrogen atoms. Using evidence from several techniques, the saturation of nitrogen in an sp2 carbon matrix is discussed. The experimental studies on a range of carbon nitride solids show no evidence for a crystalline form of carbon nitride. In addition to the experimental characterisation of a-C:N, ab initio molecular dynamics were used to investigate bonding and structure in carbon nitride. These simulations show that the most common form of nitrogen bonding was three-fold sites with a lone pair of electrons. Two-fold nitrogen sites were also found in agreement with experimental findings. An increase of nitrogen in a-C:N decreases the sp3-carbon fraction, but this is not localised on the nitrogen and the effect is most severe at high densities. A simulation of a low density/high nitrogen content network shows that the nitrogen saturation seen experimentally may be due to the formation of N2 dimers and C-N molecules which are easily driven out of the structure. The ab initio simulations also explore the nature of charged nitrogen and carbon sites in a-C:N. An analysis based on Wannier Function centres provided further information about the bonding and allowed for a detailed classification of these sites. The removal of electrons from the networks caused structural changes that could explain the two-state conductivity in ta-C:N memory devices. Finally, a theoretical study of the electron energy-loss near-edge structure (ELNES) calculated using multiple scattering theory is presented. The calculated ELNES of diamond, graphite and boron, silicon and carbon nitride structures compare well to experiment and supports the experimental finding that no crystalline carbon nitride had (or has) been produced. These ELNES calculations will however, provide a means of identifying crystalline beta-C3N4 should it be synthesised.

<p>Computational methods are combined with synchrotron-based techniques to analyze the structure and bonding of water and water plus hydroxyl at metal surfaces under UHV and at near-ambient conditions. Water-metal interaction plays a crucial role in a multitude of cosmic, atmospheric and biological phenomena as well as heterogeneous catalysis, electrochemistry and corrosion. A spotlight of renewed interest has recently been cast on water-metal systems due to their relevance for surface chemical reactions related to the production and utilization of hydrogen as a clean energy carrier. In particular, H2O and OH are essential reaction intermediates in the renewable production of hydrogen from sunlight and water and in fuel cell electrocatalysis.</p><p>Fuel cells are considered one of the most promising power generation technologies for a sustainable energy future. A mechanistic understanding of the oxygen reduction reaction (ORR) pathway, including the role of electronic and geometric structure of the catalyst, is essential to the design of more efficient fuel cell catalysts. This is intimately connected to fundamental factors that affect the ability to form water-metal bonds as well as the site occupation and orientation of the adsorbed H2O and OH at active metal surfaces.</p><p>Key relationships related to critical issues in the fuel cell reaction are illuminated by the synergy of theory and experiment in this thesis. We emerge with a detailed understanding of the structure of the water-metal interface and the factors that rule the wettability of a metal surface, including geometric and electronic structure effects and the influence of coadsorbed species. We show that the preferred microscopic orientation of the water monolayer has consequences for macroscopic properties, and reveal the origin of the hydrophobic water layer. Finally, we identify a cooperativity effect that drives the stability of the mixed water/hydroxyl layer at metal surfaces, an important ORR intermediate.</p>

<p>Aim: To examine the reaction of extreme preterm infants with regarding to body temperature and transepidermal water loss during skin-to-skin care according to Kangaroo Mother Care (KMC) during the infant’s first week of life. Method: This was a descriptive quantitatively designed study, which was a pilot study within the framework of a larger project. Nine children, with a median gestational age of 24.91 weeks, were examined by measuring body temperature (axilla and skin temperature) as well as transepidermal water loss before, during and after KMC. Results: The study showed that skin temperature tended to rise during KMC, especially for those children who were nursed with KMC for more than 60 minutes. Eight out of nine children had, after completing KMC, a normal axilla temperature. As was expected, transepidermal water loss was elevated when measured both pre and post test. Despite this, the children showed normal body temperature. Conclusion: The results of the study support that KMC can create a micro-climate that, for at least one hour, makes it possible for even extreme preterm infants to maintain a body temperature within the normal range during their first week of life.</p>

<p>This thesis is based on ten publications (Papers I-X). The phosphodiester backbone makes DNA or RNA to behave as polyelectrolyte, the pentose sugar gives the flexibility, and the aglycones promote the self-assembly or the ligand-binding process. The hydrogen bonding, stacking, stereoelectronics and hydration are few of the important non-covalent forces dictating the self-assembly of DNA/RNA. The pH-dependent thermodynamics clearly show (Papers I and II) that a change of the electronic character of aglycone modulates the conformation of the sugar moiety by the tunable interplay of stereoelectronic anomeric and <i>gauche</i> effects, which are further transmitted to steer the sugar-phosphate backbone conformation in a cooperative manner. 3'<i>-</i>anthraniloyl<b> </b>adenosine<b> </b>(a mimic of 3'-teminal CC<u>A</u>_OH of the aminoacyl-tRNA^Phe) binds to EF-Tu*GTP in preference over 2'<i>-</i>anthraniloyl<b> </b>adenosine<b>, </b>thereby showing (Paper III) that the 2’-<i>endo</i> sugar conformation is a more suitable mimic of the transition state geometry than the 3’<i>-endo</i> conformation in discriminating between correctly and incorrectly charged aminoacyl-tRNA^Phe by EF-Tu during protein synthesis. The presence of 2'-OH in RNA distinguishesit from DNA both functionallyas well as structurally. This work (Paper IV) provides straightforward NMR evidence to show that the 2'-OH is intramolecularly hydrogen bonded with the vicinal 3'-oxygen, and the exposure of the 3'<i>-</i>phosphate of the ribonucleotides to the bulk water determines the availability of the bound water around the vicinal 2'-OH, which then can play various functional role through inter- or intramolecular interactions. The pH-dependent ¹H NMR study with nicotinamide derivatives demonstrates (Paper V) that the cascade of intramolecular cation (pyridinium)-π(phenyl)-CH(methyl) interaction in edge-to-face geometry is responsible for perturbing the p<i>K</i>_a of the pyridine-nitrogen as well as for the modulation of the aromatic character of the neighboring phenyl moiety, which is also supported by the T₁ relaxation studies and <i>ab initio</i> calculations. It has been found (Papers VI-IX) that the variable intramolecular electrostatic interaction between electronically coupled nearest neighbor nucleobases (steered by their respective microenvironments) can modulate their respective pseudoaromatic characters. The net result of this pseudoaromatic cross-modulation is the creation of a unique set of aglycones in an oligo or polynucleotide, whose physico-chemical properties are completely dependent upon the propensity and geometry of the nearest neighbor interactions (extended genetic code). The propagation of the interplay of these electrostatic interactions across the hexameric ssDNA chain is considerably less favoured (effectively up to the fourth nucleobase) compared to that of the isosequential ssRNA (up to the sixth nucleobase). The dissection of the relative strength of basepairing and stacking in a duplex shows that stability of DNA-DNA duplex weakens over the corresponding RNA-RNA duplexes with the increasing content of A-T/U base pairs, while the strength of stacking of A-T rich DNA-DNA duplex increases in comparison with A-U rich sequence in RNA-RNA duplexes (Paper X).</p>

<p>Direct semiconductor wafer bonding has emerged as a technology to meet the demand foradditional flexibility in materials integration. The applications are found in microelectronics, optoelectronics and micromechanics. For instance, wafer bonding is used to produce silicon-on-insulator (SOI) wafers. Wafer bonding is also interesting to use for combining dissimilar semiconductors, such as Si and InP, with different dictated optical, electronic and mechanicalproperties. This enables a completely new freedom in the design of components and systems, e.g. for high performance optoelectronic integrated circuits (OEIC). Although wafer bonding has proved to be a useful and versatile tool, the high temperature annealing that is needed to achieve reliable properties sometimes hampers its applicability. Therefore, low temperature wafer bonding procedures may further qualify this technology.</p><p>In the present thesis, low temperature wafer bonding procedures using oxygen plasma surface activation have been studied. A specially designed fixture was adopted enabling <i>in situ </i>oxygen plasma wafer bonding. Oxygen plasma surface activation was seen to indeed yield high Si-Si bonding-strength at low temperatures. Here, the optimisation of the plasma parameters was shown to be the key to improved results. Furthermore, dependence of wafer bonded Si p-n junctions on the annealing temperature was investigated. InP-to-Si wafer bonding is also presented within this thesis. High temperature annealing was seen to induce severe material degradation. However, using oxygen plasma assisted wafer bonding reliable InP-to-Si integration was achieved already at low temperature, thereby circumventing the problems associated with the lattice and thermal mismatch that exist between these materials. As a result, low temperature InP-based epitaxial-layer transferring to Si could be presented. Finally, high-quality SiO2 insulator on InP and Si was realised at low temperatures.</p><p>It is concluded that low temperature oxygen plasma assisted wafer bonding is an interesting approach to integrate dissimilar materials, for a wide range of applications.</p>

<p>This thesis is based on nine research publications (<b>I – IX</b>) on structure and reactivity of RNA vis-à-vis DNA. The DNA and RNA are made of flexible pentose sugar units, polyelectrolytic phosphodiester backbone, and heterocyclic nucleobases. DNA stores our genetic code, whereas RNA is involved both in protein biosynthesis and catalysis. Various ligand-binding and recognition properties of DNA/RNA are mediated through inter- and intra-molecular H-bonding and stacking interactions, beside hydration, van der Waal and London dispersion forces. In this work the pH dependant chemical shift, p<i>K</i>_a values of 2'-OH group as well as those the nucleobases in different sequence context, alkaline hydrolysis of the internucleotidic phosphodiester bonds and analysis of NOESY footprints along with NMR constrained molecular dynamics simulation were used as tools to explore and understand the physico-chemical behavior of various nucleic acid sequences, and the forces involved in their self-assembly process. <b>Papers I – II</b> showed that the ionization of 2'-OH group is nucleobase-dependant. <b>Paper III</b> showed that the chemical characters of internucleotidic phosphate are non-identical in RNA compared to that of DNA. <b>Papers IV – VI</b> show that variable intramolecular electrostatic interactions between electronically coupled nearest neighbor nucleobases in a ssRNA can modulate their respective pseudoaromatic character, and result in creation of a unique set of aglycons with unique properties depending on propensity and geometry of nearest neighbor interaction. <b>Paper VII</b> showed that the cross-modulation of the pseudoaromatic character of nucleobases by the nearest neighbor is sequence-dependant in nature in oligonucleotides. <b>Paper VIII</b> showed that the purine-rich hexameric ssDNA and ssRNA retain the right-handed helical structure (B-type in ssDNA and A-type in ssRNA) in the single-stranded form even in absence of intermolecular hydrogen bonding. The directionality of stacking geometry however differs in ssDNA compared to ssRNA. In ssDNA the relatively electron-rich imidazole stacks above the electron-deficient pyrimidine in the 5' to 3' direction, in contradistinction, the pyrimidine stacks above the imidazole in the 5' to 3' direction in ssRNA. <b>Paper IX</b> showed that the p<i>K</i>_a values of the nucleobases in monomeric nucleotides can be used to show that a RNA-RNA duplex is more stable than a DNA-DNA duplex. The dissection of the relative strength of base-pairing and stacking showed that the relative contribution of former compared to that of the latter in an RNA-RNA over the corresponding DNA-DNA duplexes decreases with the increasing content of A-T/U base pairs in a sequence.</p>