Made available in DSpace on 2015-08-20T17:10:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-04-17. Added 1 bitstream(s) on 2015-08-20T17:25:52Z : No. of bitstreams: 1 000844280.pdf: 1613492 bytes, checksum: 118c1a4962800b91f632babdd4730d78 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / O 17Þ - etinilestradiol (EE2) é um hormônio esteróide sintético com baixa solubilidade em água. A contaminação por esse estrogênio tem sua origem na contínua introdução em ambientes através do descarte inadequado de esgoto sanitário e industrial, como também pelo uso do lodo ativado de estações de tratamento de esgoto na agricultura. A exposição a esse composto vem sendo associada a causas de câncer de mama, infertilidade masculina e mutações em pequenos seres vivos, como peixes, cujos efeitos podem estar associados à interação do hormônio com a membrana celular. Assim, o estudo de modelos de membrana biológica na forma de filmes de Langmuir expostos ao EE2 na subfase foi realizado com o objetivo de avaliar a interação membrana/EE2 e gerar subsídios para o desenvolvimento de sensores para detectar tais substâncias em meio aquoso (língua eletrônica). Monocamadas compostas por moléculas antifilicas de diferentes cargas foram espalhadas sobre bubfase de ágau ultrapura contendo o EE2, sendo a interação membrana/hormônio estudada por meio das isotermas de pressão de superfície vs. área molecular média (isotermas л - A). Neste estudo foram utilizados os fosfolipídios dipalmitoil fosfatidil colina (DPPC), que é zwiteriônico, dipalmitoil fosfatidil glicerol (DPPG), que é aniônico, e o surfactante brometo de dioctadecil dimetil amônio (DODAB), que é catiônico. O ácido esteárico (AE) foi utilizado como estudo complementar para se obter um melhor entendimento sobre a interação de DPPC com EE2. Todas as moléculas utilizadas como modelos de membranas apresentam interações com o EE2, de acordo com as isotermas л - A, o que foi confirmado por espectroscopia de reflexão e absorção no infravermelho com modulação da polarização (PM-IRRAS). Os estudos mostraram que as interações ocorrem através de interações eletrostáticas, principalmente na região polar dos lipídios, envolvendo não somente... / The 17 Þ - ethinyl estradiol (EE 2) is a synthetic steroid hormone with poor water solbility. Contamination by that estrogen has the origin in continuous introduction into aquatic environments through the improper disposal of domestic and industrial sewage, as well as the use of activated sludge wastewater treatment plants in agriculture. Exposure to this compound has been linked to breast cancer causes, male infertility and small mutations in living organisms such as fish, whose effects can be associated with the interaction of the hormone with the cell membrane. Thus, the study of membrane models in the form of Langmuir films exposed to EE2 in subphase was carried out to evaluate the interaction membrane/hormone. Monolayers composed of amphiphilic molecules with different charges were spread on ultrapure water subphase containing EE2, and the interaction membrane/hormone studied by surface pressure vs. mean molecular area isotherms (л - A isotherms). This study used the phospholipids dipalmitoyl phosphatidyl choline (DPPC), which is zwitterionic, dipalmitoyl phosphatidyl glycerol (DPPG), which is anionic, and the surfactant dimethyl dioctadecyl ammonium bromide (DODAB), which is cationic. The stearic acid (SA) was used to obtain a better understanding of the interaction of EE2 with DPPC and DPPG. All molecules used as membrane models presented interactions with EE2, according to л - A isotherms, which was confirmed by spectroscopic reflection and absorption in the infrared polarization modulation (PM-IRRAS). The studies have shown that interactions occur through electrostatic interations, especially in the polar region of lipids, involving not only cationic and anionic group but also the groups C=O and P=O the lipids with OH group of EE2

Made available in DSpace on 2014-12-02T11:16:41Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-03-17Bitstream added on 2014-12-02T11:21:00Z : No. of bitstreams: 1 000794151.pdf: 2726744 bytes, checksum: 0e0b03c252d9dd9acc7b80f045202ade (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Instituto Nacional de Eletrônica Orgânica (INEO) / Nas últimas décadas, a preocupação com os níveis de emissão de gases nocivos tem aumentado consideravelmente, levando os pesquisadores a desenvolver novos materiais, dispositivos e tecnologias para o seu controle. Neste vasto campo, os sensores feitos à base de camadas poliméricas condutoras vêm apresentando resultados promissores, o que pode possibilitar a construção de sistemas de medição e de análises mais eficazes e portáteis. Todavia, dois parâmetros críticos que determinam a função dos dispositivos de polímeros conjugados são sua estrutura química e sua nanoestrutura no estado sólido. As propriedades elétricas destes materiais são drasticamente alteradas devido ao acoplamento eletrônico entre as cadeias poliméricas, que é determinado pelo tipo de empacotamento e conformação no estado sólido. Além disso, os politíofenos possuem características vantajosas comparados aos demais polímeros conjugados, tais como: a facilidade de síntese química e a relativa facilidade de funcionalização de suas cadeias laterais. Dentro deste contexto, o objetivo deste trabalho foi fabricar filmes Langmuir-Blodgett (LB), de derivados alquilados de politiofeno em sua forma regiorregular misturados com ácido esteárico (SA), de forma a obter filmes de boa qualidade, visando uma posterior caracterização elétrica e óptica, com aplicação de composto orgânico voláteis (VOCs). Foram fabricados filmes LB do poli(3-butiltiofeno), poli(3-hexiltiofeno), poli(3-octiltiofeno), contendo diferentes porcentagens de SA em sua composição, pois estes polímeros puros não apresentam boa deposição através da técnica LB. As isotermas de pressão dos filmes foram analisadas de modo a avaliar as características moleculares dos filmes, e determinação dos parâmetros de deposição destes. Estes filmes foram caracterizados opticamente por espectroscopia de absorção. Ultravioleta-Visível, possibilitando avaliar o crescimento dos... / In recent decades, concern about the levels of emission of harmful gases has increased considerably, lealding the researchers to develop new materials, devices and technologies for its control. In this vast field, conductive polymer sensors have shown promising results, which can enable the construction of measurement and analysis systems more effective and portable. However, two critical parameters for organic devices are their chemical structure and their solid nanostructure. The electrical properties of these materials have been drastically altered due to electronic coupling between polymer chains which is determined by the type of packing and conformation in the solid state. Moreover, the polythiophenes possess advantageous characteristics compared to other conjugated polymers such as: ease of chemical synthesis and relative ease of functionalization of their size chains. In this context, the aim of this work was to fabricate Langmuir-Blodgett (LB) films of alkylpolythiophene derivates in its regioregular form mixed with stearic acid (SA), in order to obtain good quality films. These films were optical and electrically characterized, and also tested as active layer of volatile organic compounds (VOCs) sensors. LB films of poly(3-butylthiophene), poly(3-hexylthiophene) and poly(3-octylthiophere) containing different percentages of SA in its composition were fabricated, as these pure polymers don't show quality deposition by LB technique. The pressure isotherms of the films were analyzed to assess their molecular characteristics, and to determinate the deposition parameters. These films characterized optically by absorption spectroscopy Ultraviolet-Visible, allowing the evalution of the films growth and organization at the molecular level. Films morphology was analyzed through topographic images obtained in Atomic Force Microscope. LB films deposited onto interdigitated electrodes were used for investigation of electrical...

In Chapter 1, evidence is presented to correlate the vibronic progression in steady-state optical absorption spectra of a dimeric, organic material to its performance in field-effect transistor devices. The organic material, hPDI2, is fitted with solubilizing side chains of varying structure and length to investigate the effects that side chains have on both the optical and electronic properties of hPDI2. In solution, these side chains influence the character of aggregation and in thin films, the side chains influence film morphology. The character of aggregation in solution is determined by the change in relative peak intensities in optical absorption spectra with increasing concentration in solution. The change in relative peak intensity with increasing concentration in solution is a result of intermolecular electronic coupling, which alters the transitional symmetry of optical excitations. The character of aggregation in solution and the morphology of an organic material in thin films are akin to one another. In thin films, the intermolecular electronic coupling can facilitate the charge-transfer characteristics of an organic material in field-effect transistors. It is concluded that the structure and length of molecular side chains do indeed influence the optical and electronic properties of organic materials as a function of aggregation in solution and morphology in thin films. However, more evidence is necessary to elucidate a convincing correlation between the relative peak intensities in optical absorption spectra to the performance of the organic material in field-effect transistors. In Chapter 2, the fundamental electronic and chiroptical properties of a helical, polyaromatic molecule are demonstrated. Structurally, the organic material, NP3H, is a helix of helicenes, which generates intense circular dichroism. The circular dichroism is measured in spin-cast thin films. Electronic transfer characteristics are also presented for enantiopure NP3H as well as the racemic mixture. Upon fabricating field-effect transistors using spin-cast thin films of NP3H, the racemic mixture exhibits a marginally superior electron mobility over the enantiopure material. However, single crystals of enantiopure NP3H were grown and exhibited a two-fold increase in electron mobility when fabricated into a field-effect transistor device in comparison to its amorphous, spin-cast counterpart. It is concluded that enantiopure NP3H exhibits the necessary physical prerequisites to be useful in chiral device applications such as electron spin-filters and chiral light detectors. In Chapter 3, hPDI2 and NP3H are investigated for their ability to aggregate and form ordered films at the air-water interface of a Langmuir-Blodgett trough. Isotherms are presented and compared for each side chain derivative of hPDI2 as well as enantiopure and racemic NP3H. Additionally, an enhancement in circular dichroism is observed when a system of ordered layers of enantiopure NP3H are deposited from the Langmuir-Blodgett trough in comparison to its amorphous, spin-cast counterpart. Furthermore, ordered layers of enantiopure NP3H exhibit an enhancement in electron mobility when fabricated into field-effect transistor devices. The electron mobility is also demonstrated to enhance as the number of ordered layers that increases up to five layers. When ten ordered layers are deposited, a slight decrease is observed. Lastly, single crystals of hPDI2 were grown by solvent annealing a system of ordered layers deposited from the Langmuir-Blodgett trough, which is significant because, to the best of the author’s knowledge, a similar technique for single crystal growth of an organic material from ordered layers of Langmuir-Blodgett films has not yet been published in peer-reviewed scientific literature. It is concluded that the increased order that is induced by the Langmuir-Blodgett technique does indeed enhance the optical and electronic properties of organic materials in comparison to amorphous, spin-cast films and that this enhancement could be advantageous in device applications.

Numerical analysis of the lengths and positions of the two basal bodies (BBs), lamellar strip (LS) and anterior mitochondrion (AM) relative to each other in mid‐ and late‐stage spermatids of mosses and liverworts reveals the existence of several well denned, but previously unrecognized, features which clearly distinguish the blepharoplasts of the two groups. The ten possible quotients were calculated from measurements of anterior BB lengths, posterior BB lengths, LS lengths, distances between the anterior tips of the BBs and distances between the transition regions of the BBs in mid‐stage spermatids of 9 mosses and 16 hepatics. These critical data may be quickly compiled from a small number of electron micrographs. A Mann‐Whitney rank order t test showed highly significant differences in 6 of the 10 quotients between the moss and liverwort taxa. The primary data for late‐stage spermatids (4 mosses, 6 liverworts) also included the length of the AM. A Wilcoxon signed rank procedure revealed that the relationship between the AM and other blepharoplast components changed significantly between mid‐ and late‐stage spermatids in mosses but not in liverworts. The clear‐cut numerical differences between the blepharoplast components in each group are related to different patterns of development namely (1) bidirectional assembly of the LS in young spermatids of liverworts versus unidirectional (anterior) elongation at the same stage in mosses (2) elongation of the posterior BB over the nucleus in mid‐stage spermatids of mosses and (3) maturational elongation of the AM in mosses. Since the differences between the blepharoplasts of mosses and liverworts become apparent only during the later stages in ontogeny and since the mode of development of basal body stagger, involving the same precisely defined patterns of proximal triplet microtubule extension, is unique to mosses and liverworts, we suggest that the two groups share a common ancestry. The blepharoplasts of all the taxa used in the calculations are illustrated in a simplified form and the ‘average’ blepharoplast for mid‐ and late‐stage spermatids of both mosses and liverworts is reconstructed from all the data presently available on the two groups. The same analysis of the blepharoplasts of hornworts, birlagellate lycopods, and charophytes highlights the differences between these groups and mosses and liverworts. Most striking is the side‐by‐side orientation of the basal bodies in hornworts and charophytes compared with the staggered arrangement in mosses, liverworts and the lycopods.

The multilayered structure (MLS), a component of the locomotory complex of plant sperm, has been utilized extensively by taxonomists in establishing phylogenetic relationships between the lower plants and algae. Unfortunately, there has been almost no biochemical characterization of the MLS and, in those studies that did attempt a characterization, conflicting results were obtained. We utilized antisera to the calcium-binding protein centrin to probe thin sections of the mid-stage spermatids of the anthocerote Phaeoceros laevis, the hepatic Sphaerocarpos texanus, and the pteridophyte Ceratopteris richardii embedded in L. R. White resin. The lamellar strip (LS; layers S2-S4) of the MLS in each of these species is labelled strongly with anti-centrin, but the S1 layer, composed of microtubules, is not. In Ceratopteris, centrin is also detected in the amorphous electron opaque material that connects the basal bodies of the flagella. Both the MLS and the amorphous zones are putative microtubule organizing centers. Extracts from axenic cultures of Ceratopteris subjected for electrophoresis and Western blotting revealed a reactive band at 19.3 kDa, a protein similar in molecular mass to algal centrin. These data indicate that the MLS is composed at least partially of the protein centrin or a protein antigenically-related to centrin. This report is the first electron microscopic immunocytochemical demonstration that a centrin homologue is found in land plants and that it occurs at putative microtubule organizing centers.

El texto completo de este trabajo no está disponible en el Repositorio Académico UPC por restricciones de la casa editorial donde ha sido publicado. / In this paper, a three-dimensional bending solution of doubly-curved shells subjected to mechanical, thermal and hygrothermal load is studied. Through-the-thickness temperature of the shell is modeled by Fourier's heat conduction equation. Fick's moisture diffusion law equation is used to determine the hygro-thermal profile through-the-thickness. The partial differential equations are solved by using the Navier closed form summations which are valid only for shells with constant radii of curvature among the midsurface and with simply supported boundary conditions on its shell's edges. The shell governing equations are solved by discretizing the thickness profile via Legendre's grid distribution and by using the Differential Quadrature Method (DQM). The Layerwise capabilities of the method is guaranteed by imposing the inter-laminar continuity of out-of-the-plane stresses, displacements, temperature and hygrothermal load thickness profile. The zero-stress condition for the transverse shear stresses is imposed due to the fact that no mechanical loads are applied in those directions. Results for cylindrical, spherical panels and rectangular plates are presented. Comparisons are made with Layerwise and three-dimensional solutions available in literature. The results have strong accuracy and a benchmark problem is delivered. / Consejo Nacional de Ciencia, Tecnología e Innovación Tecnológica

No description available.

The main purpose of this work is to find a physical and numerical description related to the reaction of the multilayer nano energetic material (nEM) in dense film. Energy density of nEM is much higher than the conventional energetic material; therefore, nEM finds more applications in propulsions, thermal batteries, material synthesis, nano igniters, waste disposals, and power generations. The reaction model of a multilayer nEM in a dense film of aluminum and copper oxide deposits on a composite substrate of silica/silicon is studied and solved in different stages. The two main interests in this study are propagation speed and maximum temperature of the reaction. In order to relate speed of reaction and maximum flame temperature a number of other variables such as heat loss, the product porosity, and the reaction length should be estimated. The main aim of this study is to introduce a numerical model which estimates and relates these values in multilayer nEM in a dense film. The following is a summary of the execution steps to achieve this goal. In Part I of this thesis, flame front speed and the reaction heat loss were the main targets. The time-of-flight technique has been developed to measure the speed of flame front with an accuracy of 0.1 m/s. This measurement technique was used to measure the speed of propagation on multilayer nEM over different substrate material up to 65 m/s. A controllable environment (composite silicon\silica) was created for a multilayer standard thin film of aluminum and copper oxide to control the reaction heat loss through the substrate. A number of experimental results show that as the thickness of silica decreases, the reaction is completely quenched. Reaction is not in self-sustaining mode if the silica thickness is less than 200 nm. It is also observed that by ii increasing silica’s thickness in substrate, the quenching effect is progressively diminished. The speed of reaction seems to be constant at slightly more than 40 m/s for a silica layer with thickness greater than 500 nm. This would be the maximum heat penetration depth within the silica substrate, so the flame length was calculated based on the measured speed. In Part II, a numerical analysis of the thermal transport of the reacting film deposited on the substrate was combined with a hybrid approach in which a traditional two-dimensional black box theory was used, in conjunction with the sandwich model, to estimate the maximum flame temperature. The appropriate heat flux of the heat sources is responsible for the heat loss to the surroundings. A procedure to estimate this heat flux using stoichiometric calculations is based on the previous author’s work. This work highlights two important findings. One, there is very little difference in the temperature profiles between a single substrate of silica and a composite substrate of silicon\silica. Secondly, by increasing the substrate thickness, the quenching effect is progressively diminished at given speed. These results also show that the average speed and quenching of flames depend on the thickness of the silica substrate and can be controlled by a careful choice of the substrate. In Part III, a numerical model was developed based on the moving heat source for multilayer thin film of aluminum and copper oxide over composite substrate of silicon\silica. The maximum combustion flame temperature corresponding to the speed of flame front is the main target of this model. Composite substrate was used as a mechanism to control the heat loss during the reaction. Thickness of the substrate, the length of flame front, and the density of the product were utilized for the standard multilayer thin film with 43 m/s flame front speed. The calculated heat penetration depth in this case was compared to the experimental result for the same flame front iii speed. Numerical model was also used to estimate three major variables for a range of 30-60 m/s. In fact, the maximum combustion flame temperature that corresponds to flame speed along with the length of the flame, density of the product behind the flame, and maximum penetration depth in steady reaction, were calculated. These studies will aid in the design of nEM multilayer thin film. As further numerical and experimental results are obtained for different nEM thicknesses, a unified model involving various parameters can be developed.

Ceramic composites for high temperature applications must be designed with crack arrest capability to improve the resistance to flaws produced in service, such as by thermal shock. Laminated composites containing Al2O3 layers in 3mol%Y2O3-ZrO2 (TZ3Y) were fabricated by electrophoretic deposition (EPD) and pressureless sintering. The layering design (Al2O3 layer thickness and volume fraction) was varied to determine the influence on fracture behaviour. The residual stress in Al2O3 layers was measured using a fluorescence spectroscopy technique. The fracture strength of 15 different laminates, and monolithic Al2O3 and TZ3Y, was tested in 4-point bending at room temperature. Vickers indentation (10 kg load) was used to simulate natural flaws at the sample surface before testing as a measure of flaw tolerance. Fracture ranged from catastrophic failure, to multi-stage failure and complete delamination (in processing). Transitions in behaviour were found related to a geometrical parameter derived from the strain energy release rate for edge cracks. The strength of three Al2O/TZ3Y composites was compared with monolithic Al2O3 and TZ3Y for a range of indentation loads (up to 20 kg). The strength of the composites was similar to monolithic TZ3Y but the flaw tolerance was improved due to multi-stage fracture. The strength and flaw tolerance (using 10 kg indentation) of two Al2O3/TZ3Y composites and monolithic TZ3Y was measured < 1300°C. The multi-stage fracture behaviour disappeared > 25 °C, and there was no beneficial effect of the Al2O3 layers on the strength. Superplastic deformation of the TZ3Y layers at 1300°C was prevented by the constraint of the Al2O3 layers. Recommendations are made about the design of flaw tolerant ceramic laminates for high temperature use. / Thesis / Master of Engineering (ME)

Thesis (PhD)--Stellenbosch University, 1993 / ENGLISH ABSTRACT: An extensive literature study revealed numerous Jauman absorber examples with reasonable absorption properties. Unfortunately, tractable and detailed design techniques were found to be scarce, and often only applicable to absorbers with two or three layers. The research described in this report was therefore aimed at, and culminated in, general design methods for multilayered electric screen J auman absorbers. As a starting point, the synthesis problem is formulated by idealizing the spacers (assumed lossless and commensurate) and resistive sheets (assumed to have zero thickness), and by considering the absorption of a normally incident plane wave. An equivalent circuit model is derived, using the analogy between plane waves in stratified media, and guided waves in TEM transmission lines. The network is analyzed using Richard's frequency surrogate, S = tanh(s = cr +jw), and concise equations and algorithms are presented for symbolic and numerical analysis. Maximum bandwidth synthesis of the classic one-layer absorber, or Salisbury screen, proved to be simple, clearly illustrates the analytic approach, and apparently has not been published before. The two-layer absorber was also found to be algebraically simple enough to be synthesized in closed form, is dealt with comprehensively, and the treatment consolidates and formalizes many of the design techniques available in the literature. Networks comprising commensurate transmission lines and conductances have been investigated by Richardsl , but unfortunately the topology-driven realizability constraints on the input impedance of the Jauman network is only dealt with briefly. Fruitless investigations by the author showed this to be a formidable problem, and as a result the research concentrated on tractable and iterative synthesis algorithms for multilayered absorbers, instead of formal filter synthesis techniques. These algorithms may be summarized as follows: • A key concept in the multilayer zero-placement synthesis methods that will be presented, is the ability to physically realize a given set of reflection coefficientzeros. This involves solving a set of highly non-linear equations, and a gradientmethod iterative algorithm has been developed to achieve this . • The first application of the aforementioned algorithm is to synthesize all reflection zeros at S →∞, thereby obtaining a maximally flat reflection coefficient magnitude response. Stable and rapid convergence was found for up to at least 20 layers, thereby extending the two- and three-layer algebraic solutions available in the literature. It was found that a stringent restriction exists on the maximum dielectric constant (Er) of the spacers, thereby limiting the practical implementation of these solutions . • Through judicious manipulation of reflection zeros at distinct physical frequencies, an equiripple absorption response may be obtained. An elegant algorithm is presented to facilitate this, and it was found that these solutions represent substantial improvements over examples available in the literature. Restrictions still apply to the spacer Er, but these are more relaxed and practical equiripple absorbers are possible. In addition, the spread in sheet resistivities is much smaller than in comparable maximally flat solutions. • Numerical searches indicated that the aforementioned equiripple responses are very close to, but not absolutely optimal, in the sense of maximum bandwidth. The small bandwidth and/or absorption improvements that were found were almost negligible from a practical viewpoint, but the optimal synthesis problem is academically very important. Through use of the general Chebyshev approximation method, an algorithm is developed which finds the local optimal response in the vicinity of such a parent equiripple solution. Although it might be tempting to classify the algorithm as a brute force method, it will be shown that this is not the case, and that its solutions provide the answer to the fundamental and unsolved optimal design problem. These algorithms have been implemented, and tables of resistive sheet values are presented for N up to 8, a range of Er values corresponding to low loss foams, and for various absorption levels. / AFRIKAANSE OPSOMMING: geen opsomming