Submitted by Franciele Moreira (francielemoreyra@gmail.com) on 2018-03-29T12:30:01Z No. of bitstreams: 2 Dissertação - Marcelo dos Santos Ventura - 2018.pdf: 4739813 bytes, checksum: 52211670f6e17c893ffd08843056f075 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-03-29T13:40:08Z (GMT) No. of bitstreams: 2 Dissertação - Marcelo dos Santos Ventura - 2018.pdf: 4739813 bytes, checksum: 52211670f6e17c893ffd08843056f075 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-03-29T13:40:08Z (GMT). No. of bitstreams: 2 Dissertação - Marcelo dos Santos Ventura - 2018.pdf: 4739813 bytes, checksum: 52211670f6e17c893ffd08843056f075 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-03-09 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / This work deals with two Monte Carlo simulation studies in log-symmetric regression models, which are particularly useful for the cases when the response variable is continuous, strictly positive and asymmetric, with the possibility of the existence of atypical observations. In log- symmetric regression models, the distribution of the random errors multiplicative belongs to the log-symmetric class, which encompasses log-normal, log- Student-t, log-power- exponential, log-slash, log-hyperbolic distributions, among others. The first simulation study has as objective to examine the performance for the maximum-likelihood estimators of the model parameters, where various scenarios are considered. The objective of the second simulation study is to investigate the accuracy of popular information criteria as AIC, BIC, HQIC and their respective corrected versions. As illustration, a movie data set obtained and assembled for this dissertation is analyzed to compare log-symmetric models with the normal linear model and to obtain the best model by using the mentioned information criteria. / Este trabalho aborda dois estudos de simulação de Monte Carlo em modelos de regressão log- simétricos, os quais são particularmente úteis para os casos em que a variável resposta é contínua, estritamente positiva e assimétrica, com possibilidade da existência de observações atípicas. Nos modelos de regressão log-simétricos, a distribuição dos erros aleatórios multiplicativos pertence à classe log-simétrica, a qual engloba as distribuições log-normal, log-Student- t, log-exponencial- potência, log-slash, log-hyperbólica, entre outras. O primeiro estudo de simulação tem como objetivo examinar o desempenho dos estimadores de máxima verossimilhança desses modelos, onde vários cenários são considerados. No segundo estudo de simulação o objetivo é investigar a eficácia critérios de informação populares como AIC, BIC, HQIC e suas respectivas versões corrigidas. Como ilustração, um conjunto de dados de filmes obtido e montado para essa dissertação é analisado para comparar os modelos de regressão log-simétricos com o modelo linear normal e para obter o melhor modelo utilizando os critérios de informação mencionados.

Seja S(gl_n) a álgebra simétrica da álgebra de Lie das matrizes de tamanho nxn sobre o corpo C dos números complexos. Para \\xi em gl_n*=gl_n, seja F_{\\xi}(gl_n) a asubálgebra de Mishchenko-Fomenko de S(gl_n) construída pelo método de deslocamento de argumento associada ao parâmetro \\xi. É conhecido que se \\xi é um elemento semisimples regular ou nilpotente regular então a subálgebra F_{\\xi}(gl_n) é gerada por uma sequência regular em S(gl_n). Nesta tese é provado que em gl_3 o resultado estende para todo \\xi em gl_3, isto é, as subálgebras de Mishchenco-Fomenko F_{\\xi}(gl_3) são geradas por uma sequência regular em S(gl_3), uma consequência deste fato é que os módulo irredutíveis sobre certas subálgebras comutativas da álgebra envolvente universal U(gl_3) podem ser levantados a módulos irredutiveis sobre U(gl_3). Além disso, é provado que em gl_4 esse resultado é válido para todo elemento nilpotente \\xi em gl_4. O caso geral, que é determinar quando as subálgebras de Mishchenko-Fomenko F_{\\xi}(gl_n) , com \\xi em gl_n, são geradas por uma sequência regular em S(gl_n), é ainda um problema aberto. / Let S(gl_n) be the symmetric algebra of the Lie algebra of the matrices of size nxn over the field C of complex numbers. For \\xi in gl_n*=gl_n, let F_{\\xi}(gl_n) be the Mishchenko-Fomenko subalgebra of S(gl_n) constructed by the argument shift method associated with the parameter \\xi. It is known that if \\xi is a semisimple regular element or nilpotent regular element then the subalgebra F_(g_ln) is generated by a regular sequence in S(gl_n). In this thesis we prove that in gl_3 the result is extended to all \\xi in gl_3, this is, the Mishchenco-Fomenko subalgebras F_{\\xi}(gl3) are generated by a regular sequence in S(gl_3), A consequence of this fact is that the irreducible modules over certain commutative subalgebras of the universal enveloping algebra U(gl_3) can it be lifted to irreducible modules over U(gl_3). Furthermore, is proved that this result is true for all elements nilpotente \\xi in gl_4. The general case, which is determined when the Mishchenko-Fomenko subalgebras F_{\\xi}(gl_n), with \\xi in gl_n, are generated by a regular sequence in S(gl_n), it is still an open problem.

在線性迴歸分析中，資料的不適當，常導致研究者選擇了不當的模式，為避免此缺失，在分析資料前須先做好診斷工作。本文中將從貝氏觀點提出一些不同的診斷方法以供參考。首先推導出均數移動參數a=(a₁,…,a_k)'的事後分配，並利用a'a/k的事後均數診斷出不當資料點。接著，考慮在個別模式下以β事後分配之總變異及廣義變異為標準，診斷出離群值及具有潛在影響力之觀測值。最後，分別利用(i)β的事後分配(ii)σ²的事後分配(iii)(β,σ²)的聯合事後分配，推導出對應的對稱均方差以做為診斷標準。 / In this thesis, some different diagnostic methodologies for outliers and influential observations from Bayesian point of view are proposed. We firstly derive the marginal posterior distribution of the mean-shift parameter a=(a₁,a_k)¹, then use the posterior mean of a¹a/k to detect the spurious data items. Secondly, we use the posterior total variance and generalized variance of β as diagnostic criterions for outliers and influential observations. Finally, we utilize (i) the posterior distribution of β, (ii) the posterior distribution of σ², and (iii) the joint posterior distribution of β, σ² to find their corresponding symmetric mean square differences , which can be used as diagnostic criterions.

<p>The HIV protease is an essential enzyme for HIV replication and constitutes an important target in the treatment of HIV/AIDS. Efficient combination therapies using inhibitors of the reverse transcriptase and protease enzymes have led many to reevaluate HIV infections from a terminal condition to a chronic-but-manageable disease in the developed world. Unfortunately, the emergence of drug resistant viral strains and severe treatment-related adverse effects limit the benefits of current anti-HIV/AIDS drugs for many patients. Furthermore, less than one in ten patients infected with HIV in low- and middle-income countries have access to proper treatment. These important shortcomings highlight the need for new, cost effective anti-HIV/AIDS drugs with unique properties.</p><p>Microwave heating has recently emerged as a productivity-enhancing tool for the medicinal chemist. Reaction times can often be reduced from hours to minutes or seconds and chemistry previously considered impractical or unattainable can now be accessed.</p><p>In this thesis, the search for unique HIV-1 protease inhibitors and the development and application of new microwave-promoted synthetic methods useful in small-scale medicinal chemistry applications are presented. Protocols for rapid amino- and hydrazidocarbonylations were developed. Mo(CO)₆ was used as a solid source of carbon monoxide, enabling a safe, efficient and simple way to exploit carbonylation chemistry without the direct use of toxic carbon monoxide gas. The aminocarbonylation methodology was applied in the synthesis of two series of new HIV-1 protease inhibitors. A biological evaluation suggested that <i>ortho</i>-substitution of P1 and/or P1’ benzyl side chains might provide a new approach to HIV-1 protease inhibitors with novel properties. To assess the scope and limitations of the <i>ortho</i>-substitution concept, a new series of compounds exhibiting fair potency was prepared by various microwave-heated, palladium-catalyzed coupling reactions. Finally, computer modeling was applied to rationalize the binding-modes and structure-activity relationships of these HIV-1 protease inhibitors.</p>

The HIV protease is an essential enzyme for HIV replication and constitutes an important target in the treatment of HIV/AIDS. Efficient combination therapies using inhibitors of the reverse transcriptase and protease enzymes have led many to reevaluate HIV infections from a terminal condition to a chronic-but-manageable disease in the developed world. Unfortunately, the emergence of drug resistant viral strains and severe treatment-related adverse effects limit the benefits of current anti-HIV/AIDS drugs for many patients. Furthermore, less than one in ten patients infected with HIV in low- and middle-income countries have access to proper treatment. These important shortcomings highlight the need for new, cost effective anti-HIV/AIDS drugs with unique properties. Microwave heating has recently emerged as a productivity-enhancing tool for the medicinal chemist. Reaction times can often be reduced from hours to minutes or seconds and chemistry previously considered impractical or unattainable can now be accessed. In this thesis, the search for unique HIV-1 protease inhibitors and the development and application of new microwave-promoted synthetic methods useful in small-scale medicinal chemistry applications are presented. Protocols for rapid amino- and hydrazidocarbonylations were developed. Mo(CO)6 was used as a solid source of carbon monoxide, enabling a safe, efficient and simple way to exploit carbonylation chemistry without the direct use of toxic carbon monoxide gas. The aminocarbonylation methodology was applied in the synthesis of two series of new HIV-1 protease inhibitors. A biological evaluation suggested that ortho-substitution of P1 and/or P1’ benzyl side chains might provide a new approach to HIV-1 protease inhibitors with novel properties. To assess the scope and limitations of the ortho-substitution concept, a new series of compounds exhibiting fair potency was prepared by various microwave-heated, palladium-catalyzed coupling reactions. Finally, computer modeling was applied to rationalize the binding-modes and structure-activity relationships of these HIV-1 protease inhibitors.

A three dimensional, Navier-Stokes finite volume flow solver which uses Roe&rsquo / s upwind flux differencing scheme for spatial and Runge-Kutta explicit multi-stage time stepping scheme and implicit Lower-Upper Symmetric Gauss Seidel (LU-SGS) iteration scheme for temporal discretization on unstructured and hybrid meshes is developed for steady rocket internal viscous flow applications. The spatial accuracy of the solver can be selected as first or second order. Second order accuracy is achieved by piecewise linear reconstruction. Gradients of flow variables required for piecewise linear reconstruction are calculated with both Green-Gauss and Least-Squares approaches. The solver developed is first verified against the three-dimensional viscous laminar flow over flat plate. Then the implicit time stepping algorithms are compared against two rocket motor internal flow problems. Although the solver is intended for internal flows, a test case involving flow over an airfoil is also given. As the last test case, supersonic vortex flow between concentric circular arcs is selected.

This thesis presents numerical optimization of geometries of axially symmetric ion trap mass analyzers. The motivation for this thesis is two fold. First is to demonstrate how the automated scheme can be applied to achieve geometry parameters of axially symmetric ion traps for a desired field configuration. Second is, through the Geometries investigated in this thesis, to present practically achievable geometries for mass spectroscopists to use. Here the underlying thought has been to keep the design simple for ease of fabrication (with the possibility of miniaturization) and still ensure that the performance of these analyzers is similar to the stretched geometry Paul traps. Five geometries have been taken up for investigation: one is the well known Cylindrical ion trap (CIT), three are new geometries and the last is the Paul trap under development in our laboratory. Two of these newer geometries have a step in the region of the midline of the cylindrical ring electrode (SRIT) and the third geometry has a step in its endcap electrodes (SEIT). The optimization has been carried out around deferent objective functions composed of the desired weights of higher order multiples. The Nelder-Mead simplex method has been used to optimize trap geometries. The multipoles included in the computations are quadrupole, octopole, dodecapole, hexadecapole,ikosipole and tetraikosipole having weights A2, A4, A6, A8, A10 and A12, respectively.Poincare sections have been used to understand dynamics of ions in the traps investigated. For the CIT, it has been shown that by changing the aspect ratio of the trap the harmful ejects of negative dodecapole superposition can be eliminated, although this results in a large positive A4=A2 ratio. Improved performance of the optimized CIT is suggested by the ion dynamics as seen in Poincare sections close to the stability boundary. With respect to the SRIT, two variants have been investigated. In the first geometry, A4=A2 and A6=A2 have been optimized and in the second A4=A2, A6=A2 and A8=A2 have been optimized; in both cases, these ratios have been kept close to their values reported for stretched hyperboloid geometry Paul traps. In doing this, however, it was seen that the weights of still higher order multipole not included in the objective function, A10=A2 and A12=A2, are high; additionally, A10=A2 has a negative sign. In spite of this, for both these configurations, the Poincare sections predict good performance. In the case of the SEIT, a geometry was obtained for which A4=A2 and A6=A2 are close to their values in the stretched geometry Paul trap and the higher even multipole (A8=A2, A10=A2 and A12=A2) are all positive and small in magnitude. The Poincare sections predict good performance for this con¯guration too. Direct numerical simulations of coupled nonlinear axial/radial dynamics also predict good performance for the SEIT, which seems to be the most promising among the geometries proposed here. Finally, for the Paul trap under development in our laboratory, Poincare sections and numerical simulations of coupled ion dynamics suggest a stretch of 79:7% is the best choice.

With the advancement in knowledge of inelastic response of structures, the design and construction practices of reinforced concrete buildings have been changing worldwide. Most of the codes are incorporating the near-fault factors and performance based designs in the seismic codes. However, further investigation is needed to identify the physical behaviour of multi-storey buildings to near-fault ground motions. At present, quantitative evaluation of response and its mitigation to near field ground motions is a popular topic in earthquake engineering field. The present study discusses the inelastic response of symmetric and asymmetric multi-storey buildings to near-fault ground motions. The possibility of design approach is based on ‘expendable top storey’ for the multi-storey RC- buildings to near field records. If such behaviour is feasible one can conceive of a structure whose top storey is permitted and designed to undergo large inelastic deformations while reducing damage in the lower storey. The concept was first proposed in an earlier research (RaghuPrasad, 1977). Such a concept juxtaposes the often-mentioned ‘soft first storey’ concept. Further in this report, the performance evaluation of multi-storey buildings near Chiplun fault in Mumbai, India is also discussed. The thesis is organized in the following chapters: Introduction in Chapter-1 contains detailed literature review on inelastic response of symmetric and asymmetric buildings, response of buildings to near-fault records, elastic and inelastic vibration absorber concepts and performance based designs. The literature reveals that considerable amount of research has been carried out on the elastic, inelastic response of structures and vibration absorber concepts to ordinary ground motions. Recently, the effect of near field ground motions on the response of multi-storey buildings is gaining much importance. Most of the research publications are available on response of symmetric buildings subjected to near field ground motions. But many problems are yet to be investigated. They are, identification of important ground motion parameters in near fault records, vibration absorber concepts and torsional response of structures subjected to pulse type ground motions. These problems are clearly mentioned in the recently published state-of-the-art review by Shuang and Li-Li (2007). In this report an attempt has been made to solve these problems. Effect of near-fault ground motions on symmetric multi-storey buildings in Chapter-2, describes simplified non-dimensionalized equations of motion to study the response behaviour of multi-storey buildings to near fault records. The non-dimensionalized equations of motion are expressed in terms of near fault ground motion parameters. The objective is to find a relation between ductility demand and near field ground motion parameters through neural network approach. For this a neural network modeling was done to predict the ductility demand in terms of peak ground acceleration, peak ground velocity, epicentral distance and pulse period of the near field ground motion. A thorough sensitive analysis is carried out, to ascertain which parameters are having maximum influence on ductility demand. In this chapter further, a comparative study is made on the inelastic seismic response of multi-storey buildings to pulse type and non pulse type ground motions. The study shows that, it is necessary to consider the effect of near fault ground motions separately and make provisions for the design in the codes of practice accordingly. Vibration absorber effect in multi-storey buildings in chapter-3, discusses the behaviour of top storey as a vibration absorber during near field ground motions. For this purpose, a five storey symmetric building model is considered as an example problem to demonstrate the effectiveness of the proposed concept. Response of the structure is obtained for the various combinations of absorber storey parameters such as mass ratio, frequency ratio and yield displacement ratio. Here mass ratio means mass of the absorber storey to that of the bottom storey and similarly for the frequency and yield displacement ratios. Observing the storey-wise variation of these responses, we can say that for a range of mass ratios, frequency ratios and yield displacement ratios, the inelastic response of top storey is large compared to the lower storeys. This range is termed as ‘effective range’. Further, in this range the top storey absorbs the vibration energy of the structure by keeping the lower storeys in elastic state i.e. acts as a vibration absorber. The top storey can also be termed as ‘expendable top storey’. Effect of near-fault ground motions on asymmetric multi-storey buildings in Chapter-4, discusses the inelastic response of asymmetric buildings to single horizontal component and two horizontal components of near fault ground motions viz., fault normal and fault parallel components. For numerical investigations eight building models are considered. Eccentricity has been created by keeping the stiffness and mass centre separately. The building models are subjected to strong motion records of Imperial Valley Array-5 (1979) and Northridge-Sylmar (1994). A detailed study on the effect of base shear strength, eccentricity and pulse period of near fault ground motions on the response is investigated. Performance of multi-Storey buildings in Chapter-5, reported a detailed procedure for the performance evaluation of structures. The procedure is applied to find the performance evaluation of multi-storeyed buildings located in near fault region. Chiplun fault in Mumbai, India has been chosen for the study because several features of that fault are clearly published (RaghuKanth and Iyengar, 2006). Results of performance evaluation of five and ten storeyed symmetric buildings with and without infill panels are studied. Ground motion records consistent with the hazard spectrum for the design are considered. The performance of the building near the Chiplun fault in Mumbai, India shows operational under UHS-500 (uniform hazard spectrum) event and it collapses when the building is exposed to UHS-2500 record. The thesis is concluded in Chapter-6 with an overall summary of the report and suggestions for further scope of the work.

Darbe nagrinėjamos simetrinės trečiosios eilės liestinės sluoksniuotės, kurios apibrėžiamos kaip 3 - džetų aibės. Surasta simetrinės erdvės izotropijų grupė, o taip pat jos izomorfijų grupė. Gautos izomorfijų grupės struktūrinės lygtys, surasti erdvės Maurerio – Kartano lygčių analogai, įrodytos formulės, išreiškiančios indukuotosios afiniosios sieties kreivumo tenzorių komponentes izomorfijų grupės struktūrinėmis konstantomis. Taip pat gauta visa eilė tapatybių, siejančių kreivumo objektus ir izomorfijų grupės struktūrines konstantas (apibendrintos Ričio ir Bianchi tapatybės). / The paper examined the symmetric third order tangent bundle, defined as 3- jet space. Found symmetric space isotropy group, as well as its isomorphy group. The resulting structural equation of isomorphy group, find this area Maurer - Cartan analogues of equations, an established formula, expressing inducted affines connection component of curvature tensors of the isomorphy group structural constants. Also received identities connecting the curvature objects structural constants of isomorphy group (generalized in Riči and Bianchi identity).

Ce projet de recherche consiste en l’étude de la réactivité et de la sélectivité de nouveaux catalyseurs de métathèse d’oléfines à base de ruthénium lors de réaction de fermeture de cycle par métathèse d’oléfines (RCM). L’emphase de cette étude repose sur l’évaluation de nouveaux catalyseurs possédant un ligand NHC (carbène N-hétérocyclique) C1-symétrique développés par le laboratoire Collins pour des réactions de désymétrisations asymétriques de méso-triènes par ARCM. Le projet a été séparé en deux sections distinctes. La première section concerne la formation d’oléfines trisubstituées par ARCM de méso-triènes. La seconde section consiste en la formation d’oléfines tétrasubstituées par le biais de la RCM de diènes et de la ARCM de méso-triènes. Il est à noter qu’il n’y a aucun précédent dans la littérature concernant la formation d’oléfines tétrasubstituées suite à une désymétrisation par ARCM. Lors de l’étude concernant la formation d’oléfines trisubstituées, une étude de cinétique a été entreprise dans le but de mieux comprendre la réactivité des différents catalyseurs. Il a été possible d’observer que le groupement N-alkyle a une grande influence sur la réactivité du catalyseur. Une étude de sélectivité a ensuite été entreprise pour déterminer si le groupement N-alkyle génère aussi un effet sur la sélectivité des catalyseurs. Cette étude a été effectuée par l’entremise de réactions de désymétrisation d’une variété de méso-triènes. En ce qui a trait à la formation d’oléfines tétrasubstituées, une étude de la réactivité des différents catalyseurs a été effectuée par l’intermédiaire de malonates de diéthyldiméthallyle. Il a encore une fois a été possible d’observer que le groupement N-alkyle possède un effet important sur la réactivité du catalyseur. Une étude de sélectivité a ensuite été entreprise pour déterminer si le groupement iv N-alkyle génère aussi un effet sur la sélectivité des catalyseurs. Cette étude a été effectuée par l’entremise de réactions de désymétrisation de différents mésotriènes. / This research consists in the study of the reactivity and selectivity of new chiral Ru-based olefin metathesis catalysts in ring-closing metathesis (RCM) reactions. The study focused on evaluating new catalysts possessing C1- symmetric NHC (N-heterocyclic carbene) ligands developed in our laboratories for asymmetric desymmetrization reactions of meso-trienes. The research was divided into two distinct sections, the first concerns the asymmetric ring closing metathesis (ARCM) processes that form trisubstituted olefins from meso-trienes. The second concerns the RCM and ARCM processes that form tetrasubstituted olefins from meso-trienes. It can be observed that there is no precedent in the literature concerning the formation of tetrasubstituted olefins via ARCM. During the investigation concerning the formation of trisubstituted olefins, a kinetic study was done to have better understanding of the catalyst selectivity. With this study in hand, it was possible to observe the effect induced by the N-alkyl group on the catalysts’ reactivity. A selectivity study was done to observe if the Nalkyl group could affects the catalysts’ selectivity. These investigations were done using a variety of meso-trienes in desymmetrization reactions to afford trisubstituted olefins. Concerning the formation of tetrasubstituted olefins, the catalysts’ reactivity was investigated in RCM processes involving diethyldimethallyl malonates. Once again, an effect induced by the N-alkyl group was observed concerning the reactivity of the catalysts. A selectivity study was performed. As for ARCM processes forming trisubstituted olefins, the N-alkyl group also had an impact on the selectivity of the catalysts. This investigation was done with ARCM desymmetrization of meso-trienes.