This work provides first and second-order expressions to approximate neighboring solutions to the m-point boundary value problem. Multi-point problems arise in optimal control because of interior constraints or switching dynamics. Many problems have this form, and so this work fills a void in the study of extremal fields and neighboring optimal control of constrained systems. Only first and second-order terms are written down, but the approach is systematic and higher order expressions can be found similarly. The constraints and their parameters define an extremal field because any solution to the problem must satisfy the constraints. The approach is to build a Taylor series using constraint differentials, state differentials, and state variations. The differential is key to these developments, and it is a unifying element in the optimization of points, optimal control, and neighboring optimal control. The method is demonstrated on several types of problems including lunar descent, which has nonlinear dynamics, bounded thrust, and free final time. The control structure is bang-off-bang, and the method successfully approximates the unknown initial conditions, switch times, and final time. Compared to indirect shooting, computation time decreases by about three orders of magnitude.

A series of 6-endo-(methylthio)-bicyclo[2.2.1]heptane-2-endo-proline amides was synthesized to study the neighboring proline amide participation in electron transfer from thioethers. The thioether with endo-pyrrolidine amide formed a two-center three-electron SO bond after one electron oxidation and the oxidation potential of the thioether was lowered by 530 mV and 330 mV compared to the corresponding exo-pyrrolidine amide and the primary amide analogues, respectively. The thioether with a proline methyl ester showed the oxidation potential of 410 mV higher than that of the pyrrolidine amide. The basis for this surprising result was revealed by an X-ray crystallographic structure study of the diastereomerically pure proline methyl ester which showed amide carbonyl n → methyl ester π* interaction which removes electron density from the neighboring amide which results in less effective neighboring amide participation in thioether oxidation. This accounts for the electrochemical result. A potent synthetic route for S-tert-butyl m-terphenyl thioethers was developed and a series of such thioethers was synthesized. Electrochemical studies showed through-space S∙∙∙π interaction with lower oxidation potentials for thioethers with more electron rich aromatic groups and higher oxidation potentials with electron withdrawing aromatic groups. Selective Suzuki reactions were discovered in which mono-coupling of the precursor dibromides could be achieved. A second coupling was then possible in which two different aromatic rings are attached to the central aryl thioether ring. This enabled the synthesis of a two-sulfur three-aromatic ring extended m-terphenyl thioether as a potential electron conductor. In support of this possibility this compound showed an oxidation potential of +0.99 V which is less positive than the +1.09 V measured for the mono-sulfur analog.

付記する学位プログラム名: 霊長類学・ワイルドライフサイエンス・リーディング大学院 / 京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22295号 / 理博第4609号 / 新制||理||1661(附属図書館) / 京都大学大学院理学研究科生物科学専攻 / (主査)教授 古市 剛史, 教授 湯本 貴和, 教授 濱田 穣 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

Este trabalho tem como objetivo analisar as políticas de gestão para cidades brasileiras de fronteira internacional, para verificar se essas políticas contribuem para a integração regional entre seus países, visando à gestão compartilhada. Observou-se que há duas situações nas experiências do Brasil: um movimento social não governamental e outra que, apesar de existirem políticas regionais, não há gestão compartilhada, o que difere da experiência internacional das cidades francesas cujo movimento é governamental e há gestão compartilhada. Foram identificados a forma de organização e o papel das fronteiras na sociedade desde a origem até os dias atuais para compreender os desdobramentos contemporâneos nas relações de vizinhança internacional. A distinção do Tratado de Tordesilhas, em 1494, como a primeira concepção da fronteira linear no mundo a estabelecer os novos territórios das duas Américas, a portuguesa e a espanhola, foi fundamental para o entendimento histórico da conformação e a ocupação das fronteiras terrestres brasileiras. No período moderno, a fronteira adquire uma importância singular - é o limite da soberania nacional. As teorias concebidas no final do século XIX constituem a base da formulação dos modelos geopolíticos que se adotam na Europa e nas Américas do Norte e do Sul. No mundo atual, os conflitos entre as diferentes ou próprias nações separando-as por muros significam as práticas da exclusão entre os povos que se refletem com mais intensidade no espaço fronteiriço. Espaços de convívio se contrapõem aos fechados, abrindo os caminhos para a convivência nas fronteiras permeáveis. O método de trabalho consistiu em reconhecer, na pesquisa bibliográfica, publicações impressas e eletrônicas e nas visitas técnicas no Brasil e no exterior aos órgãos públicos, os elementos definidores para a base teórico-conceitual dos estudos de fronteira. Estes auxiliaram as análises sobre o tema proposto, permitindo uma reflexão mais profunda sobre os espaços fronteiriços e a sociedade que neles habita, especialmente no estudo de caso das cidades-gêmeas de Ponta Porã (Brasil) e Pedro Juan Caballero (Paraguai) na fronteira entre os dois países. As reflexões conclusivas levam, a partir das análises, a necessidade de o Estado, como responsável pelo planejamento do território nacional, contemplar nas políticas nacionais de forma integral, as estruturas espaciais da faixa de fronteira, permitindo que os estados e municípios possam construir o seu desenvolvimento sustentável com um novo instrumento de política pública: a gestão de forma compartilhada. / This academic work aims to analyze the management policy for the Brazilian cities located on the international border, in order to verify if these policies contribute to the regional integration between their countries, trying to reach shared management. During the research, two situations were appointed in the Brazilian experiences: one that shows a non-governmental social movement; and the other points out a non-shared management policy besides existing regional governmental policies, this situation is different from the international experience of the French border cities, for example. The kind of organization and the role of the border condition in the society have been identified, since their origin until the present days, to understand the contemporary consequences in the relations between neighbor countries. Having the Treaty of Tordesilhas in 1494 as the first to draw a border line in the world and to establish the new territories of the two Americas, the Portuguese and the Spanish, was fundamental to the historical understanding of the conformation and the occupation of Brazilian border land. In the modern period, the border acquires a singular importance - it is the limit of the national sovereignty. The theories designed in the late Nineteenth Century are the basis of the formulation of the geopolitical models adopted in Europe and North and South Americas. In todays world, the conflicts between different nations or nations themselves, separating them by walls, mean the practices of exclusion among people from different cultures that are reflected more intensely in bordering areas. Spaces of coexistence rise against enclosed areas, opening a way of new relations in these permeable bordering regions. The method used in this work was to recognize, in the bibliographic research, printed and electronic articles, and technical visits in public agencies, in Brazil and abroad, the defining elements for a theoretical-conceptual basis for the studies of the border. These ideas contributed for the analysis about the proposed subject, allowing a deeper reflection on the neighboring spaces and on the society that lives in these areas, especially in the case studied of the twin cities of Ponta Porã (Brazil) and Pedro Juan Caballero (Paraguay) on the border between the two countries. The conclusive reflections lead, based on these analyses, the need of the State, as the responsible for the planning of the national territory, contemplate a national policies in full, take the spatial structures of the bordering area, allowing states and municipalities to build their sustainable development with a new instrument of public policy: the management in a shared way.

Cytosine methylation at CpG dinucleotides is a semistable epigenetic marker critical to the normal development of vertebrates. Abnormal levels of methylation are associated with a host of human diseases and disorders, and many diagnostic tools have been developed based on analysis of methylation in tissue samples. Methylation is governed by a complex set of dynamic processes and has been observed to exhibit cyclical gains and losses, leading to the development of stochastic models of its inheritance. Many such models have assumed independence between sites and have largely focused on the proportion of methylation present in a sample, ignoring the diversity that exists in individual patterns. When analyzed at a single-base resolution, methylation patterns exhibit strong evidence of spatial dependence, and a recently proposed neighboring sites model which incorporates dependence between pairs of adjacent CpG sites has offered significant improvements over independent models. CpG sites are non-uniformly distributed throughout the genome, and the number of bases separating ""adjacent"" sites can vary greatly. In this paper, we develop and test an extension of this neighboring sites model which places a distance-dependent weight on the association between each pair of neighboring sites. Models are compared with regard to their ability to produce simulations that are statistically similar to biological data. We find that the distance-weighted model offers substantive improvements over distance-blind approaches to modeling the dependence structure, particularly in cases where firm boundaries between methylated and unmethylated regions exist in the data. / acase@tulane.edu

Most questions in proteomics require complex answers. Yet graph theory, supervised learning, and statistical model have decomposed complex questions into simple questions with simple answers. The expertise in the field of protein study often address tasks that demand answers as complex as the questions. Such complex answers may consist of multiple factors that must be weighed against each other to arrive at a globally satisfactory and consistent solution to the question. In the prediction of calcium binding in proteins, we construct a global oxygen contact graph of a protein, then apply a graph algorithm to find oxygen clusters with the fixed size of four, finally employ a geometry algorithm to judge if the oxygen clusters are calcium-binding sites or not. Additionally, we can predict the locations of those sites. Furthermore, we construct a global oxygen contact graph including oxygen-bonded carbon atoms of a protein, then apply a graph algorithm to find local biggest oxygen clusters, finally design another geometric filter to exclude the non-calcium binding oxygen clusters. In addition, we apply observed chemical properties as a chemical filter to recognize some non-calcium binding oxygen clusters. In order to explore the characteristics of calcium-binding sites in proteins, we conduct a statistic survey on four datasets derived from 1994 to 2005 about the geometric parameters and chemical properties of calcium-binding sites. In the prediction of disulfide bond connectivity, we analyze protein sequences to predict the folding of proteins relative to the cystines using nearest neighboring methods. we extend a new pattern-wise method to all available template proteins, and find global pattern of pairing cysteines with a new descriptor of cysteine separation profile on protein secondary structure.

<p>The Lattrell-Dax method of nitrite-mediated substitution of carbohydrate triflates is an efficient method to generate structures of inverse configuration. In this study it has been demonstrated that a neighboring equatorial ester group plays a highly important role in this carbohydrate epimerization reaction, inducing the formation of inversion compounds in good yields. Based on this effect, efficient synthetic routes to a range of carbohydrate structures, notably β-D-mannosides and β-D-talosides, were designed. By use of the ester activation effect for neighboring groups, a double parallel as well as a double serial inversion strategy was developed.</p>

Este trabalho tem como objetivo analisar as políticas de gestão para cidades brasileiras de fronteira internacional, para verificar se essas políticas contribuem para a integração regional entre seus países, visando à gestão compartilhada. Observou-se que há duas situações nas experiências do Brasil: um movimento social não governamental e outra que, apesar de existirem políticas regionais, não há gestão compartilhada, o que difere da experiência internacional das cidades francesas cujo movimento é governamental e há gestão compartilhada. Foram identificados a forma de organização e o papel das fronteiras na sociedade desde a origem até os dias atuais para compreender os desdobramentos contemporâneos nas relações de vizinhança internacional. A distinção do Tratado de Tordesilhas, em 1494, como a primeira concepção da fronteira linear no mundo a estabelecer os novos territórios das duas Américas, a portuguesa e a espanhola, foi fundamental para o entendimento histórico da conformação e a ocupação das fronteiras terrestres brasileiras. No período moderno, a fronteira adquire uma importância singular - é o limite da soberania nacional. As teorias concebidas no final do século XIX constituem a base da formulação dos modelos geopolíticos que se adotam na Europa e nas Américas do Norte e do Sul. No mundo atual, os conflitos entre as diferentes ou próprias nações separando-as por muros significam as práticas da exclusão entre os povos que se refletem com mais intensidade no espaço fronteiriço. Espaços de convívio se contrapõem aos fechados, abrindo os caminhos para a convivência nas fronteiras permeáveis. O método de trabalho consistiu em reconhecer, na pesquisa bibliográfica, publicações impressas e eletrônicas e nas visitas técnicas no Brasil e no exterior aos órgãos públicos, os elementos definidores para a base teórico-conceitual dos estudos de fronteira. Estes auxiliaram as análises sobre o tema proposto, permitindo uma reflexão mais profunda sobre os espaços fronteiriços e a sociedade que neles habita, especialmente no estudo de caso das cidades-gêmeas de Ponta Porã (Brasil) e Pedro Juan Caballero (Paraguai) na fronteira entre os dois países. As reflexões conclusivas levam, a partir das análises, a necessidade de o Estado, como responsável pelo planejamento do território nacional, contemplar nas políticas nacionais de forma integral, as estruturas espaciais da faixa de fronteira, permitindo que os estados e municípios possam construir o seu desenvolvimento sustentável com um novo instrumento de política pública: a gestão de forma compartilhada. / This academic work aims to analyze the management policy for the Brazilian cities located on the international border, in order to verify if these policies contribute to the regional integration between their countries, trying to reach shared management. During the research, two situations were appointed in the Brazilian experiences: one that shows a non-governmental social movement; and the other points out a non-shared management policy besides existing regional governmental policies, this situation is different from the international experience of the French border cities, for example. The kind of organization and the role of the border condition in the society have been identified, since their origin until the present days, to understand the contemporary consequences in the relations between neighbor countries. Having the Treaty of Tordesilhas in 1494 as the first to draw a border line in the world and to establish the new territories of the two Americas, the Portuguese and the Spanish, was fundamental to the historical understanding of the conformation and the occupation of Brazilian border land. In the modern period, the border acquires a singular importance - it is the limit of the national sovereignty. The theories designed in the late Nineteenth Century are the basis of the formulation of the geopolitical models adopted in Europe and North and South Americas. In todays world, the conflicts between different nations or nations themselves, separating them by walls, mean the practices of exclusion among people from different cultures that are reflected more intensely in bordering areas. Spaces of coexistence rise against enclosed areas, opening a way of new relations in these permeable bordering regions. The method used in this work was to recognize, in the bibliographic research, printed and electronic articles, and technical visits in public agencies, in Brazil and abroad, the defining elements for a theoretical-conceptual basis for the studies of the border. These ideas contributed for the analysis about the proposed subject, allowing a deeper reflection on the neighboring spaces and on the society that lives in these areas, especially in the case studied of the twin cities of Ponta Porã (Brazil) and Pedro Juan Caballero (Paraguay) on the border between the two countries. The conclusive reflections lead, based on these analyses, the need of the State, as the responsible for the planning of the national territory, contemplate a national policies in full, take the spatial structures of the bordering area, allowing states and municipalities to build their sustainable development with a new instrument of public policy: the management in a shared way.

The Lattrell-Dax method of nitrite-mediated substitution of carbohydrate triflates is an efficient method to generate structures of inverse configuration. In this study it has been demonstrated that a neighboring equatorial ester group plays a highly important role in this carbohydrate epimerization reaction, inducing the formation of inversion compounds in good yields. Based on this effect, efficient synthetic routes to a range of carbohydrate structures, notably β-D-mannosides and β-D-talosides, were designed. By use of the ester activation effect for neighboring groups, a double parallel as well as a double serial inversion strategy was developed. / QC 20101111

No description available.