A inserção de aditivos em sistemas nanométricos tem como objetivo usual a estabilização destes materiais. A distribuição do aditivo nas interfaces é fundamental para o controle do balanço energético e das características da nanopartícula. Neste trabalho, foi estudado o efeito termodinâmico da inserção de Zn2+ e Sn4+ nos pós de SnO2 e ZnO, respectivamente, sintetizados pelo método dos precursores poliméricos baseado em Pechini. A quantificação do excesso de interface pela lixiviação ácida e o estudo da evolução do tamanho das partículas e de suas áreas de superfície e de contorno de grão, permitiram calcular a distribuição do aditivo no sistema e avaliar sua influência em cada região onde este estava localizado. À 500°C, para baixas concentrações, há a solubilização dos aditivos na rede, promovendo o crescimento das nanopartículas. Para as concentrações acima de 0,05 mol%, o aditivo tende a se concentrar no contorno de grão e na superfície, promovendo uma estabilidade a estas regiões, possibilitando nanopartícula menores no que as dos pós sem aditivo e com baixa aglomeração. O ensaio cinético reforçou a ideia da correlação entre estabilidade e distribuição do aditivo nas interfaces, além de mostrar um efeito de aceleração do processo de estabilização com o aumento da concentração de aditivos. Também foi possível calcular o calor de segregação para o contorno de grão (?HsegrCG= 48,8 J.mol-1) e superfície (?HSsegr= 37,0 J.mol-1), o que permitiu determinar as energias das interfaces, mostrando que a estabilização provocada pela inserção de aditivos esta diretamente associada a diminuição destas energias. / The inclusion of additives in nanometric systems has the usual purpose of stabilizing these materials. This distribution in the interfaces is critical to the control of energy balance and nanoparticle characteristics. In this work, we studied the thermodynamic effect of the inclusion of Zn2+ and Sn4+ in the powders of SnO2 and ZnO, respectively, synthesized by the polymeric precursor method based on Pechini. The quantification of interface excess by acid leaching and the study of the evolution of particle size, surface areas and grain boundary, allowed to calculate the distribution of the additive in the system and evaluate its influence in each region where it was located. At 500 °C, for low concentrations, there is a solubilization of additives in the bulk, promoting growth of the nanoparticles. For concentrations above 0.05 mol%, the additive tends to concentrate on grain boundary and surface, promoting the stability of these regions. This stability enables smaller nanoparticles and with low agglomeration. The kinetic assay strengthened the idea of correlation between stability and distribution of the additive in the interfaces, besides showing an accelerating effect of the stabilization process by increasing the concentration of additives. It was also possible to calculate the heat of segregation of the grain boundary (?HCGsegr = 48.8 J.mol-1) and surface (?HSsegr = 37.0 J.mol-1), which allowed to determine the energies of the interfaces. This showed that the stabilization brought about by the inclusion of additives is directly associated with the reduction of these energies.

Orientador: Pedro Luiz Onofrio Volpe / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-10T12:07:02Z (GMT). No. of bitstreams: 1 Magalhaes_JucelioGobi_M.pdf: 1140868 bytes, checksum: d62e85eff178ff4099f0d70cd3421f98 (MD5) Previous issue date: 2007 / Resumo: Este trabalho consiste em um estudo experimental do volume molar em excesso 'V POT. E' m de soluções líquidas binárias de clorofórmio + n-butilamina ou + s-butilamina; ou + dietilamina; ou + trietilamina a 288,15, 293,15, 298,15 e 303,15 K em função da composição e à pressão atmosférica, com o objetivo de estudar os possíveis efeitos físicos, químicos e estruturais nestes sistemas. Os dados experimentais foram ajustados a um polinômio do tipo Redlich-Kister e os resultados foram utilizados no cálculo de outras grandezas termodinâmicas, tais como, volume parcial molar, volume parcial molar em excesso, volume molar aparente, e volume molar aparente total. O 'V POT. E' m foi determinado indiretamente pela técnica de densitometria de oscilação mecãnica. Para os quatro sistemas estudados, e em todas as temperaturas os dados de 'V POT. E' m são negativos e tornam-se mais negativos com o aumento da temperatura. Os pontos de mínimo nos gráficos de 'V POT. E' m versus fração por mol de clorofórmio situam-se entre 0,35 e 0,50, dependendo do sistema. Os volumes parciais molares à diluição infinita do clorofórmio e das aminas são negativos em todas as temperaturas estudadas, e tornam-se mais negativos com o aumento da temperatura. Os resultados sugerem um pronunciado efeito estrutural (volume molar e volume livre) no valor de 'V POT. E' m , assim como a indicação da existência de fortes interações entre clorofórmio e aminas, mais evidentes no sistema contendo trietilamina / Abstract: This work consists on a experimental study of excess molar volume 'V POT. E' m of binary liquid solutions of chloroform + n-butylamine, or + s-butylamine, or + diethylamine, or + triethylamine at 288,15, 293,15, 298,15, 303,15 K as a function of composition and at atmospheric pressure, with the objective to study the possibles physical, chemical and structural effects in these systems. The experimental data were adjusted to a Redlich-Kister type equation, and the results were used to determine other thermodynamic functions, as, partial molar volume, excess partial molar volume, apparent molar volume and total apparent molar volume. The 'V POT. E' m was determined indirectly through mechanical oscilation densitometry technique. For the four systems studied, at all temperatures the data of 'V POT. E' m are negative and become more negative with the increasing of the temperature. The points of minimum on the plots of 'V POT. E' m versus molar fraction of chloroform are in between 0,35 and 0,50, depending of the system. The partial molar volumes at infinite dilution of chloroform and of the amines are negative on every studied temperatures, and become more negative with the increasing of the temperature. The results suggest a pronounced structural effect (molar and free volume) on the value of 'V POT. E' m , as well as an indication of the existence of strong interactions between chloroform and amine, wich is more evident in the system containing triethyamine / Mestrado / Físico-Química / Mestre em Química

Este trabalho testa a validade da Hipótese das Expectativas, segundo a qual as taxas de juros de longo prazo são formadas pela média das expectativas sobre as taxas de curto prazo futuras. O estudo baseia-se em dois artigos reconhecidos internacionalmente: Fama e Bliss (1987) e Cochrane e Piazzesi (2005). Os testes são realizados utilizando-se retornos em excesso e taxas forward mensais para títulos com prazo de vencimento entre dois e cinco anos. A base de dados consiste em observações mensais da taxa à vista de contratos futuros de DI. Os resultados apontam para a rejeição da HE para o caso brasileiro. Uma combinação linear de taxas forward é capaz de explicar a variação dos retornos em excesso com R² de até 0,63 para um título com maturidade em dois anos. / This work tests the validity of Expectations Hypothesis (EH), which posts that the long-term rates are an average of future expectations of short-term rates. The study is based on two internationally recognized papers: Fama e Bliss (1987) and Cochrane e Piazzesi (2005). The tests are performed using monthly observations on excess returns and forward rates for 2 to 5 year bonds. The data consists in monthly observations of ID future contracts yields. The results suggest rejection the EH for the Brazilian case. A linear combination of forward rates is able to explain excess returns variation with R² up to 0.63 for 2-year bonds.

Na última década, o Brasil liderou o ranking de consumo de medicamentos para emagrecer per capita, e, além disso, em 2009, foi o país que realizou o maior número de lipoaspirações. Instigada por estes surpreendentes e preocupantes dados brasileiros, nesta tese de doutorado busquei pensar acerca da temática do emagrecimento, da alimentação e dos cuidados de si em suas relações com a constituição dos corpo. Inicialmente, apresento a percepção de que, na atualidade, têm funcionado o dispositivo da aversão à gordura, isto é, uma rede heterogênea de elementos estrategicamente direcionados ao governo dos corpos, com a fnalidade de prevenir e controlar o excesso de peso. Partindo do entendimento que os discursos provenientes do campo das Ciências da Saúde, de certa forma, parecem estar envolvidos no funcionamento do dispositivo da aversão à gordura, procurei investigar como os profssionais das equipes da Estratégia de Saúde da Família (ESF), através de suas práticas de prevenção e controle do excesso de peso, relacionam-se com tal dispositivo. Para isso, realizei uma pesquisa de cunho etnográfco em práticas de promoção da saúde realizadas por profssionais de uma Unidade de Saúde (US). Foram acompanhadas as reuniões de um grupo de emagrecimento e as atividades vinculadas ao Programa Saúde na Escola realizadas por esses profssionais em uma Escola de Ensino Fundamental adscrita ao território desta US. Além do caderno de campo construído através da observação participante das atividades práticas mencionadas anteriormente, a análise também compreendeu alguns documentos ofciais brasileiros – Guia Alimentar para a População Brasileira, Manual Operacional para Profssionais da Saúde e Educação, Ciência Hoje na Escola – fornecidos como subsídios teóricos e/ou didáticos para as práticas de promoção da saúde formuladas e realizadas pelas equipes de ESF. A partir destas análises, aponto que os profssionais da equipe da US acompanhada, ao inscreverem suas práticas de promoção da saúde no dispositivo da aversão à gordura, através de sua abordagem focada na prevenção das doenças, da patologização do excesso de peso, do uso de técnicas de vigilância e do ensino de tecnologias de autocontrole, acabavam reforçando a estigmatização do excesso de peso e, talvez, agravando os sentimentos de desvalia e de insatisfação corporal experienciado por alguns participantes. Entendo que o movimento de pensar e problematizar a estigmatização do excesso de peso se faz necessário, especialmente para os profssionais da saúde pública envolvidos na formulação dos documentos ofciais, nas atividades de formação profssional e na realização das práticas de promoção da saúde. De forma que as práticas de promoção da saúde, realizadas por profssionais da ESF, possam contribuir para a discussão dos padrões estéticos e de saúde da atualidade; que não reforcem a estigmatização do excesso de peso; e que possam trazer subsídios para que os cuidados com a alimentação, o engajamento em atividades físicas, dentre outras atitudes de mudança de hábitos, sejam vivenciadas como atividades de múltiplas potências e não somente como um esforço de adaptação à norma estética/médica do corpo magro/saudável. / In the past decade, Brazil topped the consumption of diet drugs per capita, and also in 2009, was the country that held the largest number of liposuctions. Prompted by these surprising and worrying Brazilian data, this doctoral thesis sought to think about the topic of weight loss, nutrition and care of self in their relations with the constitution of the body. Initially, I present the perception that, nowadays, functions the dispositive of the culture of aversion to fat, that is, a heterogeneous network of strategically targeted elements for the government of bodies, in order to prevent and control overweight. Based on the understanding that the discourses from Health Sciences, somehow, seem to be involved in the arrangements of the dispositive of the culture of aversion to fat, I looked for investigate how the professional teams of the Family Health Strategy (FHS) through their practices for prevention and control of overweight, are associated with such dispositive. For this, I performed a research using ethnographic tools in some practices of health promotion carried out by professionals from a Health Unit (HU). I followed the meetings of a group of weight loss and the activities related to the School Health Program conducted by these professionals in an Elementary School enrolled in this HU territory. In addition to the feld notebook built through participant observation of the practices mentioned above, the analysis also included some Brazilian offcial documents - Food Guide for the Brazilian Population, Operational Manual for Health and Education Professionals, Science in School Today - provided as theoretical and/or didactical support for health promotion practices formulated and carried out by FHS team. From this analysis, I point out that - through its focused approach in the prevention of disease, pathologisation of overweight, the use of surveillance techniques and the teaching self-control technologies - the professionals of the HU accompanied, by enrolling their health promotion practices in the dispositive of the culture of aversion to fat, ended up reinforcing the stigmatization of overweight, and perhaps exacerbating feelings of worthlessness and body dissatisfaction experienced by some participants. I understand that the movement to think and discuss the stigma of excess weight is necessary, especially for public health professionals involved in the formulation of offcial documents, activities, training and implementation of health promotion practices. In order that the practices of health promotion, conducted by professionals from FHS can contribute to the discussion of health and aesthetic standards of today; that do not reinforce the stigmatization of overweight; and that bring contributions which enable that care food, engaging in physical activity, among other attitudes of habits changing, could be experienced as multiple potentials activities – and not only as an effort of adaption to the aesthetic/medical standard of the lean/healthy body.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work focuses on the delimitation of the desire as a lack, in Seminar 7, of Jacques Lacan, and as an excess, in the Anti-Oedipus, of Gilles Deleuze and Félix Guattari. Lacan resumes Freud's criticism to "Love your neighbour as yourself" to discuss some ideas that came to lead what he called the analytical pastoral, focused on promises of happiness and a kind of orthopaedics of the subjects. One of the critical strategies for Lacan is the use of structuralism, which is also one of the focuses of the criticism from the Anti-Oedipus. Deleuze and Guattari oppose the desire as excess to the structured unconscious as language, permeated by a fundamental lack. When approaching the desire we consider that: a) it is impossible to create, or even to say, a concept, as well as to make a clinic without putting them as policy, b) it is impossible to think of concept or clinic without seeing them as responses to certain political issues c) the indifference in politics or philosophy is possible, but not the indifference to politics or philosophy. Thus, we focus on a study of the connections between the Seminar 7 and the Anti-Oedipus and some aspects of the intellectual-political French scene of the second half of the twentieth century that involved the participation of Lacan, Deleuze and Guattari, especially the structuralist "movement". Moreover, we focus on a study of the concept of desire as a lack, from which the coordinates are set from the Other. In the game distanceproximity of the Other, the incest s prohibition is placed as a fundamental for structuring the unconscious as a language. The decoys produced in this game connect themselves to the search of the object as a good that must be found again. But the Supreme Good is a good that has always been forbidden and, as such, a condition of the possibility of desire. The desire as excess was thought from the choice of Deleuze and Guattari for the historical perspective, which results in the defence of the posterity of the law, opposed to the existence of a primordial Law from which would be born the desire. Some implications in the field of ethics were highlight from these definitions of desire. In addition to the fact that Seminar 7 devotes itself to the ethics of psychoanalysis, established as a "not to yield to his desire," as a direct opposition to the analytical pastoral and its attempt to appease the desire, the Anti-Oedipus is also permeated by ethical issues. We mainly take into account the discussion of psychoanalysis as a theory and practice without an alibi and the Anti-Oedipus as a book of non-fascist ethics. / Este trabalho volta-se à delimitação do desejo como falta, no Seminário 7, de Jacques Lacan, e como excesso, no Anti-Édipo, de Gilles Deleuze e Félix Guattari. Lacan retoma a crítica freudiana ao Amai ao próximo como a ti mesmo para discutir alguns ideais que passaram a guiar o que ele denominou de pastoral analítica, voltada a promessas de felicidade e a uma espécie de ortopedia dos sujeitos. Uma das estratégias críticas de Lacan é o uso do estruturalismo, o qual é também um dos focos das críticas do Anti-Édipo. Ao inconsciente estruturado como linguagem, perpassado por uma falta fundamental, Deleuze e Guattari opõem o desejo como excesso. Ao abordarmos o desejo consideramos que: a) é impossível criar, ou mesmo dizer, um conceito, bem como efetuar uma clínica sem que os coloquemos como política, b) é impossível pensar conceito ou clínica sem vê-los como respostas a certas questões políticas, c) é possível a indiferença em política ou em filosofia, mas não a indiferença à política ou à filosofia. Assim, voltamo-nos a um estudo das relações entre o Seminário 7 e O anti-Édipo e alguns aspectos do cenário político-intelectual francês da segunda metade do século XX que contaram com a participação de Lacan, Deleuze e Guattari, com destaque para o movimento estruturalista. Além disso, voltamo-nos a um estudo do conceito de desejo como falta, cujas coordenadas são estabelecidas frente ao Outro. No jogo de proximidade distanciamento do Outro, a proibição do incesto é colocada como fundamento da estruturação do inconsciente como linguagem. Os engodos produzidos neste jogo ligam-se à busca do objeto como um bem que se deve reencontrar. Mas o Bem Supremo é um bem proibido desde sempre e, como tal, condição de possibilidade do desejo. O desejo como excesso foi pensado a partir da escolha de Deleuze e Guattari pela perspectiva histórica, a qual tem como um dos resultados a defesa da posteridade da lei, contraposta à existência de uma Lei primordial da qual nasceria o desejo. Destas definições de desejo destacamos algumas implicações no campo da ética. Além de o Seminário 7 dedicar-se à ética da psicanálise, estabelecida como um não ceder de seu desejo , como contraponto direto à pastoral analítica e sua tentativa de apaziguar o desejo, O Anti-Édipo também é perpassado por questões éticas. Levamos em conta principalmente a discussão da psicanálise como uma teoria-prática sem álibi e do Anti-Édipo como um livro de ética não-fascista.

The aim of this thesis is to use a cross-match between WISE, 2MASS and SDSS to identify a large sample of M dwarfs. Through the careful characterisation and quality control of these M dwarfs I aim to identify rare systems (i.e. unresolved UCD companions, young M dwarfs, late M dwarfs and M dwarfs with common proper motion companions). Locating ultracool companions to M dwarfs is important for constraining low-mass formation models, the measurement of substellar dynamical masses and radii, and for testing ultracool evolutionary models. This is done by using an optimised method for identifying M dwarfs which may have unresolved ultracool companions. To do this I construct a catalogue of 440 694 M dwarf candidates, from WISE, 2MASS and SDSS, based on optical- and near-infrared colours and reduced proper motion. With strict reddening, photometric and quality constraints I isolate a sub-sample of 36 898 M dwarfs and search for possible mid-infrared M dwarf + ultracool dwarf candidates by comparing M dwarfs which have similar optical/near-infrared colours (chosen for their sensitivity to effective temperature and metallicity). I present 1 082 M dwarf + ultracool dwarf candidates for follow-up. Using simulated ultracool dwarf companions to M dwarfs, I estimate that the occurrence of unresolved ultracool companions amongst my M dwarf + ultracool dwarf candidates should be at least four times the average for my full M dwarf catalogue. I discuss yields of candidates based on my simulations. The possible contamination and bias from misidentified M dwarfs is then discussed, from chance alignments with other M dwarfs and UCDs, from chance alignments with giant stars, from chance alignments with galaxies, and from blended systems (via visual inspection). I then use optical spectra from LAMOST to spectral type a subset of my M dwarf + ultracool dwarf candidates. These candidates need confirming as true M dwarf + ultracool dwarf systems thus I present a new method I developed to use low resolution near-infrared spectra which relies on two colour similar objects (one an excess candidate, one not) having very similar spectra. A spectral difference of these two colour similar objects should leave the signature of a UCD in the residual of their differences, which I look for using the difference in two spectral bands designed to identify UCD spectral features. I then present the methods used to identify other rare systems from my full M dwarf catalogue. Young M dwarfs were identified by measuring equivalent widths of Hα from the LAMOST spectra, and by measuring rotation periods from Kepler 2 light curves. I identify late M dwarfs photometrically (using reduced proper motion and colour cuts) and spectroscopically (using the LAMOST spectra with spectral indices from the literature). Also I present common proper motion analysis aimed at finding Tycho-2 primaries for my M dwarfs and look for physically separated M dwarf + M dwarf pairs (internally within my full M dwarf catalogue).

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15720号 / 工博第3334号 / 新制||工||1504(附属図書館) / 28265 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 津野 洋, 教授 田中 宏明, 教授 清水 芳久 / 学位規則第4条第1項該当

This thesis describes, in detail, the synthesis of novel heterobidentate ligands. These ligands were subsequently used in palladium catalysed allylic substitution reactions to synthesise enantiomerically enriched alkylated products. The thesis also describes novel approaches to asymmetric catalysis, in particular asymmetric epoxidation derived from Katsuki-Sharpless methodology. Chapter 1 - This chapter reviews the literature, discussing the significant synthetic advancements in asymmetric catalysis in the past 10-15 years. Chapter 2 - This chapter describes in detail the synthesis of new heterobidentate ligands containing nitrogen and phosphorus ligating atoms. These ligands are based on imines containing enantiomerically pure asymmetric centres in an alpha position to the nitrogen moiety. Other ligands that were synthesised were derived from C2- symmetric diamines, also containing an asymmetric centre alpha position to the nitrogen, that produce ligands with the nitrogen functionality contained in a ring. Chapter 3 - This chapter describes the use of the novel ligands synthesised in Chapter 2 in palladium catalysed allylic substitution reactions. The racemic substrate, 1 ,3-diphenyl-3-acetoxy-1-propene, was alkylated to produce an enantiomeric enriched alkylated product. The alkylated product was obtained with up to 77 % enantiomeric excess. The reaction was conducted with a palladium catalyst in the presence of a novel ligand using dimethyl malonate as a nucleophile. The development and optimisation of these ligands within this reaction is discussed. Chapter 4 - This chapter discusses some novel approaches to asymmetric epoxidation. The epoxidation is based on methodology developed by Katsuki and Sharpless. This epoxidation relies on the substrate containing an up-unsaturated alcohol. The chapter discusses the use of a reversible nucleophile in the form of cyanide. The nucleophile is designed to react with a substrate to provide an upunsaturated cyanohydrin, suitable to undergo a Katsuki-Sharpless epoxidation. Once the asymmetric epoxidation is complete, the nucleophile would be removed. This chapter describes the attempts to develop the principle further. An improvement to the system would be to provide an environment capable of sustaining a dynamic kinetic resolution. Chapter 5 - This chapter contains the experimental which provides the exact details of the reactions reported in the thesis.

This graduation theses is about brand name valuation of ProLesk company. In the theoretical part is shown marketing and law conception of brand name and different methods of valuation. Marketing conception is based on the relationship product - consumer. In law conception is important the registration of brand name by national or international organisation. In the practical part is counted the value of brand name ProLesk company. There is used two methods - using royalty fees and excess return.

Un certain nombre de films réalisés après la mort du dictateur Franco et l’entrée de l’Espagne dans la postmodernité témoignent d’une indéniable prédilection de certains cinéastes espagnols pour l’excès et le débordement. Des noms tels que Pedro Almodóvar, Bigas Luna, Álex de la Iglesia, Santiago Segura ou Juanma Bajo Ulloa, entre autres, s’imposent à l’esprit lorsqu’on s’interroge sur l’impression d’outrance qui émane d’une partie de la production cinématographique de la démocratie. Le présent travail a pour ambition d’explorer les mécanismes et les enjeux de l’outrance, à travers un corpus réunissant plusieurs longs-métrages de ces cinq réalisateurs. Pierre angulaire d’un cinéma qui déforme et dissout toutes les frontières, cette notion, à première vue difficile à saisir, sera envisagée comme véritable concept esthétique, fondé sur les principes du franchissement et de la distorsion. C’est en particulier autour du corps, constamment manipulé, déformé, voire disséqué, qu’elle se polarise : aux épanchements des organismes de chair et aux débordements du corps social dans les différents univers fictionnels, répondent, chez chaque cinéaste, les migrations et réélaborations textuelles qui se jouent au sein du corps filmique. Ces opérations de métamorphose référentielle relèvent d’un processus de recyclage éminemment postmoderne, qui suppose l’hybridation de matériaux provenant tout autant de la tradition espagnole que de la culture mondialisée contemporaine. Voie d’expression d’une « espagnolité » soumise aux logiques transformatrices de la postmodernité, l’outrance apparaît comme une esthétique qui tend définitivement à brouiller les frontières, à tel point qu’elle finit même par franchir celles du film pour contaminer la périphérie extracinématographique. / Several films produced after the death of the dictator Franco and Spain’s entry into postmodernity show an undeniable penchant among some Spanish film-makers for excess and the extreme. Names like Pedro Almodóvar, Bigas Luna, Álex de la Iglesia, Santiago Segura and Juanma Bajo Ulloa, among others, spring to mind when we wonder about the impression of excess that emanates from part of the cinematographical production of democracy. This work aims to explore the mechanisms and stakes of excess through a collection of full-length films by these five directors. It will contemplate this notion, the keystone of a cinema that deforms and dissolves all limits which at first is elusive, based on the principles of distortion and the extreme. Because it is constantly manipulated, deformed, and even dissected, the body occupies a central8place in the aesthetic of excess: the textual migrations and re-elaborations that take place within the filmic body respond to both the outpourings of the bodies of flesh and blood and the excesses of the social body in the different fictional universes. These operations of referential metamorphosis pertain to an eminently postmodern process of recycling, which involves the hybridisation of materials that come from Spanish tradition, on the one hand, with those from contemporary globalised culture on the other. Means of expression of a “Spanishness” that is subjected to the logical transformations of postmodernity, excess constitutes an aesthetic that tends to blur limits, to such a point that it crosses the boundaries of the film to contaminate the extra-cinematographical periphery