Design and Simulation of a Solar Powered UAV for Remote Sensing Tasks Technical Report

This research deals with the development of a Solar-Powered UAV designed for remote sensing, in particular to the development of the autopilot sub-system and path planning. The design of the Solar-Powered UAS followed a systems engineering methodology, by first defining system architecture, and selecting each subsystem. Validation tests and integration of autopilot is performed, in order to evaluate the performances of each subsystem and to obtain a global operational system for data collection missions. The flight tests planning and simulation results are also explored in order to verify the mission capabilities using an autopilot on a UAS. The important aspect of this research is to develop a Solar-Powered UAS for the purpose of data collection and video monitoring, especially data and images from the ground; transmit to the GS (Ground Station), segment the collected data, and afterwards analyze it with a Matlab code.

Applying Genetic Algorithms to Optimize Power in Tiled SNUCA Chip Multicore Architectures

We propose a novel technique for reducing the power consumed by the on-chip cache in SNUCA chip multicore platform. This is achieved by what we call a "remap table", which maps accesses to the cache banks that are as close as possible to the cores, on which the processes are scheduled. With this technique, instead of using all the available cache, we use a portion of the cache and allocate lesser cache to the application. We formulate the problem as an energy-delay (ED) minimization problem and solve it offline using a scalable genetic algorithm approach. Our experiments show up to 40% of savings in the memory sub-system power consumption and 47% savings in energy-delay product (ED).

Applying Genetic Algorithms to Optimize Power in Tiled SNUCA Chip Multicore Architectures

We propose a novel technique for reducing the power consumed by the on-chip cache in SNUCA chip multicore platform. This is achieved by what we call a "remap table", which maps accesses to the cache banks that are as close as possible to the cores, on which the processes are scheduled. With this technique, instead of using all the available cache, we use a portion of the cache and allocate lesser cache to the application. We formulate the problem as an energy-delay (ED) minimization problem and solve it offline using a scalable genetic algorithm approach. Our experiments show up to 40% of savings in the memory sub-system power consumption and 47% savings in energy-delay product (ED).

Efficient generation of diffraction-limited multi-sheet pattern for biological imaging

We demonstrate a new technique to generate multiple light-sheets for fluorescence microscopy. This is possible by illuminating the cylindrical lens using multiple copies of Gaussian beams. A diffraction grating placed just before the cylindrical lens splits the incident Gaussian beam into multiple beams traveling at different angles. Subsequently, this gives rise to diffraction-limited light-sheets after the Gaussian beams pass through the combined cylindrical lens-objective sub-system. Direct measurement of field at and around the focus of objective lens shows multi-sheet pattern with an average thickness of 7.5 mu m and inter-sheet separation of 380 mu m. Employing an independent orthogonal detection sub-system, we successfully imaged fluorescently-coated yeast cells (approximate to 4 mu m) encaged in agarose gel-matrix. Such a diffraction-limited sheet-pattern equipped with dedicated detection system may find immediate applications in the field of optical microscopy and fluorescence imaging. (C) 2015 Optical Society of America

3D Macroporous Solids from Chemically Cross-linked Carbon Nanotubes

We demonstrate a new technique to generate multiple light-sheets for fluorescence microscopy. This is possible by illuminating the cylindrical lens using multiple copies of Gaussian beams. A diffraction grating placed just before the cylindrical lens splits the incident Gaussian beam into multiple beams traveling at different angles. Subsequently, this gives rise to diffraction-limited light-sheets after the Gaussian beams pass through the combined cylindrical lens-objective sub-system. Direct measurement of field at and around the focus of objective lens shows multi-sheet pattern with an average thickness of 7.5 μm and inter-sheet separation of 380 μm. Employing an independent orthogonal detection sub-system, we successfully imaged fluorescently-coated yeast cells (≈4 μm) encaged in agarose gel-matrix. Such a diffraction-limited sheet-pattern equipped with dedicated detection system may find immediate applications in the field of optical microscopy and fluorescence imaging. © 2015 Optical Society of America

An experimental study of the influence of weak convection on perikinetic coagulation

A remarkably increased coagulation rate for 2-mu m PS spheres was previously reported for a perikinetic coagulation experiment performed under microgravity conditions (1998, R. Folkersma, A. J. G. van Diemen, and H. N. Stein, J. Colloid Interface Sci. 206, 482); from this experiment, it was assumed that the leading factor slowing the coagulation process under normal gravitation was free convection due to gravity (1998, R. Folkersma, and H. N. Stein, J. Colloid Interface Sci. 206, 494). To test the influence of free convection as a single-effect factor on the coagulation process, a ground-based experiment was constructed. The coagulation rate of 2-mu m PS spheres dispersed in water was determined by measuring the turbidity of the dispersion solution while convection-driven flows in the solution were checked with a visual magnification system. We found that it was possible to cease free convection-driven particle flows on the ground, as long as the experiments were carefully operated. The strength of convection was controlled by changing the temperature gradient applied to the sample cell. By monitoring both the coagulation rate and convection-driven flows simultaneously, our experiments showed that weak free convection (maximum speed <150 mu m/s) actually has negligible effects on the coagulation rate.

A study of the influence of free convection on coagulation process

It was assumed [1, 2] that gravity affects the coagulation process in two ways: free convection, which is hard to be avoided on the ground and sedimentation, which can be greatly reduced by the density-matching method. We present a ground-based experiment set-up to study the influence of convection on the perikinetic coagulation for aqueous polystyrene (PS) dispersions. The turbidity measurement was used to evaluate the relative coagulation rate and convection-driven flows in the solution were checked with a visual-magnification system. The pattern of flow field temperature profile in the sample cell is given. Our experiments show that there was no noticeable difference of coagulation rate observed no matter whether convection flows exist (with the flow speed up to 180 mu m/s) or not.

I. Spectroscopic evidence for slow vibrational relaxation in excited electronic states of diatomics in rare gas solids. II. Static crystal field effects in the electronic spectra of isotopically mixed benzene crystals

Part I

Studies of vibrational relaxation in excited electronic states of simple diatomic molecules trapped in solid rare-gas matrices at low temperatures are reported. The relaxation is investigated by monitoring the emission intensity from vibrational levels of the excited electronic state to vibrational levels of the ground electronic state. The emission was in all cases excited by bombardment of the doped rare-gas solid with X-rays.

The diatomics studied and the band systems seen are: N₂, Vegard-Kaplan and Second Positive systems; O₂, Herzberg system; OH and OD, A ²Σ⁺ - X²II_i system. The latter has been investigated only in solid Ne, where both emission and absorption spectra were recorded; observed fine structure has been partly interpreted in terms of slightly perturbed rotational motion in the solid. For N₂, OH, and OD emission occurred from v' > 0, establishing a vibrational relaxation time in the excited electronic state of the order, of longer than, the electronic radiative lifetime. The relative emission intensity and decay times for different v' progressions in the Vegard-Kaplan system are found to depend on the rare-gas host and the N₂ concentration, but are independent of temperature in the range 1.7°K to 30°K.

Part II

Static crystal field effects on the absorption, fluorescence, and phosphorescence spectra of isotopically mixed benzene crystals were investigated. Evidence is presented which demonstrate that in the crystal the ground, lowest excited singlet, and lowest triplet states of the guest deviate from hexagonal symmetry. The deviation appears largest in the lowest triplet state and may be due to an intrinsic instability of the ³B_1u state. High resolution absorption and phospho- rescence spectra are reported and analyzed in terms of site-splitting of degenerate vibrations and orientational effects. The guest phosphorescence lifetime for various benzene isotopes in C₆D₆ and sym-C₆H₃D₃ hosts is presented and discussed.

Models of the Oxygen-Evolving Complex of Photosystem II

In the five chapters that follow, I delineate my efforts over the last five years to synthesize structurally and chemically relevant models of the Oxygen Evolving Complex (OEC) of Photosystem II. The OEC is nature’s only water oxidation catalyst, in that it forms the dioxygen in our atmosphere necessary for oxygenic life. Therefore understanding its structure and function is of deep fundamental interest and could provide design elements for artificial photosynthesis and manmade water oxidation catalysts. Synthetic endeavors towards OEC mimics have been an active area of research since the mid 1970s and have mutually evolved alongside biochemical and spectroscopic studies, affording ever-refined proposals for the structure of the OEC and the mechanism of water oxidation. This research has culminated in the most recent proposal: a low symmetry Mn₄CaO₅ cluster with a distorted Mn₃CaO₄ cubane bridged to a fourth, dangling Mn. To give context for how my graduate work fits into this rich history of OEC research, Chapter 1 provides a historical timeline of proposals for OEC structure, emphasizing the role that synthetic Mn and MnCa clusters have played, and ending with our Mn₃CaO₄ heterometallic cubane complexes.

In Chapter 2, the triarylbenzene ligand framework used throughout my work is introduced, and trinuclear clusters of Mn, Co, and Ni are discussed. The ligand scaffold consistently coordinates three metals in close proximity while leaving coordination sites open for further modification through ancillary ligand binding. The ligands coordinated could be varied, with a range of carboxylates and some less coordinating anions studied. These complexes’ structures, magnetic behavior, and redox properties are discussed.

Chapter 3 explores the redox chemistry of the trimanganese system more thoroughly in the presence of a fourth Mn equivalent, finding a range of oxidation states and oxide incorporation dependent on oxidant, solvent, and Mn salt. Oxidation states from Mn^II₄ to Mn^IIIMn^IV₃ were observed, with 1-4 O^2– ligands incorporated, modeling the photoactivation of the OEC. These complexes were studied by X-ray diffraction, EPR, XAS, magnetometry, and CV.

As Ca²⁺ is a necessary component of the OEC, Chapter 4 discusses synthetic strategies for making highly structurally accurate models of the OEC containing both Mn and Ca in the Mn₃CaO₄ cubane + dangling Mn geometry. Structural and electrochemical characterization of the first Mn₃CaO₄ heterometallic cubane complex— and comparison to an all-Mn Mn₄O₄ analog—suggests a role for Ca²⁺ in the OEC. Modification of the Mn₃CaO₄ system by ligand substitution affords low symmetry Mn₃CaO₄ complexes that are the most accurate models of the OEC to date.

Finally, in Chapter 5 the reactivity of the Mn₃CaO₄ cubane complexes toward O- atom transfer is discussed. The metal M strongly affects the reactivity. The mechanisms of O-atom transfer and water incorporation from and into Mn₄O₄ and Mn₄O₃ clusters, respectively, are studied through computation and ¹⁸O-labeling studies. The μ3-oxos of the Mn₄O₄ system prove fluxional, lending support for proposals of O^2– fluxionality within the OEC.

Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

一批中国古玻璃化学成分的质子激发X射线荧光分析

质子激发X射线荧光(proton induced X-ray emission，PIXE)技术是一种高灵敏度、非破坏性、多元素定量测定的分析方法。采用外束PIXE技术对内蒙古地区和博山出土的一批古代玻璃的化学成分进行了定量测定。结果表明：内蒙古地区出土的玻璃中，西周时期的玻璃珠是含有少量K2O和CaO助熔剂的釉砂，其主要成分为SiO2；汉代的玻璃珠属于PbO—SiO2玻璃；多数元代的玻璃制品和部分北魏时期的玻璃珠属于K2O—CaO—SiO2玻璃。博山出土的元末明初的玻璃基本为KzO-CaO—SiO2系玻璃

广西合浦地区出土汉代古玻璃的质子激发X荧光分析

采用改进的外束质子激发x射线荧光、电感耦合等离子体原子发射光谱分析等技术，对广西合浦地区出土的一批汉代古玻璃样品的化学成分和结构特性等进行了检测。结果表明：两汉时期，合浦地区的古代玻璃存在K2O—SiO2、PbO-BaO-SiO2、PbO—SiO2、Na2O-K2O-PbO-SiO2、（Na2O）K2O-CaO—SiO2等多种类型，但绝大多数为K2O—SiO2玻璃。表面风化可引起K2O-SiO2玻璃表面K2O等助熔剂的流失和富硅层的形成。综合化学成分以及器型特征，认为我国汉代K2O—SiO2玻璃制造技术可

四川地区出土古玻璃的质子激发X荧光分析

abstract {Proton induced X-ray emission (PIXE) technique is an effective method for the chemical composition analysis of ancient glass samples without destruction. Chemical composition of the ancient glass samples dated from the Warring States Period (770-476 B.C.) to the Six Dynasties Period (220-589 A.D.), which were unearthed in Sichuan area, was quantitatively determined by the PIXE technique. The results show that the glass Bi (disc) and the glass eye beads of the Warring States Period all belong to the PbO-BaO-SiO₂ system. According to the composition and shape, we infer that these glass Bi and eye beads were made in China. Whereas, the chemical compositions of the glass ear pendants and beads of the Six Dynasties Period are varied, including K₂O-CaO-SiO₂, K₂O-SiO₂ and other glass systems. Based on the obtained results and those from literatures, some questions related to the technical propagation of the ancient Chinese glass are discussed.}

Os caminhos da avaliação de desempenho do setor saúde no Brasil: os dois lados do mesmo sistema de saúde

Esta revisão de literatura é fruto de indagações sobre a mudança na postura do Estado brasileiro no que concerne à avaliação na atualidade. A temática desta pesquisa é a inserção da ferramenta da avaliação de desempenho da saúde no Brasil. Mais precisamente, o estudo traz uma análise dos índices de desempenho do subsistema público (IDSUS) e do índice elaborado pela Agência Nacional de Saúde (ANS) para avaliar o subsistema privado da saúde (IDSS). Dessa maneira, esta dissertação tem como objetivo analisar os programas de qualificação do sistema de saúde brasileiro através da avaliação do Índice de Desempenho da Saúde Suplementar (IDSS) e do Índice de Desempenho do SUS (IDSUS), considerando seus impactos na relação público-privado do setor saúde. Para dar conta desses objetivos, a pesquisa examinou os Programas de Qualificação do Sistema de Saúde Brasileiro tanto na sua face pública quanto na privada, utilizando as técnicas de análise documental e bibliográfica. A análise transcorreu a partir do levantamento de documentos oficiais e da literatura produzida sobre o tema. Além da leitura de documentos da Agência Nacional de Saúde (ANS), Ministério da Saúde (MS), Instituto de Estudos da Saúde Suplementar (IESS), Federação de Seguros (FENASEG), Associação Brasileira de Medicina de Grupos (ABRAMGE) e Instituto Brasileiro de Geografia e Estatística (IBGE), foram consultados trabalhos acadêmicos e selecionados textos jornalísticos que evidenciaram o processo de implantação e utilização do Programa de Qualificação da Saúde no Brasil. A dissertação então trouxe à tona, admitindo como base a análise do IDSUS recentemente criado e do IDSS, a necessidade de se rediscutir as finalidades das avaliações de desempenho propostas. Tanto o IDSS quanto o IDSUS são iniciativas pioneiras positivas que podem e devem ser aprimoradas, para que possam de fato instrumentalizar o controle social e o gestor na priorização e no planejamento das ações de saúde. O instrumento utilizado pela ANS foi considerado eficaz, democrático e participativo no que diz respeito ao alcance dos objetivos do Programa de Qualificação das Operadoras de Planos de Saúde. O mesmo conseguiu integrar pressupostos de modelos e instrumentos de gestão referenciados pela literatura como modernos e eficazes, como a gestão por resultados. Promoveu não só mais transparência ao subsistema privado, mas induziu, em certa medida, a concorrência do setor. Já em relação à face pública, percebeu-se que mesmo em face da jovialidade da proposta do IDSUS, o mesmo mapeou alguns pontos críticos do subsistema e apontou a necessidade de se trabalhar o setor de forma mais eficiente. Entretanto, esta pesquisa concluiu que ambos os movimentos de avaliação dos subsistemas público e privado não se completam, não dialogam como deveriam, evidenciando uma dificuldade em perceber e organizar o sistema como um todo.

Crise e oportunidade: O caso dos hospitais filantrópicos da região centro sul fluminense do Estado do Rio de Janeiro.

De acordo com dados do DATASUS, o setor filantrópico no país possui cerca de 2.100 estabelecimentos hospitalares, com mais de 155.000 leitos, o que representa 31% do total de leitos do país. Ou seja, 1/3 dos leitos existentes no país são filantrópicos, caracterizando o setor como importante prestador de serviços ao Sistema Único de Saúde, assim como à saúde suplementar. Estes números demonstram a importância do setor filantrópico para o país, mas também para muitas regiões, como a região centro sul fluminense do Estado do Rio de Janeiro. A enorme complexidade e diversidade da rede hospitalar filantrópica traz muitos e variados desafios, tanto para a operação hospitalar, como para as políticas governamentais de manutenção do setor saúde. Além da defasagem da tabela do SUS, outros problemas também são enfrentados por estes hospitais como os tetos financeiros, que levam ao pagamento menor do que é efetivamente produzido, atrasos de pagamentos, que dificultam o planejamento e o equilíbrio financeiro, fechamento de linhas de créditos, dificuldades nas negociações com gestores, entre muitos outros. Todas essas dificuldades têm reflexos críticos na gestão dessas organizações que passam por crises financeiras, necessidade de qualificação profissional e de adequações em suas instalações e equipamentos. Esta pesquisa propõe-se a estudar a situação dos hospitais filantrópicos da região Centro-Sul Fluminense do Estado do Rio de Janeiro no âmbito financeiro, assim como conhecer a percepção dos gestores sobre as dificuldades do setor, suas perspectivas e propostas de possíveis soluções. A metodologia utilizada foi de natureza exploratória, com abordagem qualitativa e quantitativa, com estudo de casos múltiplos, utilizando-se de diversas fontes para coleta de dados, como fontes primárias, secundárias e entrevista semi-estruturada. Os resultados demonstraram a importância dos hospitais filantrópicos na produção de serviços de saúde para o SUS e a necessidade da formulação de políticas especificas para a manutenção do setor filantrópico conveniado ao SUS. Na região centro sul fluminense há uma complementaridade entre a rede pública e a rede filantrópica. Embora seja reconhecida a importância histórica e estratégica desses hospitais na prestação de serviços ao SUS, mantidas as condições atuais nos âmbitos de capacidade instalada, organizacional ou financeira, não há dúvidas de que o futuro dessas instituições será incerto com riscos importantes para a continuidade dos serviços prestados e da própria sobrevivência dos hospitais.Existe a necessidade urgente de que os gestores públicos busquem a implantação de modelos flexíveis de gestão, visando o estabelecimento de um relacionamento de parceria com os hospitais filantrópicos e suas ações sejam definidas por metas tangíveis e alcançáveis.