Coastal management measures for the lower Maumee Watershed, Lake Erie

In January 2006 the Maumee Remedial Action Plan (RAP) Committee submitted a State II Watershed Restoration Plan for the Maumee River Great Lakes Area of Concern (AOC) area located in NW Ohio to the State of Ohio for review and endorsement (MRAC, 2006). The plan was created in order to fulfill the requirements, needs and/or use of five water quality programs including: Ohio Department of Natural Resources (DNR) Watershed Coordinator Program; Ohio EPA Great Lakes RAP Program; Ohio DNR Coastal Non-point Source Pollution Control Program; Ohio EPA Total Maximum Daily Load Program; and US Fish & Wildlife Service Natural Resources Damage Program. The plan is intended to serve as a comprehensive regional management approach for all jurisdictions, agencies, organizations, and individuals who are working to restore the watershed, waterways and associated coastal zone. The plan includes: background information and mapping regarding hydrology, geology, ecoregions, and land use, and identifies key causes and sources for water quality concerns within the six 11-digit hydrological units (HUCs), and one large river unit that comprise the Maumee AOC. Tables were also prepared that contains detailed project lists for each major watershed and was organized to facilitate the prioritization of research and planning efforts. Also key to the plan and project tables is a reference to the Ohio DNR Coastal Management Measures that may benefit from the implementation of an identified project. This paper will examine the development of the measures and their importance for coastal management and watershed planning in the Maumee AOC. (PDF contains 4 pages)

Three-dimensional supercell simulation of novel semiconductor nanostructures

In this thesis we investigate atomic scale imperfections and fluctuations in the quantum transport properties of novel semiconductor nanostructures. For this purpose, we have developed a numerically efficient supercell model of quantum transport capable of representing potential variations in three dimensions. This flexibility allows us to examine new quantum device structures made possible through state-of-the-art semiconductor fabrication techniques such as molecular beam epitaxy and nanolithography. These structures, with characteristic dimensions on the order of a few nanometers, hold promise for much smaller, faster and more efficient devices than those in present operation, yet they are highly sensitive to structural and compositional variations such as defect impurities, interface roughness and alloy disorder. If these quantum structures are to serve as components of reliable, mass-produced devices, these issues must be addressed.

In Chapter 1 we discuss some of the important issues in resonant tunneling devices and mention some of thier applications. In Chapters 2 and 3, we describe our supercell model of quantum transport and an efficient numerical implementation. In the remaining chapters, we present applications.

In Chapter 4, we examine transport in single and double barrier tunneling structures with neutral impurities. We find that an isolated attractive impurity in a single barrier can produce a transmission resonance whose position and strength are sensitive to the location of the impurity within the barrier. Multiple impurities can lead to a complex resonance structure that fluctuates widely with impurity configuration. In addition, impurity resonances can give rise to negative differential resistance. In Chapter 5, we study interface roughness and alloy disorder in double barrier structures. We find that interface roughness and alloy disorder can shift and broaden the n = 1 transmission resonance and give rise to new resonance peaks, especially in the presence of clusters comparable in size to the electron deBroglie wavelength. In Chapter 6 we examine the effects of interface roughness and impurities on transmission in a quantum dot electron waveguide. We find that variation in the configuration and stoichiometry of the interface roughness leads to substantial fluctuations in the transmission properties. These fluctuations are reduced by an attractive impurity placed near the center of the dot.

Coupled plasmonic systems and devices : applications in visible metamaterials, nanophotonic circuits, and CMOS imaging

With the size of transistors approaching the sub-nanometer scale and Si-based photonics pinned at the micrometer scale due to the diffraction limit of light, we are unable to easily integrate the high transfer speeds of this comparably bulky technology with the increasingly smaller architecture of state-of-the-art processors. However, we find that we can bridge the gap between these two technologies by directly coupling electrons to photons through the use of dispersive metals in optics. Doing so allows us to access the surface electromagnetic wave excitations that arise at a metal/dielectric interface, a feature which both confines and enhances light in subwavelength dimensions - two promising characteristics for the development of integrated chip technology. This platform is known as plasmonics, and it allows us to design a broad range of complex metal/dielectric systems, all having different nanophotonic responses, but all originating from our ability to engineer the system surface plasmon resonances and interactions. In this thesis, we demonstrate how plasmonics can be used to develop coupled metal-dielectric systems to function as tunable plasmonic hole array color filters for CMOS image sensing, visible metamaterials composed of coupled negative-index plasmonic coaxial waveguides, and programmable plasmonic waveguide network systems to serve as color routers and logic devices at telecommunication wavelengths.

Alleviating poverty and enhancing food security through fish production in man-made lakes

Man-made lakes inhabit diverse species of which the fish fauna constitutes the most targeted species of exploitation. For man-made lakes to serve as means of alleviating poverty an enhancing food security through increased fish production in Nigeria, sound management of the lake is strongly recommended. It will include the maintenance of good water quality, stocking with good species, control of over fishing, conservation of extinction and declining species as well as adequate legislation to regulate fishing activities. Recreational and tourism facilities can also be incorporated along with fish production in these man-made lakes to provide additional income and revenue for individual and Government. Some other practical ways by which these water bodies can be improved for effective and sustainable fish production as well as alleviating poverty was discussed

Physical characterization of the rack effect and hydrogen bond networks in blue copper proteins

A summary of previous research is presented that indicates that the purpose of a blue copper protein's fold and hydrogen bond network, aka, the rack effect, enforce a copper(II) geometry around the copper(I) ion in the metal site. In several blue copper proteins, the C-terminal histidine ligand becomes protonated and detaches from the copper in the reduced forms. Mutants of amicyanin from Paracoccus denitrificans were made to alter the hydrogen bond network and quantify the rack effect by pK_a shifts.

The pK_a's of mutant amicyanins have been measured by pH-dependent electrochemistry. P94F and P94A mutations loosen the Northern loop, allowing the reduced copper to adopt a relaxed conformation: the ability to relax drives the reduction potentials up. The measured potentials are 265 (wild type), 380 (P94A), and 415 (P94F) mV vs. NHE. The measured pK_a's are 7.0 (wild type), 6.3 (P94A), and 5.0 (P94F). The additional hydrogen bond to the thiolate in the mutants is indicated by a red-shift in the blue copper absorption and an increase in the parallel hyperfine splitting in the EPR spectrum. This hydrogen bond is invoked as the cause for the increased stability of the C-terminal imidazole.

Melting curves give a measure of the thermal stability of the protein. A thermodynamic intermediate with pH-dependent reversibility is revealed. Comparisons with the electrochemistry and apoamicyanin suggest that the intermediate involves the region of the protein near the metal site. This region is destabilized in the P94F mutant; coupled with the evidence that the imidazole is stabilized under the same conditions confirms an original concept of the rack effect: a high energy configuration is stabilized at a cost to the rest of the protein.

Efficient methods for stochastic optimal control

The Hamilton Jacobi Bellman (HJB) equation is central to stochastic optimal control (SOC) theory, yielding the optimal solution to general problems specified by known dynamics and a specified cost functional. Given the assumption of quadratic cost on the control input, it is well known that the HJB reduces to a particular partial differential equation (PDE). While powerful, this reduction is not commonly used as the PDE is of second order, is nonlinear, and examples exist where the problem may not have a solution in a classical sense. Furthermore, each state of the system appears as another dimension of the PDE, giving rise to the curse of dimensionality. Since the number of degrees of freedom required to solve the optimal control problem grows exponentially with dimension, the problem becomes intractable for systems with all but modest dimension.

In the last decade researchers have found that under certain, fairly non-restrictive structural assumptions, the HJB may be transformed into a linear PDE, with an interesting analogue in the discretized domain of Markov Decision Processes (MDP). The work presented in this thesis uses the linearity of this particular form of the HJB PDE to push the computational boundaries of stochastic optimal control.

This is done by crafting together previously disjoint lines of research in computation. The first of these is the use of Sum of Squares (SOS) techniques for synthesis of control policies. A candidate polynomial with variable coefficients is proposed as the solution to the stochastic optimal control problem. An SOS relaxation is then taken to the partial differential constraints, leading to a hierarchy of semidefinite relaxations with improving sub-optimality gap. The resulting approximate solutions are shown to be guaranteed over- and under-approximations for the optimal value function. It is shown that these results extend to arbitrary parabolic and elliptic PDEs, yielding a novel method for Uncertainty Quantification (UQ) of systems governed by partial differential constraints. Domain decomposition techniques are also made available, allowing for such problems to be solved via parallelization and low-order polynomials.

The optimization-based SOS technique is then contrasted with the Separated Representation (SR) approach from the applied mathematics community. The technique allows for systems of equations to be solved through a low-rank decomposition that results in algorithms that scale linearly with dimensionality. Its application in stochastic optimal control allows for previously uncomputable problems to be solved quickly, scaling to such complex systems as the Quadcopter and VTOL aircraft. This technique may be combined with the SOS approach, yielding not only a numerical technique, but also an analytical one that allows for entirely new classes of systems to be studied and for stability properties to be guaranteed.

The analysis of the linear HJB is completed by the study of its implications in application. It is shown that the HJB and a popular technique in robotics, the use of navigation functions, sit on opposite ends of a spectrum of optimization problems, upon which tradeoffs may be made in problem complexity. Analytical solutions to the HJB in these settings are available in simplified domains, yielding guidance towards optimality for approximation schemes. Finally, the use of HJB equations in temporal multi-task planning problems is investigated. It is demonstrated that such problems are reducible to a sequence of SOC problems linked via boundary conditions. The linearity of the PDE allows us to pre-compute control policy primitives and then compose them, at essentially zero cost, to satisfy a complex temporal logic specification.

Structural and Biophysical Characterization of Variants of the Mechanosensitive Channel of Large Conductance (MSCL)

The ability to sense mechanical force is vital to all organisms to interact with and respond to stimuli in their environment. Mechanosensation is critical to many physiological functions such as the senses of hearing and touch in animals, gravitropism in plants and osmoregulation in bacteria. Of these processes, the best understood at the molecular level involve bacterial mechanosensitive channels. Under hypo-osmotic stress, bacteria are able to alleviate turgor pressure through mechanosensitive channels that gate directly in response to tension in the membrane lipid bilayer. A key participant in this response is the mechanosensitive channel of large conductance (MscL), a non-selective channel with a high conductance of ~3 nS that gates at tensions close to the membrane lytic tension.

It has been appreciated since the original discovery by C. Kung that the small subunit size (~130 to 160 residues) and the high conductance necessitate that MscL forms a homo-oligomeric channel. Over the past 20 years of study, the proposed oligomeric state of MscL has ranged from monomer to hexamer. Oligomeric state has been shown to vary between MscL homologues and is influenced by lipid/detergent environment. In this thesis, we report the creation of a chimera library to systematically survey the correlation between MscL sequence and oligomeric state to identify the sequence determinants of oligomeric state. Our results demonstrate that although there is no combination of sequences uniquely associated with a given oligomeric state (or mixture of oligomeric states), there are significant correlations. In the quest to characterize the oligomeric state of MscL, an exciting discovery was made about the dynamic nature of the MscL complex. We found that in detergent solution, under mild heating conditions (37 °C – 60 °C), subunits of MscL can exchange between complexes, and the dynamics of this process are sensitive to the protein sequence.

Extensive efforts were made to produce high diffraction quality crystals of MscL for the determination of a high resolution X-ray crystal structure of a full length channel. The surface entropy reduction strategy was applied to the design of S. aureus MscL variants and while the strategy appears to have improved the crystallizability of S. aureus MscL, unfortunately the diffraction qualities of these crystals were not significantly improved. MscL chimeras were also screened for crystallization in various solubilization detergents, but also failed to yield high quality crystals.

MscL is a fascinating protein and continues to serve as a model system for the study of the structural and functional properties of mechanosensitive channels. Further characterization of the MscL chimera library will offer more insight into the characteristics of the channel. Of particular interest are the functional characterization of the chimeras and the exploration of the physiological relevance of intercomplex subunit exchange.

Composição e abundância das espécies de anfíbios e répteis em uma paisagem fragmentada de Mata Atlântica no Estado do Rio de Janeiro

Neste estudo, procuramos avaliar a composição e abundância de espécies de anfíbios e répteis em uma paisagem fragmentada de Mata Atlântica, no município de Cachoeiras de Macacu, Estado do Rio de Janeiro. Amostramos a herpetofauna da região na área contínua de floresta da Reserva Ecológica de Guapiaçu (REGUA), em 12 fragmentos do entorno com tamanhos e graus de isolamento diferentes, e áreas de pasto (matriz). Utilizamos para amostragem destes animais as metodologias de buscas ativas visuais e armadilhas de interceptação e queda, além de encontros ocasionais. No total foram registradas 55 espécies de anfíbios anuros pertencentes a 12 famílias e entre os répteis foram registradas 26 espécies, sendo uma espécie de anfisbena, uma de jacaré, nove de lagartos e 15 de serpentes. Para os anfíbios, houve uma dominância de espécies da família Hylidae, que representaram mais da metade do total de espécies encontradas no estudo. Já entre os répteis, houve uma predominância de espécies de serpentes da família Dipsadidae. Considerando apenas os registros feitos pelas metodologias empregadas, a área contínua de floresta da REGUA possui uma riqueza de espécies de anfíbios (N = 30) e de lagartos (N = 4) menor do que o conjunto de fragmentos (N = 36 e N = 8), mas superior ao que foi encontrado na matriz (N = 25 e N = 1). Entretanto, para os anfíbios, mais de um terço das espécies (N = 11) que ocorreu na mata contínua não ocorreu nos fragmentos ou na matriz, o que sugere que estas espécies podem ser mais sensíveis a alterações do hábitat. A maior riqueza de espécies encontrada no conjunto de fragmentos pode ser parcialmente explicada pelo fato de muitas espécies tanto de anfíbios quanto de lagartos que são típicas de áreas abertas, terem sua ocorrência favorecida neste tipo de condição de ambiente relativamente menos fechado dos fragmentos. Quando avaliamos o efeito de métricas da paisagem, observamos diferentes respostas entre os anfíbios e os lagartos. Enquanto para os anfíbios houve uma tendência de fragmentos mais distantes terem uma menor riqueza de espécies e de modos reprodutivos associados a estas espécies, para os lagartos a área dos fragmentos parece ser uma importante variável na estruturação das comunidades. Entretanto, por particularidades das características fisiológicas e ecológicas de anfíbios e lagartos, é possível que outros fatores expliquem a distribuição diferenciada das espécies. De forma geral, as áreas de matriz amostradas pareceram ser hostis a espécies florestais tanto de anfíbios quanto de lagartos. Além disso, para anfíbios, a presença de ambientes reprodutivos pode ser fator crucial para a ocorrência de algumas espécies. De forma similar ao encontrado em outros estudos, para a manutenção da diversidade de anfíbios e lagartos na paisagem fragmentada tratada neste estudo é necessário preservar o grande bloco florestal e aumentar a conectividade deste com os fragmentos, o que poderia permitir a área contínua servir de área-fonte de dispersores para os remanescentes florestais.

Sistemas fotovoltaicos integrados ao perfil de uso da edificação

Nos últimos anos, o consumo de energia vem crescendo mundialmente nos grandes centros urbanos, e esforços na área de eficiência energética estão sendo implantados, a fim de reduzir o consumo no horário da ponta e interrupções da rede. O aproveitamento das fontes renováveis, como o fotovoltaico em uma edificação se torna um atrativo a mais para a matriz energética num momento em que o país prima pela universalização dos serviços de energia e a classificação de edifícios comerciais, de serviço e públicos, além dos residenciais quanto à eficiência energética através do Procel Edifica (RTQ-C e RTQ-R). Os sistemas fotovoltaicos podem configurar perfis de uso nas edificações de modo a gerar energia para consumo próprio ou ligado à rede e ainda ter influência na arquitetura do prédio com revestimento: os perfis podem está em telhados, fachadas ou janelas, amenizando em alguns casos a carga térmica no prédio com sombreamento arquitetônico. Hoje, com o avanço da tecnologia no setor de armazenagem é possível, o atendimento com segurança e eficiência a uma edificação ou direcionar esta armazenagem a uma demanda específica como o atendimento à demanda de ciclo profundo, tais como, iluminação externa e recarga de veículos elétricos. Partindo da premissa de sistemas interruptos de energia, UPS, uso de fonte secundária como FV, baterias e Flywheel é apresentado uma forma de melhor gerenciar a energia armazenada, podendo estender a vida útil da bateria e conseqüentemente de todo o sistema fotovoltaico na edificação. Esta forma de armazenar energia proporciona um serviço de uso contínuo sem percepção das interrupções da rede com garantia de 20 anos, tal qual o módulo fotovoltaico, com esta proposta as perdas de energia elétrica na edificação serão atenuadas, pois a eletricidade será utilizada de forma eficiente e inteligente. O ponto de partida do estudo de caso no prédio do IBAM são os sistemas fotovoltaicos com geração distribuída (mini-redes) conectados à rede que são instalados para fornecer energia ao consumidor, complementando a quantidade de energia demandada, caso haja algum aumento do consumo de energia na edificação, ou ainda utilizar o sistema fotovoltaico na hora da ponta e interrupções do sistema da rede no período fora da ponta. A estocagem inercial por meio do Flywheel tem um papel fundamental nesta mini-rede (Flywheel, bateria VRLA, UPS, inversor e STS), pois a sua utilização pode ser apontada como uma inovação tecnológica quanto à regulação de tensão no sistema de energia elétrica, além de preparar a edificação para o smart-grid. Esta configuração de acumulação de energia permitiu a analise do deslocamento desta energia armazenada para o consumo no horário de ponta, mudando o conceito de sistemas fotovoltaicos autônomos no meio urbano e rural no país. Este conceito de armazenagem se confirma então como um aporte na eficiência de energia na edificação, podendo carrear economia de energia substancial, além de proporcionar uma confiabilidade no serviço de energia, com um baixo retorno do investimento e com uma garantia de funcionamento com pequena ou nenhuma manutenção durante o período de vida de 20 anos.

Governança no setor público: a aderência dos relatórios de gestão do Poder Executivo aos princípios e padrões de boas práticas de governança

A administração pública apresenta vários problemas, que vão desde a ausência de avaliações quanto aos aspectos de eficiência, eficácia e efetividade na utilização de recursos e das políticas públicas adotadas, até a prática perversa da corrupção em suas diversas formas. Grande parte destes problemas decorre da falta de mecanismos de controle e acompanhamento para saber se as ações promovidas pelos gestores públicos estão de acordo com os objetivos da sociedade. Os problemas que decorrem desta relação de conflito de interesses entre aqueles que delegam a administração de suas organizações e aqueles que recebem esta delegação e administram, são chamados de problemas da relação entre principal e agente. No setor público pode-se considerar que agente é o gestor público (recebe a delegação e administra) e principal é o cidadão ou a própria sociedade (que delega). Estes conceitos têm origem na teoria da agência. Esta teoria é um dos fundamentos da governança, seja no setor privado ou no setor público. E a governança adota princípios como a transparência e a accountability para propor práticas de controle e acompanhamento da administração, a fim de evitar os problemas da relação agente e principal. Deste modo, a presente pesquisa tem por objetivo avaliar se os relatórios de gestão do Poder Executivo municipal são aderentes aos princípios e padrões de boas práticas de governança para o setor público acerca da transparência e da accountability na utilização dos recursos, bem como dos resultados gerados em decorrência das políticas públicas adotadas. Para tanto, a metodologia utilizada neste trabalho foi a seguinte: através da pesquisa bibliográfica, identificou-se na literatura quais os princípios e padrões de boas práticas de governança para a administração pública, e criou-se um quadro-síntese para servir de base para avaliação dos relatórios de gestão quanto aos aspectos de transparência e accountability; através da pesquisa documental foram selecionados os relatórios de gestão da Prefeitura da Cidade do Rio de Janeiro a serem analisados, que foi a cidade escolhida para realização da pesquisa pela proximidade com o autor e pela disponibilização de diversos documentos em seu sítio eletrônico; a seguir, pela análise de conteúdo, fez-se a avaliação dos documentos utilizando-se o quadrosíntese produzido. Os resultados da pesquisa demonstraram que os relatórios de gestão analisados possuem pouca aderência aos princípios e padrões de boa governança, evidenciando-se uma aderência de apenas 37,71% em relação aos elementos estabelecidos no quadro-síntese. Assim, apontou claramente para o fato de que há pouca transparência nos relatórios de gestão, fato este que prejudica a accountability na administração pública.

Fachada de chapa perforada: análisis de su comportamiento acústico

[ES]Este proyecto tiene como objetivo servir de punto de partida al estudio del comportamiento acústico de las chapas perforadas como solución para el revestimiento de fachadas. Para ello se presentan dos posibles modelos de fachada analizados a través del software SoundFlow que determina su coeficiente de absorción. Con el fin de encontrar la solución más adecuada nos centraremos en las siguientes variables: separación de la chapa a la pared (d), diámetro del agujero de las chapas (Ø), y porcentaje de área perforada de la chapa o porosidad (p). Previamente se estudiarán las principales fuentes de contaminación acústica y su espectro de ruido para determinar la frecuencia en la que deben centrarse nuestros esfuerzos por aumentar el coeficiente de absorción.

Simulación del robot Delta mediante MATLAB

[ES]El presente Trabajo Fin de Grado: SIMULACIÓN DEL ROBOT DELTA MEDIANTE MATLAB trata sobre el robot Delta. El objetivo principal del trabajo es servir de base para futuros proyectos. Incluye información sobre los robots Delta, así como de sus aplicaciones. Este tipo de robots tienen numerosas aplicaciones y beneficios gracias a las numerosas características favorables que se mencionan a lo largo del trabajo, como lo es por ejemplo la gran velocidad a la que se puede mover. En el trabajo se verán las resoluciones de los problemas cinemáticos: directo e inverso. Además, se podrán describir trayectorias tomando como base los anteriores problemas cinemáticos. Finalmente, es especialmente interesante la introducción de los interpoladores en la generación de trayectorias y los beneficios que ello trae consigo.

单长周期光栅迈克耳孙干涉仪特性研究

单长周期光栅迈克耳孙（Michelson）干涉仪是由尾纤端面蒸镀高反膜的单根长周期光纤光栅构成。入射光经长周期光栅后，部分被耦合到包层中传输。经过包层和纤芯传输的光信号经尾纤端面反射后，重新耦合回到长周期光栅中，在光栅区域形成干涉。通过理论计算分析了各种因素对其光谱响应的影响。从实验上得到了干涉光谱的谐振峰波长位移与光纤段温度变化成良好的线性关系，测得其温度系数为31．3pm／℃。表明这种结构可用于高温传感或作为波分复用滤波器。

The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

O município como ator de política pública: o consórcio como alternativa para lidar com os impactos causados pelo Comperj

A proposta do Associativismo entre Municípios, especialmente entre aqueles de menor porte, seria alternativa para lidar com o problema de escassez de recursos, provocado pela falta de autonomia financeira dos Municípios. Embora, com a Constituição Democrática de 1988, o Município tenha sido alçado ao status de ente federativo autônomo, esta realidade não veio atrelada à necessária autonomia financeira, tampouco possui escala para a prestação de serviços públicos essenciais à população local. Neste trabalho, enfoque especial é dado a esta questão, principalmente diante dos impactos causados por grandes empreendimentos industriais, como é o caso do Comperj (Complexo Petroquímico do Rio de Janeiro), nos Municípios de Itaboraí, São Gonçalo e cidades vizinhas. Estes Municípios, ainda que possuam características distintas entre si, podem alcançar vantagens se atuarem em conjunto, gerindo melhor os escassos recursos e proporcionando serviços públicos aptos a atender aos seus munícipes. Confirmando a importância do associativismo, seja sob a forma de regiões metropolitanas, microrregiões, ou mesmo o consórcio intermunicipal, objeto central do presente estudo, a recente Lei de Consórcios Públicos (Lei n 11.107/2005) veio destacar a relevância da utilização dos consórcios, trazendo mais segurança aos que deles se utilizam, contando com o apoio dos governos estadual e federal. Os Municípios afetados pelo Comperj, percebendo a importância desta união de esforços, criaram o Conleste (Consórcio Municipal do Leste Fluminense) já com respaldo na nova lei, com este propósito, qual seja, lidar com os impactos deste grande empreendimento, buscando mitigar os efeitos negativos e propondo soluções que sejam aplicáveis a todos, planejando e pensando no futuro.