Design for Survival: Sustainability for Planet and Structure

Buildings in Port Aransas encounter drastic environmental challenges: the potential catastrophic storm surge and high winds from a hurricane, and daily conditions hostile to buildings, vehicles, and even most vegetation. Its location a few hundred feet from the Gulf of Mexico and near-tropical latitude expose buildings to continuous high humidity, winds laden with scouring sand and corrosive salt, and extremes of temperature and ultraviolet light. Building construction methods are able to address each of these, but doing so in a sustainable way creates significant challenges. The new research building at the Marine Science Institute has been designed and is being constructed to meet the demand for both survivability and sustainability. It is tracking towards formal certification as a LEED Gold structure while being robust and resistant to the harsh coastal environment. The effects of a hurricane are mitigated by elevating buildings and providing a windproof envelope. Ground-level enclosures are designed to be sacrificial and non-structural so they can wash or blow away without imposing damage on the upper portions of the building, and only non-critical functions and equipment will be supported within them. Design features that integrate survivability with sustainability include: orientation of building axis; integral shading from direct summer sunlight; light wells; photovoltaic arrays; collection of rainwater and air conditioning condensate for use in landscape irrigation; reduced impervious cover; xeriscaping and indigenous plants; recycling of waste heat from air conditioning systems; roofing system that reflects light and heat; long life, low maintenance stainless steel, high-tensile vinyl, hard-anodized aluminum and hot-dipped galvanized mountings throughout; chloride-resistant concrete; reduced visual impact; recycling of construction materials.

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.

A contribuição da Metodologia de Projeto em Design no processo de desenvolvimento de recursos de Tecnologia Assistiva

O presente trabalho apresenta o processo utilizado por terapeutas ocupacionais no desenvolvimento de objetos de Tecnologia Assistiva. São apresentadas definições e teorias relacionadas ao desenvolvimento de produtos de Tecnologia Assistiva a qual trata de um grupo de produtos desenvolvidos para pessoas com deficiência. São apresentados: o design de produtos voltados para inclusão, modelos de ações voltados às pessoas com deficiência, princípios para o desenvolvimento de produtos para pessoas com deficiência, o mercado brasileiro e o perfil do público-alvo, e os métodos e técnicas de desenvolvimento de Tecnologia Assistiva. Sendo o terapeuta ocupacional um profissional que no processo de reabilitação desenvolve produtos de Tecnologia Assistiva, explicita-se o seu papel no desenvolvimento desses produtos. Tendo o Ergodesign como base metodológica para o desenvolvimento de produtos de Tecnologia Assistiva, apresentam-se questões pertinentes à essa teoria dentro da ergonomia e do design. Expõem-se os resultados da pesquisa de campo realizada com terapeutas ocupacionais que produzem produtos de Tecnologia Assistiva, com terapeutas ocupacionais que encaminham para outro profissional realizar a produção, com professores de disciplinas de Tecnologia Assistiva dos cursos de Terapia Ocupacional da cidade do Rio de Janeiro e com usuários desses produtos. A partir da pesquisa bibliográfica e dos resultados obtidos na pesquisa de campo, este trabalho tem como objetivo principal contribuir, através de uma proposta metodológica, para a formação do terapeuta ocupacional no processo de desenvolvimento de objetos para pessoas com deficiência

Modular Multimodal Iron Oxide-Based Nanocarriers for Image-Guided dsRNA Immunostimulation and Platinum Anticancer Drug Design

237 p.

Diálogos entre Anísio Teixeira e Darcy Ribeiro: o projeto educacional de Brasília (1960) e o Programa Especial de Educaç ão - I PEE Rio de Janeiro (1980)

O presente estudo analisa dois programas educacionais que se materializaram por meio das Escolas Classe/Escola Parque de Brasília e dos Centros Integrados de Educação Pública - CIEPs, no Rio de Janeiro. O primeiro, na década de 1960, mediante o Plano de Construções Escolares de Brasília, formulado por Anísio Teixeira, e o segundo, implementado na década de 1980, em conformidade com o Programa Especial de Educação - I PEE, proposto e executado por Darcy Ribeiro no Rio de Janeiro. No entrecruzamento dos projetos desses dois intelectuais, busco compreender as dissensões, imbricações e convergências dessas iniciativas e o seu legado para a política educacional. Para tanto, me apoio nas produções acadêmicas de dois Grupos de Pesquisa, que têm como objeto os programas educacionais implantados respectivamente, por Anísio e Darcy. Em Brasília, encontramos em seu acervo a memória dos pioneiros da experiência das Escolas Classe/Escola Parque no Distrito Federal, intitulando-se "Educação Básica Pública do Distrito Federal: Origens de um Projeto Inovador (1956-1964), PPGE/UnB, tendo como coordenadora a professora Eva Waisros Pereira. Na cidade do Rio de Janeiro, observamos estudos sobre os CIEPs, produzidos pelo Laboratório Educação e República LER/ProPEd/UERJ, sendo líder da pesquisa a professora Lia Faria. Ainda nessa investigação são consideradas as determinações e os investimentos pessoais e profissionais, tanto de Darcy Ribeiro como de Anísio Teixeira, intelectuais que assumiram a dimensão prática na produção das ideias, considerando a relação dessas ideias com o mundo. Ao recuperar as produções desses dois Grupos, desvelamos também os calorosos debates relacionados às diferentes concepções de educação Integral. A análise destaca o projeto educacional de nação a partir da escola pública em seu caráter republicano. A reflexão proposta visa contribuir, juntamente com as demais pesquisas já realizadas, com a temática da educação integral e da escola pública de horário integral - para a formulação de políticas públicas na área educacional. Nesse sentido, pretendo colaborar para o desenho de propostas governamentais, especialmente para o PNE 2011-2020, buscando valorizar os pesquisadores que nos antecedem em seus trabalhos

Quahogs in Eastern North America: Part I, Biology, Ecology, and Historical Uses

The northern quahog, Mercenaria mercenaria, ranges along the Atlantic Coast of North America from the Canadian Maritimes to Florida, while the southern quahog, M. campechiensis, ranges mostly from Florida to southern Mexico. The northern quahog was fished by native North Americans during prehistoric periods. They used the meats as food and the shells as scrapers and as utensils. The European colonists copied the Indians treading method, and they also used short rakes for harvesting quahogs. The Indians of southern New England made wampum from quahog shells, used it for ornaments and sold it to the colonists, who, in turn, traded it to other Indians for furs. During the late 1600’s, 1700’s, and 1800’s, wampum was made in small factories for eventual trading with Indians farther west for furs. The quahoging industry has provided people in many coastal communities with a means of earning a livelihood and has provided consumers with a tasty, wholesome food whether eaten raw, steamed, cooked in chowders, or as stuffed quahogs. More than a dozen methods and types of gear have been used in the last two centuries for harvesting quahogs. They include treading and using various types of rakes and dredges, both of which have undergone continuous improvements in design. Modern dredges are equipped with hydraulic jets and one type has an escalator to bring the quahogs continuously to the boats. In the early 1900’s, most provinces and states established regulations to conserve and maximize yields of their quahog stocks. They include a minimum size, now almost universally a 38-mm shell width, and can include gear limitations and daily quotas. The United States produces far more quahogs than either Canada or Mexico. The leading producer in Canada is Prince Edward Island. In the United States, New York, New Jersey, and Rhode Island lead in quahog production in the north, while Virginia and North Carolina lead in the south. Connecticut and Florida were large producers in the 1990’s. The State of Campeche leads in Mexican production. In the northeastern United States, the bays with large openings, and thus large exchanges of bay waters with ocean waters, have much larger stocks of quahogs and fisheries than bays with small openings and water exchanges. Quahog stocks in certifi ed beds have been enhanced by transplanting stocks to them from stocks in uncertified waters and by planting seed grown in hatcheries, which grew in number from Massachusetts to Florida in the 1980’s and 1990’s.

Avaliação de ligações entre vigas de perfil I ou H e colunas em perfis tubulares circulares.

Considerando uma nova realidade com o incremento do uso de perfis tubulares, este trabalho apresenta uma análise de ligações soldadas tipo T com perfis tubulares circulares (CHS) para a coluna e perfil I ou H para a viga com flexão no plano, efetuado com base nas normas EC3, CIDECT e a NBR 16239 comparando com o critério de deformação limite, proposto por Lu et al., através de um modelo em elementos finitos desenvolvido no programa Ansys versão 12.0. A não-linearidade geométrica foi introduzida no modelo através da Formulação de Lagrange Atualizado. Com base nos resultados numéricos avaliados foram traçadas curvas momento-rotação para cada modelo com o objetivo de obter o momento resistente de cada ligação bem como a classificação da ligação quanto a capacidade de rotação, a influência dos parâmetros geométricos em cada modelo e o modo de falha que controlará o dimensionamento da ligação.