991 resultados para Natural interfaces
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89 ripe female brooders of the catfish, Clarias anguillaris (Body wt. Range 150g-1, 200g) were induced to spawn by hormone (Ovaprim) induced natural spawning technique over a period of 10 weeks. Matching ripe males were used for pairing the females at the ratio of two males to a female. Six ranges of brood stock body weights were considered as follows; <200g; 200g-399g; 400g-599g; 600-799g; 800g-999g; > 1000g and the number of fry produced by each female brooder was scored/recorded against the corresponding body weight range. The number of fry per unit quantity of hormone and the cost of production a fry based on the current price of Ovaprim (hormon) were determined so as to ascertain most economic size range. The best and most economic size range was between 400g-599g body weight with about 20,000 fry per ml of hormone and N0.028 per fry, while the females above 1000g gave the poorest results of 9,519 fry per ml of hormone and N0.059 per fry. For optimum production of Clarias anguillaris fry and maximum return on investment female brooders of body weights ranging between 400g-599g are recommended for hormone induced natural breeding exercises
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89 ripe female brooders of the catfish, Clarias anguillaris (Body wt. Range 150g-1, 200g) were induced to spawn by hormone (Ovaprim) induced natural spawning technique over a period of 10 weeks. Matching ripe males were used for pairing the females at the ratio of two males to a female. Six ranges of brood stock body weights were considered as follows; <200g; 200g-399g; 400g-599g; 600-799g; 800g-999g; > 1000g and the number of fry produced by each female brooder was scored/recorded against the corresponding body weight range. The number of fry per unit quantity of hormone and the cost of production a fry based on the current price of Ovaprim (hormon) were determined so as to ascertain most economic size range. The best and most economic size range was between 400g-599g body weight with about 20,000 fry per ml of hormone and N0.028 per fry, while the females above 1000g gave the poorest results of 9,519 fry per ml of hormone and N0.059 per fry. For optimum production of Clarias anguillaris fry and maximum return on investment female brooders of body weights ranging between 400g-599g are recommended for hormone induced natural breeding exercises
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The core-level energy shifts observed using X-ray photoelectron spectroscopy (XPS) have been used to determine the band bending at Si(111) surfaces terminated with Si-Br, Si-H, and Si-CH3 groups, respectively. The surface termination influenced the band bending, with the Si 2p3/2 binding energy affected more by the surface chemistry than by the dopant type. The highest binding energies were measured on Si(111)-Br (whose Fermi level was positioned near the conduction band at the surface), followed by Si(111)-H, followed by Si(111)-CH3 (whose Fermi level was positioned near mid-gap at the surface). Si(111)-CH3 surfaces exposed to Br2(g) yielded the lowest binding energies, with the Fermi level positioned between mid-gap and the valence band. The Fermi level position of Br2(g)-exposed Si(111)-CH3 was consistent with the presence of negatively charged bromine-containing ions on such surfaces. The binding energies of all of the species detected on the surface (C, O, Br) shifted with the band bending, illustrating the importance of isolating the effects of band bending when measuring chemical shifts on semiconductor surfaces. The influence of band bending was confirmed by surface photovoltage (SPV) measurements, which showed that the core levels shifted toward their flat-band values upon illumination. Where applicable, the contribution from the X-ray source to the SPV was isolated and quantified. Work functions were measured by ultraviolet photoelectron spectroscopy (UPS), allowing for calculation of the sign and magnitude of the surface dipole in such systems. The values of the surface dipoles were in good agreement with previous measurements as well as with electronegativity considerations. The binding energies of the adventitious carbon signals were affected by band bending as well as by the surface dipole. A model of band bending in which charged surface states are located exterior to the surface dipole is consistent with the XPS and UPS behavior of the chemically functionalized Si(111) surfaces investigated herein.
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The propellane alkaloids comprise a large class of natural products that possess varying degrees of structural complexity and biological activity. The earliest of these to be isolated was acutumine, a chlorinated alkaloid that has been shown to exhibit selective T-cell cytotoxicity and antiamnesic properties. Alternatively, the hasubanan family of natural products has garnered considerable attention from the synthetic community in part due to its structural similarities to morphine. While these alkaloids have been the subject of numerous synthetic studies over the last forty years, very few enantioselective total syntheses have been reported to date.
As part of a research program directed towards the synthesis of various alkaloid natural products, we have developed a unified strategy for the preparation of the hasubanan and acutumine alkaloids. Specifically, a highly diastereoselective 1,2-addition of organometallic reagents to benzoquinone-derived tert-butanesulfinimines was established, which provides access to enantioenriched 4-aminocyclohexadienone products. This methodology enabled the enantioselective construction of functionalized dihydroindolones, which were found to undergo intramolecular Friedel-Crafts conjugate additions to furnish the propellane cores of several hasubanan alkaloids. As a result of these studies, the first enantioselective total syntheses of 8-demethoxyrunanine and cepharatines A, C, and D were accomplished in 9-11 steps from commercially available starting materials.
More recent efforts have focused on applying the sulfinimine methodology to the synthesis of a more structurally complex propellane alkaloid, acutumine. Extensive studies have determined that a properly functionalized dihydroindolone undergoes a photochemical [2+2] cycloaddition followed by a lactone fragmentation/Dieckmann cyclization to establish the carbocyclic framework of the natural product. The preparation of more appropriately oxidized propellane intermediates is currently under investigation, and is anticipated to facilitate our synthetic endeavors toward acutumine.
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Theoretical and experimental investigations of charge-carrier dynamics at semiconductor/liquid interfaces, specifically with respect to interfacial electron transfer and surface recombination, are presented.
Fermi's golden rule has been used to formulate rate expressions for charge transfer of delocalized carriers in a nondegenerately doped semiconducting electrode to localized, outer-sphere redox acceptors in an electrolyte phase. The treatment allows comparison between charge-transfer kinetic data at metallic, semimetallic, and semiconducting electrodes in terms of parameters such as the electronic coupling to the electrode, the attenuation of coupling with distance into the electrolyte, and the reorganization energy of the charge-transfer event. Within this framework, rate constant values expected at representative semiconducting electrodes have been determined from experimental data for charge transfer at metallic electrodes. The maximum rate constant (i.e., at optimal exoergicity) for outer-sphere processes at semiconducting electrodes is computed to be in the range 10-17-10-16 cm4 s-1, which is in excellent agreement with prior theoretical models and experimental results for charge-transfer kinetics at semiconductor/liquid interfaces.
Double-layer corrections have been evaluated for semiconductor electrodes in both depletion and accumulation conditions. In conjuction with the Gouy-Chapman-Stern model, a finite difference approach has been used to calculate potential drops at a representative solid/liquid interface. Under all conditions that were simulated, the correction to the driving force used to evaluate the interfacial rate constant was determined to be less than 2% of the uncorrected interfacial rate constant.
Photoconductivity decay lifetimes have been obtained for Si(111) in contact with solutions of CH3OH or tetrahydrofuran containing one-electron oxidants. Silicon surfaces in contact with electrolyte solutions having Nernstian redox potentials > 0 V vs. SCE exhibited low effective surface recombination velocities regardless of the different surface chemistries. The formation of an inversion layer, and not a reduced density of electrical trap sites on the surface, is shown to be responsible for the long charge-carrier lifetimes observed for these systems. In addition, a method for preparing an air-stable, low surface recombination velocity Si surface through a two-step, chlorination/alkylation reaction is described.
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The diterpenoid constituents of the Isodon plants have attracted reasearchers interested in both their chemical structures and biological properties for more than a half-century. In recent years, the isolations of new members displaying previously unprecedented ring systems and highly selective biological properties have piqued interest from the synthetic community in this class of natural products.
Reported herein is the first total synthesis of such a recently isolated diterpenoid, (–)-maoecrystal Z. The principal transformations implemented in this synthesis include two highly diastereoselective radical cyclization reactions: a Sm(II)-mediated reductive cascade cyclization, which forms two rings and establishes four new stereocenters in a single step, and a Ti(III)-mediated reductive epoxide-acrylate coupling that yields a functionalized spirolactone product, which forms a core bicycle of maoecrystal Z.
The preparation of two additional ent-kauranoid natural products, (–)-trichorabdal A and (–)-longikaurin E, is also described from a derivative of this key spirolactone. These syntheses are additionally enabled by the palladium-mediated oxidative cyclization reaction of a silyl ketene acetal precursor that is used to install the bridgehead all-carbon quaternary stereocenter and bicyclo[3.2.1]octane present in each natural product. These studies have established a synthetic relationship among three architecturally distinct ent-kaurane diterpenoids and have forged a path for the preparation of interesting unnatural ent-kauranoid structural analogs for more thorough biological study.
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The asymmetric synthesis of quaternary stereocenters remains a challenging problem in organic synthesis. Past work from the Stoltz laboratory has resulted in methodology to install quaternary stereocenters α- or γ- to carbonyl compounds. Thus, the asymmetric synthesis of β-quaternary stereocenters was a desirable objective, and was accomplished by engineering the palladium-catalyzed addition of arylmetal organometallic reagents to α,β-unsaturated conjugate acceptors.
Herein, we described the rational design of a palladium-catalyzed conjugate addition reactions utilizing a catalyst derived from palladium(II) trifluoroacetate and pyridinooxazole ligands. This reaction is highly tolerant of protic solvents and oxygen atmosphere, making it a practical and operationally simple reaction. The mild conditions facilitate a remarkably high functional group tolerance, including carbonyls, halogens, and fluorinated functional groups. Furthermore, the reaction catalyzed conjugate additions with high enantioselectivity with conjugate acceptors of 5-, 6-, and 7-membered ring sizes. Extension of the methodology toward the asymmetric synthesis of flavanone products is presented, as well.
A computational and experimental investigation into the reaction mechanism provided a stereochemical model for enantioinduction, whereby the α-methylene protons adjacent the enone carbonyl clashes with the tert-butyl groups of the chiral ligand. Additionally, it was found that the addition of water and ammonium hexafluorophosphate significantly increases the reaction rate without sacrificing enantioselectivity. The synergistic effects of these additives allowed for the reaction to proceed at a lower temperature, and thus facilitated expansion of the substrate scope to sensitive functional groups such as protic amides and aryl bromides. Investigations into a scale-up synthesis of the chiral ligand (S)-tert-butylPyOx are also presented. This three-step synthetic route allowed for synthesis of the target compound of greater than 10 g scale.
Finally, the application of the newly developed conjugate addition reaction toward the synthesis of the taiwaniaquinoid class of terpenoid natural products is discussed. The conjugate addition reaction formed the key benzylic quaternary stereocenter in high enantioselectivity, joining together the majority of the carbons in the taiwaniaquinoid scaffold. Efforts toward the synthesis of the B-ring are presented.
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Petróleo e gás natural são recursos naturais não renováveis que possuem grande participação na matriz energética mundial e tendência de crescimento na matriz nacional, cujo marco regulatório limita-se a definir critérios técnicos e procedimentais sem incorporar o modelo de sustentabilidade instituído pela Constituição Federal de 1988. A natureza finita dos recursos não renováveis, como o petróleo e o gás natural, exige uma visão do planejamento de sua exploração de longo prazo na definição dos objetivos e metas. Essa perspectiva de longo prazo traduz uma das preocupações do desenvolvimento sustentável: a garantia de direitos para as futuras gerações. Assim, ao procurar fornecer elementos para a tradução do modelo de desenvolvimento sustentável no arcabouço institucional e legal da indústria petrolífera vigente no Brasil, o presente trabalho busca contribuir para o aprimoramento da regulação petrolífera nacional e a qualidade de vida das gerações presentes e futuras. E, mais do que propor a elaboração de um projeto de lei, como modalidade de implantação de uma política pública, queremos contribuir para o fortalecimento das práticas e ações governamentais voltadas para a aplicação do desenvolvimento sustentável, consoante apregoa a Constituição Federal brasileira. Trata-se aqui de demonstrar, através de metodologia quali-quantitativa, a tese de que é possível incorporar o princípio constitucional de desenvolvimento sustentável na atividade de exploração e produção de petróleo e gás natural, formulando uma política pública que incorpore, no regime de propriedade do petróleo, a variável ambiental e o uso intergeracional que já haviam sido e continuam sendo aplicados a algumas fontes renováveis de energia. Inicialmente, identificamos a composição da matriz energética brasileira desde a inserção do petróleo como uma questão de Estado a partir dos anos 50 do século XX. Em seguida, analisamos a concepção legal e doutrinária para propor, então, a conceituação de um modelo de desenvolvimento energético sustentável, estruturante para a proposição de uma política nacional para a indústria petrolífera. Com base nessa conceituação, analisamos o marco regulatório e os procedimentos institucionais praticados atualmente para identificar as lacunas existentes no ordenamento a serem supridas pela política nacional proposta. A partir da análise dos contextos legal e institucional, e das políticas energética e ambiental, propomos a tradução de conceitos, objetivos, princípios e instrumentos num projeto de lei de Política Nacional de Uso Sustentável das Reservas de Petróleo e Gás Natural. Concluímos tecendo considerações gerais e específicas sobre a proposição aqui formulada com vistas ao aprimoramento do modelo nacional de gestão de recursos energéticos e ao fomento das discussões voltadas para a sustentabilidade das políticas públicas e as práticas privadas enraizadas na exploração irracional de recursos não renováveis
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[ES]Diseño de una instalación de cogeneración basada en un motor de combustible gas natural para una empresa de tratamientos térmicos y superficiales. Para satisfacer las necesidades energéticas de la planta, la potencia eléctrica la suministrará un alternador conectado al motor y, a su vez, la entalpía de los humos de escape del motor se aprovechará para la producción de vapor de agua, necesario para la actividad industrial de la empresa. Por otro lado, el calor que es necesario disipar de dicho motor se recuperará para el calentamiento de agua de red, con la finalidad de limpiar la taladrina de las piezas tratadas.
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A análise da matriz energética mundial, assim como a brasileira, nos mostra que o gás natural representará em breve um importante insumo energético favorecendo a balança de pagamentos nacional, visto que o gás poderá ser usado tanto para consumo interno, quanto para exportação. O aumento das reservas nacionais de hidrocarbonetos se deve ao desenvolvimento de tecnologias, que favoreceram o conhecimento das bacias brasileiras quanto ao seu potencial produtor de combustíveis fósseis, permitindo a descoberta de novas jazidas. O amadurecimento do mercado nacional quanto ao consumo de gás natural passa pela construção de uma infraestrutura robusta, eficiente e que possibilite a captação, o armazenamento e distribuição do mesmo. O Brasil tem todos os requisitos necessários para adentrar ao seleto grupo de países exportadores de hidrocarbonetos, a descoberta do Pré-sal tende a incrementar a importância do gás natural para o país. Ao final do trabalho são descritos cenários futuros (quanto o consumo de energéticos), onde se vê que o consumo de energia para os próximos anos crescerá a taxas superiores as das duas últimas décadas. Análise destes cenários permite antecipar o interesse de futuros investimentos no desenvolvimento do conhecimento geológico para áreas promissoras.
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Este trabalho tem como objetivo estudar a indústria do petróleo, gás natural e biocombustíveis no contexto brasileiro e no mundial. Visa também analisar as vantagens e desvantagens dos biocombustíveis e seu possível impacto na indústria do petróleo, assim como os principais indicativos e projeções da indústria do petróleo, como reserva, produção, preço e consumo, através de coleta de dados e geração de gráficos pesquisados e comparados de grandes agências e empresas de energia. Os biocombustíveis podem ser um grande aliado da indústria do petróleo tendo em vista a duração das reservas mundiais de hidrocarbonetos. O uso dos biocombustíveis implicará no desenvolvimento de tecnologias renováveis e de reutilização de materiais antes descartados, trazendo benefício a toda sociedade. A indústria do petróleo é impactada pelas flutuações no mercado internacional e pela demanda, assim como pela manipulação da produção de combustíveis fósseis pelos países produtores. Esses aspectos apresentados interligados criam uma complexa indústria que a presente dissertação se propõe a analisar.