915 resultados para total irradiance
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21 p.
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Part I: An approach to the total synthesis of the triterpene shionone is described, which proceeds through the tetracyclic ketone i. The shionone side chain has been attached to this key intermediate in 5 steps, affording the olefin 2 in 29% yield. A method for the stereo-specific introduction of the angular methyl group at C-5 of shionone has been developed on a model system. The attempted utilization of this method to convert olefin 2 into shionone is described.
Part II: A method has been developed for activating the C-9 and C-10 positions of estrogenic steroids for substitution. Estrone has been converted to 4β,5β-epoxy-10β-hydroxyestr-3-one; cleavage of this epoxyketone using an Eschenmoser procedure, and subsequent modification of the product afforded 4-seco-9-estren-3,5-dione 3-ethylene acetal. This versatile intermediate, suitable for substitution at the 9 and/or 10 position, was converted to androst-4-ene-3-one by known procedures.
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The determination of bi- and trivalent iron in proximity, in mineral waters has gained in significance, on biological and technical grounds. This short paper describes the procedure of the determination of bivalent iron and total iron in a water sample.
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Tryptophan and unnatural tryptophan derivatives are important building blocks for the total synthesis of natural products, as well as the development of new drugs, biological probes, and chiral small molecule catalysts. This thesis describes various catalytic methods for the preparation of tryptophan derivatives as well as their functionalization and use in natural product total synthesis.
Herein, the tandem Friedel–Crafts conjugate addition/asymmetric protonation reaction between 2-substituted indoles and methyl 2-acetamidoacrylate to provide enantioenriched trytophans is reported. This method inspired further work in the area of transition metal catalyzed arylation reactions. We report the development of the coppercatalyzed arylation of tryptamine and tryptophan derivatives. The utility of these transformations is highlighted in the five-step syntheses of the natural products (+)-naseseazine A and B. Further work on the development of a mild and general Larock indolization protocol to access unnatural tryptophans is also discussed.
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Diketopiperazine (DKP) motif is found in a wide range of biologically active natural products. This work details our efforts toward two classes of DKP-containing natural products.
Class one features the pyrroloindoline structure, derived from tryptophans. Our group developed a highly enantioselective (3 + 2) formal cycloaddition between indoles and acrylates to provide pyrroloindoline products possessing three stereocenters. Utilizing this methodology, we accomplished asymmetric total synthesis of three natural products: (–)-lansai B, (+)-nocardioazines A and B. Total synthesis of (–)-lansai B was realized in six steps, and featured an amino acid dimerization strategy. The total synthesis of (+)-nocardioazine B was also successfully completed in ten steps. Challenges were met in approaching (+)-nocardioazine A, where a seemingly easy last-step epoxidization did not prove successful. After re-examining our synthetic strategy, an early-stage epoxidation strategy was pursued, which eventually yielded a nine-step total synthesis of (+)-nocardioazine A.
Class two is the epidithiodiketopiperazine (ETP) natural products, which possesses an additional episulfide bridge in the DKP core. With the goal of accessing ETPs with different peripheral structures for structure-activity relationship studies, a highly divergent route was successfully developed, which was showcased in the formal synthesis of (–)-emethallicin E and (–)-haematocin, and the first asymmetric synthesis of (–)-acetylapoaranotin.
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Precise measurements of the total reaction cross section for 3He(3He,2p)4He He have been made in the range of center-of-mass energies between 1100 keV and 80 keV. A differentially pumped gas target modified to operate with a limited quantity of the target gas was employed to minimize the uncertainties in the primary energy and energy straggle. Beam integration inside the target gas was carried out by a calorimetric device which measures the total energy spent in a heat sink rather than the total charge in a Faraday cup. Proton energy spectra have been obtained using a counter telescope consisting of a gas proportional counter and a surface barrier detector and angular distributions of these protons have been measured at seven bombarding energies. Cross section factors, S(E), have been calculated from the total cross sections and fitted to a linear function of energy over different ranges of energy. For Ecm < 500 keV
S(Ecm) = S0 + S1 Ecm
where S0 = (5.0 +0.6-0.4) MeV - barns and S1 = (-1.8 ± 0.5) barns.
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A L-arginina é reconhecida como um nutriente de fundamental importância na resposta imune, apesar de seus efeitos serem, por vezes, considerados inconstantes. O autoimplante esplênico tem sido proposto como alternativa à esplenectomia total isolada, mas existem preocupações quanto à eficácia do restabelecimento da resposta imune, haja vista que o paciente pode permanecer com risco aumentado de desenvolvimento de infecção fulminante pós esplenectomia, mesmo após a regeneração morfológica do órgão. O objetivo deste estudo foi avaliar a participação da suplementação dietética com L-arginina em subpopulações linfocitárias no sangue, no baço e nos autoimplantes esplênicos de ratos submetidos a esplenectomia isolada ou combinada com autoimplante esplênico. Foram utilizados 42 ratos Sprague-Dawley machos, randomicamente distribuídos em seis grupos: 1 Controle operação simulada; 2 esplenectomia total; 3 esplenectomia total combinada com autoimplante esplênico; 4 Controle operação simulada, com suplementação de L-arginina; 5 esplenectomia total, com suplementação de L-arginina; e 6 esplenectomia total combinada com autoimplante esplênico, com suplementação de L-arginina. Os animais dos grupos 4, 5 e 6 receberam suplementação de L-arginina, uma vez ao dia, durante 15 dias anteriores a coleta sangüínea realizada imediatamente antes dos procedimentos operatórios (semanas 0 e 12). A dose utilizada foi de 1,0 g/kg/dia, administrada por via intragástrica em bolus. As avaliações foram realizadas por meio de hemograma e citometria de fluxo. A análise estatística utilizou testes paramétricos e nãoparamétricos, sendo p<0,05 considerado para a rejeição da hipótese nula. A suplementação com L-arginina acarretou elevação da contagem relativa e absoluta de neutrófilos periféricos, 12 semanas após a realização de esplenectomia total combinada com autoimplante esplênico. A esplenectomia total ocasionou diminuição da contagem relativa de linfócitos T totais, T CD4+ e T CD8β no sangue, mas a suplementação dietética com L-arginina evitou a diminuição do percentual de células T totais e T CD8β no sangue dos animais submetidos a autoimplante esplênico. Tanto a realização de autoimplante esplênico como a suplementação de L-arginina previnem a diminuição da subpopulação de linfócitos T CD4+ no sangue periférico, fato que usualmente ocorre após realização de esplenectomia total. Houve maior proliferação de células brancas / g de tecido nos autoimplante esplênico dos animais suplementados, porém a suplementação não influenciou a contagem de linfócitos T, T CD4+ e B de zona marginal de baço. A suplementação do aminoácido L-arginina após a realização de esplenectomia total combinada com autoimplante esplênico em ratos foi capaz de reverter alterações observadas em algumas das subpopulações linfocitárias, ocasionadas pela esplenectomia.
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An approach to the synthesis of the pentacyclic triterpene germanicol is discussed.
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PART I
The total cross-section for the reaction 21Ne(α, n)24Mg has been measured in the energy range 1.49 Mev ≤ Ecm ≤ 2.6 Mev. The cross-section factor, S(O), for this reaction has been determined, by means of an optical model calculation, to be in the range 1.52 x 1012 mb-Mev to 2.67 x 1012 mb-Mev, for interaction radii in the range 5.0 fm to 6.6 fm. With S(O) ≈ 2 x 1012 mb-Mev, the reaction 21Ne(α, n)24Mg can produce a large enough neutron flux to be a significant astrophysical source of neutrons.
PART II
The reaction12C(3He, p)14N has been studied over the energy range 12 Mev ≤ Elab ≤ 18 Mev. Angular distributions of the proton groups leading to the lowest seven levels in 14N were obtained.
Distorted wave calculations, based on two-nucleon transfer theory, were performed, and were found to be reliable for obtaining the value of the orbital angular momentum transferred. The present work shows that such calculations do not yield unambiguous values for the spectroscopic factors.
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A set of recursive formulas for diffractive optical plates design is described. The pure-phase plates simulated by this method homogeneously concentrate more than 96% of the incident laser energy in the desired focal-plane region. The intensity focal-plane profile fits a lath-order super-Gaussian function and has a nearly perfect flat top. Its fit to the required profile measured in the mean square error is 3.576 x 10(-3). (C) 1996 Optical Society of America
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Este trabalho pretende contribuir para o entendimento sobre a produtividade na agricultura brasileira, bem como propõe uma reflexão sobre o debate da produtividade total dos fatores. Para isso, buscou-se, antes de tudo, debater as medidas de produtividade, sobretudo as medidas de produtividade total dos fatores e, em seguida, apresentar estimativas da produtividade total na agricultura no Brasil e no mundo. Propõem-se também uma estimativa preliminar dessa metodologia para o cálculo da produtividade total dos fatores na cultura do milho através do índice de Tornqvist. O objetivo é, então, revisar a literatura teórica e empírica sobre a produtividade total dos fatores na agricultura e calcular as produtividades parciais e totais na cultura do milho para os estados brasileiros. Apesar da maior parte dos resultados encontrados no cálculo da produtividade total para a cultura do milho no Brasil não terem sido consistentes, a conclusão geral do levantamento bibliográfico foi que tanto a agricultura brasileira quanto a agricultura mundial, independente da metodologia utilizada, apresentou uma tendência ao crescimento da produtividade total dos fatores.
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The Inter-American Tropical Tuna Commission (IATTC) staff has been sampling the size distributions of tunas in the eastern Pacific Ocean (EPO) since 1954, and the species composition of the catches since 2000. The IATTC staff use the data from the species composition samples, in conjunction with observer and/or logbook data, and unloading data from the canneries to estimate the total annual catches of yellowfin (Thunnus albacares), skipjack (Katsuwonus pelamis), and bigeye (Thunnus obesus) tunas. These sample data are collected based on a stratified sampling design. I propose an update of the stratification of the EPO into more homogenous areas in order to reduce the variance in the estimates of the total annual catches and incorporate the geographical shifts resulting from the expansion of the floating-object fishery during the 1990s. The sampling model used by the IATTC is a stratified two-stage (cluster) random sampling design with first stage units varying (unequal) in size. The strata are month, area, and set type. Wells, the first cluster stage, are selected to be sampled only if all of the fish were caught in the same month, same area, and same set type. Fish, the second cluster stage, are sampled for lengths, and independently, for species composition of the catch. The EPO is divided into 13 sampling areas, which were defined in 1968, based on the catch distributions of yellowfin and skipjack tunas. This area stratification does not reflect the multi-species, multi-set-type fishery of today. In order to define more homogenous areas, I used agglomerative cluster analysis to look for groupings of the size data and the catch and effort data for 2000–2006. I plotted the results from both datasets against the IATTC Sampling Areas, and then created new areas. I also used the results of the cluster analysis to update the substitution scheme for strata with catch, but no sample. I then calculated the total annual catch (and variance) by species by stratifying the data into new Proposed Sampling Areas and compared the results to those reported by the IATTC. Results showed that re-stratifying the areas produced smaller variances of the catch estimates for some species in some years, but the results were not significant.
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The most important fisheries of Maputo Bay (Mozambique) are the gill netting of the Hilsa kelee and the trawling of the shrimps Penaeus indicus and Metapenaeus monoceros . Data of capture and yields are presented and the number of artisanal fishing boats and semi-industrial fishing vessels is given.