Part I. Coenzyme B12 as a hydroformylation-type catalyst. Part II. Mechanisms of hydrogen transfer in the methylmalonyl coenzyme a mutase reaction

Part I

The mechanism of the hydroformylation reaction was studied. Using cobalt deuterotetracarbonyl and 1-pentene as substrates, the first step in the reaction, addition of cobalt tetracarbonyl to an olefin, was shown to be reversible.

Part II

The role of coenzyme B₁₂ in the isomerization of methylmalonyl coenzyme A to succinyl coenzyme A by methylmalonyl coenzyme A mutase was studied. The reaction was allowed to proceed to partial completion using a mixture of methylmalonyl coenzyme A and 4, 4, 4-tri-²H-methylmalonyl coenzyme A as substrate. The deuterium distribution in the product, succinyl coenzyme A, was shown to best fit a model in which hydrogen is transferred from C-4 of methylmalonyl coenzyme A to C-5’ of the adenosyl moiety of coenzyme B₁₂ in the rate determining step. The three hydrogens at the 5’-adenosyl position of the coenzyme B₁₂ intermediate are then able to become enzymatically equivalent before hydrogen is transferred from the coenzyme B₁₂ intermediate to form succinyl coenzyme A.

A scaling technique for the design of idealized electromagnetic lenses

A technique is developed for the design of lenses for transitioning TEM waves between conical and/or cylindrical transmission lines, ideally with no reflection or distortion of the waves. These lenses utilize isotropic but inhomogeneous media and are based on a solution of Maxwell's equations instead of just geometrical optics. The technique employs the expression of the constitutive parameters, ɛ and μ, plus Maxwell's equations, in a general orthogonal curvilinear coordinate system in tensor form, giving what we term as formal quantities. Solving the problem for certain types of formal constitutive parameters, these are transformed to give ɛ and μ as functions of position. Several examples of such lenses are considered in detail.

Estimation of catalyst activity profiles and deactivation parameters from reactor operating data with applications to naphtha reforming

Techniques are developed for estimating activity profiles in fixed bed reactors and catalyst deactivation parameters from operating reactor data. These techniques are applicable, in general, to most industrial catalytic processes. The catalytic reforming of naphthas is taken as a broad example to illustrate the estimation schemes and to signify the physical meaning of the kinetic parameters of the estimation equations. The work is described in two parts. Part I deals with the modeling of kinetic rate expressions and the derivation of the working equations for estimation. Part II concentrates on developing various estimation techniques.

Part I: The reactions used to describe naphtha reforming are dehydrogenation and dehydroisomerization of cycloparaffins; isomerization, dehydrocyclization and hydrocracking of paraffins; and the catalyst deactivation reactions, namely coking on alumina sites and sintering of platinum crystallites. The rate expressions for the above reactions are formulated, and the effects of transport limitations on the overall reaction rates are discussed in the appendices. Moreover, various types of interaction between the metallic and acidic active centers of reforming catalysts are discussed as characterizing the different types of reforming reactions.

Part II: In catalytic reactor operation, the activity distribution along the reactor determines the kinetics of the main reaction and is needed for predicting the effect of changes in the feed state and the operating conditions on the reactor output. In the case of a monofunctional catalyst and of bifunctional catalysts in limiting conditions, the cumulative activity is sufficient for predicting steady reactor output. The estimation of this cumulative activity can be carried out easily from measurements at the reactor exit. For a general bifunctional catalytic system, the detailed activity distribution is needed for describing the reactor operation, and some approximation must be made to obtain practicable estimation schemes. This is accomplished by parametrization techniques using measurements at a few points along the reactor. Such parametrization techniques are illustrated numerically with a simplified model of naphtha reforming.

To determine long term catalyst utilization and regeneration policies, it is necessary to estimate catalyst deactivation parameters from the the current operating data. For a first order deactivation model with a monofunctional catalyst or with a bifunctional catalyst in special limiting circumstances, analytical techniques are presented to transform the partial differential equations to ordinary differential equations which admit more feasible estimation schemes. Numerical examples include the catalytic oxidation of butene to butadiene and a simplified model of naphtha reforming. For a general bifunctional system or in the case of a monofunctional catalyst subject to general power law deactivation, the estimation can only be accomplished approximately. The basic feature of an appropriate estimation scheme involves approximating the activity profile by certain polynomials and then estimating the deactivation parameters from the integrated form of the deactivation equation by regression techniques. Different bifunctional systems must be treated by different estimation algorithms, which are illustrated by several cases of naphtha reforming with different feed or catalyst composition.

Effects of magnetostriction and superlattice formation in ferromagnetic thin films

The contribution to the magnetic uniaxial perpendicular anisotropy which arises from substrate constraint through magnetostrictive effects has been measured in Ni-Fe and Ni-Co thin films evaporated on substrates at room temperature. This was accomplished by measuring the perpendicular anisotropy before and after removal of the film from the substrate. Data are given for the fcc crystal structure regions of both alloy systems, but data for Ni-Co include compositions with less than 60% Ni which have a small percentage of the hcp phase mixed with the fcc phase. The constraint contribution to the perpendicular anisotropy correlates well with the value of the bulk magnetostriction constant using the equation ∆K_˔=3/2λ_sσ. Measured values of isotropic stress for films thicker than 600 Å were 1.6 x 10¹⁰ dyn/cm². In films less than 600 Å thick the isotropic stress decreased with decreasing thickness. After removal of the films from the substrates, the measured perpendicular anisotropy deviated from the expected geometrical shape anisotropy near pure Ni in both alloys. This indicates that additional significant sources of anisotropy exist at these compositions.

The effect of substrate constraint on the crystalline anisotropy K₁ of Ni-Fe epitaxial films has been studied by use of a film removal technique, which involves the evaporation of an epitaxial layer of LiF on MgO, the epitaxial growth of the metallic film on the LiF, and the stripping of the film with water soluble tape. Films ranging in composition from 50% to 100% Ni have been studied. For compositions below 90% Ni the experimental values agree reasonably well with the first order theoretical prediction, ∆K₁=[-9/4(C₁₁-C₁₂)λ² 100+9/2C₄₄λ²111].

In order to compare the magnetic properties of epitaxial thin films more completely with the properties of bulk single crystals, Ni-Fe films ranging in composition from 60% to 90% Ni, which were evaporated epitaxially on (100) MgO substrates, have been subsequently annealed at 400°C in a vacuum of less than 10^-7 Torr to form the ordered Ni₃Fe structure near the 75% composition. This ordered structure has been confirmed by electron diffraction.

The saturation magnetization at Ni₃Fe increased about 6% with ordering which is in good agreement with previous bulk data. Measurements of the magnetocrystalline anisotropy energy K₁ for the epitaxial films show the same large changes with ordering as observed in bulk single crystal samples. In the (001) plane the magnetostriction constants ^λ100, ^λ111 are directly related to the induced anisotropy due to a uniform uniaxial strain in the [100] and [110] directions respectively. Assuming that the elastic constants of a film are the same as in bulk material and are unchanged by ordering, the changes in strain sensitivity with ordering for the epitaxial films are found to be in good agreement with values predicted from bulk data. The exchange constant A as measured by ferromagnetic resonance has been measured at the Ni₃Fe composition and found to increase 25% with ordering. This seems to indicate a significant increase in the Curie temperature which has only been inferred indirectly for bulk material.

ICF靶场中光束口径与列阵间隔的研究

从靶场反射镜架模块的机械结构设计布局所需几何空间的角度出发，根据大口径、列阵器件的特殊要求，给出符合“神光Ⅲ”装置总体技术要求的ICF靶场光束口径与列阵间隔之间的关系，得出靶场△纵、△横应满足的公式．

Tunable focal depth of an apodized focusing optical system

The axial intensity distribution and focal depth of an apoclized focusing optical system are theoretically investigated with two kinds of incident light fields: a uniform-intensity-distribution beam and a Gaussian beam. Both a low-numerical-aperture and a high-numerical-aperture optical system are considered. Numerical results show that the depth of focus can be adjusted by changing the geometrical parameters and transmissivity of the apodizer in the focusing optical system. When a Gaussian beam is employed as the incident beam, the waist width also affects the depth of focus. The tunable range of the focal depth is very considerable. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Tunable three-dimensional intensity distribution by a pure phase-shifting apodizer

The three-dimensional distribution of light intensity that is modulated by a pure phase-shifting apodizer is studied. Results show that the Strehl ratio can be altered by the proposed apodizer and by the waist width of incident Gaussian beams. By changing geometrical parameters of the proposed apodizer, we can increase the focal depth to several times that of the original system. The proposed apodizer can also be used to realize focal splitting and local minimum of intensity, which may be advantageous for constructing an optical trap. Furthermore, the local minimum of intensity number is tunable by changing the parameters of the apodizer. (c) 2005 Optical Society of America

Tunable focal depth of an apodized focusing optical system

The axial intensity distribution and focal depth of an apoclized focusing optical system are theoretically investigated with two kinds of incident light fields: a uniform-intensity-distribution beam and a Gaussian beam. Both a low-numerical-aperture and a high-numerical-aperture optical system are considered. Numerical results show that the depth of focus can be adjusted by changing the geometrical parameters and transmissivity of the apodizer in the focusing optical system. When a Gaussian beam is employed as the incident beam, the waist width also affects the depth of focus. The tunable range of the focal depth is very considerable. (c) 2005 Society of Photo-Optical Instrumentation Engineers.

Gradient force pattern, focal shift, and focal switch in an apodized optical system

In this paper, the evolution of the gradient force pattern, focal shift, and focal switch induced by a three-portion pure phase-shifting apodizer is numerically investigated in detail. The results show that the proposed apodizer may induce tunable gradient force on the particles in the focal region, focal shift, and focal switch. By adjusting the geometrical parameters of the phase-shifting apodizer, multiple traps may occur with changeable distance between them, and the shape of the optical trap also evolves evidently. More interestingly, for certain geometrical parameters of the proposed apodizer, by changing the phase shift of inner annular portion, the considerable focal shift may occur with focal switch accompanying, which is discussed to show that this kind of apodizer may be a very promising method of transporting trapped particles. © 2005 Elsevier GmbH. All rights reserved.

Argilas pilarizadas: uma tecnologia limpa na reação de isomerização do óxido de estireno

Neste trabalho, fracionou-se e tratou-se a argila Brasgel. Esta argila foi pilarizada em vários estágios de facionamento e/ou tratamento com 5 meq de Al / g de argila: (i) Al-PILC, a argila passou por todos os estágios de fracionamento e tratamento (ARG), (ii) Al-PILCFe, a argila não passou pela etapa de retirada de Fe livre (ARGFe) e (iii) Al-PILCFe/silte, a argila não passou pelas etapas de retirada de silte e Fe livre (ARGFE/silte). Em análise por DRX observou-se que as Al-PILCs apresentaram uma distância basal maior que as argilas de partida. A análise textural indicou que as argilas Al-PILCs e ARGs são materiais mesoporosos, com poros do tipo fenda estreita e do tipo fenda, respectivamente. Além disso, as Al-PILCs apresentaram área superficial razoavelmente maior que as ARGs correspondentes. Outras análises feitas nas argilas foram: teor de Si, Fe e Al; CTC; FTIR; TGA e TGD. As argilas Brasgel pilarizadas foram usadas como catalisador na reação de isomerização do óxido de estireno em hexano sob refluxo. A reação foi seletiva na formação de fenilacetaldeído. As argilas Al-PILCFe e Al-PILCFe/silte apresentaram melhor desempenho catalítico (100 % de conversão em 20 min de reação). Assim, as argilas Brasgel pilarizadas se apresentaram como uma Tecnologia Limpa na reação de isomerização do óxido de estireno ao fenilacetaldeído. Palavras-chave: Desenvolvimento Sustentável. Tecnologia Limpa. Química Verde. Argilas Pilarizadas. Isomerização de Epóxidos.

Plastidic Phosphoglucose Isomerase Is an Important Determinant of Starch Accumulation in Mesophyll Cells, Growth, Photosynthetic Capacity, and Biosynthesis of Plastidic Cytokinins in Arabidopsis

Phosphoglucose isomerase (PGI) catalyzes the reversible isomerization of glucose-6-phosphate and fructose-6-phosphate. It is involved in glycolysis and in the regeneration of glucose-6-P molecules in the oxidative pentose phosphate pathway (OPPP). In chloroplasts of illuminated mesophyll cells PGI also connects the Calvin-Benson cycle with the starch biosynthetic pathway. In this work we isolated pgi1-3, a mutant totally lacking pPGI activity as a consequence of aberrant intron splicing of the pPGI encoding gene, PGI1. Starch content in pgi1-3 source leaves was ca. 10-15% of that of wild type (WT) leaves, which was similar to that of leaves of pgi1-2, a T-DNA insertion pPGI null mutant. Starch deficiency of pgi1 leaves could be reverted by the introduction of a sex1 null mutation impeding beta-amylolytic starch breakdown. Although previous studies showed that starch granules of pgi1-2 leaves are restricted to both bundle sheath cells adjacent to the mesophyll and stomata guard cells, microscopy analyses carried out in this work revealed the presence of starch granules in the chloroplasts of pgi1-2 and pgi1-3 mesophyll cells. RT-PCR analyses showed high expression levels of plastidic and extra-plastidic beta-amylase encoding genes in pgi1 leaves, which was accompanied by increased beta-amylase activity. Both pgi1-2 and pgi1-3 mutants displayed slow growth and reduced photosynthetic capacity phenotypes even under continuous light conditions. Metabolic analyses revealed that the adenylate energy charge and the NAD(P) H/NAD(P) ratios in pgi1 leaves were lower than those of WT leaves. These analyses also revealed that the content of plastidic 2-C-methyl-D-erythritol 4-phosphate (MEP)-pathway derived cytokinins (CKs) in pgi1 leaves were exceedingly lower than in WT leaves. Noteworthy, exogenous application of CKs largely reverted the low starch content phenotype of pgi1 leaves. The overall data show that pPGI is an important determinant of photosynthesis, energy status, growth and starch accumulation in mesophyll cells likely as a consequence of its involvement in the production of OPPP/glycolysis intermediates necessary for the synthesis of plastidic MEP-pathway derived hormones such as CKs.

Coupling efficiency of laser beam to multimode fiber

The coupling efficiency of laser beam to multimode fiber is given by geometrical optics, and the relation between the maximum coupling efficiency and the beam propagation factor M-2 is analyzed. An equivalent factor M-F(2) for the multimode fiber is introduced to characterize the fiber coupling capability. The coupling efficiency of laser beam to multimode fiber is calculated in respect of the ratio M-2/M-F(2) by the overlapping integral theory. The optimal coupling efficiency can be roughly estimated by the ratio of M-2 to M-F(2) but with a large error range. The deviation comes from the lacks of information on the detail of phase and intensity profile in the beam factor M-2. (C) 2007 Elsevier B.V. All rights reserved.

Diseño y fabricación de un conjunto de estriberas y semimanillares para moto de competición.

[ES]El objeto del presente trabajo consiste en diseñar un conjunto de estriberas y semimanillares para una moto de competición, que cumplan con una serie de requerimientos geométricos y que garanticen las mejores prestaciones posibles en cuanto a competición, entre las que destacan la seguridad y comodidad del piloto. A continuación se procederá a elegir los procesos más adecuados para la fabricación de los mismos, teniendo en cuenta requisitos económicos y de calidad, para sacar al mercado un producto lo más competitivo posible. El estudio se basa principalmente en el análisis de diferentes alternativas que se pueden adoptar para obtener el diseño de los productos y posterior fabricación. Para ello se estudiarán los objetivos y condiciones que se deben cumplir. Cabe destacar que la idea de desarrollo de este proyecto surgió dentro de otro de mayor envergadura, la competición MotoStudent. MotoStudent es una competición internacional entre universidades de todo el mundo en la que los equipos de estudiantes se enfrentan al desafío de diseñar y desarrollar un prototipo de motocicleta de competición similar a la categoría mundialista de Moto3.

A paixão de olhar: a cidade no cinema brasileiro

Desde a criação do cinema, em 1895, a cidade vem sendo retratada de forma surpreendente para quem a vivencia em seu cotidiano. A arte do cinema amplia o sentido de realidade e provoca um impacto sobre o universo psicológico e social do homem. O cinema brasileiro acompanha, através de sua vasta produção, o percurso da cidade no tocante ao desenvolvimento estético, social, cultural, político e econômico, apresentando a forma através da qual o homem se relaciona com essas variáveis. O historiador Michel de Certeau desenvolve em sua obra o tema da inventividade do cotidiano, no que se refere à prática do espaço. Os conceitos de espaço (um lugar praticado), e de lugar (um espaço geométrico), permitem aprofundar o estudo do papel do homem no cotidiano da cidade. É este o eixo teórico da presente pesquisa, que pretende estudar o imaginário da cidade no cinema brasileiro a partir de três questões principais: a formação do imaginário urbano, a criação da forma da cidade no cinema (locações, cenários e fisionomias) e o estado de solidão e isolamento vivido pelo homem nas grandes cidades. Para tal, foram escolhidas para análise as seguintes produções brasileiras: Dias de Nietzsche em Turim (2001) de Julio Bressane, O Príncipe (2002) de Ugo Giorgetti e O Outro Lado da Rua (2004) de Marcos Bernstein. A cidade representada nesses filmes nos dá a oportunidade de exercitar o olhar e refletir sobre o cotidiano da vida urbana e seus reflexos no universo psicológico do homem contemporâneo