Theoretical study of reactivity and dynamics of hybride-bridged diruthenium complexes and silylium

Esta tesis presenta un estudio computacional de los sistemas con hidruros puente. En la primera parte se estudia la química de complejos de dirutenio con cuatro hidruros puente. Esto incluye las siguientes reacciones: el intercambio del hidruro con hidrógeno molecular; la activación del enlace C-H del etileno para formar el complejo de bis(vinilo)-etileno; el acoplamiento C-C entre el etileno coordinado y dos ligandos vinilo para producir el complejo rutenaciclopentadieno. Al final de esta parte, se discuten a detalle los mecanismos de estas reacciones. Además, se demostró la importancia de la flexibilidad de los ligandos hidruro y la cooperación entre los dos centros metálicos. En la segunda parte, se estudió el comportamiento fluxional de dos complejos μ-silileno y de un catión sililio. Con esto, se estableció la ruta más favorable en donde se realiza el intercambio de los ligandos hidruro y de los grupos metilo en los complejos μ-silileno. Finalmente, se encontró que hay dos posibles rutas relativas al cambio en la posición del puente Si-H-Si en el cation sililio poliagóstico, asociadas con la rotación interna de los grupos sililo.

Urbanismo ambiental y evaluación estratégica

La tesis doctoral "Urbanismo Ambiental y Evaluación Estratégica" investiga y propone un renovado papel del urbanismo y muy especialmente de la ordenación del territorio como instrumentos no tan sólo de valor para la protección del medio ambiente sino también para la consecución de las políticas hacia un desarrollo sostenible. Con tal fín se reflexiona y potencia la visión/función del suelo como recurso ambiental, también en su función urbanística, y de su mano las consecuencias e interacciones que tal conceptuación puede tener en la Comunidad Europea desde su competencia compartida con los Estados Miembros en materia de medio ambiente, concretamente en su capacidad para incidir, mediante técnicas normativas y no normativas en el urbanismo y la ordenación del territorio en cuanto instrumentos de regulación y ordenación del recurso ambiental suelo. En esta nueva andadura del urbanismo ambientalizado o, si se prefiere, en la carrera hacia el desarrollo urbanístico sostenible, la técnica de evaluación ambiental estratégica de determinados planes y programas se revela como fundamental, especialmente si se consigue que su transposición a los ordenamientos internos de los Estados Miembros se lleve a cabo con pleno respeto a las notas insosyalables defendidas en la tesis de técnica preventiva y no reparativa, dinámica, con capacidad de incidencia en la elección misma del modelo de plan y con miras finalistas a la sostenibilidad. Con ella podrá generalizarse el urbanismo ambiental y acelerarse el proceso de revisión que tienen pendiente las materias de urbanismo y ordenación del territorio desde la nueva concepción del suelo como recurso ambiental y mediante la recepción e integración de los principios ambientalistas.

On the concept of the public: the local museums’ case

Globally, the public is understood as the whole of a service’s users. In the specific case of the museums, the users are all those who make use of the service offered by the museum institution. Thus, the museum’s public corresponds not only to the visitors (people who enter or have entered the museum), but also to the part of those who, in some way, with no relationship of presence within the museum, have enjoyed the services or property made available by it (for instance the ordering of books or other material by catalogue, visit to travelling exhibitions, end users of pedagogical actions carried out in schools…) On the other hand, when we refer to the public, it is necessary to make another distinction: between the real or effective public and the potential public. The former is the group of individuals who have visited or have used the museum, while in the second case are included all the people who, due to their specific characteristics, are susceptible to become the real or effective public.

Trabalho colaborativo : alavanca do desenvolvimento profissional docente

Longe vão os tempos em que a formação inicial dos docentes era tida como suficiente para o desempenho da profissão. Hoje, a sociedade e o poder político requisitam aos professores maior abrangência nas suas competências profissionais, no sentido de estes serem capazes de responder adequadamente às exigências que enfrentam. A tutela, por seu turno, responde com programas de apoio do tipo TEIP (Território Educativo de Intervenção Prioritária) à enorme variedade de alunos e contextos socioeconómicos. É no seio desta realidade que se coloca a questão: como implementar práticas colaborativas, potenciadoras do desenvolvimento profissional dos professores do Departamento de Matemática e Ciências Experimentais, numa escola TEIP? Fullan e Hargreaves (2001) defendem que só a existência de um trabalho conjunto, a responsabilidade partilhada, o empenhamento e o aperfeiçoamento coletivos, a maior disponibilidade para participar na difícil atividade de reflexão crítica, acerca do trabalho realizado, e uma cultura colaborativa é que poderão conduzir a progressos significativos, na melhoria dos resultados e, consequentemente, no real desenvolvimento profissional docente. Contudo, quer a abertura das salas de aula ao exterior, quer a inclusão de todos os alunos nas mesmas, representam ainda, e em geral, um desafio para muitos docentes. É neste contexto que se apresenta um projeto de formação que tem, como campo de análise, a formação de professores, centrada na escola e ancorada na colaboração e supervisão interpares. A formação referida visa: desenvolver uma cultura de positividade e propositividade; criar, promover, analisar e partilhar experiências e inovações realizadas em contexto; desenvolver experiências consequentes sob o ponto de vista do desenvolvimento profissional docente, ao nível da sala de aula; refletir, em conjunto, sobre estratégias exequíveis e indutoras da melhoria do comportamento e das aprendizagens dos discentes. Com estes propósitos, ancorar-se-á a oficina de formação na criação de tarefas a serem experimentadas em contexto, na observação de aulas e na experiência dos intervenientes, baseada na reflexão sobre as práticas e focalizada nos problemas correntes. A expectativa sobre os resultados a obter com esta formação é grande e alicerça-se no trabalho empírico levado a cabo, tendo os principais resultados apontado, claramente, no sentido da necessidade e disponibilidade, por parte dos docentes, para participarem numa oficina de formação cujos objetivos fossem os citados.

La ciudad colonial andina en los ojos de Guamán Poma de Ayala (Estudios)

En su célebre Nueva Corónica y Buen Gobierno, Felipe Guaman Poma de Ayala dejó estampada una visión propia del urbanismo colonial. El autor de este estudio realiza un análisis tanto del texto escrito como de los dibujos que el cronista indígena compuso, con el fin de mostrar que ellos traducen una compleja y rica combinación de descripción de la red urbana realmente existente a inicios del siglo XVII, con una serie de ideales de ordenamiento espacial, urbanístico y geográfico, propio de los imaginarios andinos. Así, el orden de las calles y plazas en damero, con la iglesia en el centro, se combina con la afirmación de jerarquías de la red de lugares centrales del mundo prehispánico.

Ordenamiento territorial, recursos naturales y Asamblea Constituyente en Bolivia: ¿hacia un Estado Plurinacional? (Otros Temas)

El planeamiento del autor hace referencia a como el ordenamiento territorial y el control –estatal, comunal o privado– de los recursos estratégicos del país serán el tema central de debate en la Asamblea Constituyente de Bolivia. Garcés pasa revista a las propuestas de las organizaciones y del gobierno boliviano y finaliza señalando que será un desafío para la Asamblea y para el gobierno de Morales tomar en cuenta los planteamientos de las organizaciones indígenas y campesinas del país.

Periodic Reordering

For many networks in nature, science and technology, it is possible to order the nodes so that most links are short-range, connecting near-neighbours, and relatively few long-range links, or shortcuts, are present. Given a network as a set of observed links (interactions), the task of finding an ordering of the nodes that reveals such a range-dependent structure is closely related to some sparse matrix reordering problems arising in scientific computation. The spectral, or Fiedler vector, approach for sparse matrix reordering has successfully been applied to biological data sets, revealing useful structures and subpatterns. In this work we argue that a periodic analogue of the standard reordering task is also highly relevant. Here, rather than encouraging nonzeros only to lie close to the diagonal of a suitably ordered adjacency matrix, we also allow them to inhabit the off-diagonal corners. Indeed, for the classic small-world model of Watts & Strogatz (1998, Collective dynamics of ‘small-world’ networks. Nature, 393, 440–442) this type of periodic structure is inherent. We therefore devise and test a new spectral algorithm for periodic reordering. By generalizing the range-dependent random graph class of Grindrod (2002, Range-dependent random graphs and their application to modeling large small-world proteome datasets. Phys. Rev. E, 66, 066702-1–066702-7) to the periodic case, we can also construct a computable likelihood ratio that suggests whether a given network is inherently linear or periodic. Tests on synthetic data show that the new algorithm can detect periodic structure, even in the presence of noise. Further experiments on real biological data sets then show that some networks are better regarded as periodic than linear. Hence, we find both qualitative (reordered networks plots) and quantitative (likelihood ratios) evidence of periodicity in biological networks.

Characteristics of silica-rich pedofeatures in a buried paleosol

Whitish and whitish-light brown milky-like textural pedofeatures and impregnations were found in the voids and the matrix of buried paleosols older than 2.7 million years in a site in Sardinia, Italy. The pedofeatures were described and analysed using micromorphology, X-ray diffraction and microprobe techniques, and their spatial distribution correlated with field evidence. The suite of analyses showed that the main components of the pedofeatures were more or less ordered silica phases. As well as forming a matrix cement, these pedofeatures also occurred as coatings and infillings in pores. Significant amounts of alumina and, less, Mg, Ca and Fe were also present in the pedofeatures, possibly in the form of silicate coatings and inclusions/impurities, or alumino-silicates of the adjacent soil matrix. A number of hypotheses are drawn on the possible mechanisms of formation of these silica-rich pedofeatures, including the possibility of prolonged weathering of volcanic materials and the resulting formation of colloids and more or less ordered silica phases, with successive dehydration and progressive ordering of phases during the at least 2.5 million years. (C) 2003 Elsevier B.V. All rights reserved.

Displacement of Zn through acidic light-textured soils

In order to gain understanding of the movement of pollutant metals in soil. the chemical mechanisms involved in the transport of zinc were studied. The displacement of zinc through mixtures of sand and cation exchange resin was measured to validate the methods used for soil. With cation exchange capacities of 2.5 and 5.0 cmol(c) kg(-1). 5.6 and 8.4 pore volumes of 10 mM CaCl2, respectively, were required to displace a pulse of ZnCl2. A simple Burns-type model (Wineglass) using an adsorption coefficient (K-d) determined by fitting a straight line relationship to an adsorption isotherm gave a good fit to the data (K-d=0.73 and 1.29 ml g(-1), respectively). Surface and subsurface samples of an acidic sandy loam (organic matter 4.7 and 1.0%. cation exchange capacity (CEC) 11.8 and 6.1 cmol(c) kg(-1) respectively) were leached with 10 mM calcium chloride. nitrate and perchlorate. With chloride. the zinc pulse was displaced after 25 and 5 pore volumes, respectively. The Kd values were 6.1 and 2.0 ml g(-1). but are based on linear relationships fitted to isotherms which are both curved and show hysteresis. Thus. a simple model has limited value although it does give a general indication of rate of displacement. Leaching with chloride and perchlorate gave similar displacement and Kd values, but slower movement occurred with nitrate in both soil samples (35 and 7 pore volumes, respectively) which reflected higher Kd values when the isotherms were measured using this anion (7.7 and 2.8 ml g(-1) respectively). Although pH values were a little hi-her with nitrate in the leachates, the differences were insufficient to suggest that this increased the CEC enough to cause the delay. No increases in pH occurred with nitrate in the isotherm experiments. Geochem was used to calculate the proportions of Zn complexed with the three anions and with fulvic acid determined from measurements of dissolved organic matter. In all cases, more than 91% of the Zn was present as Zn2+ and there were only minor differences between the anions. Thus, there is an unexplained factor associated with the greater adsorption of Zn in the presence of nitrate. Because as little as five pore volumes of solution displaced Zn through the subsurface soil, contamination of ground waters may be a hazard where Zn is entering a light-textured soil, particularly where soil salinity is increased. Reductions in organic matter content due to cultivation will increase the hazard. (C) 2004 Elsevier B.V. All rights reserved.