Mineralisation of 2,4-dichlorophenol and glucose placed into the same or different hydrological domains as a bacterial inoculant

The spatial location of microorganisms in the soil three-dimensional structure with respect to their substrates plays an important role in the persistence and turnover of natural and xenobiotic organic compounds. To study the effect of spatial location on the mineralisation of ¹⁴C-2,4-dichlorophenol (2,4-DCP, 0.15 or 0.31 μmol g^-1) and ¹⁴C-glucose (2.77 μmol g^-1), columns packed with autoclaved soil aggregates (2-5 mm) were used. Using a chloride tracer of water movement, the existence of 'immobile' water, which was by-passed by preferentially flowing 'mobile' water, was demonstrated. By manipulation of the soil moisture content, the substrates were putatively placed to these conceptual hydrological domains (immobile and mobile water). Leaching studies revealed that approximately 1.7 (glucose) and 3.4 (2.4-DCP) times the amount of substrate placed in mobile water was recovered in the first 4 fractions of leachate when compared to substrate placed in immobile water. The marked difference in the breakthrough curves was taken as evidence of successful substrate placement. The 2,4-DCP degrading bacterium, Burkholderia sp. RASCc2, was inoculated in mobile water (1.8-5.2 × 10⁷ cells g^-1 soil) and parameters (asymptote, time at maximum rate, calculated maximum rate) describing the mineralisation kinetics of 2,4-DCP and glucose previously added to immobile or mobile water domains were compared, For glucose, there was no significant effect (P > 0.1) of substrate placement on any of the mineralisation parameters. However, substrate placement had a significant effect (P < 0.05) on parameters describing 2,4-DCP mineralisation. In particular, 2,4-DCP added in mobile water was mineralised with a greater maximum rate and with a reduced time at maximum rate when compared to 2,4-DCP added to immobile water. The difference in response between the two test substrates may reflect the importance of sorption in controlling the spatial bioavailability of compounds in soil. © 2002 Elsevier Science Ltd. All rights reserved.

Development of a single photon counting computed tomography system using MPGDs

The development of computed tomography systems with energy resolving detectors is a current challenge in medical physics and biomedical engineering. A computed tomography system of this kind allows getting complementary informations relatively to conventional systems, that can help the medical diagnosis, being of great interest in medicine. The work described in this thesis is related to the development of a computed tomography system using micropattern gaseous detectors, which allow storing, simultaneously, information about the interaction position and the energy of each single photon that interacts with the detector. This kind of detectors has other advantages concerning the cost and characteristics of operation when compared with solid state detectors. Tomographic acquisitions were performed using a MicroHole & Strip Plate based detector, which allowed reconstructing cross-sectional images using energy windows, applying the energy weighting technique and performing multi-slice and tri-dimensional reconstructions. The contrast-to-noise ratio was improved by 31% by applying the energy weighting technique, comparing with the corresponding image obtained with the current medical systems. A prototype of a computed tomography with flexibility to change the detector was developed, making it possible to apply different detectors based on Thick-COBRA. Several images acquired with these detectors are presented and demonstrate their applicability in X-ray imaging. When operating in NeCH4, the detector allowed a charge gain of 8 104, an energy resolution of 20% (full width at half maximum at 8 keV), a count rate of 1 106 Hz/mm2, a very stable operation (gain fluctuations below 5%) and a spacial resolution of 1.2 mm for an energy photon of 3.6 keV. Operating the detector in pure Kr allowed increasing the detection efficiency and achieving a charge gain of 2 104, an energy resolution of 32% (full width at half maximum at 22 keV), a count rate of 1 105 Hz/mm2, very stable operation and a spatial resolution of 500 m. The software already existing in the group was improved and tools to correct geometric misalignments of the system were also developed. The reconstructions obtained after geometrical correction are free of artefacts due to the referred misalignments.

Os mais velhos nas organizações : um desafio para a gestão

Numa era em que a força de trabalho está a envelhecer, fruto do envelhecimento da população mundial, as organizações enfrentam desafios consideráveis no que toca à gestão, motivação e retenção dos trabalhadores mais velhos. As atitudes dos gestores perante os trabalhadores mais velhos configuram restrições consideráveis à superação desses desafios. Neste sentido, foram realizados três estudos visando desenvolver e validar um instrumento de medida das atitudes dos gestores perante os trabalhadores mais velhos. No primeiro estudo, exploraram-se (a) as atitudes dos gestores perante os trabalhadores mais velhos, e (b) as perceções dos aposentados sobre suas últimas experiências antes da aposentação. No segundo estudo, foram desenvolvidos 51 itens, que emergiram tanto do primeiro estudo, como da literatura. O questionário resultante foi então aplicado a uma amostra de 224 gestores portugueses, que foram também convidados a tomar decisões em três cenários envolvendo trabalhadores mais jovens e mais velhos. O terceiro estudo é uma réplica do segundo, numa amostra de 249 gestores brasileiros. As principais conclusões são: (a) cinco tipos de atitudes dos gestores perante os trabalhadores mais velhos foram identificados; (b) essas atitudes predizem as decisões dos gestores no que se refere à seleção de um trabalhador mais jovem versus mais velho, em processos de contratação e na seleção de colaboradores para participar em programas de formação; (c) os padrões empíricos identificados nas amostras de portugueses e brasileiros são semelhantes; (d) apesar dos gestores reconhecerem qualidades positivas significativas nos trabalhadores mais velhos, tendem a discriminá-los; (e) os gestores desenvolvem diferentes perfis atitudinais em relação aos trabalhadores mais velhos, os quais têm consequências nas decisões que tomam sobre esses trabalhadores. Um quarto estudo foi levado a cabo, com o objetivo de tentar compreender se a estrutura penta-dimensional do instrumento de medida das atitudes dos gestores perante os trabalhadores mais velhos pode ser replicado numa amostra de estudantes, e se essas mesmas atitudes ajudam a explicar as decisões dos estudantes em cenários similares aos dos apresentados aos gestores. Os resultados principais foram os seguintes: (a) apesar dos estudantes reconhecerem qualidades nos trabalhadores mais velhos, levam a cabo práticas discriminatórias relativamente a esses trabalhadores; (b) um número significativo de estudantes prefere um trabalhador mais jovem, mesmo quando o mais velho é descrito de forma mais positiva. Um quinto estudo foi efetuado, visando testar em que medida as atitudes dos gestores perante os trabalhadores mais velhos explicam a segurança psicológica das equipas. O estudo envolveu 52 equipas. Os respetivos líderes descreveram as suas atitudes perante os mais velhos, e 266 membros dessas equipas descreveram a segurança psicológica da equipa. Os resultados sugerem que os líderes com atitudes mais positivas perante os trabalhadores mais velhos tendem a desenvolver equipas psicologicamente mais seguras. Todavia, estudos futuros são necessários para testar mecanismos mediadores e moderadores que tornem essa relação mais clara.

Thermally driven surface winds in the tropics

Thesis (Ph. D.)--University of Washington, 1998

Synthesis and computer-assisted design of mitochondrial electron transport-chain inhibitors as antimalarial agents

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2014

Computational design with flexible backbone sampling for protein remodeling and scaffolding of complex binding sites

Dissertation presented to obtain the Doutoramento (Ph.D.) degree in Biochemistry at the Instituto de Tecnologia Qu mica e Biol ogica da Universidade Nova de Lisboa

Études Structurales par Résonance Magnétique Nucléaire (RMN) du Site Actif du Ribozyme VS de Neurospora.

Nous étudions le ribozyme VS de Neurospora, en tant que système modèle, pour augmenter nos connaissances sur la relation entre la structure et la fonction chez les ARNs, ainsi que pour mieux comprendre le mécanisme de clivage de ce ribozyme. Il a été proposé précédemment que la boucle interne A730 dans la tige-boucle VI (SLVI) contient le site actif du ribozyme et lie un ou plusieurs ions métalliques qui pourraient participer au mécanisme réactionnel. Nous avons déterminé par spectroscopie RMN la structure de la tige-boucle SLVI contenant la boucle A730 afin d’éclaircir ce mécanisme. La structure obtenue est en accord avec les études biochimiques antérieures et présente un ou plusieurs sites de liaison au magnésium associé à la boucle interne. Suite à des études de cinétique et de mutagenèse, il a été proposé qu’une adénine localisée dans le site actif, A756, participe à la catalyse par acide/base générale. Des études de pH effectuées précédemment ont identifié un pKa catalytique (5.2-5.8) qui correspond probablement à l’équilibre de protonation du A756. À l’aide de méthodes utilisant le carbone-13, nous avons identifié un pKa modifié appartenant au A756, ce qui supporte le rôle de ce résidu dans la catalyse par acide/base générale. Les études structurales présentées ici aident donc à augmenter notre compréhension du mécanisme de clivage chez le ribozyme VS.

El paradigma del Desarrollo Urbano Sostenible -DUS- como referente del proceso de toma de decisiones legislativas en Colombia. Análisis de la agenda legislativa del Congreso de la República entre 1991 y 2006

Este trabajo contribuye al análisis de la incidencia del paradigma del Desarrollo Urbano Sostenible en el proceso de toma de decisiones legislativas en Colombia, concentrándose en la discusión y definición de la agenda legislativa sobre asuntos urbanos, durante el periodo 1991-2006.

Diseño y Pedagogía en el ciclo de BUP.

Hacer un estudio profundo acerca del Diseño y todo su entorno y posteriormente marcar un programa, una metodología sobre el Diseño. Didáctica del Diseño. Qué se entiende por Diseño. Cómo y cuándo nace el Diseño. Diseño y comunicación visual. Diseño: forma-función. Retroguardia, vanguardia, investigación. Metodología del Diseño. Necesidad de nuevos métodos. Adaptar el programa a los individuos y no a la inversa. Crítica a los métodos y temario en las asignaturas de Diseño. Índices de las asignaturas Diseño 1 y 2. Diseño bi-dimensional: nuevo esquema planteado por el autor. Diseño tri-dimensional: nuevo esquema planteado por el autor. Bibliografía. Análisis teórico. El objetivo principal del Diseño se refiere a la forma de las cosas producidas pero no hay que olvidar que lo que se percibe de modo inmediato está determinado por la disposición y estructura interna, por el material utilizado y por el procedimiento de fabricación, todos ellos aspectos del Diseño. El Diseño nace con el interés de muchos países industrializados durante los años 1959-60. Los nuevos tipos de complejidad están fuera del alcance del proceso tradicional del Diseño: son necesarios nuevos métodos. Un programa de enseñanza tiene que adaptarse a los individuos y no a la inversa: el programa de base se prepara teniendo en cuenta los elementos principales y la finalidad del curso; el que enseña ha de tener la elasticidad y rapidez necesarias para preparar las lecciones de acuerdo con las necesidades que se presenten en cada caso. Elabora el autor dos esquemas de diseño bidimensional y tridimensional plantados por él, los cuales no se pueden reseñar. Fecha finalización tomada del código del documento.

Characterization of cytotoxic ribonucleases: from the internalization pathway to the importance of dimeric structures

En aquesta tesi s'ha caracteritzat la ruta d'internalització de l'onconasa, una RNasa citotòxica. Els resultats indiquen que l'onconasa entra a les cèl·lules per la via dependent de clatrina i del complex AP-2. Seguidament es dirigeix als endosomes de reciclatge i es a través d'aquesta ruta que la proteïna exerceix la citotoxicitat. Per altra banda, els resultats d'aquest treball demostren que PE5, una variant citotòxica de la ribonucleasa pancreàtica humana (HP-RNasa), interacciona amb la importina  mitjançant diferents residus que tot i que no són seqüencials, es troben propers en l'estructura tridimensional d'aquesta proteïna. PM8 és una HP-RNasa amb estructura cristal·logràfica dimèrica constituïda per intercanvi de dominis N-terminals. En aquesta tesi s'han establert les condicions per estabilitzar aquest dimer en solució i també es proposa un mecanisme per la dimerització.

How may tropical cyclones change in a warmer climate?

Tropical Cyclones (TC) under different climate conditions in the Northern Hemisphere have been investigated with the Max Planck Institute (MPI) coupled (ECHAM5/MPIOM) and atmosphere (ECHAM5) climate models. The intensity and size of the TC depend crucially on resolution with higher wind speed and smaller scales at the higher resolutions. The typical size of the TC is reduced by a factor of 2.3 from T63 to T319 using the distance of the maximum wind speed from the centre of the storm as a measure. The full three dimensional structure of the storms becomes increasingly more realistic as the resolution is increased. For the T63 resolution, three ensemble runs are explored for the period 1860 until 2100 using the IPCC SRES scenario A1B and evaluated for three 30 year periods at the end of the 19th, 20th and 21st century, respectively. While there is no significant change between the 19th and the 20th century, there is a considerable reduction in the number of the TC by some 20% in the 21st century, but no change in the number of the more intense storms. Reduction in the number of storms occurs in all regions. A single additional experiment at T213 resolution was run for the two latter 30-year periods. The T213 is an atmospheric only experiment using the transient Sea Surface Temperatures (SST) of the T63 resolution experiment. Also in this case, there is a reduction by some 10% in the number of simulated TC in the 21st century compared to the 20th century but a marked increase in the number of intense storms. The number of storms with maximum wind speeds greater than 50ms-1 increases by a third. Most of the intensification takes place in 2 the Eastern Pacific and in the Atlantic where also the number of storms more or less stays the same. We identify two competing processes effecting TC in a warmer climate. First, the increase in the static stability and the reduced vertical circulation is suggested to contribute to the reduction in the number of storms. Second, the increase in temperature and water vapor provide more energy for the storms so that when favorable conditions occur, the higher SST and higher specific humidity will contribute to more intense storms. As the maximum intensity depends crucially on resolution, this will require higher resolution to have its full effect. The distribution of storms between different regions does not, at first approximation, depend on the temperature itself but on the distribution of the SST anomalies and their influence on the atmospheric circulation. Two additional transient experiments at T319 resolution where run for 20 years at the end of the 20th and 21st century, respectively using the same conditions as in the T213 experiments. The results are consistent with the T213 study. The total number of tropical cyclones were similar to the T213 experiment but were generally more intense. The change from the 20th to the 21st century was also similar with fewer TC in total but with more intense cyclones.

Dynamical evolution of the 2003 southern hemisphere stratospheric winter using Envisat trace-gas observations

Data from the MIPAS instrument on Envisat, supplemented by meteorological analyses from ECMWF and the Met Office, are used to study the meteorological and trace-gas evolution of the stratosphere in the southern hemisphere during winter and spring 2003. A pole-centred approach is used to interpret the data in the physically meaningful context of the evolving stratospheric polar vortex. The following salient dynamical and transport features are documented and analysed: the merger of anticyclones in the stratosphere; the development of an intense, quasi-stationary anticyclone in spring; the associated top-down breakdown of the polar vortex; the systematic descent of air into the polar vortex; and the formation of a three-dimensional structure of a tracer filament on a planetary scale. The paper confirms and extends existing paradigms of the southern hemisphere vortex evolution. The quality of the MIPAS observations is seen to be generally good. though the water vapour retrievals are unrealistic above 10 hPa in the high-latitude winter.

Atmospheric factors governing banded orographic convection

Atmospheric factors Governing Banded Orographic Convection The three-dimensional structure of shallow orographic convection is investigated through simulations performed with a cloud-resolving numerical model. In moist flows that overcome a given topographic barrier to form statically unstable cap clouds, the organization of the convection depends on both the atmospheric structure and the mechanism by which the convection is initiated. Convection initiated by background thermal fluctuations embedded in the flow over a smooth mountain (without any small-scale topographic features) tends to be cellular and disorganized except that shear-parallel bands may form in flows with strong unidirectional vertical shear. The development of well-organized bands is favored when there is weak static instability inside the cloud and when the dry air surrounding the cloud is strongly stable. These bands move with the flow and distribute their cumulative precipitation evenly over the mountain upslope. Similar shear-parallel bands also develop in flows where convection is initiated by small-scale topographic noise superimposed onto the main mountain profile, but in this case stronger circulations are also triggered that create stationary rainbands parallel to the low-level flow. This second dominant mode, which is less sensitive to the atmospheric structure and the strength of forcing, is triggered by lee waves that form over small-scale topographic bumps near the upstream edge of the main orographic cloud. Due to their stationarity, these flow-parallel bands can produce locally heavy precipitation amounts.

The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes

Four new antimony sulphides, [T(dien)(2)]Sb6S10 center dot xH(2)O [T = Ni (1), Co (2) x approximate to 0.45], [Co(en)(3)]SbsSI(3) (3) and [Ni(en)(3)]Sb12S19 (4), have been synthesised under solvothermal conditions. In compounds (1) - (3), Sb12S228- secondary building units are connected to form layered structures. In (1) and (2), Sb-6 S-2- layers containing Sb16S16 heterorings are separated by [T(dien]2](2+) cations, whilst in (3), Sb8 S2- layers 10 13 contain [Co(en)3]2+ cations within large Sb22S22 pores. Compound (4) adopts a three-dimensional structure in which [Ni(en)3 12 cations lie within ca. 5 A wide channels. (c) 2007 Elsevier Ltd. All rights reserved.

Structural studies on acridine derivatives binding to telomeric DNA

Acridine derivatives can inhibit a variety of nuclear enzymes by binding or intercalating to DNA. This class of compounds is of great interest in the development of novel anticancer agents. Despite the availability of crystallographic data for some of the compounds complexed with DNA, uncertainties remain about the mechanisms of action, binding preferences and biological targets. To investigate the intercalation of several acridine derivatives, a variety of techniques are being employed. Single-crystal X-ray diffraction is being used to determine the high resolution three-dimensional structure of short sequences of quadruplex telomeric DNA with bound drug. This will be compared to the effect of drug binding to long segments of double-stranded DNA using fibre diffraction, with neutron diffraction studies planned to analyse the hydrogen bonding patterns of the DNA-drug complexes. Small-angle neutron scattering (SANS) will also be applied to study drug binding to both short and long sequences of quadruplex and double-stranded DNA in solution. Initial SANS measurements of the telomeric repeat d(TGGGGT) imply that this hexamer is present as a quadruplex. (c) 2006 Elsevier B.V. All rights reserved.