Development of CO-releasing molecular for the treatment of inflammatory diseases

Dissertation presented to obtain a Ph.D. degree (Doutoramento) in Chemistry at the Instituto de Tecnologia Quimica e Biol6gica da Universidade Nova de Lisboa

Cyclopentadienyl-functionalised N-heterocyclic carbenes: synthesis, coordination to Mo, Ru, Rh

Dissertation presented to obtain the Ph.D degree in Chemistry

Ditopic molecular architectures for the recognition of anionic species

Dissertation presented to obtain the Ph.D degree in Chemistry

Development of suberin films driven by an ionic liquid-based depolymerisation process

Dissertation presented to obtain the Ph.D degree in Chemistry

On the physical-chemical properties of ceramide C16

Dissertation presented to obtain the Ph.D degree in Chemistry.

A nanopore-based stochastic detection method: Single molecule characterisation of nanoparticles using ()- hemolysin

Dissertation presented to obtain the Ph.D degree in Chemistry.

DOTA-based Ga(III) and Gd(III) chelates for medical imaging (PET, SPECT and MRI)

PhD Thesis in Sciences Specialization in Chemistry

Garnet-chloritoid-kyanite metapelites from the Raspas Complex (SW Ecuador): a key eclogite-facies assemblage

The Raspas Complex (Ecuador) contains one of the few eclogitic bodies in the northern Andes. It consists of metaperidotites, eclogites, and metapelites. The latter display three assemblages: (i) garnet + chloritoid + kyanite, (ii) garnet + chloritoid and (iii) garnet + chlorite, in all cases with quartz and muscovite in addition. The growth of these assemblages was coeval with the main ductile deformation, and was followed by minor reequilibration (chlorite growth in garnet + chloritoid samples and chloritoid + quartz aggregates replacing garnet and kyanite in garnet + chloritoid + kyanite samples). Detailed microprobe analyses show increasing magnesian compositions for garnet (from core to rim) and chloritoid (inclusions within garnet compared to matrix grains) in kyanite-bearing samples. The above data are interpreted in the framework of the KFMASH system. Reaction progress along the divariant reaction Cld = Grt + Ky explains the change in chemistry of coexisting phases. The divariant Grt-Cld-Ky assemblage has a narrow stability field, and the P-T conditions are estimated at about 20 kbar, 550-600degreesC. Decompression, recorded by chloritoid-quartz pseudomorphs of garnet, probably occurred as temperature decreased.

Simulation methods with extended stability for stiff biochemical kinetics

Background: With increasing computer power, simulating the dynamics of complex systems in chemistry and biology is becoming increasingly routine. The modelling of individual reactions in (bio)chemical systems involves a large number of random events that can be simulated by the stochastic simulation algorithm (SSA). The key quantity is the step size, or waiting time, τ, whose value inversely depends on the size of the propensities of the different channel reactions and which needs to be re-evaluated after every firing event. Such a discrete event simulation may be extremely expensive, in particular for stiff systems where τ can be very short due to the fast kinetics of some of the channel reactions. Several alternative methods have been put forward to increase the integration step size. The so-called τ-leap approach takes a larger step size by allowing all the reactions to fire, from a Poisson or Binomial distribution, within that step. Although the expected value for the different species in the reactive system is maintained with respect to more precise methods, the variance at steady state can suffer from large errors as τ grows. Results: In this paper we extend Poisson τ-leap methods to a general class of Runge-Kutta (RK) τ-leap methods. We show that with the proper selection of the coefficients, the variance of the extended τ-leap can be well-behaved, leading to significantly larger step sizes.Conclusions: The benefit of adapting the extended method to the use of RK frameworks is clear in terms of speed of calculation, as the number of evaluations of the Poisson distribution is still one set per time step, as in the original τ-leap method. The approach paves the way to explore new multiscale methods to simulate (bio)chemical systems.

The biochemistry of drug metabolism : an introduction : part 6, Inter-individual factors affecting drug metabolism.

This review is part of a series of review articles on the metabolism of drugs and other xenobiotics published in Chemistry & Biodiversity. After a thorough discussion of metabolic reactions and their enzymes, this article focuses on genetically determined differences in drug and xenobiotic metabolism. After a short introduction on the causes for genetic differences, the first focus is on species differences in drug and xenobiotic metabolism. A major chapter is then dedicated to clinically relevant genetic polymorphisms in human drug metabolism and resultant ethnic differences. The last two chapters deal with sex-dependent differences in drug metabolism and personalized pharmacotherapy related to inter-individual differences in drug metabolism.

Equilibration and disequilibration between monazite and garnet: indication from phase-composition and quantitative texture analysis

The integration of information which can be gained from accessory [i.e. age (t)] and rock-forming minerals [i.e. temperature (T) and pressure (P)] requires a more profound understanding of the equilibration kinetics during metamorphic processes. This paper presents an approach comparing conventional P-T estimate from equilibrated assemblages of rock-forming minerals with temperature data derived from yttrium-garnet-monazite (YGM) and yttrium-garnet-xenotime (YGX) geothermometry. Such a comparison provides an initial indication on differences between equilibration of major and trace elements. Regarding this purpose, two migmatites, two polycyclic and one monocyclic gneiss from the Central Alps (Switzerland, northern Italy) were investigated. While the polycyclic samples exhibit trace-element equilibration between monazite and garnet grains assigned to the same metamorphic event, there are relics of monazite and garnet obviously surviving independent of their textural position. These observations suggest that surface processes dominate transport processes during equilibration of those samples. The monocyclic gneiss, on the contrary, displays rare isolated monazite with equilibration of all elements, despite comparably large transport distances. With a nearly linear crystal-size distribution of the garnet grain population, growth kinetics, related to the major elements, were likely surface-controlled in this sample. In contrast to these completely equilibrated examples, the migmatites indicate disequilibrium between garnet and monazite with a change in REE patterns on garnet transects. The cause for this disequilibrium may be related to a potential disequilibrium initiated by a changing bulk chemistry during melt segregation. While migmatite environments are expected to support high transport rates (i.e. high temperatures and melt presence), the evolution of equilibration in migmatites is additionaly related to change in chemistry. As a key finding, surface-controlled equilibration kinetics seem to dominate transport-controlled processes in the investigated samples. This may be decisive information towards the understanding of age data derived from monazite.

Acylation of chiral alcohols: a simple procedure for chiral GC analysis

The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC.

Currículo de licenciatura em química da universidade de brasília: uma proposta em implantação

This article presents the conception, principles and academic structure of the evening course leading to the formation of a Licentiate in Chemistry, at the University of Brasília. The curriculum has been carried out since the beginning of 1993. This curriculum has as its basic axis the graduation of future teachers integrated with the conceptual formation in Chemistry. Interdisciplinary actions are planned between the Chemistry Department, the Psychology Institute and the Faculty of Education so as to provide mechanisms which would allow the licenciate to acquire teaching experience along the course.

A evolução da pós-graduação em química no Brasil

The post-graduate teaching of chemistry in Brazil over the last years is discussed, including comparisons with some other sciences and also experiences in the United States and the United Kingdom. We have also compared the more recent situation with the previous decade, which leads us to a favourable conclusion as to the results obtained in the teaching of post-graduate students in chemistry. Some conclusions and recommendations are made with respect to the near future.

As tecnologias interativas no ensino

The way new interactive computer technologies and the resources of the Internet could be used by teachers and students are explored. The possibilities of some of the Internet resources in chemistry are described.