Cambios en el régimen de pensiones en Colombia y su efecto en el margen intensivo de la oferta laboral

En Colombia, como en muchos países de América Latina, en los años 80 y 90 se hicieron cambios importantes en los regímenes de pensiones. Este trabajo hace un análisis de uno de esos cambios en Colombia. El cambio consistió en aumentar el tiempo de cotización necesario para reclamar los beneficios pensionales y la inclusión del salario dentro de la fórmula del monto de pensiones. Para este propósito se estudia el impacto sobre la oferta laboral de un cambio exógeno en estas condiciones usando un diseño de regresión discontinua. Se encuentra un efecto positivo sobre las horas promedio trabajadas en la semana.

Rhodium(I) catalyzed [2+2+2] cycloaddition reactions: experimental and theoretical studies

The [2+2+2] cycloaddition reaction involves the formation of three carbon-carbon bonds in one single step using alkynes, alkenes, nitriles, carbonyls and other unsaturated reagents as reactants. This is one of the most elegant methods for the construction of polycyclic aromatic compounds and heteroaromatic, which have important academic and industrial uses. The thesis is divided into ten chapters including six related publications. The first study based on the Wilkinson’s catalyst, RhCl(PPh3)3, compares the reaction mechanism of the [2+2+2] cycloaddition process of acetylene with the cycloaddition obtained for the model of the complex, RhCl(PH3)3. In an attempt to reduce computational costs in DFT studies, this research project aimed to substitute PPh3 ligands for PH3, despite the electronic and steric effects produced by PPh3 ligands being significantly different to those created by PH3 ones. In this first study, detailed theoretical calculations were performed to determine the reaction mechanism of the two complexes. Despite some differences being detected, it was found that modelling PPh3 by PH3 in the catalyst helps to reduce the computational cost significantly while at the same time providing qualitatively acceptable results. Taking into account the results obtained in this earlier study, the model of the Wilkinson’s catalyst, RhCl(PH3)3, was applied to study different [2+2+2] cycloaddition reactions with unsaturated systems conducted in the laboratory. Our research group found that in the case of totally closed systems, specifically 15- and 25-membered azamacrocycles can afford benzenic compounds, except in the case of 20-membered azamacrocycle (20-MAA) which was inactive with the Wilkinson’s catalyst. In this study, theoretical calculations allowed to determine the origin of the different reactivity of the 20-MAA, where it was found that the activation barrier of the oxidative addition of two alkynes is higher than those obtained for the 15- and 25-membered macrocycles. This barrier was attributed primarily to the interaction energy, which corresponds to the energy that is released when the two deformed reagents interact in the transition state. The main factor that helped to provide an explanation to the different reactivity observed was that the 20-MAA had a more stable and delocalized HOMO orbital in the oxidative addition step. Moreover, we observed that the formation of a strained ten-membered ring during the cycloaddition of 20-MAA presents significant steric hindrance. Furthermore, in Chapter 5, an electrochemical study is presented in collaboration with Prof. Anny Jutand from Paris. This work allowed studying the main steps of the catalytic cycle of the [2+2+2] cycloaddition reaction between diynes with a monoalkyne. First kinetic data were obtained of the [2+2+2] cycloaddition process catalyzed by the Wilkinson’s catalyst, where it was observed that the rate-determining step of the reaction can change depending on the structure of the starting reagents. In the case of the [2+2+2] cycloaddition reaction involving two alkynes and one alkene in the same molecule (enediynes), it is well known that the oxidative coupling may occur between two alkynes giving the corresponding metallacyclopentadiene, or between one alkyne and the alkene affording the metallacyclopentene complex. Wilkinson’s model was used in DFT calculations to analyze the different factors that may influence in the reaction mechanism. Here it was observed that the cyclic enediynes always prefer the oxidative coupling between two alkynes moieties, while the acyclic cases have different preferences depending on the linker and the substituents used in the alkynes. Moreover, the Wilkinson’s model was used to explain the experimental results achieved in Chapter 7 where the [2+2+2] cycloaddition reaction of enediynes is studied varying the position of the double bond in the starting reagent. It was observed that enediynes type yne-ene-yne preferred the standard [2+2+2] cycloaddition reaction, while enediynes type yne-yne-ene suffered β-hydride elimination followed a reductive elimination of Wilkinson’s catalyst giving cyclohexadiene compounds, which are isomers from those that would be obtained through standard [2+2+2] cycloaddition reactions. Finally, the last chapter of this thesis is based on the use of DFT calculations to determine the reaction mechanism when the macrocycles are treated with transition metals that are inactive to the [2+2+2] cycloaddition reaction, but which are thermally active leading to new polycyclic compounds. Thus, a domino process was described combining an ene reaction and a Diels-Alder cycloaddition.

Integrable Hamiltonian systems defined on the Lie groups SO(3) and SU(2): an application to the attitude control of a spacecraft

This paper considers left-invariant control systems defined on the Lie groups SU(2) and SO(3). Such systems have a number of applications in both classical and quantum control problems. The purpose of this paper is two-fold. Firstly, the optimal control problem for a system varying on these Lie Groups, with cost that is quadratic in control is lifted to their Hamiltonian vector fields through the Maximum principle of optimal control and explicitly solved. Secondly, the control systems are integrated down to the level of the group to give the solutions for the optimal paths corresponding to the optimal controls. In addition it is shown here that integrating these equations on the Lie algebra su(2) gives simpler solutions than when these are integrated on the Lie algebra so(3).

Neural Networks as Cybernetic Systems (3rd and revised edition) - Part 2

eural Networks as Cybernetic Systems is a textbox that combines classical systems theory with artificial neural network technology. This third edition essentially compares with the 2nd one, but has been improved by correction of errors and by a rearrangement and minor expansion of the sections referring to recurrent networks. These changes hopefully allow for an easier comprehension of the essential aspects of this important domain that has received growing attention during the last years.

Splicing Systems: Accepting Versus Generating.

In this paper we propose a condition for rejecting the input word by an accepting splicing system which is defined by a finite set of forbidding words. We investigate the computational power of the new variants of accepting splicing systems. We show that the new condition strictly increases the computational power of accepting splicing systems. Rather surprisingly, accepting splicing systems considered here can accept non-regular languages, a situation that has never occurred in the case of (extended) finite splicing systems without additional restrictions.

Combining ERP systems with enterprise 2.0

The paper discusses both the complementary factors and contradictions of adoption ERP based systems with enterprise 2.0. ERP is well known as its' efficient business process management. Also the high failure rate the system implementation is famous as well. According to [1], ERP systems could achieve efficient business performance by enabling a standardized business process design, but at a cost of flexibility in operations. However, enterprise 2.0 supports flexible business process management, informal and less structured interactions [3],[4],[21]. Traditional researcher claimed efficiency and flexibility may seem incompatible in that they are different business objectives and may exist in different organizational environments. However, the paper will break traditional norms that combine ERP and enterprise 2.0 in a single enterprise to improve both efficient and flexible operations simultaneously. Based on the multiple cases studies, four cases presented different attitudes on usage ERP systems and enterprise social systems. Based on socio-technical theory, the paper presents in-depth analysis benefits of combination ERP with enterprise 2.0 for these firms.

Systems 1 and 2 thinking processes and cognitive reflection testing in medical students

Background: Diagnostic decision-making is made through a combination of Systems 1 (intuition or pattern-recognition) and Systems 2 (analytic) thinking. The purpose of this study was to use the Cognitive Reflection Test (CRT) to evaluate and compare the level of Systems 1 and 2 thinking among medical students in pre-clinical and clinical programs. Methods: The CRT is a three-question test designed to measure the ability of respondents to activate metacognitive processes and switch to System 2 (analytic) thinking where System 1 (intuitive) thinking would lead them astray. Each CRT question has a correct analytical (System 2) answer and an incorrect intuitive (System 1) answer. A group of medical students in Years 2 & 3 (pre-clinical) and Years 4 (in clinical practice) of a 5-year medical degree were studied. Results: Ten percent (13/128) of students had the intuitive answers to the three questions (suggesting they generally relied on System 1 thinking) while almost half (44%) answered all three correctly (indicating full analytical, System 2 thinking). Only 3-13% had incorrect answers (i.e. that were neither the analytical nor the intuitive responses). Non-native English speaking students (n = 11) had a lower mean number of correct answers compared to native English speakers (n = 117: 1.0 s 2.12 respectfully: p < 0.01). As students progressed through questions 1 to 3, the percentage of correct System 2 answers increased and the percentage of intuitive answers decreased in both the pre-clinical and clinical students. Conclusions: Up to half of the medical students demonstrated full or partial reliance on System 1 (intuitive) thinking in response to these analytical questions. While their CRT performance has no claims to make as to their future expertise as clinicians, the test may be used in helping students to understand the importance of awareness and regulation of their thinking processes in clinical practice.

The fMRI response of the LGN and V1 to cardinal red-green, blue-yellow, and achromatic visual stimuli

We compared the responsiveness of the LGN and the early retinotopic cortical areas to stimulation of the two cone-opponent systems (red - green and blue - yellow) and the achromatic system. This was done at two contrast levels to control for any effect of contrast. MR images were acquired on seven subjects with a 4T Bruker MedSpec scanner. The early visual cortical areas were localised by phase encoded retinotopic mapping with a volumetric analysis (Dumoulin et al, 2003 NeuroImage 18 576 - 587). We initially located the LGN in four subjects by using flickering stimuli in a separate scanning session, but subsequently identified it using the experimental stimuli. Experimental stimuli were sine-wave counterphasing rings (2 Hz, 0.5 cycle deg-1), cardinal for the selective activation of the L/M cone-opponent (RG), S cone-opponent (BY), and achromatic (Ach) systems. A region of interest analysis was performed. When presented at equivalent absolute contrasts (cone contrast = 5% - 6%), the BOLD response of the LGN is strongest to isoluminant red - green stimuli and weakest to blue - yellow stimuli, with the achromatic response falling in between. Area V1, on the other hand, responds best to both chromatic stimuli, with the achromatic response falling below. The key change from the LGN to V1 is a dramatic boost in the relative blue - yellow response, which occurred at both contrast levels used. This greatly enhanced cortical response to blue - yellow relative to the red - green and achromatic responses may be due to an increase in cell number and/or cell response between the LGN and V1. We speculate that the effect might reflect the operation of contrast constancy across colour mechanisms at the cortical level.

On the Hamilton-Waterloo problem

The Hamilton-Waterloo problem asks for a 2-factorisation of K-v in which r of the 2-factors consist of cycles of lengths a(1), a(2),..., a(1) and the remaining s 2-factors consist of cycles of lengths b(1), b(2),..., b(u) (where necessarily Sigma(i)(=1)(t) a(i) = Sigma(j)(=1)(u) b(j) = v). In thus paper we consider the Hamilton-Waterloo problem in the case a(i) = m, 1 less than or equal to i less than or equal to t and b(j) = n, 1 less than or equal to j less than or equal to u. We obtain some general constructions, and apply these to obtain results for (m, n) is an element of {(4, 6)1(4, 8), (4, 16), (8, 16), (3, 5), (3, 15), (5, 15)}.

Apropriação de conteúdos do conhecimento explícito da língua por alunos do 2.º ano do 1.º ciclo do ensino básico

Relatório de Estágio apresentado à Escola Superior de Educação de Lisboa para obtenção de grau de mestre em Ensino do 1.º e 2.º Ciclo do Ensino Básico

Importance of influx and efflux systems and xenobiotic metabolizing enzymes in intratumoral disposition of anticancer agents.

In this review, intratumoral drug disposition will be integrated into the wide range of resistance mechanisms to anticancer agents with particular emphasis on targeted protein kinase inhibitors. Six rules will be established: 1. There is a high variability of extracellular/intracellular drug level ratios; 2. There are three main systems involved in intratumoral drug disposition that are composed of SLC, ABC and XME enzymes; 3. There is a synergistic interplay between these three systems; 4. In cancer subclones, there is a strong genomic instability that leads to a highly variable expression of SLC, ABC or XME enzymes; 5. Tumor-expressed metabolizing enzymes play a role in tumor-specific ADME and cell survival and 6. These three systems are involved in the appearance of resistance (transient event) or in the resistance itself. In addition, this article will investigate whether the overexpression of some ABC and XME systems in cancer cells is just a random consequence of DNA/chromosomal instability, hypo- or hypermethylation and microRNA deregulation, or a more organized modification induced by transposable elements. Experiments will also have to establish if these tumor-expressed enzymes participate in cell metabolism or in tumor-specific ADME or if they are only markers of clonal evolution and genomic deregulation. Eventually, the review will underline that the fate of anticancer agents in cancer cells should be more thoroughly investigated from drug discovery to clinical studies. Indeed, inhibition of tumor expressed metabolizing enzymes could strongly increase drug disposition, specifically in the target cells resulting in more efficient therapies.

Heterologous expression and biochemical characterization of an α1,2-mannosidase encoded by the Candida albicans MNS1 gene

Protein glycosylation pathways, commonly found in fungal pathogens, offer an attractive new area of study for the discovery of antifungal targets. In particular, these post-translational modifications are required for virulence and proper cell wall assembly in Candida albicans, an opportunistic human pathogen. The C. albicans MNS1 gene is predicted to encode a member of the glycosyl hydrolase family 47, with 1,2-mannosidase activity. In order to characterise its activity, we first cloned the C. albicans MNS1 gene into Escherichia coli, then expressed and purified the enzyme. The recombinant Mns1 was capable of converting a Man9GlcNAc2 N-glycan core into Man8GlcNAc2 isomer B, but failed to process a Man5GlcNAc2-Asn N-oligosaccharide. These properties are similar to those displayed by Mns1 purified from C. albicansmembranes and strongly suggest that the enzyme is an ±1,2-mannosidase that is localised to the endoplasmic reticulum and involved in the processing of N-linked mannans. Polyclonal antibodies specifically raised against recombinant Mns1 also immunoreacted with the soluble ±1,2-mannosidases E-I and E-II, indicating that Mns1 could share structural similarities with both soluble enzymes. Due to the high degree of similarity between the members of family 47, it is conceivable that these antibodies may recognise ±1,2-mannosidases in other biological systems as well.

Glyphosate behavior in a Rhodic Oxisol under no-till and conventional agricultural systems

The behavior of glyphosate in a Rhodic Oxisol, collected from fields under no-till and conventional management systems in Ponta Grossa, Parana state (Brazil) was investigated. Both agricultural systems had been in production for 23 years. Glyphosate mineralization, soil-bound forms, sorption and desorption kinetics, sorption/desorption batch experiments, and soil glyphosate phythoavailability (to Panicum maximum) were determined. The mineralization experiment was set up in a completely randomized design with a 2 x 2 factorial scheme (two management systems and two 14C radiolabelled positions in the glyphosate), with five replicates. 14CO2 evolution was measured in 7-day intervals during 63 days. The glyphosate sorption kinetics was investigated in a batch experiment, employing a glyphosate concentration of 0.84 mg L-1. The equilibration solution was 0.01 mol L-1 CaCl2 and the equilibration times were 0, 10, 30, 60, 120, 240, and 360 min. Sorption/desorption of glyphosate was also investigated using equilibrium batch experiments. Five different concentrations of the herbicide were used for sorption (0.42, 0.84, 1.68, 3.36, and 6.72 mg L-1) and one concentration for desorption. Glyphosate phytoavailability was analyzed in a 2 x 5 factorial scheme with two management systems and five glyphosate concentrations added to soil (0, 4.2, 8.4, 42.0, and 210.0 µg g-1) in a completely randomized design. Phytotoxicity symptoms in P. maximum were evaluated for different periods. The soil under both management systems showed high glyphosate sorption, which impeded its desorption and impaired the mineralization in the soil solution. Practically the total amount of the applied glyphosate was quickly sorbed (over 90 % sorbed within 10 min). Glyphosate bound to residues did not have adverse effects on P. maximum growth. The mineralization of glyphosate was faster under no-till and aminomethylphosphonic acid was the main glyphosate metabolite.

Cycle de vie et travaux ménagers en Suisse : les travaux ménagers des hommes et des femmes lors des étapes de la vie familiale

L'analyse longitudinale et transversale des données du PSM montre que l'augmentation des travaux ménagers consécutive à l'entrée en cohabitation, au mariage et surtout à la parentalité est prise en charge par les femmes, l'investissement masculin restant stable. Le genre semble bien être ici un facteur explicatif central. En outre, l'hétérogénéité des temps ménagers féminins s'expliquerait par le fait que les femmes ne mobilisent leurs ressources personnelles, ni pour entrer en négociation avec leur partenaire et le conduire à s'investir plus, ni pour remettre en question la distribution traditionnelle des tâches. Elles les utilisent plutôt pour exploiter les opportunités contextuelles à disposition afin de diminuer une charge de travail qui, sinon, leur reviendrait.