Efficiency and Equity in Learning Communities and schools

Traditionally, school efficiency has been measured as a function of educational production. In the last two decades, however, studies in the economics of education have indicated that more is required to improve school efficiency: researchers must explore how significant changes in school organization affect the performance of at-risk students. In this paper we introduce Henry Levin’s adoption of the X-efficiency approach to education and we describe the efficient and cost-effective characteristics of one Learning Communities Project School that significantly improved its student outcomes and enrollment numbers and reduced its absenteeism rate to zero. The organizational change that facilitated these improvements defined specific issues to address. Students’ school success became the focus of the school project, which also offered specific incentives, selected teachers, involved parents and community members in decisions, and used the most efficient technologies and methods. This case analysis reveals new two elements—family training and community involvement—that were not explicit parts of Levin’s adaptation. The case of the Antonio Machado Public School should attract the attention of both social scientists and policy makers

New insights into boar sperm function and survival from integrated field and laboratory studies

En aquesta tesi s'han dut a terme dos tipus d'estudis diferents. L'objectiu del primer era la preservació del semen de porcí a 15ºC i el del segon eren els co-cultius homòlegs de cèl·lules epitelials de l'oviducte i espermatozoides de porcí. Pel que fa al primer estudi, s'ha observat que l'addició de la prostaglandina F2α i àcid hialurònic a les dosis seminals no malmena la qualitat espermàtica i que la tolerància dels espermatozoides als canvis d'osmolalitat del medi es pot correlacionar proves de fertilitat i prolificitat.. Respecte el segon, s'ha determinat que les cèl·lules oviductals afecten els paràmetres espermàtics i que la presència d'espermatozoides sobreexpressa els gens que codifiquen per les proteïnes de xoc tèrmic. Així, se suggereix que aquestes proteïnes tenen algun paper en els processos reproductius que tenen lloc a l'oviducte, malgrat que s'hagi observat, mitjançant la tècnica de la interferència de l'RNA, que la HSP90AA1 no està implicada en el perllongament de la viabilitat espermàtica.

Environmental governance from a gender perspective. Theoretical reflections and case studies

In the second half of the twentieth century we saw the environmental debate escalate into one of the most challenging and complex issues that authorities at international, national, regional and municipal levels have to deal with. The inherent complexity of environmental problems, which brings out the interconnections between the economic, socio-cultural and ecological dimensions of the territory, is increased by the social, scientific and political focuses of the debate, and their interdependencies. In the framework of governance, scientific and technical assessments are a relevant but not “unique” source for legitimating environmental policymaking. The discussion is opened towards the consideration of different existing perspectives on the environment. The main objective of the present study is to systematize and explore in-depth the perspectives brought by feminism and gender to environmental governance. What is the specificity of a feminist and gender outlook? In what sense does it bring new light to environmental governance processes? Such questions are explored empirically and theoretically.

Managanese and dicopper complexes for bioinspired oxidation reactions: catalytic and mechanistic studies on C-H and C=C oxidations

Enzymes are high-weight molecules which catalyze most of the metabolic processes in living organisms. Very often, these proteins contain one or more 1st row transition metal ions in their active center (Fe, Cu, Co, Mn, Zn, etc.), and are known as metalloenzymes or metalloproteins. Among these, metalloenzymes that activate molecular oxygen and use it as terminal oxidant stand out because of the wide range of catalyzed reactions and their exquisite selectivity. In this PhD dissertation we develop low-weight synthetic bioinspired complexes that can mimic structural and/or functional features of the active center of oxigenases. In the first part, we describe the use of unsymmetric dinuclear Cu complexes which are capable of performing the oxidation of phenols and phenolates in a analogous manner of the tyrosinase protein. In the second part, we describe the use of mononuclear manganese complexes in the oxidation of alcanes and alquenes.

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.

Dynamic management and restoration of virtual paths in broadband networks based on distributed software agents

La gestió de xarxes és un camp molt ampli i inclou molts aspectes diferents. Aquesta tesi doctoral està centrada en la gestió dels recursos en les xarxes de banda ampla que disposin de mecanismes per fer reserves de recursos, com per exemple Asynchronous Transfer Mode (ATM) o Multi-Protocol Label Switching (MPLS). Es poden establir xarxes lògiques utilitzant els Virtual Paths (VP) d'ATM o els Label Switched Paths (LSP) de MPLS, als que anomenem genèricament camins lògics. Els usuaris de la xarxa utilitzen doncs aquests camins lògics, que poden tenir recursos assignats, per establir les seves comunicacions. A més, els camins lògics són molt flexibles i les seves característiques es poden canviar dinàmicament. Aquest treball, se centra, en particular, en la gestió dinàmica d'aquesta xarxa lògica per tal de maximitzar-ne el rendiment i adaptar-la a les connexions ofertes. En aquest escenari, hi ha diversos mecanismes que poden afectar i modificar les característiques dels camins lògics (ample de banda, ruta, etc.). Aquests mecanismes inclouen els de balanceig de la càrrega (reassignació d'ample de banda i reencaminament) i els de restauració de fallades (ús de camins lògics de backup). Aquests dos mecanismes poden modificar la xarxa lògica i gestionar els recursos (ample de banda) dels enllaços físics. Per tant, existeix la necessitat de coordinar aquests mecanismes per evitar possibles interferències. La gestió de recursos convencional que fa ús de la xarxa lògica, recalcula periòdicament (per exemple cada hora o cada dia) tota la xarxa lògica d'una forma centralitzada. Això introdueix el problema que els reajustaments de la xarxa lògica no es realitzen en el moment en què realment hi ha problemes. D'altra banda també introdueix la necessitat de mantenir una visió centralitzada de tota la xarxa. En aquesta tesi, es proposa una arquitectura distribuïda basada en un sistema multi agent. L'objectiu principal d'aquesta arquitectura és realitzar de forma conjunta i coordinada la gestió de recursos a nivell de xarxa lògica, integrant els mecanismes de reajustament d'ample de banda amb els mecanismes de restauració preplanejada, inclosa la gestió de l'ample de banda reservada per a la restauració. Es proposa que aquesta gestió es porti a terme d'una forma contínua, no periòdica, actuant quan es detecta el problema (quan un camí lògic està congestionat, o sigui, quan està rebutjant peticions de connexió dels usuaris perquè està saturat) i d'una forma completament distribuïda, o sigui, sense mantenir una visió global de la xarxa. Així doncs, l'arquitectura proposada realitza petits rearranjaments a la xarxa lògica adaptant-la d'una forma contínua a la demanda dels usuaris. L'arquitectura proposada també té en consideració altres objectius com l'escalabilitat, la modularitat, la robustesa, la flexibilitat i la simplicitat. El sistema multi agent proposat està estructurat en dues capes d'agents: els agents de monitorització (M) i els de rendiment (P). Aquests agents estan situats en els diferents nodes de la xarxa: hi ha un agent P i diversos agents M a cada node; aquests últims subordinats als P. Per tant l'arquitectura proposada es pot veure com una jerarquia d'agents. Cada agent és responsable de monitoritzar i controlar els recursos als que està assignat. S'han realitzat diferents experiments utilitzant un simulador distribuït a nivell de connexió proposat per nosaltres mateixos. Els resultats mostren que l'arquitectura proposada és capaç de realitzar les tasques assignades de detecció de la congestió, reassignació dinàmica d'ample de banda i reencaminament d'una forma coordinada amb els mecanismes de restauració preplanejada i gestió de l'ample de banda reservat per la restauració. L'arquitectura distribuïda ofereix una escalabilitat i robustesa acceptables gràcies a la seva flexibilitat i modularitat.