1000 resultados para peer reactions


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Since 2003 the School of Medicine at the Universidad del Rosario in Bogotá, Colombia, offers to the students a program named Peer Tutors. The program’s objectives are: to generate a social interaction mechanism that favors knowledge construction side by side with advanced peers; to promote the development of ethical, moral and coexistence oriented values through an academic experience, and to generate a space to explore specific academic interests and teacher´s potential. This article presents the theoretic frame that supports the importance of social interaction in knowledge construction, as well as some indicators that allow a first appraisal of the program. Several achievements that account for the synergic value of an experience that not only fulfills the function of initiating a process of teaching formation and academic support, but that also builds a proactive attitude before learning, are highlighted.

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I look for classroom peer effects for psychoactive substance consumption among Colombian high school students and attempt to identify channels that rationalize for these effects. To do so, I use data for Colombian schools from 2011. I identify peer effects using household consumption behavior to instrument average classroom consumption. I find that an increase of 10% in the proportion of classroom users of alcohol, cannabis, and cocaine increases the probability of students to use alcohol, cannabis, and cocaine in 3.14%, 4.29%, and 2.38% respectively. I find no significant effect on cigarette smoking for the full sample but after exploring heterogeneous effects I find suggestive evidence that the effect is positive in some grades. I find some evidence that indicate that peer effects on alcohol, cannabis, and cocaine consumption operate through risk perception and easiness of access to psychoactive substances, meaning that the increase of likelihood of consumption could be explained because it is easier to access to drugs for students that interact with consumers or because a decrease in the risk students perceive of consuming these substances. Finally, through the use of a SUR and a 3SLS estimator I find strong correlations between smoking cigarettes and consuming cannabis (55 %), and cocaine (60 %).

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En el mundo que nos rodea existen múltiples ejemplos de sustancias que cambian y producen nuevas sustancias. El estudio de estos cambios en los materiales y de las reacciones que se producen entre sí es parte de la química.Este texto nos permite conocer cómo ésta se desarrolla no sólo en los laboratorios y entre científicos, sino también en fábricas y plantas químicas, y con múltiples aplicaciones: en la fabricación de fibras sintéticas para los tejidos, de explosivos para los fuegos artificiales, de disolventes para las pinturas, de fertilizantes para los cultivos y de medicamentos para tratar enfermedades.

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Explica que son los metales, sus propiedades, las aleaciones, y las reacciones que se producen con otros materiales, lo que los científicos llaman reactividad. Está adaptado a alumnos de once a catorce años, que cursan la etapa 3 (Key Stage 3)del curriculo nacional inglés.

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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.

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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.

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En aquesta tesi s'han estudiat mecanismes de reaccions de cicloanulació en carbens de Fischer a través de mètodes teòrics, concretament fent servir el nivell de teoria B3LYP/(Wachters' basis / 6-31G**). Els alcoxi- i amino carbens de pentacarbonil crom, ja siguin vinílics o aromàtics, reaccionen amb acetilè per produir fenols, naftols o derivats ciclopentadiè o indè substituïts amb el Cr(CO)3 coordinat, d'una manera regioselectiva. L'objectiu d'aquest treball és discutir ambudes reaccions competitives particularment a la reacció de Dötz, la qual durant els darrers anys ha estat explorada experimentalment per W.D. Wulff, C.P. Casey, R. Aumann i J. Barluenga entre altres diferents propostes mecanístiques. A més K.H. Dötz va demostrar que la coordinació del Cr(CO)3, un cop l'anell ja està format, pot patir canvis haptotròpics, és a dir, la caminada del complex metàl·lic d'un anell a un altre -generalment almenys substituït- canviant la seva hapticitat (coordinació pi amb els membres de l'anell). Llavors, s'han estudiat les migracions haptotròpiques intramoleculars en petits hidrocarbons aromàtics policíclics amb l'objectiu d'analitzar les rutes de reacció per les quals aquestes reaccions es porten a terme

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Objetivo: A presente dissertação de mestrado teve como principal objetivo estudar a associação entre o suporte parental e dos pares na atividade física das crianças e adolescentes dos 10 aos 17 anos de idade. Método: Foi efetuada uma revisão sistemática de literatura (RSL) onde se sumarizou o estado da arte sobre a temática. Posteriormente foi realizado um estudo observacional transversal onde se investigou como o suporte dos pais (tangível e intangível) e dos pares estão associados com a atividade física entre crianças e adolescentes, examinando as diferenças entre géneros e a sua variação com a idade. Participaram no estudo 1876 crianças e adolescentes, de ambos os sexos, entre os 10 aos 17 anos de idade, participantes do projeto PESSOA. Resultados: Os resultados do estudo transversal corroboram os resultados de alguns estudos da revisão sistemática de literatura uma vez que, apesar das diferenças metodológicas entre os estudos, foram encontradas correlações significativas entre o suporte parental e o nível de atividade física das crianças e adolescentes. Há diferenças entre géneros no tipo de suporte parental e no suporte dos pares. O estudo transversal demonstrou uma associação positiva entre o suporte dos pares e a idade. Esta associação destaca-se na transição da infância para a adolescência. Em ambos os géneros, o suporte dos pares registou uma maior associação à atividade física do que o suporte dos pais. Conclusões: A realização deste estudo demonstra que os pais e os pares são fatores chave na atividade física das crianças e adolescentes. Em diferentes fases da infância e da adolescência, o papel de cada um deles altera-se de acordo com vários fatores do envolvimento físico e social. É necessário mais investigação nesta área, preferencialmente estudos longitudinais que permitam uma melhor compreensão de como as diferentes fontes (pais e pares) e os diferentes tipos de suporte (tangível e intangível) evoluem ao longo da infância e da adolescência e qual o seu impacto nos diferentes níveis de atividade física.