Cognitive appraisals, emotional reactions, and their associations with three forms of peer-victimization

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Material changes and reactions.

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.

The reactions of metals.

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.

Organizational injustice : Third parties’ reactions to mistreatmentof employee

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Interpretation, emotional reactions and daily life implications of hallucination-like experiences in clinical and nonclinical populations

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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.

Theoretical study of catalytic reactions of carbenes: haptotropic rearrangements and the Dötz reaction

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

Geochemical mapping of carbonate sediments in the Makgadikgadi basin, Botswana using moderate resolution remote sensing data

This paper maps the carbonate geochemistry of the Makgadikgadi Pans region of northern Botswana from moderate resolution (500 m pixels) remotely sensed data, to assess the impact of various geomorphological processes on surficial carbonate distribution. Previous palaeo-environmental studies have demonstrated that the pans have experienced several highstands during the Quaternary, forming calcretes around shoreline embayments. The pans are also a significant regional source of dust, and some workers have suggested that surficial carbonate distributions may be controlled, in part, by wind regime. Field studies of carbonate deposits in the region have also highlighted the importance of fluvial and groundwater processes in calcrete formation. However, due to the large area involved and problems of accessibility, the carbonate distribution across the entire Makgadikgadi basin remains poorly understood. The MODIS instrument permits mapping of carbonate distribution over large areas; comparison with estimates from Landsat Thematic Mapper data show reasonable agreement, and there is good agreement with estimates from laboratory analysis of field samples. The results suggest that palaeo-lake highstands, reconstructed here using the SRTM 3 arc-second digital elevation model, have left behind surficial carbonate deposits, which can be mapped by the MODIS instrument. Copyright (c) 2006 John Wiley & Sons, Ltd.

Geochemical precursors to volcanic activity at Mount St. Helens, USA

The importance of the interplay between degassing and crystallization before and after the eruption of Mount St. Helens (Washington, USA) in 1980 is well established. Here, we show that degassing occurred over a period of decades to days before eruptions and that the manner of degassing, as deduced from geochemicai signatures within the magma, was characteristic of the eruptive style. Trace element (lithium) and short-lived radioactive isotope (lead-210 and radium-226) data show that ascending magma stalled within the conduit, leading to the accumulation of volatiles and the formation of lead-210 excesses, which signals the presence of degassing magma at depth.

Soil geochemical analyses as an indication of metal working at the excavation of a house in the Roman City at Silchester (UK)

Silchester is the site of a major late Iron Age and Roman town (Calleva Atrebatum), situated in northern Hampshire (England (UK)) and occupied between the late first century BC and the fifth or sixth century AD. Extensive evidence of the nature of the buildings and the plan of the town was obtained from excavations undertaken between 1890 and 1909. The purpose of this study was to use soil geochemical analyses to reinforce the archaeological evidence particularly with reference to potential metal working at the site. Soil analysis has been used previously to distinguish different functions or land use activity over a site and to aid identification and interpretation of settlement features (Entwistle et al., 2000). Samples were taken from two areas of the excavation on a 1-metre grid. Firstly from an area of some 500 square metres from contexts of late first/early second century AD date throughout the entirety of a large 'town house' (House 1) from which there was prima facie evidence of metalworking.

Geochemical changes to dredged canal sediments following land spreading: a review.

This paper brings together some of the recent research on trace metals in dredged sediments, and in particular freshwater canal sediments. Following a description of the general UK background, geochemical processes that affect metal release and retention in dredged canal sediments are considered, particularly the role of redox and sulphur on metal associations, and the use of sequential extraction for the derivation of metal associations in sediments. The review outlines the importance of oxidation on metal-mobility and shows that many studies have illustrated the increase in metal-leachability from sediments during oxidation. Suggestions are given for sediment-testing requirements which should include an examination of both anoxic and oxidised sediment as well as ecotoxicology in order to account for changes to metal-speciation after disposal to land.

Heavy metals - geochemical bogey men?

Heavy metals is a loose term usually used to indicate environmentally "bad" metals. It is poorly defined with a multitude of often contradictory definitions based on density, atomic weight, atomic number or other properties of the elements or their compounds. Alternative. scientifically rigorous definitions exist for subgroups of metals and should be used instead. (C) 2003 Elsevier Ltd. All rights reserved.

The role of gypsum in the reactions of phosphate with soils

The aim of this study was to examine the mechanisms by which gypsum increases the sorption of fertilizer-P in soils of and and semi-arid regions. Either gypsum or soil (Usher from the UK; pH 7.8, 7% organic matter, 21% CaCO3: Yasouj from Iran; pH 8.2, 1.4% OM, 18% CaCO3: Ghanimeh from Saudi Arabia; pH 7.8, 1% OM, 26% CaCO3, 13% gypsum) was shaken for 24 It with KH2PO4 solutions in 10 mM CaCl2. With gypsum, grinding increased sorption by a factor of about 3, and increase in pH from 5.6 to 7.5 greatly increased sorption. Scanning electron micrographs (SEM) and EDX quantitative analysis showed that small crystals of gypsum disappeared and roughly spherical particles of dicalcium phosphate (DCPD) were formed. Analysis of equilibrium Solutions showed, using GEOCHEM, that octa-calcium phosphate (OCP) coated the DCPD. For the soils, sorption was in the order Ghanimeh > Yasouj > Usher. Removal of gypsum from Ghanimeh reduced sorption, with precipitated gypsum having a greater effect than gypsum mixed physically with the soil. Addition to Usher had no effect. SEM and EDX could not be used in the soil matrix, but solubility analysis again showed that solutions were close to equilibrium with OCP. Usher was unresponsive to added gypsum, presumably because of its small sorption capacity and high organic matter content. In Ghanimeh and Yasouj soils, gypsum increased sorption by being a source of readily available Ca2+ (c) 2005 Elsevier B.V. All rights reserved.