Dipodal Ferrocene Derivatives for Nanostructured Redox-Functionalised Surfaces

Self-assembled monolayers (SAMs) on solid surfaces are of great current interest in science and nanotechnology. This thesis describes the preparation of several symmetrically 1,1’-substituted ferrocene derivatives that contain anchoring groups suitable for chemisorption on gold and may give rise to SAMs with electrochemically switchable properties. The binding groups are isocyano (-NC), isothiocyanato (-NCS), phosphanyl (-PPh2), thioether (-SR) and thienyl. In the context of SAM fabrication, isothiocyanates and phosphanes are adsorbate systems which, surprisingly, have remained essentially unexplored. SAMs on gold have been fabricated with the adsorbates from solution and investigated primarily by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. The results of these analytical investigations are presented and discussed in matters of the film quality and possible binding modes. The quality of self-assembled monolayers fabricated from 1,1’-diisocyanoferrocene and 1,1’-diisothiocyanatoferrocene turned out to be superior to that of films based on the other adsorbate species investigated. Films of those absorbates as well as of dppf afforded well-defined SAMs of good quality. All other films of this study based on sulfur containing anchoring groups exhibit chemical inhomogeneity and low orientational order of the film constituents and therefore failed to give rise to well-defined SAMs. Surface coordination chemistry is naturally related to molecular coordination chemistry. Since all SAMs described in this thesis were prepared on gold (111) surfaces, the ferrocene-based ligands of this study have been investigated in their ability for complexation towards gold(I). The sulfur-based ferrocene ligands [fc(SR)2] failed to give stable gold(I) complexes. In contrast, 1,1’-diisocyanoferrocene (1) proved to be an excellent ligand for the complexation of gold(I). Several complexes were prepared and characterised utilising a series of gold(I) acetylides. These complexes show interesting structural motifs in the solid state, since intramolecular aurophilic interactions lead to a parallel orientation of the isocyano moieties, combined with an antiparallel alignment of neighbouring units. The reaction of 1 with the gold(I) acetylide [Au(C≡C–Fc)]n turned out to be very unusual, since the two chemically equivalent isocyano groups undergo a different reaction. One group shows an ordinary coordination and the other one undergoes an extraordinary 1,1-insertion into the Au-C bond. As a sideline of the research of this thesis several ferrocene derivatives have been tested for their suitability for potential surface reactions. Copper(I) mediated 1,3-dipolar cycloadditions of azidoferrocene derivatives with terminal alkynes appeared very promising in this context, but failed to a certain extent in terms of ‘click’ chemistry, since the formation of the triazoles depended on the strict exclusion of oxygen and moisture and yields were only moderate. Staudinger reactions between dppf and azidoferrocene derivatives were also tested. The nucleophilic additions of secondary amines to 1,1’-diisothiocyanatoferrocene led to the respective thiourea derivatives in quantitative yields.

Assessment of the strategies of organic fruit production and fruit drying in Uganda

Organic agriculture in Uganda is developing at a fast pace and despite this trend Uganda is still unable to produce enough fresh and dry organic fruits mainly pineapple to meet the exporters demand. This current research investigated the strategies of farmers at production level by assessing the pros and cons of fruit growing, organic agriculture and fruit drying in order to understand the underlying causal factor for the low production of organic dry fruits in a major fruit producing district of Uganda. The study was carried out in two separate and distinctive areas; one which only produces and export fresh organic pineapple and the other which exports dried fruits (mainly pineapple and papaya). About 10% of the farmers in the two study areas were surveyed using questionnaires which were further followed by semi-structured interviews and participatory rural appraisals activities with various types of farmers in order to understand the different decisions and strategies of farmers. 82% and 74% of farmers in the two study areas grew fruits as it gave better economic returns and for 77% and 90% respectively in the two study areas, the reasons for growing fruit was the ease of selling compared to other crops. All the farmers were relying on coffee husk for growing organic pineapples. However, 50% of the farmers want to grow pineapples (either organic or conventional) but couldn't afford to buy coffee husk. Fruit drying was mainly a strategy to utilize cheap fruits during harvesting seasons for value addition. 71% and 42% of farmers in the two study areas wanted to dry fruits but it was beyond their economic capacity to buy the driers. Decision of the farmers whether to grow fruits or cereals, organic or conventional agriculture and selling the fruits as fresh or dry were dependent mainly on the economic, knowledge and resource availability of each type of practices. It is concluded that the main barrier for an increase in the production of organic dried fruits is at the processing level, and the limited capacity for investments in drying facilities.

Untersuchung der Adsorptionskinetik photoschaltbarer azobenzolfunktionalisierter selbstorganisierter Monolagen mit optischer Frequenzverdopplung

In dieser Arbeit wurde das Adsorptionsverhalten zweier azobenzolfunktionalisierter Liganden auf Goldoberflächen untersucht. Diese Liganden zeichnen sich dadurch aus, dass sie mithilfe von Licht bestimmter Wellenlängen zwischen zwei Isomerisierungszuständen – sowohl in Lösung als auch in den auf der Oberfläche resultierenden Monolage – hin und her geschaltet werden können. Somit ist es möglich, Oberflächen herzustellen, deren physikalische und chemische Eigenschaften zwischen zwei Zuständen variiert werden können. Die Messungen des Adsorptionsverhaltens wurden mittels optischer Frequenzverdopplung durchgeführt. Diese Messmethode ist höchst grenzflächensensitiv und ermöglicht es somit die Adsorption der Liganden in situ und ich Echtzeit zu verfolgen. Neben den Adsorptionsmessungen wurde auch die Phase des frequenzverdoppelten Signals über eine Interferenzmethode gemessen. Die Ergebnisse dieser Phasenmessungen ermöglichen es, eine Aussage über eine mögliche Nichtlinearität der untersuchten Moleküle zu treffen. An die in den Adsorptionsmessungen gewonnenen Messdaten wurden drei kinetische Standardmodelle angepasst. Beschreibt eines dieser Modelle den im Experiment bestimmten Adsorptionsverlauf, kann eine Aussage über die zugrunde liegenden Prozesse des Adsorptionsvorganges getroffen werden. Die Ergebnisse der Adsorptionsmessungen zeigen einen deutlichen Einfluss des Isomerisierungszustandes der Liganden auf den Verlauf der Adsorption. Liegen die Moleküle im geschalteten Zustand vor, so verläuft die Adsorption langsamer. Weiterhin konnte gezeigt werden, dass ebenso intermolekulare Wechselwirkungen über Wasserstoffbrückenbindungen einen verlangsamenden Einfluss auf die Adsorption der Liganden haben. In den durchgeführten Phasenmessungen zeigte sich darüber hinaus, dass Liganden, die über an die Azobenzolgruppe angebundene Amidgruppen verfügen, eine Nichtlinearität aufweisen. Diese Nichtlinearität ist zudem vom Isomerisierungszustand der Liganden abhängig. In den kinetischen Untersuchungen konnte darüber hinaus gezeigt werden, dass sich die Adsorption der Liganden bis auf eine Ausnahme durch die Langmuirkinetik 2. Ordnung beschreiben lässt. Somit handelt es ich bei der Adsorption der untersuchten Liganden um eine Reaktion, der eine Bindungsspaltung voran geht. Dieser Befund konnte durch Vergleich mit weiteren Experimenten bestätigt werden.

Effect of rural transportation system on agricultural productivity in Oyo State, Nigeria

Food farming in Oyo North, Nigeria is characterised by an increasing use of Intermediary Mode of Transportation (IMT) to ease inputs and outputs mobility and farm access. To assess the influence on food farmer’s productivity, a random sample of 230 respondents was selected and data collected on their socio-economic and farm specific characteristics. Descriptive statistics, Herfindhal Index and Technical Efficiency Approach were used to analyse the data. The results indicate that majority of food farmers were in their middle age with mean age of 50 years and most of them used one plot at a location between 5 and 10km to their village of residence. They acquired land by inheritance and practiced intensive crop diversification as risk management strategy. The transportation modes used in addition to walking include bicycle, motorcycle, and car with increasing trend in the use of motorcycle. The mean Technical Efficiency (TE) of food farmers was 0.82 with significant inefficiency effects. The inefficiency analysis indicates positive effect of distance, crop diversification and un-tarred type of road on farmer’s productivity, while poor level of education among farmers, use of bicycle; trekking and weekly working time negatively affect farmer’s efficiency. The negative effect of trekking and use of bicycle and the excess working time suggest the adoption of more IMT of motorized type to optimize farming time and increase farmer’s productivity.

Módulo 0 : primer curso de Educación Infantil (Grupo B) : año académico 2008-09.

Publicación realizada al amparo de los Proyectos de Innovación Educativa tipo A-2, en el contexto de la Convergencia Europea (R-232/2008, de 22 de abril de la Universidad de Murcia), financiados por la Universidad de Murcia y por la Comunidad Autónoma de la Región de Murcia.

Fronts from integrodifference equations and persistence effects on the Neolithic transition

We extend a previous model of the Neolithic transition in Europe [J. Fort and V. Méndez, Phys. Rev. Lett. 82, 867 (1999)] by taking two effects into account: (i) we do not use the diffusion approximation (which corresponds to second-order Taylor expansions), and (ii) we take proper care of the fact that parents do not migrate away from their children (we refer to this as a time-order effect, in the sense that it implies that children grow up with their parents, before they become adults and can survive and migrate). We also derive a time-ordered, second-order equation, which we call the sequential reaction-diffusion equation, and use it to show that effect (ii) is the most important one, and that both of them should in general be taken into account to derive accurate results. As an example, we consider the Neolithic transition: the model predictions agree with the observed front speed, and the corrections relative to previous models are important (up to 70%)

Agenda escolar : curso 08-09.

Tít. tomado de la cub.

Agenda escolar : curso 08-09.

Tít. tomado de la cub.

La costa occidental asturiana.

Resumen basado en la publicación

Agenda escolar del Principado de Asturias 09-10 : Educaci??n Primaria

Esta publicaci??n pretende ser un recurso din??mico que facilite el trabajo diario y estreche el v??nculo de colaboraci??n entre los centros docentes y las familias. La Agenda Escolar del Principado de Asturias 2009-2010 incluye actividades y contenidos que ayudan al alumnado a organizar su tiempo, planificar el d??a a d??a escolar y controlar las tareas. En ella, alumnado y familias, tendr??n informaci??n b??sica de su centro docente, el horario de clase, los ejercicios de evaluaci??n, el calendario escolar oficial, las actividades extraescolares y complementarias, entre otros muchos recursos de tutor??a dise??ados para facilitar la comunicaci??n e incentivar la colaboraci??n de todos los miembros de la Comunidad educativa.

Agenda escolar del Principado de Asturias 09-10 : Educaci??n Secundaria

Esta publicaci??n pretende ser un recurso din??mico que facilite el trabajo diario y estreche el v??nculo de colaboraci??n entre los centros docentes y las familias. La Agenda Escolar del Principado de Asturias 2009-2010 incluye actividades y contenidos que ayudan al alumnado a organizar su tiempo, planificar el d??a a d??a escolar y controlar las tareas. En ella, alumnado y familias, tendr??n informaci??n b??sica de su centro docente, el horario de clase, los ejercicios de evaluaci??n, el calendario escolar oficial, las actividades extraescolares y complementarias, entre otros muchos recursos de tutor??a dise??ados para facilitar la comunicaci??n e incentivar la colaboraci??n de todos los miembros de la Comunidad educativa.

Proyecto para la convivencia : memoria 08-09. IV

Seleccionado en la convocatoria: Ayudas para desarrollar proyectos de convivencia, Gobierno de Arag??n 2008-09

Géopoint-82. Les territoires de la vie quotidienne

Relació i resum de les ponències del IV Col•loqui Geopoint 82, celebrat el maig d’aquell any a Avinyó on es van desenvolupar les ponències “Le territoire dans ses rapports avec les espaces géographiques: concept ancien, utilisation nouvelle.”, “Le Pays, niveau géographique.”, “Le territoire de la vie quotidienne et le référentiel-habitant.”, “Réseaux et niveaux de territorialité”, “Pratique de l'eco-développement.”, “Le territoire en milieu urbain.” i “La territorialité.”

Nova et Vetera : edición 09, Mayo 28 de 2007

Nova et Vetera, ISSN 1692-5866, Año 8, No. 09 (Mayo 28 de 2007)

Nova et Vetera : edición 09, Mayo 19 de 2008

Nova et Vetera, ISSN 1692-5866, Año 3, No. 09 (Mayo 19 de 2008)