Macrocicles nitrogenats contenint unitats de ferrocè i llurs complexos de Pal·ladi(0). Estudi estructural i aplicacions en catàlisi

La present tesi doctoral s'ha basat en la caracterització estructural i en l'estudi de les propietats catalítiques de nous complexos de pal·ladi(0) amb lligands olefínics contenint unitats de ferrocè. En una primera fase s'ha desenvolupat la síntesi d'estructures de tipus (E, E, E)-1,6,11-trisarilsulfonil-1,6,11-triazaciclopentadeca-3,8,13-triè contenint des d'una fins a tres unitats de ferrocè i s'ha estudiat la seva complexació amb pal·ladi(0). Mitjançant estudis electroquímics s'ha avaluat la seva possible aplicació en el reconeixement molecular electroquímic. Encara que aquest tipus d'estructures no han resultat vàlides per aquest tipus de processos de reconeixement, l'estudi electroquímic ha permès determinar que la presència del grup ferrocenil influeix en les propietats redox del metall complexat. S'ha descrit també l'obtenció de macrocicles pentaolefínics anàlegs de 25 membres contenint unitats de ferrocè i s'ha estudiat paral·lelament la seva complexació amb pal·ladi(0).En una segona part del treball s'han avaluat les propietats catalítiques del complex (E, E, E)-6,11-bis[(p-metilfenil)sulfonil]-1-ferrocenilsulfonil-1,6,11-triazaciclopentadeca-3,8,13-trièpal·ladi(0), en reaccions clàssicament catalitzades per pal·ladi tals com l'acoblament creuat de Suzuki o la reacció de Heck, i s'ha pogut determinar que és un catalitzador actiu en aquest tipus de reaccions, essent a més possible, la seva recuperació i reutilització. En el cas concret de la reacció de Heck s'han emprat sals de diazoni com a agents arilants i cal destacar que s'ha descrit el primer sistema catalític recuperable i reutilitzable per aquest tipus de reaccions. Mitjançant espectrometria de masses amb ionització per electrospray ha estat possible determinar el rol mecanístic del nostre complex de pal·ladi en la reacció de Heck amb sals de diazoni.Finalment, en una tercera part estructural del treball s'ha estudiat el comportament espectroscòpic dels complexos de pal·ladi(0) anteriorment mencionats, contenint des de tres unitats aríliques iguals fins a tres unitats aríliques diferents. Mitjançant RMN i difracció de raigs-X s'ha determinat que la complexitat estereoquímica dels complexos deriva dels isòmers que es poden formar mitjançant complexació del metall amb cada una de les cares dels tres dobles enllaços continguts a l'estructura.

New mono- and dinuclear ruthenium complexes containing the 3,5-bis(2-pyridyl)pyrazole ligand. Synthesis, characterization and applications

Se han sintetizado dos nuevos complejos mononucleares de Ru, con formula [RuCl2(Hbpp)(dmso)2], a partir de la reacción entre [RuCl2(dmso)4] y Hbpp (3,5-bis(2-piridil)pirazola). El hecho que sólo tres de los seis posibles estereoisómeros se obtengan a partir de esta reacción, se ha racionalizado en base a factores estructurales y electrónicos. Estos complejos se han caracterizado de forma estructural, espectroscópica y electroquímica. En acetonitrilo en medio básico, el isómero trans,cis-[RuCl2(Hbpp)(dmso)2] da lugar a procesos de isomerización de enlace de un ligando dmso cuando el Ru(II) se oxida a Ru(III). Las constantes termodinámicas y cinéticas para el proceso se han determinado por voltametria cíclica. La irradiación de trans,cis-[RuCl2(Hbpp)(dmso)2] y cis(out),cis-[RuCl2(Hbpp)(dmso)2] con luz UV o solar da lugar a reacciones de fotosustitución de un ligando dmso por una molécula de acetonitrilo para dar un nuevo compuesto el cual ha sido caracterizado en solución por técnicas espectroscópicas y electroquímicas. Ambos complejos resultan catalizadores útiles en la transferencia de hidrógeno de isopropanol a acetofenona, obteniéndose 1-feniletanol como único producto y un 42.1% de conversión (36.1 ciclos metálicos) a 80ºC con el isómero trans,cis-[RuCl2(Hbpp)(dmso)2], que resulta significativamente más eficaz que el complejo cis(out),cis-[RuCl2(Hbpp)(dmso)2]. La reacción de cis(out),cis-[RuCl2(Hbpp)(dmso)2] con trpy (2,2':6',2"-terpiridina) da lugar a los dos isómeros geométricos del complejo [Ru(Hbpp)(trpy)(Cl)]+, el in y el out. Estos complejos se han aislado y caracterizado por técnicas estructurales, espectroscópicas y electroquímicas. Estos cloro complejos han sido utilizados como precursores para la síntesis de los complejos análogos con ligandos aqua (in,out-[Ru(Hbpp)(trpy)(H2O)]2+) y piridina (in,out-[Ru(Hbpp)(trpy)(py)]2+), los cuales también han sido aislados y caracterizados. Las propiedades ácido-base de los aqua complejos, y del complejo out-py se han estudiado detalladamente por voltametria cíclica y mediante valoraciones espectrofotométricas ácido-base. El tratamiento matemático de los datos así obtenidos nos ha permitido determinar los valores de pKa para los distintos equilibrios de protonación de los complejos en los estados de oxidación II y III. El complejo out-aqua ha demostrado ser un buen catalizador para la oxidación electroquímica del alcohol benzílico, presumiblemente a benzaldehido. La constante de velocidad de segundo orden para el proceso ha sido determinada como 17.1 M-1 s-1, por simulación matemática. El dímero con un puente cloro, [Ru2Cl(bpp)(trpy)2]2+ ha sido preparado por dos rutas sintéticas diferentes. El dímero análogo con un puente acetato se ha obtenido por reacción del cloro dímero con un exceso de acetato sódico. El dímero con dos ligandos aqua [Ru2(bpp)(trpy)2(OH2)2]3+ puede obtenerse por hidrólisis ácida del complejo con un acetato puente o por hidrólisis básica del complejo con un puente cloro. Estos complejos han sido caracterizados por técnicas estructurales, espectroscópicas y electroquímicas. Las soluciones del dímero con dos ligandos aqua en medio ácido resultan inestables a la coordinación de aniones de la solución con el tiempo. Las propiedades ácido-base del dímero con dos aguas coordinadas han sido estudiadas por voltametria cíclica y mediante experimentos de electrólisis a potencial controlado. El pKa para la desprotonación de uno de los ligandos aqua ha sido determinado mediante una valoración espectrofotométrica ácido-base como 6.7. Este valor tan bajo de pKa se atribuye a la formación de la entidad {Ru2O2H3}, favorable termodinámicamente. Los espectros UV-vis para los distintos estados de oxidación del aqua dímero, de RuIIRuII a RuIIIRuIV, han sido obtenidos por oxidación química y electroquímica del complejo. Se han llevado a cabo estudios cinéticos de la oxidación, paso a paso, de RuII,II a RuIV,IV , y se han determinado las constantes de oxidación de segundo orden para los distintos procesos de oxidación. La capacidad del aqua dímero en la oxidación del agua a oxígeno molecular ha sido investigada en solución homogénea utilizando CeIV como oxidante. La evolución de oxígeno se ha demostrado por cromatografia de gases. Se ha obtenido una eficiencia del 73% y 18.6 ciclos catalíticos, cuando 1.83 x 10-6 moles de dímero se han mezclado con un exceso de 100 equivalentes de cerio. El dímero con dos aguas cataliza también la oxidación del agua de forma heterogénea, con el complejo adsorbido sobre una membrana de nafion, aunque la eficiencia es menor. Se ha propuesto un mecanismo intramolecular para la reacción de oxidación del agua. Consiste en la oxidación a 4 electrones del dímero, de RuII,II a RuIV,IV, el cual reacciona con el agua para formar oxígeno y revierte nuevamente al estado de oxidación II,II. Este modelo es consistente con estudios catalíticos de la evolución de oxígeno en función de las concentraciones de cerio y catalizador, llevados a cabo en solución ácida homogénea, que demuestran que la oxidación a 4 electrones del agua se encuentra catalizada por una sola molécula de complejo bajo concentraciones elevadas de cerio. La constante de pseudo-primer-orden para la evolución de oxígeno tiene un valor de 1.4 x 10-2 s-1, que es uno de los valores de constante más elevados obtenidos hasta la fecha. Desafortunadamente, el aqua dímero se desactiva durante el proceso de catálisis dando lugar a una especie naranja, la cual estamos actualmente tratando de caracterizar.

Socio-cultural visions of interactivity within Museums

The ideas on which this paper is based are drawn from my thesis “Interactivity in Museums. A Relationship Building Perspective” written in 2007 for the fulfillment of the Master Degree in Museology at the Reinwardt Academy in Amsterdam. The main arguments are that the notion of Interactivity conceptualized within a technological orientation coupled with the pedagogic approach of mere information transmission need to be reconsidered; that Interactivity in museums is a conception both misinterpreted and under-implemented; and that the problems of understanding Interactivity will resolve by identifying the aspects which define Interactivity and most importantly focus on why they matter in a broader socio-cultural context within museums. Without an intention to attribute all the developments and advances associated with new museological practice, in some deterministic way, solely to politics and economic change, I argue that the new strategies adopted by museums towards progression and broader accessibility –at least regarding interactivity, seem to be linked more with a dominant commercialization of culture and education, than with a belief towards an effect on social change through the promotion of social interaction within a pluralistic and multicultural society, acknowledging the diversity of nature, opinion and practices, which can be combined instead of contrasting each other.

The School of Museology Celje: regular, continuous, topical, quality form of education

At the School of Museology, a project with ten years of tradition, we carry out module-based programmes to educate and qualify different target audiences working in the filed of cultural heritage. Our development and realization of educational programmes and training courses directed at practical applicability, including life-long learning of adults, topic complementarity with related professional and scientific fields, connection with universities offering undergraduate and postgraduate studies of heritages, promotion of theoretical museological discourses raising awareness of the meaning of cultural heritage, firm placement in an international network of related institutions and promotion of international relations with special emphasis on neighbouring countries. We encourage project partnership and cooperate with different domestic and foreign associates in forming and carrying out programmes.

The rise of urban tourism in Havana since 1989

This article looks at the development of urban tourism in Havana, Cuba, in the period since the collapse of state socialism in the USSR and Eastern Europe. It provides an interesting case study of the adoption of an outward-oriented state development policy in the context of a socialist state. The dramatic rise of urban-based tourism in Havana since 1989 is described, followed by a review of the socio-economic impacts of such tourism. These include: income generation; job creation; the rise of the informal economy, including crime and prostitution; increased migration to the primary city, along with spatial concentration on the coastal strip, and associated environmental impacts. In conclusion, the article considers the fat that the promotion of tourism has returned Havana to some of the conditions that existed in the city Socialist Revolution in 1959.

Health Benefits of Organic Food: effects of the environment

Public concern over impacts of chemicals in plant and animal production on health and the environment has led to increased demand for organic produce, which is usually promoted and often perceived as containing fewer contaminants, more nutrients, and being positive for the environment. These benefits are difficult to quantify, and potential environmental impacts on such benefits have not been widely studied. This book addresses these key points, examining factors such as the role of certain nutrients in prevention and promotion of chronic disease, potential health benefits of bioactive compounds in plants, the prevalence of food-borne pesticides and pathogens and how both local and global environmental factors may affect any differences between organic and conventionally produced food. This book is an essential resource for researchers and students in human health and nutrition, environmental science, agriculture and organic farming. Main Contents 1. Organic farming and food systems: definitions and key characteristics. 2. The health benefits of n-3 fatty acids and their concentrations in organic and conventional animal-derived foods. 3. Environmental impacts on n-3 content of foods from ruminant animals. 4. Health benefits and selenium content of organic vs conventional foods. 5. Environmental impacts concerning the selenium content of foods. 6. Contaminants in organic and conventional food: the missing link between contaminant levels and health effects. 7. Mycotoxins in organic and conventional foods and effects of the environment. 8. Human pathogens in organic and conventional foods and effects of the environment. 9. What does consumer science tell us about organic foods? 10. The beneficial effects of dietary flavonoids: sources, bioavailability and biological functions. 11. Environmental regulation of flavonoid biosynthesis. 12. Nitrates in the human diet. 13. Impacts of environment and management on nitrate in vegetables and water. 14. Effects of the environment on the nutritional quality and safety of organically produced foods: Round-up and summary.

The social life of ruins: sites of memory and the politics of a Zimbabwean periphery

This article explores conflicts over a series of ruins located within Zimbabwe's flagship National Park. The relics have long been regarded as sacred places by local African communities evicted from their vicinity, and have come to be seen as their ethnic heritage. Local intellectuals' promotion of this heritage was an important aspect of a defensive mobilization of cultural difference on the part of a marginalized minority group. I explore both indigenous and colonial ideas about the ruins, the different social movements with which they have been associated and the changing social life they have given the stone relics. Although African and European ideas sometimes came into violent confrontation - as in the context of colonial era evictions - there were also mutual influences in emergent ideas about tribe, heritage and history. The article engages with Pierre Nora's notion of 'sites of memory', which has usefully drawn attention to the way in which ideas of the past are rooted and reproduced in representations of particular places. But it criticizes Nora's tendency to romanticize pre-modern 'memory', suppress narrative and depoliticize traditional connections with the past. Thus, the article highlights the historicity of traditional means of relating to the past, highlighting the often bitter and divisive politics of traditional ritual, myth, kinship, descent and 'being first'. It also emphasizes the entanglement of modern and traditional ideas, inadequately captured by Nora's implied opposition between history and memory. (c) 2005 Elsevier Ltd. All rights reserved.

Promoting sustainability: Efficacy and adoption of tobacco-based insecticides in Nigeria

The promotion of technologies seen to be aiding in the attainment of agricultural sustainability has been Popular amongst Northern-based development donors for many years. One of these, botanical insecticides (e.g., those based on neem, Pyrethrum and tobacco) have been a particular favorite as they are equated with being 'natural' and hence less damaging to human health and the environment. This paper describes the outcome of interactions between one non-government organisation (NGO), the Diocesan Development Services (DDS), based in Kogi State, Nigeria, and a major development donor based in Europe that led to the establishment of a programme designed to promote the Virtues of a tobacco-based insecticide to small-scale farmers. The Tobacco Insecticide Programme (TIP) began in the late 1980s and ended in 200 1, absorbing significant quantities of resource in the process. TIP began with exploratory investigations of efficacy on the DDS seed multiplication farm followed by stages of researcher-managed and farmer-managed on-farm trials. A survey in 2002 assessed adoption of the technology by farmers. While yield benefits from using the insecticide were nearly always positive and statistically significant relative to an untreated control, they were not as good as commercial insecticides. However, adoption of the tobacco insecticide by local farmers was poor. The paper discusses the reasons for poor adoption, including relative benefits in gross margin, and uses the TIP example to explore the differing power relationships that exist between donors, their field partners and farmers. (C) 2004 by The Haworth Press, Inc. All rights reserved.

Model catalyst studies of the strong metal-support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110)

Model catalysts of Pd nanoparticles and films on TiO2 (I 10) were fabricated by metal vapour deposition (MVD). Molecular beam measurements show that the particles are active for CO adsorption, with a global sticking probability of 0.25, but that they are deactivated by annealing above 600 K, an effect indicative of SMSI. The Pd nanoparticles are single crystals oriented with their (I 11) plane parallel to the surface plane of the titania. Analysis of the surface by atomic resolution STM shows that new structures have formed at the surface of the Pd nanoparticles and films after annealing above 800 K. There are only two structures, a zigzag arrangement and a much more complex "pinwheel" structure. The former has a unit cell containing 7 atoms, and the latter is a bigger unit cell containing 25 atoms. These new structures are due to an overlayer of titania that has appeared on the surface of the Pd nanoparticles after annealing, and it is proposed that the surface layer that causes the SMSI effect is a mixed alloy of Pd and Ti, with only two discrete ratios of atoms: Pd/Ti of 1: 1 (pinwheel) and 1:2 (zigzag). We propose that it is these structures that cause the SMSI effect. (c) 2005 Elsevier Inc. All rights reserved.

Marketing organic products: Exploring some of the pervasive issues

This article explores the marketing of organic products. It identifies the issues that pervade the national, organisational, and individual differences within the global organic industry. These are discussed using the marketing mix framework of product, price, promotion, and place of distribution. It concludes that a large percentage of customers, who are spread throughout the community, purchase organic products, most of whom only purchase it occasionally. The most important attributes of organic products are health, quality, and environment. Promotion of these benefits has the potential to demonstrate that, even at the higher price, they still offer value for money.

Identifying and understanding factors influencing the uptake of new technologies on dairy farms in SW England using the theory of reasoned action

Whilst much is known of new technology adopters, little research has addressed the role of their attitudes in adoption decisions; particularly, for technologies with evident economic potential that have not been taken up by farmers. This paper presents recent research that has used a new approach which examines the role that adopters' attitudes play in identifying the drivers of and barriers to adoption. The study was concerned with technologies for livestock farming systems in SW England, specifically oestrus detection, nitrogen supply management, and, inclusion of white clover. The adoption behaviour is analysed using the social-psychology theory of reasoned action to identify factors that affect the adoption of technologies, which are confirmed using principal components analysis. The results presented here relate to the specific adoption behaviour regarding the Milk Development Council's recommended observation times for heat detection. The factors that affect the adoption of this technology are: cost effectiveness, improved detection and conception rates as the main drivers, whilst the threat to demean the personal knowledge and skills of a farmer in 'knowing' their cows is a barrier. This research shows clearly that promotion of a technology and transfer of knowledge for a farming system need to take account of the beliefs and attitudes of potential adopters. (C) 2006 Elsevier Ltd. All rights reserved.

Food consumption impacts of adherence to dietary norms in the United States: a quantitative assessment

Promotion of adherence to healthy-eating norms has become an important element of nutrition policy in the United States and other developed countries. We assess the potential consumption impacts of adherence to a set of recommended dietary norms in the United States using a mathematical programming approach. We find that adherence to recommended dietary norms would involve significant changes in diets, with large reductions in the consumption of fats and oils along with large increases in the consumption of fruits, vegetables, and cereals. Compliance with norms recommended by the World Health Organization for energy derived from sugar would involve sharp reductions in sugar intakes. We also analyze how dietary adjustments required vary across demographic groups. Most socio-demographic characteristics appear to have relatively little influence on the pattern of adjustment required to comply with norms, Income levels have little effect on required dietary adjustments. Education is the only characteristic to have a significant influence on the magnitude of adjustments required. The least educated rather than the poorest have to bear the highest burden of adjustment. Out- analysis suggests that fiscal measures like nutrient-based taxes may not be as regressive as commonly believed. Dissemination of healthy-eating norms to the less educated will be a key challenge for nutrition policy.

Food consumption impacts of adherence to dietary norms in the United States: a quantitative assessment

Promotion of adherence to healthy-eating norms has become an important element of nutrition policy in the United States and other developed countries. We assess the potential consumption impacts of adherence to a set of recommended dietary norms in the United States using a mathematical programming approach. We find that adherence to recommended dietary norms would involve significant changes in diets, with large reductions in the consumption of fats and oils along with large increases in the consumption of fruits, vegetables, and cereals. Compliance with norms recommended by the World Health Organization for energy derived from sugar would involve sharp reductions in sugar intakes. We also analyze how dietary adjustments required vary across demographic groups. Most socio-demographic characteristics appear to have relatively little influence on the pattern of adjustment required to comply with norms, Income levels have little effect on required dietary adjustments. Education is the only characteristic to have a significant influence on the magnitude of adjustments required. The least educated rather than the poorest have to bear the highest burden of adjustment. Out- analysis suggests that fiscal measures like nutrient-based taxes may not be as regressive as commonly believed. Dissemination of healthy-eating norms to the less educated will be a key challenge for nutrition policy.

Water deficits promote flowering in Rhododendron via regulation of pre and post initiation development

Flowering is generally considered to be advanced by water deficits in many woody perennial species. A long-standing paradigm being that as a plant senses severe environmental conditions resources are diverted away from vegetative growth and towards reproduction before death. It is demonstrated that in Rhododendron flowering is promoted under water deficit treatments. However, the promotion of flowering is not achieved via all increase in floral initiation, but through separate developmental responses. If regulated deficit irrigation (RDI) is imposed prior to the time of initiation, fewer vegetative nodes are formed before the apical meristems switch to floral initiation, and chronologically, floral initiation occurs earlier. Both RDI and partial rootzone drying (PRD) treatments stimulate the development of more flowers Oil each inflorescence if the treatments are continued after the plant has undergone floral initiation. However, floral initiation is inhibited by soil water deficits. If the soil water deficit continues beyond the stages of floral development then anthesis call occur prematurely oil the fully formed floral buds without a need for a winter chilling treatment. It is hypothesised that inhibition of floral initiation in plants experiencing severe soil water deficits results from the inhibitory action Of ABA transportation to the apical meristem from stressed roots. It is demonstrated that ABA applications to well-watered Rhododendron inhibit floral initiation. (c) 2008 Elsevier B.V. All rights reserved.