Half-sandwich Complexes of Ruthenium; Synthesis and Application to Catalysis

This thesis describes syntheses and catalytic reactivity of several half-sandwich complexes of ruthenium. The neutral ruthenium trihydride complex, Cp(PPri3)RuH3(1), can efficiently catalyse the H/D exchange reaction between various organic substrates and deuterium sources, such as benzene-d6. Moreover, the H/D exchange reactions of polar substrates were also observed in D2O, which is the most attractive deuterium source due to its low cost and low toxicity. Importantly, the H/D exchange under catalytic conditions was achieved not only in aromatic compounds but also in substituted liphatic compounds. Interestingly, in the case of alkanes and alkyl chains, highly selective deuterium incorporation in the terminal methyl positions was observed. It was discovered that the methylene units are engaged in exchange only if the molecule contains a donating functional group, such as O-and N-donors, C=C double bonds, arenes and CH3. The cationic half-sandwich ruthenium complex [Cp(PPri3)Ru(CH3CN)2]+(2) catalyses the chemoselective mono-addition of HSiMe2Ph to pyridine derivatives to selectively give the 1,4-regiospecific, N-silylated products. An ionic hydrosilylation mechanismis suggested based on the experiments. To support this mechanistic proposal, kinetic studies under catalytic conditions were performed. Also, the 1,4-regioselective mono-hydrosilylation of nitrogen containing compounds such as phenanthroline, quinoline and acridine can be achieved with the related Cp*complex [Cp*(phen)Ru(CH3CN)]+(3) (phen = 1,10-phenanthroline) and HSiMe2Ph under mild conditions. The cationic ruthenium complex 2 can also be used as an efficient catalyst for transfer hydrogenation of various organic substrates including carbonyls, imines, nitriles and esters. Secondary alcohols, amines, N-isopropylidene amines and ether compounds can be obtained in moderate to high yields. In addition, other ruthenium complexes, 1,3 and [Cp*(PPri3)Ru(CH3CN)2]+(4), can catalyse transfer hydrogenation of carbonyls although the reactions were sluggish compared to the ones of 2. The possible intermediate, Cp(PPri3)Ru(CH3CN)(H), was characterized by NMR at low temperature and the kinetic studies for the transfer hydrogenation of acetophenone were performed. Recently, chemoselective reduction of acid chlorides to aldehydes catalysed by the complex 2 was reported. To extend the catalytic reactivity of 2, reduction of iminoyl chlorides, which can be readily obtained from secondary amides, to the corresponding imines and aldehydes was investigated. Various substituted iminoyl chlorides were converted into the imines and aldehydes under mild conditions and several products were isolated with moderate yields.

Direct functionalization of heterocyclic and non-heterocyclic arenes

L’application des métaux de transition à la fonctionnalisation directe a ouvert la voie à une nouvelle classe de réactions pour la formation de liens carbone-carbone. De par l'omniprésence des liaisons C–H, l’introduction de nouvelles fonctionnalités chimiques par voie directe et pré-activation minimale s’impose comme une stratégie de synthèse très attrayante. Ainsi, il est envisageable de préparer de manière rapide et efficace des supports complexes menant à des molécules complexes, qui pourraient être utiles dans divers domaines de la chimie. L'objectif principal de la présente thèse vise la fonctionnalisation directe des arènes hétérocycliques et non hétérocycliques et, plus précisément, les techniques d’arylation. Dans un premier temps, nous allons aborder le thème de l’arylation directe tout en mettant l’accent sur les pyridines (Chapitre 1). Ces molécules sont à la base d'une multitude de composés biologiquement actifs et jouent un rôle important dans le domaine des sciences des matériaux, de l’agrochimie et de la synthèse des produits naturels. Dans un deuxième temps, nous discuterons de nos travaux sur l’arylation directe catalysé par un complex de palladium sur des ylures de N-iminopyridinium en soulignant la dérivatisation du sel de pyridinium après une phénylation sp2 (Chapitre 2). L’étude de ce procédé nous a permis de mettre en lumière plusieurs découvertes importantes, que nous expliquerons en détails une à une : l’arylation benzylique directe lorsque des ylures N-iminopyridinium substituées avec un groupement alkyl à la position 2 sont utilisés comme partenaires dans la réaction; les allylations Tsuji-Trost catalysée par un complex de palladium; et l’alkylation directe et sans métal via une catalyse par transfert de phase. Plusieurs défis restent à relever pour le développement de procédés directs utilisant des métaux de transition peu coûteux, d’autant plus que la synthèse par transformation directe des pyridines 2-alcényles, lesquelles sont pertinentes sur le plan pharmacologique, n’a pas encore été rapportée à ce jour. Avec cette problématique en tête, nous avons réussi à mettre au point une alcénylation directe catalysé par un complex de cuivre sur des ylures de N-iminopyridinium. Nous discuterons également d’une nouvelle méthode pour la préparation des iodures de vinyle utilisés dans les couplages. Ces réactions sont non seulement remarquablement chimiosélectives, mais sont aussi applicables à plusieurs substrats (Chapitre 3). En optimisant ce procédé direct, nous avons découvert une façon unique de synthétiser les pyrazolo[1,5-a]pyridines 2-substituées (Chapitre 4). Le mécanisme global met en jeu une séquence tandem de fonctionnalisation-cyclisation directe et un procédé direct en cascade, qui n’avais jamais été rapporté. Cela simplifie ansi la synthèse autrement compliquée de ces substrats en y apportant une solution à un problème de longue date. Dans les deux derniers chapitres, nous examinerons en détail les techniques d’arylation directe qui n'impliquent pas les partenaires de couplage hétérocycliques. Entre autres, au Chapitre 5, nous soulignerons notre découverte d’un umpolung dirigé et catalysé par un complexe de palladium du benzène et de quelques autres dérivés arènes. Il s’agit là du premier cas de fonctionnalisation directe dans laquelle le groupe directeur se trouve sur le partenaire halogène et il s’ajoute à la courte liste d’exemples connus dans la littérature rapportant une arylation directe du benzène. Finalement, au Chapitre 6, nous passerons en revue une nouvelle arylation directe catalysée au fer, qui se veut un procédé peu coûteux, durable et présentant une économie d’atomes. Nous discutons des substrats possibles ainsi des études mécanistiques réalisés.

Building Blocks : Children's Literature and the Formation of a Nation, 1750-1825

«Building Blocks: Children’s Literature and the Formation of a Nation, 1750-1825» examine la façon dont la littérature pour enfants imprègne les jeunes lecteurs avec un sens de nationalisme et d'identité nationale à travers la compréhension des espaces et des relations spatiales. La thèse étudie les œuvres d’enfants par Thomas Day, Sarah Fielding, Mary Wollstonecraft, Richard Lovell et Maria Edgeworth, Charles et Mary Lamb, Sarah Trimmer, Lucy Peacock, Priscilla Wakefield, John Aikin, et Anna Laetitia Barbauld. Les différents sujets thématiques reflètent la façon dont les frontières entre les dimensions extérieures et intérieures, entre le monde physique et le domaine psychologique, sont floues. En s'appuyant sur les travaux de penseurs éducatifs, John Locke et Jean-Jacques Rousseau, les écritures pour les enfants soulignent l'importance des expériences sensorielles qui informent l’évolution interne des individus. En retour, la projection de l'imagination et l'investissement des sentiments aident à former la manière dont les gens interagissent avec le monde matériel et les uns envers les autres afin de former une nation. En utilisant une approche Foucaldienne, cette thèse montre comment la discipline est inculquée chez les enfants et les transforme en sujets réglementés. Grâce à des confessions et des discours, les enfants souscrivent à la notion de surveillance et de transparence tandis que l'appréciation de l'opinion publique encourage la pratique de la maîtrise de soi. Les enfants deviennent non seulement des ébauches, sensibles à des impressions, mais des corps d'écriture lisibles. Les valeurs et les normes de la société sont internalisées pendant que les enfants deviennent une partie intégrale du système qu'ils adoptent. L'importance de la visibilité est également soulignée dans la popularité du système de Linné qui met l'accent sur l'observation et la catégorisation. L'histoire naturelle dans la littérature enfantine renforce la structure hiérarchique de la société, ce qui souligne la nécessité de respecter les limites de classes et de jouer des rôles individuels pour le bien-être de la collectivité. Les connotations religieuses dans l'histoire naturelle peuvent sembler justifier l'inégalité des classes, mais elles diffusent aussi des messages de charité, de bienveillance et d'empathie, offrant une alternative ou une forme d’identité nationale «féminine» qui est en contraste avec le militarisme et le nationalisme patricien. La seconde moitié de la thèse examine comment la théorie des « communautés imaginées » de Benedict Anderson devient une possibilité à travers le développement du goût national et une compréhension de l'interconnexion entre les individus. Le personnage du barde pointe à la centralité de l'esprit communautaire dans l'identité nationale. Parallèlement à la commercialisation croissante de produits culturels et nationaux durant cette période, on retrouve l’augmentation de l’attachement affectif envers les objets et la nécessité de découvrir l'authentique dans la pratique de la réflexion critique. La propriété est redéfinie à travers la question des «vrais» droits de propriété et devient partagée dans l'imaginaire commun. Des cartes disséquées enseignent aux enfants comment visualiser des espaces et des frontières et conceptualisent la place de l’individu dans la société. Les enfants apprennent que des actions disparates effectuées dans la sphère domestique ont des répercussions plus importantes dans le domaine public de la nation.

Production and immunogenicity of selected proteins of Salmonella Enteritidis

Au cours des dernières années, Salmonella Enteritidis est devenus les sérotypes les plus souvent isolés chez les patients canadiens, les cas étant liés à la consommation de viande de poulet et d’œufs crus. Les vaccins tués commercialement disponibles pour la volaille, stimulent mal l'immunité mucosale, tandis que l'utilisation de vaccins vivants reste controversée. Par conséquent, un vaccin sous-unitaire par voie orale peut être une solution. Cinq protéines bactériennes ont été choisies comme candidates potentielles et identifiées, soit Glyceraldehyde-3-phosphate dehydrogenase, Enolase, Lipoamide dehydrogenase, DNA protection during starvation protein et Elongation factor-Tu. Notre objectif a été de produire et de purifier ces protéines et de démontrer leur immunogénicité. Les gènes des protéines ont été amplifiés et clonés dans le vecteur pQE-30 pour expression dans Escherichia coli M15. La purification a été effectuée par FPLC. Des poules pondeuses SPF ont été séparées en 6 groupes et injectées par voie intramusculaire à different âges avec une des 5 protéines, ou le PBS chez le groupe témoin. Les œufs ont été ramassés pendant l'expérience et du sang a été prélevé à 36 semaines d'âge. Les anticorps IgY ont été extraits à partir du jaune d'oeuf et du sérum, et les IgA à partir du blanc d'oeuf. Des immunodots, westernblots et ELISA ont évalué l'immunogénicité des protéines et les niveaux d'anticorps induits . Nous avons constaté que ces cinq protéines pourraient stimuler la production d'anticorps spécifiques in vivo. GAPDH, Enolase et DPS ont induit des titres d'anticorps plus élevés que LpdA et EF-Tu.

Physicochemical and Biochemical Characterization of Enzymes Immobilized on lnorganic Matrices

Biotechnology is currently considered as a useful altemative to conventional process technology in industrial and catalytic fields. The increasing awareness of the need to create green and sustainable production processes in all fields of chemistry has stimulated materials scientists to search for innovative catalysts supports. lmmobilization of enzymes in inorganic matrices is very useful in practical applications due to the preserved stability and catalytic activity of the immobilized enzymes under extreme conditions. Nanostructured inorganic, organic or hybrid organic-inorganic nanocomposites present paramount advantages to facilitate integration and miniaturization of the devices (nanotechnologies), thus affording a direct connection between the inorganic, organic and biological worlds. These properties, combined with good chemical stability, make them competent candidates for designed biocatalysts, protein-separation devices, drug delivery systems, and biosensors Aluininosilicate clays and layered double hydroxides, displaying, respectively, cation and anion exchange properties, were found to be attractive materials for immobilization because of their hydrophilic, swelling and porosity properties, as well as their mechanical and thermal stability.The aim of this study is the replacement of inorganic catalysts by immobilized lipases to obtain purer and healthier products.Mesocellular silica foams were synthesized by oil-in-water microemulsion templating route and were functionalized with silane and glutaraldehyde. " The experimental results from IR spectroscopy and elemental analysis demonstrated the presence of immobilized lipase and also functionalisation with silane and glutaraldehyde on the supports.The present work is a comprehensive study on enzymatic synthesis of butyl isobutyrate through esterification reaction using lipase immobilized onto mesocellular siliceous foams and montmorillonite K-10 via adsorption and covalent binding. Moreover, the irnrnobil-ization does not modify the nature of the kinetic mechanism proposed which is of the Bi-Bi Ping—Pong type with inhibition by n-butanol. The immobilized biocatalyst can be commercially exploited for the synthesis of other short chain flavor esters. Mesocellular silica foams (MCF) were synthesized by microemusion templating method via two different routes (hydrothermal and room temperature). and were functionalized with silane and glutaraldehyde. Candida rugosa lipase was adsorbed onto MCF silica and clay using heptane as the coupling medium for reactions in non-aqueous media. I From XRD results, a slight broadening and lowering of d spacing values after immobilization and modification was observed in the case of MCF 160 and MCF35 but there was no change in the d-spacing in the case of K-10 which showed that the enzymes are adsorbed only on the external surface. This was further confirmed from the nitrogen adsorption measurements

Price, profitability and employment in the handloom industry in kerala

The present study is on the nature, problems and prospects of the handloom industry in Kerala. The problems of the industry are mostly in the nature of low earnings of the workers, underutilisation of the existing capacity and low profit in its various sectors. The majority of the handloom co-operative societies are either dormant or facing liquidation. The income and employment of weavers are so pitiably low that they are living in utter poverty and starvation. Frequent price fluctuations of yarns, dyes and chemicals increase the cost of production and reduce the profitability. Consequently handloom fabrics are not able to compete with mill cloths and powerloom products. Accumulating the unsold stocks in the godowns of co-operative societies and with master weavers has become the practice of the day. Spinning mills in Kerala are producing only lower counts of yarns. S, handloom industry has to depend on textile mills in Tamil Nadu for higher counts of yarn. They create artificial scarcity and increase the prices exflorbitantly. Wage rates prevailing in Kerala are higher than those in Tamil Hadu. So rich master weavers are migrating to Tamil.Nadu and exporting the fabrics. under the label 'Kera1a Handlooms'. Governmental efforts to tackle the crisis by way of rebates and subsidies are found to be futile.

Management approaches in organic potato and tomato production

The presented thesis considered three different system approach topics to ensure yield and plant health in organically grown potatoes and tomatoes. The first topic describes interactions between late blight (Phytophthora infestans) incidence and soil nitrogen supply on yield in organic potato farming focussing in detail on the yield loss relationship of late blight based on results of several field trials. The interactive effects of soil N-supply, climatic conditions and late blight on the yield were studied in the presence and absence of copper fungicides from 2002-2004 for the potato cultivar Nicola. Under conditions of central Germany the use of copper significantly reduced late blight in almost all cases (15-30 %). However, the reductions in disease through copper application did not result in statistically significant yield increases (+0 – +10 %). Subsequently, only 30 % of the variation in yield could be attributed to disease reductions. A multiple regression model (R²Max), however, including disease reduction, growth duration and temperature sum from planting until 60 % disease severity was reached and soil mineral N contents 10 days after emergence could explain 75 % of the observed variations in yield. The second topic describes the effect of some selected organic fertilisers and biostimulant products on nitrogen-mineralization and efficiency, yield and diseases in organic potato and tomato trials. The organic fertilisers Biofeed Basis (BFB, plant derived, AgroBioProducts, Wageningen, Netherlands) and BioIlsa 12,5 Export (physically hydrolysed leather shavings, hair and skin of animals; ILSA, Arizignano, Italy) and two biostimulant products BioFeed Quality (BFQ, multi-compound seaweed extract, AgroBioProducts) and AUSMA (aqueous pine and spruce needle extract, A/S BIOLAT, Latvia), were tested. Both fertilisers supplied considerable amounts of nitrogen during the main uptake phases of the crops and reached yields as high or higher as compared to the control with horn meal fertilisation. The N-efficiency of the tested fertilisers in potatoes ranged from 90 to 159 kg yield*kg-1 N – input. Most effective with tomatoes were the combined treatments of fertiliser BFB and the biostimulants AUSMA and BFQ. Both biostimulants significantly increased the share of healthy fruit and/or the number of fruits. BFQ significantly increased potato yields (+6 %) in one out of two years and reduced R. solani-infestation in the potatoes. This suggests that the biostimulants had effects on plant metabolism and resistance properties. However, no effects of biostimulants on potato late blight could be observed in the fields. The third topic focused on the effect of suppressive composts and seed tuber health on the saprophytic pathogen Rhizoctonia solani in organic potato systems. In the present study 5t ha-1 DM of a yard and bio-waste (60/40) compost produced in a 5 month composting process and a 15 month old 100 % yard waste compost were used to assess the effects on potato infection with R. solani when applying composts within the limits allowed. Across the differences in initial seed tuber infestation and 12 cultivars 5t DM ha-1 of high quality composts, applied in the seed tuber area, reduced the infestation of harvested potatoes with black scurf, tuber malformations and dry core tubers by 20 to 84 %, 20 to 49 % and 38 to 54 %, respectively, while marketable yields were increased by 5 to 25 % due to lower rates of wastes after sorting (marketable yield is gross yield minus malformed tubers, tubers with dry core, tubers with black scurf > 15% infested skin). The rate of initial black scurf infection of the seed tubers also affected tuber number, health and quality significantly. Compared to healthy seed tubers initial black scurf sclerotia infestation of 2-5 and >10 % of tuber surface led in untreated plots to a decrease in marketable yields by 14-19 and 44-66 %, a increase of black scurf severity by 8-40 and 34-86 % and also increased the amount of malformed and dry core tubers by 32-57 and 109-214 %.

Attitudes and behaviour towards food attributes and organic food – a triangular methodological investigation of occasional organic consumers

Organic food is increasingly available in the conventional food retail, where organic products are offered alongside with various other types of products and compete mainly with conventional and the so-called conventional-plus products. The latter are conventional products displaying particular quality attributes on the product packaging, such as ‘no artificial additives’, or ‘from animal welfare husbandry’. Often, these quality attributes also apply to organic products. Occasional organic consumers might prefer such conventional-plus alternatives that are perceived to be ‘between’ organic and conventional products. The overall objective of this PhD thesis was to provide information about the segment of occasional organic consumers. In particular, the thesis focussed on consumer perceptions and attitudes towards the quality of, and preferences for, organic, conventional and conventional-plus products in two countries: Germany and Switzerland. To achieve these objectives, qualitative and quantitative consumer research was combined in order to explore occasional organic consumers’ perceptions and attitudes as well as to observe their preferences and buying behaviour regarding different types of food products: organic, conventional and conventional-plus products. The qualitative research showed that, depending on single criteria, organic production was both positively as well as negatively assessed by consumers. Consumer perception of organic food was found to be highly selective and primarily focussed on the final stage of the particular production process. A major problem is that consumers are still mostly unfamiliar with factors associated with organic production, have a lack of confidence, and often confuse organic with conventional products. Besides this, consumer expectations of organic products are different from the expectations of conventional products. The quantitative research revealed that attitudes strongly determine consumers’ preferences for organic, conventional and conventional-plus products. Consumer attitudes tended to differ more between organic and conventional choices rather than conventional-plus and conventional choices. Furthermore, occasional organic consumers are heterogeneous in their preferences. They can be grouped into two segments: the consumers in one segment were less price sensitive and preferred organic products. The consumers in the other segment were more price sensitive and rather preferred conventional-plus or conventional products. To conclude, given the selective and subjective nature of consumer perception and the strong focus of consumer perception on the final stage of the food production process, specific additional values of organic farming should be communicated in clear and catchy messages. At the same time, these messages should be particularly focussed on the final stage of organic food production. The communication of specific added values in relation with organic products to improve the perceived price-performance-ratio is important since conventional-plus products represent an interesting alternative particularly for price sensitive occasional organic consumers. Besides this, it is important to strengthen affirmative consumer attitudes towards organic production. Therefore, policy support should emphasise on long-term communication campaigns and education programmes to increase the consumer awareness and knowledge of organic food and farming. Since consumers expect that organic food is regionally or at least domestically produced while they less accept organic imports, policy support of domestic and regional producers is a crucial measure to fill the current gap between the increasing consumer demand of organic food and the stagnation of the domestic and regional organic food supply.

Determinants of crop diversity and composition in Enset-coffee agroforestry homegardens of Southern Ethiopia

Households in much of the tropics depend for their livelihoods on the variety and continued production of food and other products that are provided by their own farms. In such systems, maintenance of agrobiodiversity and ensuring food security are important for the well being of the population. The enset-coffee agroforestry homegardens of Southern Ethiopia that are dominated by two native perennial crops, Coffee (Coffea arabica L.) and Enset (Enset ventricosum Welw. Cheesman), are examples of such agricultural systems. This study was conducted in Sidama administrative zone of Southern Ethiopia to determine the factors that influence the diversity and composition of crops in the systems. Data were collected from 144 sample homegardens selected from four districts. Stepwise multiple regression analysis was used to relate indices of crop diversity and area share of major crops with the physical and socioeconomic factors. The study revealed that socioeconomic factors, mainly proximity to markets, affected negatively crop species richness. The production area of the main crops enset and coffee decreased with increasing proximity to market and road while that of maize and khat increased. At household level, farm size had a significant effect on area share of enset and coffee. As farm size increased the share of the cash crop, coffee increased but that of the staple, enset declined. Enset, which is the backbone of the system in terms of food security, is declining on small farms and the share of monoculture maize system is increasing. The trend towards declining agrobiodiversity, and reduction in the production area of the main perennial crops and their gradual replacement with monoculture fields could make the systems liable to instability and collapse. As these sites are high potential agricultural areas, intensification can be achieved by integrating high-value and more productive crops, such as fruits, spices and vegetables, while maintaining the integrated and complex nature of the systems.

It will be succesful to have a commercial relation between France and Colombia focus on the milk sector ?

Globalization has led to a drastic change on the international trade, this has caused that many countries such as France and Colombia find new business partners. This is the raison because I develop the investigation about How these countries can be integrated commercially in the dairy sector? Colombia and France had active trade relations for more than 8 years, but this has been declining for several factors. In the case of France, it has found that Germany is an excellent producer of raw milk, which can supply domestic demand and can export large quantities with a low price to European countries because of its proximity. For this reason, Colombia is a country that can not compete with Germany directly in raw milk, but I concluded that Colombia could become a major competitor with organic milk. This is the result of a research of the way they raise and feed the cows in the two countries, Colombia is generally on open country and Germany is on cow housing. In Colombia, the country found that Venezuela could offer many benefits in the processing of raw milk, and other processes that require high technology. But today Colombia has had several disputes with Venezuela and many Colombian companies are affected in this sector. Additionally, France is one of the largest producers and distributors of processed milk and its derivatives; it launches annually many manufactured products with high technology. At this point, Colombia can take out the best advantage because it can create an strategic alliance with French companies to bring most innovative and processed products such as cheese and yoghurts. The theoretical framework of this thesis consists on the analysis of competitiveness, because it is relevant to see if these two countries are competitive or if one has the comparative advantage over the other. The related authors are: Michael Porter, Adam Smith and David Ricardo. To complete the theoretical part, we found that France has a comparative advantage over Colombia in this sector thanks to its high technology, and Colombia is not currently competitive in the area of raw milk because the milk price is higher and the distance is a barrier, and it has no technology. But this research indicates that Colombia could become a competitive country selling organic milk.

A comparative study of two Casas de la Cultura in Bogota: Tunjuelito and Usaquen

Es un estudio descriptivo/exploratorio de dos Casas de la Cultura en Bogotá (Tunjuelito/Usaquén), basado en la revisión de documentos y recolección de datos a través de herramientas cualitativas, con aspectos cuantitativos en la presentación de datos por medio de cuadros de comparación. Presenta resultados de las siguientes categorías: grupos de interés, aspectos administrativos y productos.

Development of molecular-based techniques for the detection, identification and quantification of food-borne pathogens

La presencia de microorganismos patógenos en alimentos es uno de los problemas esenciales en salud pública, y las enfermedades producidas por los mismos es una de las causas más importantes de enfermedad. Por tanto, la aplicación de controles microbiológicos dentro de los programas de aseguramiento de la calidad es una premisa para minimizar el riesgo de infección de los consumidores. Los métodos microbiológicos clásicos requieren, en general, el uso de pre-enriquecimientos no-selectivos, enriquecimientos selectivos, aislamiento en medios selectivos y la confirmación posterior usando pruebas basadas en la morfología, bioquímica y serología propias de cada uno de los microorganismos objeto de estudio. Por lo tanto, estos métodos son laboriosos, requieren un largo proceso para obtener resultados definitivos y, además, no siempre pueden realizarse. Para solucionar estos inconvenientes se han desarrollado diversas metodologías alternativas para la detección identificación y cuantificación de microorganismos patógenos de origen alimentario, entre las que destacan los métodos inmunológicos y moleculares. En esta última categoría, la técnica basada en la reacción en cadena de la polimerasa (PCR) se ha convertido en la técnica diagnóstica más popular en microbiología, y recientemente, la introducción de una mejora de ésta, la PCR a tiempo real, ha producido una segunda revolución en la metodología diagnóstica molecular, como pude observarse por el número creciente de publicaciones científicas y la aparición continua de nuevos kits comerciales. La PCR a tiempo real es una técnica altamente sensible -detección de hasta una molécula- que permite la cuantificación exacta de secuencias de ADN específicas de microorganismos patógenos de origen alimentario. Además, otras ventajas que favorecen su implantación potencial en laboratorios de análisis de alimentos son su rapidez, sencillez y el formato en tubo cerrado que puede evitar contaminaciones post-PCR y favorece la automatización y un alto rendimiento. En este trabajo se han desarrollado técnicas moleculares (PCR y NASBA) sensibles y fiables para la detección, identificación y cuantificación de bacterias patogénicas de origen alimentario (Listeria spp., Mycobacterium avium subsp. paratuberculosis y Salmonella spp.). En concreto, se han diseñado y optimizado métodos basados en la técnica de PCR a tiempo real para cada uno de estos agentes: L. monocytogenes, L. innocua, Listeria spp. M. avium subsp. paratuberculosis, y también se ha optimizado y evaluado en diferentes centros un método previamente desarrollado para Salmonella spp. Además, se ha diseñado y optimizado un método basado en la técnica NASBA para la detección específica de M. avium subsp. paratuberculosis. También se evaluó la aplicación potencial de la técnica NASBA para la detección específica de formas viables de este microorganismo. Todos los métodos presentaron una especificidad del 100 % con una sensibilidad adecuada para su aplicación potencial a muestras reales de alimentos. Además, se han desarrollado y evaluado procedimientos de preparación de las muestras en productos cárnicos, productos pesqueros, leche y agua. De esta manera se han desarrollado métodos basados en la PCR a tiempo real totalmente específicos y altamente sensibles para la determinación cuantitativa de L. monocytogenes en productos cárnicos y en salmón y productos derivados como el salmón ahumado y de M. avium subsp. paratuberculosis en muestras de agua y leche. Además este último método ha sido también aplicado para evaluar la presencia de este microorganismo en el intestino de pacientes con la enfermedad de Crohn's, a partir de biopsias obtenidas de colonoscopia de voluntarios afectados. En conclusión, este estudio presenta ensayos moleculares selectivos y sensibles para la detección de patógenos en alimentos (Listeria spp., Mycobacterium avium subsp. paratuberculosis) y para una rápida e inambigua identificación de Salmonella spp. La exactitud relativa de los ensayos ha sido excelente, si se comparan con los métodos microbiológicos de referencia y pueden serusados para la cuantificación de tanto ADN genómico como de suspensiones celulares. Por otro lado, la combinación con tratamientos de preamplificación ha resultado ser de gran eficiencia para el análisis de las bacterias objeto de estudio. Por tanto, pueden constituir una estrategia útil para la detección rápida y sensible de patógenos en alimentos y deberían ser una herramienta adicional al rango de herramientas diagnósticas disponibles para el estudio de patógenos de origen alimentario.

Water vapor variability in the tropics and its links to dynamics and precipitation

The distribution and variability of water vapor and its links with radiative cooling and latent heating via precipitation are crucial to understanding feedbacks and processes operating within the climate system. Column-integrated water vapor (CWV) and additional variables from the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year reanalysis (ERA40) are utilized to quantify the spatial and temporal variability in tropical water vapor over the period 1979–2001. The moisture variability is partitioned between dynamical and thermodynamic influences and compared with variations in precipitation provided by the Climate Prediction Center Merged Analysis of Precipitation (CMAP) and the Global Precipitation Climatology Project (GPCP). The spatial distribution of CWV is strongly determined by thermodynamic constraints. Spatial variability in CWV is dominated by changes in the large-scale dynamics, in particular associated with the El Niño–Southern Oscillation (ENSO). Trends in CWV are also dominated by dynamics rather than thermodynamics over the period considered. However, increases in CWV associated with changes in temperature are significant over the equatorial east Pacific when analyzing interannual variability and over the north and northwest Pacific when analyzing trends. Significant positive trends in CWV tend to predominate over the oceans while negative trends in CWV are found over equatorial Africa and Brazil. Links between changes in CWV and vertical motion fields are identified over these regions and also the equatorial Atlantic. However, trends in precipitation are generally incoherent and show little association with the CWV trends. This may in part reflect the inadequacies of the precipitation data sets and reanalysis products when analyzing decadal variability. Though the dynamic component of CWV is a major factor in determining precipitation variability in the tropics, in some regions/seasons the thermodynamic component cancels its effect on precipitation variability.

Errors associated with the preparation of aseptic products in UK hospital pharmacies: lessons from the national aseptic error reporting scheme

Background Pharmacy aseptic units prepare and supply injectables to minimise risks. The UK National Aseptic Error Reporting Scheme has been collecting data on pharmacy compounding errors, including near-misses, since 2003. Objectives The cumulative reports from January 2004 to December 2007, inclusive, were analysed. Methods The different variables of product types, error types, staff making and detecting errors, stage errors detected, perceived contributory factors, and potential or actual outcomes were presented by cross-tabulation of data. Results A total of 4691 reports were submitted against an estimated 958 532 items made, returning 0.49% as the overall error rate. Most of the errors were detected before reaching patients, with only 24 detected during or after administration. The highest number of reports related to adult cytotoxic preparations (40%) and the most frequently recorded error was a labelling error (34.2%). Errors were mostly detected at first check in assembly area (46.6%). Individual staff error contributed most (78.1%) to overall errors, while errors with paediatric parenteral nutrition appeared to be blamed on low staff levels more than other products were. The majority of errors (68.6%) had no potential patient outcomes attached, while it appeared that paediatric cytotoxic products and paediatric parenteral nutrition were associated with greater levels of perceived patient harm. Conclusions The majority of reports were related to near-misses, and this study highlights scope for examining current arrangements for checking and releasing products, certainly for paediatric cytotoxic and paediatric parenteral nutrition preparations within aseptic units, but in the context of resource and capacity constraints.

Impact on CVD risk of modifying milk fat to decrease intake of SFA and increase intake of cis-MUFA

Despite the acknowledged benefits of reducing SFA intake few countries within the EU meet recognised targets. Milk and dairy products represent the single largest source of dietary SFA in most countries, yet epidemiological evidence indicates that milk has cardioprotective properties such that simply reducing consumption of dairy foods to meet SFA targets may not be a sound public health approach. The present paper explores the options for replacing some of the SFA in milk fat with cis-MUFA through alteration of the diet of the dairy cow, and the evidence that such changes can improve the indicators for CHD and CVD in general for the consumer. In addition, the outcome of such changes on risk factors for CHD and CVD at the population level is examined in the light of a modelling exercise involving data for eleven EU member states. Given the current and projected costs of health care, the results indicate that urgent consideration should be given to such a strategy.