Acoplamientos catalizados por paladio en cationes heteroaromáticos: síntesis y propiedades ópticas no lineales de cromóforos catiónicos

Texto en español y resumen en inglésThe development of new organic materials with nonlinear optical properties (NLO) was one of the aims of research over the past decades due to their potential use in the field of telecommunications, optical computing and processing and optical data storage, among others. The advantages of organic compounds compared to inorganic crystals are its low cost, ease of processing and high number of structural variability, which makes them very attractive to industry. Most organic compounds with non-linear optical (NLO) properties are based on highly conjugated molecules with donors and acceptors substituted at the two ends of the molecule, called donor-acceptor (?push-pull?) systems, and these are amongst the most interesting structures for new compounds with efficient NLO responses. The PhD project presented in this report is framed in the context of a search for new molecules push-pull type, based on heteroaromatic cations as acceptors of the system (for these systems has been appointed a new name as "NLO-catiophores), and partly in the development of the synthesis of new macrocyclic rigid cationic nature. First we describe the synthesis and study of nonlinear optical properties by Hyper-Rayleigh Scattering (HRS) of new push-pull system based on heteroaromatic cations. They were obtained through the development of the Suzuki, Heck and Sonogashira reactions. We have demonstrated that organotrifluroborates are better efficient partners than boronic acids for the Suzuki coupling reaction with pyridinium and, Moreover, the ease with which these potassium organotrifluoroborates reacted with azinium and quinolizinium salts in water and the coupling products can be isolated is a further advantage of the procedure and provides a new means for accessing to a great variety of substituted cations. It has proved possible to Heck coupling with aryl iodides with the four isomers of vinilquinolizinium. We have achived the synthesis of a series of D-A and D-A-D catio-phores by Sonogashira cross-coupling reaction from aziniun and quinolizinium bromoderivatives. Noting the overall study ONL values of selected molecules can be obtained the following conclusions: a) heteroaromatic cations type azinium and quinolizinium have good NLO properties (βHRS values between 25-500 10-30 esu). In general, for the pyridinium cation, substitution at the C4 produces best response NLO and in case of cation quinolizinium position C2 is best. b) electrodonating substituent favor the charge transfer on the system Donnor-Acceptor. Moreover it was found that the quinolizinium cation is better acceptor increasing the value of hyperpolarizability. On the other hand, in this context of development of new materials, we considered introducing the quinolizinium system on macrocyclic structures shape-persistent type, i.e. a rigid skeleton formed by aryl units linked together by triple bonds, which resulting in large molecular surfaces. These properties make the AEMs (arylene-ethynylene macrocycles), structures of interest in the field of organic materials

Acoplamientos catalizados por paladio en cationes heteroaromáticos: síntesis y propiedades ópticas no lineales de cromóforos catiónicos

Texto en español y resumen en inglésThe development of new organic materials with nonlinear optical properties (NLO) was one of the aims of research over the past decades due to their potential use in the field of telecommunications, optical computing and processing and optical data storage, among others. The advantages of organic compounds compared to inorganic crystals are its low cost, ease of processing and high number of structural variability, which makes them very attractive to industry. Most organic compounds with non-linear optical (NLO) properties are based on highly conjugated molecules with donors and acceptors substituted at the two ends of the molecule, called donor-acceptor (?push-pull?) systems, and these are amongst the most interesting structures for new compounds with efficient NLO responses. The PhD project presented in this report is framed in the context of a search for new molecules push-pull type, based on heteroaromatic cations as acceptors of the system (for these systems has been appointed a new name as "NLO-catiophores), and partly in the development of the synthesis of new macrocyclic rigid cationic nature. First we describe the synthesis and study of nonlinear optical properties by Hyper-Rayleigh Scattering (HRS) of new push-pull system based on heteroaromatic cations. They were obtained through the development of the Suzuki, Heck and Sonogashira reactions. We have demonstrated that organotrifluroborates are better efficient partners than boronic acids for the Suzuki coupling reaction with pyridinium and, Moreover, the ease with which these potassium organotrifluoroborates reacted with azinium and quinolizinium salts in water and the coupling products can be isolated is a further advantage of the procedure and provides a new means for accessing to a great variety of substituted cations. It has proved possible to Heck coupling with aryl iodides with the four isomers of vinilquinolizinium. We have achived the synthesis of a series of D-A and D-A-D catio-phores by Sonogashira cross-coupling reaction from aziniun and quinolizinium bromoderivatives. Noting the overall study ONL values of selected molecules can be obtained the following conclusions: a) heteroaromatic cations type azinium and quinolizinium have good NLO properties (βHRS values between 25-500 10-30 esu). In general, for the pyridinium cation, substitution at the C4 produces best response NLO and in case of cation quinolizinium position C2 is best. b) electrodonating substituent favor the charge transfer on the system Donnor-Acceptor. Moreover it was found that the quinolizinium cation is better acceptor increasing the value of hyperpolarizability. On the other hand, in this context of development of new materials, we considered introducing the quinolizinium system on macrocyclic structures shape-persistent type, i.e. a rigid skeleton formed by aryl units linked together by triple bonds, which resulting in large molecular surfaces. These properties make the AEMs (arylene-ethynylene macrocycles), structures of interest in the field of organic materials

Publicitarte

Conocer la relación entre arte y publicidad, pintura y diseño es el fundamento base del presente proyecto. A través de un breve recorrido histórico se relata las variaciones producidas en la relación entre estas dos disciplinas hermanadas. Con esta serie pictórica basada en el apropiacionismo cultural y la contra publicidad, planteo y cuestiono: el poder de adaptación y transformación de la obra a partir de la unicidad y la reproducción impresa, el espacio expositivo como parte activa, siendo éste de índole pública, la tipografía como forma anclada a un significado textual y el carácter político que cobra hoy día pintar imágenes.Knowing the relationship between art and advertising, painting and design, is the basic foundation of this project. Through a brief historical overlook, this work deals with the variations produced in the relationship between these two twinned disciplines. With this pictorial series based on cultural appropriationism and counter-advertising, I expose and question the power of adaptation and transformation of the artwork from uniqueness and printed reproduction. The gallery space takes an active role of public nature. Typography as a form anchored to a textual meaning and the political character that painting images implies today

Efficient functionalization of quinolizinium cations with organotrifluoroborates in water

An efficient functionalization of the quinolizinium system is reported. The reaction of the four isomeric bromoquinolizinium salts with different organotrifluoroborates afforded alkyl-, vinyl-, aryl-, and heteroaryl quinolizinium derivatives in moderate or good yields. Reactions are carried out in water using a counterion exchange for the isolation of the cationic-coupled compounds.Comunidad de Madri

Bienestar animal de corderos ternascos durante su espera en matadero

El presente trabajo consistió en valorar la respuesta de estrés al que son sometidos los corderos desde que llegan al matadero hasta su sacrificio en distintas épocas del año, primavera y verano. Se tomaron muestras de sangre durante el sacrificio del animal para la valoración de diferentes parámetros sanguíneos de respuesta de estrés y tras el faenado se valoró la calidad de la canal y de la carne de los corderos. Se encontraron diferencias significativas con mayores valores para los corderos sacrificados en verano en el número de linfocitos, lactato deshidrogenasa (LDH), cortisol y pHs y menores en el número de leucocitos, neutrófilos, relación neutrófilos/linfocitos, volumen corpuscular medio, concentración de glucosa y rendimiento de la canal. Los corderos sacrificados en verano tuvieron más comprometido su nivel de bienestar por el mayor nivel de cortisol y LDH junto con unos pHs más elevados, lo que hace que la calidad de la carne sea inferior a los sacrificados en primavera

Efecto de la suplementación con antioxidantes en la dieta de corderos sobre la calidad de su carne enriquecida en ácidos grasos omega-3

Se ha evaluado el efecto antioxidante de la suplementación en la dieta de corderos con vitamina E o con extracto de uva rico en polifenoles en carne enriquecida en ácidos grasos omega-3 mediante la alimentación y conservada durante 0, 6 y 12 días en atmósfera modificada. Se observó una interacción significativa (p<0.001) entre el tipo de suplementación y el tiempo de conservación para los valores de oxidación lipídica y de proporción de metamioglobina, mostrando la carne suplementada con vitamina E los valores más bajos al final de la conservación. Los niveles de ácidos grasos poliinsaturados descendieron durante la conservación en el grupo control y en el grupo suplementado con extracto de uva, permaneciendo más estables en el grupo suplementado con vitamina E. Se observó una interacción significativa (p<0.001) entre la suplementación y el tiempo de conservación para el porcentaje de ácidos grasos omega- 3, manteniéndose los valores estables durante la conservación en la carne suplementada con vitamina E. La suplementación en la dieta con vitamina E mostró un efecto antioxidante en la carne durante su conservación mayor que el resto de dietas estudiadas

Efecto de la adicción de extracto de vino tinto en la conservación de hamburguesas de cordero enriquecidas en ácidos grasos omega-3

Red wine is a great source of polyphenols compounds, which exert a high antioxidant capacity. The effect of red wine extract (EV) on the oxidative stability of lamb patties in terms of metmyoglobin (MetMb) formation, lipid oxidation, protein oxidation, and the stability of docosahexaenoic fatty acid (DHA) was investigated. Ground lamb meat enriched in ω3 fatty acids was divided into four treatments. Three treatments were supplemented with 3 doses of EV being 50 (EV1), 100 (EV2) and 200 (EV3) mg GAE/kg meat and, the last one, without antioxidant supplementation, was kept as control (C). The lamb patties were stored under MAP (70% O2/30% CO2) during 9 days. There was an interaction between treatment (L) and storage period (PC) for MetMb proportion (p<0.001) and DHA content (p<0.01). Groups EV2 and EV3 showed less MetMb proportion and higher DHA content at the end of storage period in comparison to groups EV1 and C. Lipid and protein oxidation was affected by storage period (p<0.001), increasing in all treatments.El vino tinto es una gran fuente de compuestos polifenólicos que presentan una gran capacidad antioxidante. El objetivo de este estudio fue evaluar el efecto de la adición de extracto de vino (EV) en la estabilidad oxidativa de hamburguesas de cordero, estudiando la formación de metamioglobina (MetMb), la oxidación lipídica, la oxidación proteica y el contenido en ácido docosahexaenoico (DHA). Se realizaron 4 lotes de carne picada de cordero, todos enriquecidos en ácidos grasos ω3. A tres lotes se les adicionó EV para obtener una concentración final de 50 (EV1), 100 (EV2) y 200 (EV3) mg GAE/kg de carne y el último lote, sin antioxidantes, se mantuvo como control (C). Las hamburguesas se conservaron en MAP (70% O2/30% CO2) durante 9 días. Se observó una interacción entre el lote (L) y el periodo de conservación (PC) para la proporción de MetMb (p<0,001) y el contenido en DHA (p<0,01). Los lotes EV2 y EV3 presentaron menor proporción de MetMb y mayor contenido en DHA que los lotes EV1 y C. La oxidación lipídica y proteica estuvo afectada por el periodo de conservación (p<0,001) aumentando en todos los tratamientos

The effects of artificial rearing and fostering on the growth, carcass and meat quality of lambs

Lamb rearing is a key point to ensure good quality at the end of the production cycle. Fostering and artificial rearing are techniques commonly used when natural rearing is compromised. However, there is a lack of research investigating their impact on the product´s quality, especially when lambs are slaughtered late, around 6 months of age. The current study investigated the effects of artificially reared and fostered lambs on growth, carcass and meat quality. The three foster methods under study were birth fluids, cervical stimulation combined with birth fluids and restraint. Animals were weaned at 3 months of age, and processed at 6 months of age. Artificially reared lambs presented lower weight gains than ewe reared ones at young ages. They also presented worse conformation scores at the processing plant. No differences could be found for growth rates, carcass or meat quality among the foster methods tested