Análisis de la concentración espacial de la industria: aplicación de nuevos indicadores en el caso de España

Comunicación presentada en la XXXIII Reunión de Estudios Regionales, Competitividad, cohesión y desarrollo regional sostenible, León, 15-16 noviembre 2007.

El sector nororiental de la Cuenca de Antepaís del Guadalquivir (Cordillera Bética, Mioceno Superior): estratigrafía, cronología y evolución sedimentaria

Estudios estratigráficos y sedimentológicos de afloramiento y el análisis paleoecológico y bioestratigráfico mediante foraminíferos, han permitido realizar una reinterpretación sedimentaria de las unidades de margas y areniscas miocenas del sector nororiental de la Cuenca del Guadalquivir. El relleno sedimentario ha sido dividido en cuatro unidades litoestratigráficas (I-IV), todas ellas depositadas durante el Tortoniense, entre 10 y 7.89 Ma, aproximadamente. La Unidad I (Tortoniense antiguo no basal) está fomada por arenas y calizas de algas, y es interpretada como una unidad transgresiva y expansiva sobre el basamento que evoluciona desde ambientes marinos someros a rampa de carbonatos tipo rhodalgal. La Unidad II (Tortoniense inferior, biozona MMi11: entre 10 y 9.54 Ma) está caracterizada por una alternancia rítmica de margas arcillosas y silíceas, depositadas en ambientes pelágicos y profundos de aguas frías-eutróficas, si bien con repetidos cambios en la estratificación y distribución de nutrientes en la columna de agua. Esta unidad registra una importante somerización en su parte superior, dando paso gradual a la Unidad III. La Unidad III (Tortoniense inferior, biozonaMMi11: desde 9.54 Ma) está dominada por areniscas, aunque lateralmente aparecen brechas intraformacionales con estratos contorsionados. Está nutrida por deltas desde la costa y se interpreta como el depósito de bancos arenosos movilizados por la acción de corrientes mareales y el oleaje de tormentas en rampas. La Unidad IV (Tortoniense superior, biozona MMi12: desde 8.35 Ma) está representada por margas pelágicas similares a las de la Unidad II, de la que difiere por la presencia de intercalaciones arenosas genéticamente relacionadas con procesos mareales y de tormentas.

Copper-Free Oxime–Palladacycle-Catalyzed Sonogashira Alkynylation of Deactivated Aryl Bromides and Chlorides in Water under Microwave Irradiation

Palladium-catalyzed Heck alkynylation cross-coupling reactions between terminal alkynes and deactivated aryl chlorides and aryl bromides can be performed in the absence of copper cocatalyst with water as solvent at 130 °C under microwave irradiation. An oxime-derived chloro-bridged palladacycle is an efficient precatalyst for this transformation with 2-dicyclohexylphosphanyl-2′,4′,6′-triisopropylbiphenyl (XPhos) as ancillary ligand, pyrrolidine as base, and SBDS as surfactant. All of the reactions can be performed under air and with reagent-grade chemicals under low loading conditions (0.1–1 mol-% Pd).

Enantioselective Synthesis of Succinimides by Michael Addition of Aldehydes to Maleimides Organocatalyzed by Chiral Primary Amine-Guanidines

The monoguanylation of (1S,2S)- and (1R,2R)-cyclohexane-1,2-diamine affords chiral primary amine-guanidines that are used as chiral organocatalysts in the enantioselective Michael addition of aldehydes, particularly α,α-disubstituted aldehydes, to maleimides. The reaction is carried out in the presence of imidazole, as an additive, in aqueous N,N-dimethylformamide, as the solvent, and affords the corresponding enantioenriched succinimides in high or quantitative yields with enantioselectivities up to 96 % ee. Theoretical calculations (DFT and M06–2X) suggest a different hydrogen-bonding coordination pattern between the maleimide (C=O) and the catalyst (NH groups) is responsible for the enantioinduction switch that is observed when the reaction is carried out using primary amine-guanidines versus primary amine-thioureas as the organocatalysts.

Enantioselective Synthesis of Succinimides by Michael Addition of 1,3-Dicarbonyl Compounds to Maleimides Catalyzed by a Chiral Bis(2-aminobenzimidazole) Organocatalyst

A wide variety of chiral succinimides have been prepared in high yields and enantioselectivities by asymmetric conjugate addition of 1,3-dicarbonyl compounds to maleimides under very mild reaction conditions using a bifunctional benzimidazole-derived organocatalyst. Computational and NMR studies support the hydrogen-bonding activation role of the catalyst and the origin of the stereoselectivity of the process.

NHC-Ligand Effectiveness in the Fluorine-Free Hiyama Reaction of Aryl Halides

1-Benzyl-3-(2-hydroxy-2-phenylethyl)imidazolium chloride (5), which is a precursor of an N-heterocyclic carbene ligand, in combination with palladium acetate, has been employed as an effective catalyst for the fluorine-free Hiyama reaction. A systematic study of the catalytic mixture, by a 32 factorial design, has revealed that both the amount of palladium and the Pd/NHC precursor ratio are important factors for obtaining good yields of the coupling products, indicating an interaction between them. The best catalytic system involves mixing 0.1 mol-% palladium acetate in a 1:5 ratio (Pd/salt 5), which allows the effective coupling of a range of aryl bromides and chlorides with trimethoxy(phenyl)silane. The Hiyama reactions are carried out in NaOH solution (50 % H2O w/w), at 120 °C under microwave irradiation during 60 min.

Intramolecular Bromoamination of Conjugated N-Tosylaminodienes Using N-Bromosuccinimide. Synthesis of Bromoallyl-Substituted N-Heterocycles and Their Applications as Building Blocks

The bromonium-promoted cyclization of conjugated aminodienes is described. The reaction proceeds smoothly in the presence of N-bromosuccinimide as halonium promoter, and using N-tosyl-protected aminodienes as substrates, to give the corresponding halocyclization products in high yields and with high diastereoselectivities. It can be envisaged that the formation of these products is the result of an SN2′-type ring-opening of a terminal bromonium intermediate in a 5-exo-trig or 6-exo-trig cyclization mode. The presence of an allyl bromide moiety in the haloamination products makes these molecules highly attractive from a synthetic point of view, as it opens the way for further transformations. Thus, allylic substitution reactions with different nucleophiles (acetate, azide, cyanide, and malonate), palladium-catalysed Suzuki coupling, and silver-mediated bromine displacement reactions were carried out successfully.

1,2-Functionalized Imidazoles as Palladium Ligands: An Efficient and Robust Catalytic System for the Fluorine-Free Hiyama Reaction

A variety of hydroxy- and amino-functionalized imidazoles were prepared from 1-methyl- and 1-(diethoxymethyl)imidazole by means of isoprene-mediated lithiation followed by reaction with an electrophile. These compounds in combination with palladium acetate were screened as catalyst systems for the Hiyama reaction under fluorine-free conditions using microwave irradiation. The systematic study of the catalytic system showed 1-methyl-2-aminoalkylimidazole derivative L1 to be the best ligand, which was employed under solvent-free conditions with a 1:2 Pd/ligand ratio and TBAB (20 mol-%) as additive. The study has revealed an interaction between the Pd/ligand ratio and the amount of TBAB. The established catalytic system presented a certain degree of robustness, and it has been successfully employed in the coupling of a range of aryl bromides and chlorides with different aryl siloxanes. Furthermore, both reagents were employed in an equimolecular amount, without an excess of organosilane.

Pyrimidine-Derived Prolinamides as Recoverable Bifunctional Organocatalysts for Enantioselective Inter- and Intramolecular Aldol Reactions under Solvent-Free Conditions

Chiral L-prolinamides 2 containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a 2-pyrimidinyl unit are synthesized and used as general organocatalysts for intermolecular and intramolecular aldol reactions with 1,6-hexanedioic acid as a co-catalyst under solvent-free conditions. The intermolecular reaction between ketone–aldehyde and aldehyde–aldehyde must be performed under wet conditions with catalyst (S,S)-2b at 10 °C, which affords anti-aldols with high regio-, diastereo-, and enantioselectivities. For the Hajos–Parrish–Eder–Sauer–Wiechert reaction, both diastereomers of catalyst 2 give similar results at room temperature in the absence of water to give the corresponding Wieland–Miescher ketone and derivatives. Both types of reactions were scaled up to 1 g, and the organocatalysts were recovered by extractive workup and reused without any appreciable loss in activity. DFT calculations support the stereochemical results of the intermolecular process and the bifunctional role played by the organocatalyst by providing a computational comparison of the H-bonding networks occurring with catalysts 2a and 2b.

Synthesis of Chromen[4,3-b]pyrrolidines by Intramolecular 1,3-Dipolar Cycloadditions of Azomethine Ylides: An Experimental and Computational Assessment of the Origin of Stereocontrol

Azomethine ylides, generated from imine-derived O-cinnamyl or O-crotonyl salicylaldeyde and α-amino acids, undergo intramolecular 1,3-dipolar cycloaddition, leading to chromene[4,3-b]pyrrolidines. Two reaction conditions are used: (a) microwave-assisted heating (200 W, 185 °C) of a neat mixture of reagents, and (b) conventional heating (170 °C) in PEG-400 as solvent. In both cases, a mixture of two epimers at the α-position of the nitrogen atom in the pyrrolidine nucleus was formed through the less energetic endo-approach (B/C ring fusion). In many cases, the formation of the stereoisomer bearing a trans-arrangement into the B/C ring fusion was observed in high proportions. Comprehensive computational and kinetic simulation studies are detailed. An analysis of the stability of transient 1,3-dipoles, followed by an assessment of the intramolecular pathways and kinetics are also reported.

Solvent-Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate-Monoprotected 1,2-Diamines

A simple change in the polarity of the solvent allows both enantiomers of substituted succinimides to be obtained in the enantioselective conjugate addition reaction of aldehydes, mainly α,α-disubstituted, to maleimides catalysed by chiral carbamate-monoprotected trans-cyclohexane-1,2-diamines. Using a single enantiomer of the organocatalyst, both enantiomers of the resulting Michael adducts are obtained in high yields by simply changing the reaction solvent from aqueous DMF (up to 84 % ee) to chloroform (up to 86 % ee). Theoretical calculations are used to explain this uncommon reversal of the enantioselectivity; two transition state orientations of different polarities are differently favoured in polar or nonpolar solvents.

Towards understanding resprouting at the global scale

Understanding and predicting plant response to disturbance is of paramount importance in our changing world. Resprouting ability is often considered a simple qualitative trait and used in many ecological studies. Our aim is to show some of the complexities of resprouting while highlighting cautions that need be taken in using resprouting ability to predict vegetation responses across disturbance types and biomes. There are marked differences in resprouting depending on the disturbance type, and fire is often the most severe disturbance because it includes both defoliation and lethal temperatures. In the Mediterranean biome, there are differences in functional strategies to cope with water deficit between resprouters (dehydration avoiders) and nonresprouters (dehydration tolerators); however, there is little research to unambiguously extrapolate these results to other biomes. Furthermore, predictions of vegetation responses to changes in disturbance regimes require consideration not only of resprouting, but also other relevant traits (e.g. seeding, bark thickness) and the different correlations among traits observed in different biomes; models lacking these details would behave poorly at the global scale. Overall, the lessons learned from a given disturbance regime and biome (e.g. crown-fire Mediterranean ecosystems) can guide research in other ecosystems but should not be extrapolated at the global scale.

Proyecto FIRST (Flexible Interactive Reading Support Tool): desarrollo de una herramienta para ayudar a personas con autismo mediante la simplificación de textos

El Trastorno de Espectro Autista (TEA) es un trastorno que impide el correcto desarrollo de funciones cognitivas, habilidades sociales y comunicativas en las personas. Un porcentaje significativo de personas con autismo presentan además dificultades en la comprensión lectora. El proyecto europeo FIRST está orientado a desarrollar una herramienta multilingüe llamada Open Book que utiliza Tecnologías del Lenguaje Humano para identificar obstáculos que dificultan la comprensión lectora de un documento. La herramienta ayuda a cuidadores y personas con autismo transformando documentos escritos a un formato más sencillo mediante la eliminación de dichos obstáculos identificados en el texto. En este artículo se presenta el proyecto FIRST así como la herramienta desarrollada Open Book.

Diseño y desarrollo de redes sociales aplicadas al Espacio Europeo de Educación Superior

En la actual sociedad del conocimiento y con el continuo desarrollo de las nuevas tecnologías, las redes sociales están cobrando cada vez mayor relevancia para la interacción y el intercambio de información. El predominio de las redes sociales, como Twitter, Facebook o Google+ va en aumento, e incluso se integran en los procesos educativos para mejorar la interacción y comunicación entre profesor-alumno y alumno-alumno. El objetivo de esta investigación es estudiar las redes sociales existentes y específicamente, las que se utilizan en el ámbito educativo, para analizar y determinar los requerimientos necesarios con el fin de proponer una nueva red social orientada especialmente al ámbito educativo del Espacio Europeo de la Educación Superior (EEES). Esto nos permitirá conocer qué aspectos es conveniente reutilizar de las redes sociales genéricas, pero también, que limitaciones encontramos y qué nuevas funcionalidades serían de gran utilidad para mejorar los procesos educativos en el EEES. Por tanto, nuestra investigación plantea, además, el diseño preliminar de dicha propuesta de red social que será evaluado por estudiantes de los Grados de Ingeniería en Informática y Grado de Ingeniería Multimedia para conocer su grado de satisfacción hacia la misma.