Reutilización del Treebank de dependencias del euskera para la construcción del gold standard de la sintaxis superficial de la gramática de restricciones (CG)

El objetivo del trabajo consiste en reutilizar el Treebank de dependencias EPECDEP (BDT) para construir el gold standard de la sintaxis superficial del euskera. El paso básico consiste en el estudio comparativo de los dos formalismos aplicados sobre el mismo corpus: el formalismo de la Gramática de Restricciones (Constraint Grammar, CG) y la Gramática de Dependencias (Dependency Grammar, DP). Como resultado de dicho estudio hemos establecido los criterios lingüísticos necesarios para derivar la funciones sintácticas en estilo CG. Dichos criterios han sido implementados y evaluados, así en el 75% de los casos se derivan automáticamente las funciones sintácticas para construir el gold standard.

Synthetic scope and DFT analysis of the chiral binap-gold (I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

The 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(Sa)-Binap·AuTFA]2. The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF) level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

Acciones públicas de sensibilización de género: el esfuerzo de la administración regional y local en comunicación publicitaria (1999-2007)

El artículo analiza las iniciativas de comunicación relacionadas con la igualdad de oportunidades entre mujeres y hombres. El objetivo es analizar con enfoque de género las acciones realizadas por parte de las instituciones públicas regionales y locales para sensibilizar y promover la conciliación entre la vida familiar y laboral de seis comunidades autónomas (Andalucía, Cataluña, Comunidad Valenciana, Galicia, Madrid y País Vasco) y de sus capitales, desde 1999 (cuando se aprueba la ley de conciliación) hasta 2007 (se aprueba la ley de igualdad). La información sobre publicidad convencional fue proporcionada por Infoadex. Para la recogida de otro tipo de iniciativas a través de medios menos convencionales se acudió a cuatro fuentes institucionales: 1) Ayuntamientos de las capitales, como fuente estrictamente local, 2) Diputaciones de la capital de la Comunidad Autónoma, como fuente provincial, 3) Direcciones Generales de la Mujer o instituciones análogas como fuente de información a nivel regional o autonómico y, por último, 4) otras concejalías vinculadas al tema de la corresponsabilidad, cuyo radio de acción también es autonómico. Los resultados, aunque con diferencias entre regiones, reflejan carencias en la cobertura de las acciones que llevan a cuestionar la falta de estrategia política en términos de comunicación, pese a la introducción sistemática de estos objetivos en la agenda internacional (ONU y UE) y del gobierno español. En consecuencia, las campañas publicitarias e iniciativas recogidas contribuyen a la visibilización del problema y al empoderamiento, pero no tanto al objetivo de la paridad.

Enantioselective Michael addition of isobutyraldehyde to nitroalkenes organocatalyzed by chiral primary amine-guanidines

Primary amine-guanidines derived from trans-cyclohexane-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of isobutyraldehyde to arylated and heteroarylated nitroalkenes. The reaction was performed in the presence of imidazole as the additive in aqueous DMF as the solvent at 0 °C. The corresponding Michael adducts bearing a new stereocenter were obtained in high yields and with enantioselectivities of up to 80%. Theoretical calculations are used to justify the observed sense of the stereoinduction.

Enantioselective Michael addition of aldehydes to maleimides organocatalysed by chiral 1,2-diamines: an experimental and theoretical study

Simple and commercially available chiral 1,2-diamines were used as organocatalysts for the enantioselective conjugate addition of aldehydes, including α,α-disubstituted, to maleimides. The reaction was carried out in the presence of hexanedioic acid as an additive in aqueous solvents at room temperature. By employing (1S,2S)- and (1R,2R)-cyclohexane-1,2-diamine as organocatalysts, the corresponding Michael adducts bearing new stereocenters were obtained in high or quantitative yields with enantioselectivities of up to 92%, whereas the use of (1S,2S)-1,2-diphenylethane-1,2-diamine gave a much lower ee. Theoretical calculations were used to justify the observed sense of the stereoinduction.

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.

The aid of machine learning to overcome the classification of real health discharge reports written in Spanish

Hospitals attached to the Spanish Ministry of Health are currently using the International Classification of Diseases 9 Clinical Modification (ICD9-CM) to classify health discharge records. Nowadays, this work is manually done by experts. This paper tackles the automatic classification of real Discharge Records in Spanish following the ICD9-CM standard. The challenge is that the Discharge Records are written in spontaneous language. We explore several machine learning techniques to deal with the classification problem. Random Forest resulted in the most competitive one, achieving an F-measure of 0.876.

Internalization of quality management in service organizations

Purpose – The purpose of this paper is to analyze the internalization of quality management (QM) on the basis of quality certifiable standards – also referred to as meta-standards – in service organizations. More specifically, the paper analyzes the case of the internalization of a quality standard in the Spanish hotel industry. Design/methodology/approach – The paper examines the relationships between the measures of internalization, benefit, QM tools and motivation, using partial least squares in the framework of the structural equation modeling technique. Findings – The results show that the hotels that have internalized the standard to a greater extent are more likely to be driven by internal motivation, develop more QM tools and achieve greater benefits than the hotels with a lower degree of internalization. Originality/value – As previous studies have examined these issues in relation to the internalization of ISO standards, the present study adds to this important stream of research and contributes by advancing the understanding of these issues through the case of a specific standard for the hotel industry.

Efficient Diastereo- and Enantioselective Synthesis of exo-Nitroprolinates by 1,3-Dipolar Cycloadditions Catalyzed by Chiral Phosphoramidite⋅Silver(I) Complexes

Chiral complexes formed by privileged phosphoramidites and silver triflate or silver benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between azomethine ylides generated from α-amino acid-derived imino esters and nitroalkenes affording with high dr the exo-cycloadducts 4,5-trans-2,5-cis-4-nitroprolinates in high ee at room temperature. In general, better results are obtained using silver rather than copper(II) complexes. In many cases the exo-cycloadducts can be obtained in enantiomerically pure form just after simple recrystallization. The mechanism and the justification of the experimentally observed stereodiscrimination of the process are supported by DFT calculations. These enantiomerically enriched exo-nitroprolinates can be used as reagents for the synthesis of nitropiperidines, by ester reduction and ring expansion, which are inhibitors of farnesyltransferase.

Enantioselective Synthesis of exo-4-Nitroprolinates from Nitro­alkenes and Azomethine Ylides Catalyzed by Chiral Phosphor­amidite·Silver(I) or Copper(II) Complexes

Chiral complexes formed by privileged phosphoramidites derived from chiral binol and optically pure Davies’ amines, and copper(II) triflate, silver(I) triflate or silver(I) benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between nitroalkenes and azomethine ylides generated from α-amino acid derived imino esters. These three methods can be conducted at room temperature to afford the exo-cycloadducts (4,5-trans-2,5-cis-4-nitroprolinates) with high diastereoselectivity and high enantioselectivity. In general, the three procedures are complementary but silver catalysts are more versatile and less sensitive to sterically congested starting materials.

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.

The International Competitiveness of the Biscayan Iron and Steel Industry (1880-1913)

This study has a double objective: to provide foreign colleagues with an insight into the controversy surrounding the international competitiveness of pig iron produced in Bilbao and also to present previously unpublished documentation regarding the European iron industry, which I have retrieved from the historical archive of Credit Lyonnais of Paris. This information includes the costs of Biscayan, French, British, German and Belgium pig iron broken down into five components (iron ore, coke, flux, labour and other costs), which is useful in determining the reasons why the pig iron from Bilbao became less competitive. The article is made up of three parts. Firstly, I will synthesise the controversy surrounding the competitiveness of the Basque iron and steel industry. Then I will present the itemised costs which provide information to illustrate how Biscayan pig iron was not competitive because it was produced with English coal which was more expensive than that consumed by the European factories located "on top of" or near coal seams. The article will finish with a section that, by way of conclusion, explains the comparative advantage and disadvantage of Bilbao, applying the first model of Alfred Weber's Theory of Industrial Location to three technological advances, occurring between the 1860s and 1913 (malleable iron, Bessemer steel and Thomas steel).

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.

Primary Amine–2-Aminopyrimidine Chiral Organocatalysts for the Enantioselective Conjugate Addition of Branched Aldehydes to Maleimides

Chiral primary amines containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a pyrimidin-2-yl unit are synthesized and used as general organocatalysts for the Michael reaction of α-branched aldehydes to maleimides. The reaction takes place with 10 mol% organocatalyst loading and hexanedioic acid as cocatalyst in aqueous N,N-dimethylformamide at 10 °C affording the corresponding succinimides in good yields and enantioselectivities. DFT calculations support the stereochemical results and the role played by the solvents.

Enantioselective addition of aryl ketones and acetone to nitroalkenes organocatalyzed by carbamate-monoprotected cyclohexa-1,2-diamines

Enantiomerically pure carbamate-monoprotected trans-cyclohexane-1,2-diamines are used as chiral organocatalysts for the addition of aryl ketones and acetone to nitroalkenes to give enantioenriched β-substituted γ-nitroketones. The reaction was performed in the presence of 3,4-dimethoxybenzoic acid as an additive, in chloroform as the solvent at room temperature, achieving enantioselectivities up to 96%. Theoretical calculations are used to justify the observed sense of the stereoinduction.