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.

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.

El lenguaje gráfico de Eduardo Chillida como aportación conceptual para la identidad tipográfica de la Universidad del País Vasco —UPV/EHU—

Este proyecto de investigación financiado por la Universidad del País Vasco/Euskal Herriko Unibertsitatea —UPV/EHU-PES 11/31—, a través de su programa de investigación estratégica, tiene como objetivo la creación de la tipografía de identidad visual corporativa de la Universidad del País Vasco —UPV/EHU—, cuyo inicio conceptual para dotar de unas características de identidad visual corporativa a la UPV/EHU, ha sido planteado desde las especulaciones estéticas sobre la forma, materializadas por Eduardo Chillida. En la producción gráfica de este artista encontramos una sutil coincidencia con principios vitales para la creación tipográfica, en cuanto al planteamiento de formas dinámicas y constructivas, en las que el rigor geométrico es vencido por una suerte de organicidad que parte del núcleo mismo de la estructura —«cursus»—, por: la fuerza vital que imprime la acción modulada del gesto —«ductus»—; por la dialéctica entre lo lleno y lo vacío —forma/contraforma—, por el impulso y la espontaneidad — carácter—, o por la afirmación de un lenguaje plástico en la cultura diferenciada del medio en el que se vive —identidad—.

Bifunctional primary amine 2-aminobenzimidazole organocatalyst anchored to trans-cyclohexane-1,2-diamine in enantioselective conjugate additions of aldehydes

Bifunctional chiral primary amine 8 containing an (S,S)-trans-cyclohexane-1,2-diamine scaffold and a 2-benzimidazole unit is used as a general organocatalyst for the Michael addition of α,α-branched aldehydes to nitroalkenes and maleimides. The reactions take place, with 20 mol % of catalyst in dichloromethane at rt for nitroalkenes and with 15 mol % catalyst loading in toluene at 10 °C for maleimides, in good yields and enantioselectivities. DFT calculations demonstrate the bifunctional character of this organocatalyst activating the aldehyde by enamine formation and the Michael acceptor by double hydrogen bonding.

La sostenibilidad en la planificación territorial de escala regional en España: estudio de casos

En las dos últimas décadas, la expresión «desarrollo territorial sostenible» se ha incorporado con éxito en los documentos de ordenación del territorio, hasta convertirse en un principio rector principal. El objetivo de este artículo es analizar la incorporación de los principios de sostenibilidad en la planificación territorial española, valorando los resultados prácticos que ello ha significado. Se ha realizado un análisis de las leyes y planes de ordenación del territorio de escala regional, destacando en cuatro casos de estudio (País Vasco, Navarra, Andalucía y Comunidad Valenciana) por la relevancia que este principio rector ha cobrado en sus procesos de planificación territorial. Se ha completado la información con la realización de entrevistas a actores clave de la ordenación del territorio en esos espacios regionales. Los resultados muestran que, a pesar de las buenas intenciones que incluyen los textos de leyes y planes, por lo común, el proceso de integración de la sostenibilidad a la planificación territorial de escala regional es lento y sus efectos prácticos todavía son escasamente visibles.

Enantioselective Synthesis of Polysubstituted Spiro-nitroprolinates Mediated by a (R,R)-Me-DuPhos·AgF-Catalyzed 1,3-Dipolar Cycloaddition

The synthesis of constrained spirocycles is achieved effectively by means of 1,3-dipolar cyclodditions employing α-imino γ-lactones as azomethine ylide precursors and nitroalkenes as dipolarophiles. The complex formed by (R,R)-Me-DuPhos 18 and AgF is the most efficient bifunctional catalyst. Final spiro-nitroprolinates cycloadducts are obtained in good to moderate yields and both high diastereo- and enantioselectivities. Density functional theory (DFT) calculations supported the expected absolute configuration as well as other stereochemical parameters.

Tiburzio Spannocchi’s project for the fortifications of Fuenterrabía in 1580

Fuenterrabía (Hondarribia) is a town located on the Franco-Spanish border. Between the 16th and 19th centuries it was considered to be one of the most outstanding strongholds in the Basque Country due to its strategic position. The bastion system of fortification was extremely prevalent in this stronghold. It was one of the first Spanish towns to adopt the incipient Renaissance designs of the bastion. The military engineers subsequently carried out continuous fortification projects that enabled the structure to withstand the advances being made in artillery and siege tactics. After the construction of the citadel of Pamplona had begun in 1571, following the design of the prestigious military engineer, Jacobo Palear Fratín and being revised by Viceroy Vespasiano Gonzaga, the aforementioned engineer undertook an ambitious project commissioned by Felipe II to modernise the fortifications of Fuenterrabía. Neither the plans nor the report of this project have been conserved, but in the year 2000, César Fernández Antuña published the report written by Spannocchi on the state of the fortifications of Fuenterrabía when he arrived to the Spanish peninsula, discovered in the Archivo Histórico Provincial de Zaragoza. This document conducts an in-depth analysis of Spannocchi’s project and how it was related to Fratín’s previous project. It concludes that this project encountered problems in updating the new bastions at the end of the 16th century, and identifies the factors which prevented the stronghold from being extended as was the case in Pamplona after Fratín’s project.

MMTV-trBrca 1 mice display strain-dependent abnormalities in vaginal development

The breast cancer susceptibility gene Brca1 encodes a large multi-functional protein which is implicated as a caretaker of the genome, through its role in regulation of DNA damage response pathways, including apoptosis. Here we show that in mice expressing a dominant-negative Brca1 transgene on a BALB/c background, vaginal entrance remodeling is inhibited, and that the incidence of this phenotype is increased on a p53 +/- genotype. Given that this developmental process is mediated primarily by apoptosis, we hypothesized that disruption of BRCA1 may confer a resistance to apoptosis in normal epithelial cells. Consistent with this, we show that expression of this transgene in vitro leads to resistance to ionizing radiation induced cell killing in mammary epithelial cells. This is the first time that BRCA1 has been implicated in an apoptosis-mediated normal developmental process.

The elderly care and domestic services sector during the recent economic crisis. The case of Italy, Spain and France.

Over the past ten years in Italy, Spain and France, the demographic pressure and the increasing women’s participation in labour market have fuelled the expansion of the private provision of domestic and care services. In order to ensure the difficult balance between affordability, quality and job creation, each countries’ response has been different. France has developed policies to sustain the demand side introducing instruments such as vouchers and fiscal schemes, since the mid of the 2000s. Massive public funding has contributed to foster a regular market of domestic and care services and France is often presented as a “best practices” of those policies aimed at encouraging a regular private sector. Conversely in Italy and Spain, the development of a private domestic and care market has been mostly uncontrolled and without a coherent institutional design: the osmosis between a large informal market and the regular private care sector has been ensured on the supply side by migrant workers’ regularizations or the introduction of new employment regulations . The analysis presented in this paper aims to describe the response of these different policies to the challenges imposed by the current economic crisis. In dealing with the retrenchment of public expenditure and the reduced households’ purchasing power, Italy, Spain and France are experiencing greater difficulties in ensuring a regular private sector of domestic and care services. In light of that, the paper analyses the recent economic conjuncture presenting some assumptions about the future risk of deeper inequalities rising along with the increase of the process of marketization of domestic and care services in all the countries under analysis.    

Assessment of faculty training program for the use of e-learning platforms: analysis of current use

5th International Conference on Education and New Learning Technologies (Barcelona, Spain. 1-3 July, 2013)

Identification and functional analysis of novel genes expressed in the Anterior Visceral Endoderm

During early vertebrate development, the correct establishment of the body axes is critical. The anterior pole of the mouse embryo is established when Distal Visceral Endoderm (DVE) cells migrate to form the Anterior Visceral Endoderm (AVE). Symmetrical expression of Lefty1, Cer1 and Dkk1 determines the direction of DVE migration and the future anterior side. In addition to the establishment of the Anterior-Posterior axis, the AVE has also been implicated in anterior neural specification. To better understand the role of the AVE in these processes, we have performed a differential screening using Affymetrix GeneChip technology with AVE cells isolated from cer1P-EGFP transgenic mouse embryos. We found 175 genes which were upregulated in the AVE and 36 genes in the Proximal-posterior sample. Using DAVID software, we characterized the AVE cell population regarding cellular component, molecular function and biological processes. Among the genes that were found to be upregulated in the AVE, several novel genes were identified. Four of these transcripts displaying high-fold change in the AVE were further characterized by in situ hybridization in early stages of development in order to validate the screening. From those four selected genes, one, denominated Adtk1, was chosen to be functionally characterized by targeted inactivation in ES cells. Adtk1 encodes for a serine/threonine kinase. Adtk1 null mutants are smaller and present short limbs due to decreased mineralization, suggesting a potential role in chondrogenesis during limb development. Taken together, these data point to the importance of reporting novel genes present in the AVE.

El lenguaje gráfico de Eduardo Chillida como aportación conceptual para la identidad tipográfica de la Universidad del País Vasco UPV/EHU

El valor de la documentación especializada en las fases del diseño / The value of specialized documentation in the design process este proyecto de investigación financiado por la Universidad del País Vasco/Euskal Herriko Unibertsitatea UPV/EHU-PES 11/31, a través de su programa de investigación estratégica, tiene como objetivo la creación de la tipografía de identidad visual corporativa de la Universidad del País Vasco UPV/EHU, cuyo inicio conceptual para dotar de unas características de identidad visual corporativa a la UPV/EHU, ha sido planteado desde las especulaciones estéticas sobre la forma, materializadas por Eduardo Chillida. En la producción gráfica de este artista encontramos una sutil coincidencia con principios vitales para la creación tipográfica, en cuanto al planteamiento de formas dinámicas y constructivas, en las que el rigor geométrico es vencido por una suerte de organicidad que parte del núcleo mismo de la estructura "cursus", por: la fuerza vital que imprime la acción modulada del gesto "ductus"; por la dialéctica entre lo lleno y lo vacío forma/contraforma, por el impulso y la espontaneidad carácter, o por la afirmación de un lenguaje plástico en la cultura diferenciada del medio en el que se vive la identidad.

Suivi stationnel de l’herbier à Zostera noltei de la masse d’eau FRFT8 Bidassoa – 2014 - Bassin Hydrographique Adour-Garonne

The new protocol established by Auby et al. (2012) was applied in 2014 to the seagrass monitoring in the Water body FRFT8 – Bidassoa - Type T03. Based on 3 metrics ("taxonomy", "extension" and "abundance"), the quality index of this water body for the angiosperm indicator, was "good". The displacement of the seagrass bed led us to adapt the sampling grid in 2014