New sulfur-phosphine ligands derived from sugars: synthesis and application in palladium-catalyzed allylic alkylation and in rhodium asymmetric hydrogenation

An efficient route to mixed phosphine / thioglycoside ligands type IV starting from glucose pentaacetate is reported. In only five steps the key epoxide 6 has been obtained in high yield and its structure determined by X-ray analysis. The ring opening of the tert-butyl 4,6-O-benzylidene- 2,3-anhydro-1-thio-β-D-allopyranoside 6 with diphenylphosphinyl lithium afforded the desired ligand as a single diastereoisomer. The prepared compounds act as a bidentate ligands as shown by X-ray analysis of the Rh(I)-complex 12. Preliminary results on the behaviour of these ligands in Pd(0)-catalyzed allylic alkylation, and in Rh(I)-catalyzed enamide hydrogenation are also reported.Dirección General de Investigaciones Científicas y Técnicas CTQ2006- 15515-CO2-01 y CTQ2007-61185Junta de Andalucía P06-FQM-01852 y P07- FQM-2774Fundación Ramón Arece

Persistencia de medicamentos biológicos durante ocho años en pacientes con artritis reumatoide y espondiloartritis

Objective: To calculate the persistence, over a period of eight years, the retention rate of first and second-line of treatment with biological agents in patients with rheumatoid arthritis, spondyloarthritis and psoriatic arthritis and to compare retention rates of the various drugs for each pathology. Method: Retrospective observational study that included patients affected by rheumatoid arthritis, spondyloarthritis and psoriatic arthritis, who started treatment with biological agents between January 2009 and December 2012 and followed until December 2016. Results: 132, 87 and 33 patients were included in rheumatoid arthritis, spondyloarthritis and psoriatic arthritis, respectively. The median retention duration of all biological agents for the first and second-line, was 30.9 months and 14.0 months, respectively for rheumatoid arthritis; 63.06 months and 25.6 months, respectively in spondyloarthritis. Psoriatic arthritis did not reach the median (> 70 months in first-line) (first line p = 0.002). Individual drug survival in first line: the median retention duration of tocilizumab was 58.3 months, followed by etanercept (p = 0.79) in rheumatoid arthritis. For spondyloarthritis, golimumab and etanercept had greater retention than the other drugs (they did not reach the median): adalimumab was 63.0 months and for infliximab was 50.1 months. In psoriatic arthritis, golimumab, infliximab and etanercept not reach the median and they had greater retention arthritis, and golimumab for spondyloarthritis and psoriatic arthritis. Conclusions: Tocilizumab and etanercept in rheumatoid arthritis, and golimumab in spondyloarthritis and psoriatic arthritis also, were the most persistent drugs in first-line and second-line treatmentObjetivo: Calcular y analizar la persistencia global y por medicamento, en primera y segunda línea de tratamiento, en pacientes con artritis reumatoide, espondiloartritis axial radiográfica y no radiográfica y artritis psoriásica durante un periodo de ocho años. Método: Estudio retrospectivo observacional de persistencia en pacientes que iniciaron su terapia con medicamentos biológicos entre enero de 2009 y diciembre de 2012 en seguimiento hasta diciembre de 2016. Resultados: Se analizaron 132, 87 y 33 pacientes con artritis reumatoide, espondiloartritis y artritis psoriásica, respectivamente. La persistencia mediana global para los biológicos en primera y segunda línea fueron: 30,9 meses y 14 meses, respectivamente, en artritis reumatoide; 63,06 meses y 25,6 meses en espondiloartritis. No se alcanzó la persistencia mediana en los ocho años de seguimiento en artritis psoriásica (> 70 meses) (p = 0,002 para la función de supervivencia entre patologías en primera línea). Persistencia mediana alcanzada en primera línea por medicamento: tocilizumab (58,3 meses), seguido de etanercept (44 meses) en artritis reumatoide (p = 0,79); en espondiloartritis golimumab y etanercept fueron los más persistentes (no alcanzaron la mediana), seguidos de adalimumab (44 meses) e infliximab (50,1 meses). En artritis psoriásica, golimumab seguido de infliximab y etanercept fueron los más persistentes (no alcanzaron la mediana), y adalimumab (59,4 meses). Persistencia mediana alcanzada en segunda línea por medicamento: tocilizumab (22,1 meses) en artritis reumatoide. Golimumab fue el más persistente en espondiloartritis y artritis psoriásica (sin alcanzar la mediana). Conclusiones: Tocilizumab y etanercept fueron los medicamentos más persistentes en artritis reumatoide, y golimumab en espondiloartritis y artritis psoriásica en primera y segunda línea de tratamient

In silico investigation and surmounting of lipopolysaccharide barrier in Gram-negative bacteria: how far has molecular dynamics come?

Lipopolysaccharide (LPS), a main component of the outer membrane of Gram-negative bacteria, has crucial implications on both antibiotic resistance and the overstimulation of the host innate immune system. Fighting against these global concerns calls for the molecular understanding of the barrier function and immunostimulatory ability of LPS. Molecular dynamics (MD) simulations have become an invaluable tool for uncovering important findings in LPS research. While the reach of MD simulations for investigating the immunostimulatory ability of LPS has been already outlined, little attention has been paid to the role of MD simulations for exploring its barrier function and synthesis. Herein, we give an overview about the impact of MD simulations on gaining insight into the shield role and synthesis pathway of LPS, which have attracted considerable attention to discover molecules able to surmount antibiotic resistance, either circumventing LPS defenses or disrupting its synthesis. We specifically focus on the enhanced sampling and free energy calculation methods that have been combined with MD simulations to address such research. We also highlight the use of special-purpose MD supercomputers, the importance of appropriate LPS and ions parameterization to obtain reliable results, and the complementary views that MD and wet-lab experiments provide. Thereby, this work, which covers the last five years of research, apart from outlining the phenomena and strategies that are being explored, evidences the valuable insights that are gained by MD, which may be useful to advance antibiotic design, and what the prospects of this in silico method could be in LPS research.Financial support from the Spanish Ministry of Science, Innovation and Universities under the project RTI2018-093310-B-I00 is gratefully acknowledged

Perceptions concerning intergenerational education from the perspective of participants

This article presents an evaluation of an intergenerational education experience at the University of Castilla-La Mancha (Spain). For this evaluation, following a review of the literature regarding the state of the issue, we undertake an analysis of benefits and disadvantages from the perspective of the participants. Among the benefits we find that the majority of those questioned would repeat the program, and that classroom atmosphere improved notably. Participants listed the exceptional nature of the program and the teachers needing to make methodological adjustments to improve the experience (the pace of teaching, adaptation to the profile of the participants) among the disadvantages.Depto. de Trabajo Social y Servicios SocialesFac. de Trabajo SocialTRUEpu

Cultural resources and creative industries in spanish medium-sized cities

In recent years, stress has been put on the relationship between cultural resources and creative industries and their ability to dynamise the economy and generate development processes. At the same time, much geographical research and some public powers and institutions have highlighted the role that medium-sized towns and cities can play by acting as intermediaries between large cities and rural areas. Seeking to combine these two theoretical reference frameworks, this article aims to analyse the presence of cultural resources and creative industries in Spanish medium-sized towns and cities. A typology of these towns and cities is also proposed based on these resources and industries.En los últimos años, se ha acentuado el interés por las relaciones entre recursos culturales e industrias creativas y su capacidad para dinamizar la economía y generar procesos de desarrollo. Al mismo tiempo, una importante parte de la investigación geográfica, de los poderes públicos y otras instituciones han destacado la potencialidad de las ciudades medias para actuar como intermediarias entre las grandes ciudades y las áreas rurales. Con la intención de combinar estos dos marcos teóricos de referencia, este artículo pretende analizar la presencia de recursos culturales e industrias creativas en las ciudades medias españolas. A este respecto, se propone una tipología de estas ciudades basada en este tipo de recursos e industrias.Spanish National Plan R&D&i and ERDF fund

Economía creativa en la aglomeración metropolitana de Sevilla: agentes, redes locales de colaboración y principales actuaciones

Desde hace ya más de una década se viene atribuyendo un valor estratégico a la economía creativa al entender que puede contribuir a estimular la creación de empleo y a promover nuevos modelos de desarrollo territorial. Con este contexto general de referencia, el objetivo de este artículo es contribuir al conocimiento de la economía creativa en la aglomeración metropolitana de Sevilla, centrando especialmente la atención en los agentes a ella vinculados, en las redes de cooperación socio-institucional que entre dichos agentes se conforman y en sus principales actuaciones.For over a decade a strategic value has been placed on the so-called creative economy in the understanding that it can help to drive both job creation and promote new economic models. Given this general reference context, the aim of this article is to contribute to knowledge of the creative economy in the Urban Agglomeration of Seville, with special focus on the public and private agents with links to the area, on the local socio-institutional cooperation networks created by these agents, and on their main actions.Proyecto de Investigación del Plan Nacional de I+D+

Disruptive behaviour in the spanish school system. Legislative development

En la actualidad el incremento de los problemas de disciplina en el aula supone una preocupación para el profesorado y un obstáculo para el desarrollo del proceso de enseñanza-aprendizaje. Para que la intervención educativa sea eficaz, es necesario diferenciar los distintos tipos de conflictos, abordándolos desde diversas perspectivas. En este artículo se ha realizado un análisis documental de las sucesivas leyes educativas españolas, buscando en cada una la frecuencia de aparición de palabras claves referidas al comportamiento del alumnado, se ha analizado la respuesta ante la conflictividad y la diferencia entre el abordaje de la conducta grave y la disruptiva, menos grave. Como resultado se observa una evolución positiva de la normativa, influida por una sociedad más concienciada de la importancia de un buen clima escolar para conseguir el sano desarrollo personal y mejor aprendizaje del alumnado. La ley actual diferencia entre conductas graves y leves y muestra una mayor preocupación, no solo por frenar el incremento de estos comportamientos, sino también por prevenirlos. Pero todavía queda mucho por avanzar, pues aún no se dan orientaciones claras que ayuden al profesorado a abordar las conductas leves de forma adecuada, pese a las dificultades que suponen para el proceso de aprendizaje.Nowadays, increasing discipline problems in the classroom have become a concern for teachers and an obstacle for the development of the teaching-learning process. To adequately develop an effective educational intervention, it is essential to distinguish between different types of conflicts and to approach them from different perspectives. This paper presents an analysis of the successive educational Spanish laws, specifically examining the frequency of appearance of those keywords regarding students’ behavior in each law. The responses provided to approach conflict were studied, differentiating from serious misconduct and less serious disruptive behavior.Results show a positive evolution of the Spanish regulations: This is due to the increase of social awareness regarding the importance of creating a favourable school environment to ensure a healthy personal development and better learning. The current law distinguishes misconduct and disruptive behavior and also expresses its concern about the increase in this kind of behavior and provides ways of preventing it. However, further progress is still to be achieved as there is a need for clear guidelines for teachers to properly deal with disruptive behavior. Despite the difficulties that this kind of behavior entail to the learning process, these recommendations are still not laid down despite the difficulties faced by the learning process

Spectral response of dielectric nano-antennas in the far- and near-field regimes

Recent studies show that the spectral behaviour of localized surface plasmon resonances (LPSRs) in metallic nanoparticles su er from both a redshift and a broadening in the transition from the far- to the near-field regimes. An interpretation of this efect was given in terms of the evanescent and propagating components of the angular spectrum representation of the radiated eld. Due to the increasing interest awakened by magnetodielectric materials as a both low-loss material option for nanotechnology applications, and also for their particular scattering properties, here we study the spectral response of a magnetodielectric nanoparticle as a basic element of a dielectric nano-antenna. This study is made by analyzing the changes su ered by the scattered electromagnetic field when propagating from the surface of this dielectric nanostructure to the far-zone in terms of propagating and evanescent plane wave components of the radiated fields.This research was supported by MICINN (Spanish Ministry of Science and Innovation) with project FIS2013- 45854-P

Validación de la técnica de análisis masivo ("shotgun") con péptidos no marcados para el estudio del proteoma de Botrytis cinerea

Comunicaciones a congreso