Vinylic Addition Polynorbornene in Catalysis

Vinylic addition polynorbornenes (VA-PNB) result from the insertion polymerization of norbornene or specific norbornene derivatives catalyzed by transition metal com- plexes. The VA-PNB skeleton is completely aliphatic and keeps the bicyclic structure of norbornene. This saturated polymer is thermally and chemically very stable and it is a very robust scaffold to support catalysts or reagents for catalytic applications. Several VA-PNBs are now available with suitable functional groups (halogen, alkenyl, carbonates) that can be used as starting materials to introduce the functionalization of choice by post-polymerization reactions. This has been applied to anchor organocatalysts on VA-PNB as well as ligands that can be used to synthesize supported metal catalysts. The reported examples of the use of VA-PNB-linked catalysts and their recyclability will be presented. VA-PNBs have also proved useful in the context of organotin chemistry to solve the problem of tin contamination by an efficient separation and the reuse of tin byproducts. Its uses in the Stille cross-coupling reaction and tin-hydride radical proc- esses will be discussed.MINECO (SGPI, grant CTQ2016-80913-P)Junta de Castilla y León (grants VA062G18 and VA051P17 and a fellowship to RGL

Publicidade digital, storytelling e transmedia narrativa: educomunicação do consumidor

The present text tries to analyze the relationships between the concept of digital storytelling applied to advertising starting from the base of the transmedia narrative. This is: how the new transmediatic narrative helps the construction of advertising discourses based on the notion of storytelling and how it establishes the bases for an educommunication of the consumer, the spectator and / or the target.El presente texto trata de analizar las relaciones entre el concepto de storytelling digital aplicado a la publicidad partiendo de la base de la narrativa transmedia. Esto es: cómo la nueva narrativa transmediática ayuda a la construcción de discursos publicitarios basados en la noción de storytelling y cómo ello establece las bases para una educomunicación del consumidor, del espectador y/o del target.O presente texto tenta analisar as relações entre o conceito de narrativa digital aplicado à publicidade a partir da base da narrativa transmedia. Isto é: como a nova narrativa transmediaica ajuda a construção de discursos publicitários com base na noção de narrativa e como estabelece as bases para uma educação do consumidor, o espectador e / ou o target

Evaluating the role of aggregate gradation on cracking performance of asphalt concrete for thin overlays

Thin asphalt concrete overlays are a maintenance technique that mainly restore the functional properties of pavements. One of the main issues in thin overlays is reflective cracking that can cause early deterioration and reduce their service life. For this reason, the purpose of this investigation is to evaluate the effect of material selection on cracking performance of asphalt concrete mixtures for thin overlays. In particular, this paper evaluates the role of aggregate skeleton gradation. The study of the effect of aggregate gradation was divided into two stages: (1) fine fraction content and (2) maximum nominal aggregate size. Based on this, up to seven asphalt mixture gradations were designed and evaluated through the Fénix test at different test temperatures. The results showed a significant correlation between the fine fraction content, and maximum nominal aggregate size, and the cracking performance of the asphalt concrete mixtures. Mixtures manufactured with a low content of fine aggregates, as well as small nominal maximum size, experienced a further improvement of their toughness. These results reflected the importance of considering not only the effect of asphalt binder and environmental conditions but also aggregate gradation in the design of asphalt concrete mixtures in order to achieve a desirable cracking performance.Peer ReviewedPostprint (published version

Poly(ω-bromoalkylnorbornenes-co-norbornene) by ROMP-Hydrogenation: a Robust Support Amenable to Post-Polymerization Functionalization

Producción CientíficaThe ring opening metathesis copolymerization of norbornene and bromoalkylnorbornenes NB- (CH2)nBr (n = 1, 4) by Grubbs’ 2nd generation catalyst, followed by hydrogenation, gives insoluble saturated polynorbornenes (ROMPH-PNBs) that have pendant -bromoalkyl chains (4a, b). These materials can be functionalized by nucleophilic substitution of bromide to give a variety of substituted polymers (ROMPH-PNB-(CH2)nNu where Nu = CN, SPh, OOCMe, N3, SnR3. The stannylated polymers were tested in a Pd-catalyzed reaction, the Stille coupling. The azido polynorbornenes ROMPH-PNB-(CH2)nN3 easily undergo the click 1,3-dipolar cycloaddition with alkynes, which could be a useful strategy to anchor other functionalities of interest. The aliphatic nature of the ROMPH-PNB-(CH2)nBr backbone makes robust supports and the presence of the bromo substituent imparts versatility so they are good candidates to be used as a general starting material to anchor a group required for a specific synthetic purpose.2017-01-01Ministerio de Economía, Industria y Competitividad (CTQ2013-48406-P)Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA302U13

Who are diverse?: conceptualisations of cultural diversity in schools behind desks and at chalkface

This paper analyses the meanings and values attached to‘culturaldiversity’as a descriptive and interpretative category in the fieldof education in Spain, including its application to define differentgroups in elementary and primary schools there. It reports from acomparative study that considers the discursive production of‘cultural diversity’in Spanish academia together with thediscourse of teaching staff from three schools with specificprogrammes aimed at cultural diversity. Results attest to threedifferent uses of‘cultural diversity’: individualisation, differenceand inequalities, as well as two different assessments: enrichmentand problem. It also analyses how the discourse of teachers ismore complex than those of the academy, because, among otherreasons, they link diversity with situations produced by socialinequality, by the fact that many students are migrants, and by adifferent ethnic condition. In general, the academic discoursetends to present a more institutionalised, idealised and blindvision of social inequalit

New approach to characterize cracking resistance of asphalt binders

Asphalt binder characterization is a complex and difficult task due to its rheological behaviour. Indeed it has been traditionally realized by means of simple tests at an established temperature. An added challenge is that low temperatures, as well as binder aging, lead to significant changes in the viscoelastic behaviour of binders. This study aimed to characterize asphalt binders, not through the traditional procedures, but through the ductility and tenacity that they provide to a mixture, being these two properties directly related to the cracking response of the binder. To this end, a new approach for asphalt binder characterization was proposed based on the application of the Fénix test on a standard mixture with a defined aggregate gradation and composition, without fines or filler, manufactured with different types of binders and tested at different temperatures, as well as subjected to accelerated aging in laboratory. The obtained results showed the thermal susceptibility of binders, which evidence the need to characterize binder performance at different temperatures to obtain a reliable cracking response. In addition, binder aging results in a more brittle cracking fracture, being the aging effects more pronounced in high penetration binders.Peer ReviewedPostprint (author's final draft

Microtargeting and electoral segmentation in advertising and political communication through social networks: case study

Western political debate, like other areas, has entered the digital world. Political actors have had to adapt to new communication strategies linked to technology in general and to social networks in particular. A new debate has opened that has provoked changes in the traditional system of political communication with its different audiences. Thus, the configuration of negotiation and dominance in democratic systems is linked to technological change. This research aims to provide a descriptive interpretation of the role of social networks, specifically Facebook, by the Popular Party to win the elections of June 26, 2016 in Spain. How the strategies of microtargeting, data mining and geolocation were hollowed out in order to capture the indecisive vote and thus obtain the seats necessary to expand the electoral advantage. To this end, a comparison will be made with Barack Obama's campaigns in 2008 and especially 2012, which were also carried out by The Messina Group (TMG) and whose results were a great success. The results show that Facebook is one of the social networks more successfully used in the campaigns

Effect of conductivity and frequency on detection of heterogeneities in solid/liquid interfaces using local electrochemical impedance Theoretical and experimental study

This short communication demonstrates, by solving the Laplace equation with proper boundary conditions (BC) using finite element method (FEM), that it is not possible to establish a correlation between what happens in the electrolyte near an active boundary and what really occurs at the actual boundary if adequate ranges of electrolyte conductivity and input AC signal frequency are not selected, especially when inhomogeneities approximated by Neumann BC are present. Experimental evidence obtained by local electrochemical impedance mapping (LEIM) supports the theoretical results.This work has been supported by the Ministry of Science and Inno-vationofSpain(MAT2006-04486andIPT-020000-2010-0001Projects

Algal lipids reveal unprecedented warming rates in alpine areas of SW Europe during the industrial period

Alpine ecosystems of the southern Iberian Peninsula are among the most vulnerable and the first to respond to modern climate change in southwestern Europe. While major environmental shifts have occurred over the last ~ 1500 years in these alpine ecosystems, only changes in the recent centuries have led to abrupt environmental responses, but factors imposing the strongest stress have been unclear until now. To understand these environmental responses, this study, for the first time, has calibrated an algal lipid-derived temperature proxy (based on long-chain alkyl diols) to instrumental historical data extending alpine temperature reconstructions to 1500 years before present. These novel results highlight the enhanced effect of greenhouse gases on alpine temperatures during the last ~ 200 years and the longterm modulating role of solar forcing. This study also shows that the warming rate during the 20th century (~ 0:18 ºC per decade) was double that of the last stages of the Little Ice Age (~ 0:09 ºC per decade), even exceeding temperature trends of the high-altitude Alps during the 20th century. As a consequence, temperature exceeded the preindustrial record in the 1950s, and it has been one of the major forcing processes of the recent enhanced change in these alpine ecosystems from southern Iberia since then. Nevertheless, other factors reducing the snow and ice albedo (e.g., atmospheric deposition) may have influenced local glacier loss, since almost steady climate conditions predominated from the middle 19th century to the first decades of the 20th century.This research has been supported by the Seventh Framework Programme (grant no. NAOSIPUK (623027)), the Ministerio de Economía y Competitividad, Secretaría de Estado de Investigación, Desarrollo e Innovación (grant no. CGL2017-85415- R), the Ministerio de Economía y Competitividad, Secretaría de Estado de Investigación, Desarrollo e Innovación (grant no. CGL2013- 47038-R), the Ministerio de Economía y Competitividad, Secretaría de Estado de Investigación, Desarrollo e Innovación (grant no. CGL2011-23483), and the Consejería de Economía, Innovación, Ciencia y Empleo, Junta de Andalucía, Agencia de Innovación y Desarrollo de Andalucía (grant no. P11-RNM 7332). This research has also been supported by grant no. 87/2007 of the Organismo Autónomo Parques Nacionales (OAPN)-Ministerio de Medio Ambiente, the research group no. RNM-190 of the Plan Andaluz de Investigación, Desarrollo e Innovación (Junta de Andalucía), and the Ramón y Cajal Fellowship (fellowship no. RYC-2015-18966) of the Ministerio de Economía y Competitividad, Secretaría de Estado de Investigación, Desarrollo e Innovación

Validation of a tactical analysis methodology for the study of pick and roll in basketball

P. 277-281Este estudio examina el diseño y la validación de una propuesta de metodología de análisis táctico para el estudio del pick and roll en el baloncesto, aplicando los principios de la metodología de observación y el registro de acciones en su contexto natural. Hemos desarrollado tres fases: Fase 1) Identificación y selección de las variables de análisis, en las que se identificaron y catalogaron las variables de comportamiento (pick and roll), las variables de análisis contextual (área de corte, tiempo de posesión y período de juego) y las variables de análisis evaluativo. (resultado de la acción); Fase 2) Creación ad hoc de instrumentos de grabación, en la que se adaptó una herramienta informática (VA-Sports Software: Basketball) para abordar las particularidades y necesidades específicas del estudio de las situaciones de pick and roll ; y Fase 3) Control de calidad de los datos, en el que se establecieron los criterios de selección para la muestra, se llevó a cabo el proceso de capacitación de los observadores y se verificó el nivel de acuerdo interno y la concordancia intra-observador para evaluar la confiabilidad de la metodología. En este estudio se analizaron un total de 192 situaciones de pick and roll correspondientes a 6 partidos de la Liga ACB española. Los resultados sugieren un alto nivel de confiabilidad de la metodología diseñada; en conjunto, obtuvo un valor Kappa promedio alto (.994), lo que lleva a la conclusión de que las variables de análisis propuestas son precisas en su definición y categorización para estudiar las situaciones de pick and roll. Las variables de análisis: el tiempo de posesión, el período de juego y los resultados de la acción mostraron un nivel máximo de acuerdo (valor Kappa 1.000), mientras que las variables de análisis: el área de pick and roll y de corte también muestran un alto grado de objetividad (valores Kappa de .990 y .981 respectivamente)S