Solventless continuous flow homogeneous hydroformylation of 1-octene

The hydroformylation of 1-octene under continuous flow conditions is described. The system involves dissolving the catalyst, made in situ from [ Rh(acac)(CO)(2)] (acacH = 2,4- pentanedione) and [RMIM][TPPMS] ( RMIM = 1-propyl (Pr), 1-pentyl (Pn) or 1-octyl (O)-3-methyl imidazolium, TPPMS = Ph2P(3-C6H4SO3)), in a mixture of nonanal and 1-octene and passing the substrate, 1-octene, together with CO and H-2 through the system dissolved in supercritical CO2 (scCO(2)). [PrMIM][TPPMS] is poorly soluble in the medium so heavy rhodium leaching (as complexes not containing phosphine) occurs in the early part of the reaction. [PnMIM][ PPMS] affords good rates at relatively low catalyst loadings and relatively low overall pressure (125 bar) with rhodium losses <1 ppm, but the catalyst precipitates at higher catalyst loadings, leading to lower reaction rates. [OMIM][ TPPMS] is the most soluble ligand and promotes high reaction rates, although preliminary experiments suggested that rhodium leaching was high at 5-10 ppm. Optimisation aimed at balancing flows so that the level within the reactor remained constant involved a reactor set up based around a reactor fitted with a sight glass and sparging stirrer with the CO2 being fed by a cooled head HPLC pump, 1-octene by a standard HPLC pump and CO/H-2 through a mass flow controller. The pressure was controlled by a back pressure regulator. Using this set up, [OMIM][ TPPMS] as the ligand and a total pressure of 140 bar, it was possible to control the level within the reactor and obtain a turnover frequency of ca. 180 h(-1). Rhodium losses in the optimised system were 100 ppb. Transport studies showed that 1-octene is preferentially transported over the aldehydes at all pressures, although the difference in mol fraction in the mobile phase was less at lower pressures. Nonanal in the mobile phase suppresses the extraction of 1-octene to some extent, so it is better to operate at high conversion and low pressure to optimise the extraction of the products relative to the substrate. CO and H2 in the mobile phase also suppress the extraction effciency by as much as 80%.

El diagnóstico de la crisis de la cultura en España: del recorte público a la crisis sistémica

Desde su invención en los años cincuenta, la política cultural ha sido objeto de análisis y reflexión por parte de las ciencias sociales. No obstante, en España presenta una serie de características diferenciadoras frente a las democracias occidentales europeas como consecuencia del periodo franquista. Con la recuperación de la democracia España adquiere el paradigma dominante de una política cultural democrática basada en la libertad, el pluralismo y el derecho a la cultura. Sin embargo, tras décadas de gobiernos democráticos el diagnóstico de la política cultural en España presenta rasgos de crisis sistémica, además de los efectos de la crisis global financiera de inicios del siglo XXI. En este contexto, los autores diagnostican, aplicando la metodología Delphi y recurriendo a fuentes secundarias, un conjunto de discursos sociales y narrativas que parecen funcionar como recursos cognitivos solucionistas en la esfera artística y cultural y que no están exentos de contradicciones y aporías, fruto de su contraste empírico.

Patrimonio e Identidad en la Investigación Educativa Basada en las Artes desde un Enfoque Multimodal

Este artículo describe dos experiencias de investigación de nuestro grupo interconectadas, la primera desarrollada durante el año 2007 a través del proyecto internacional CALVINO del Programa Cultura 2000 de la Unión Europea, y la segunda implementada durante el año 2014 en el marco del Proyecto Investigación e Innovación en Secundaria en Andalucía (PIIISA). Ambos proyectos tienen en común el eje temático de la identidad a partir de una idea de patrimonio y el hecho de haber puesto en práctica metodologías de investigación basadas en las artes visuales con un enfoque multimodal. Desde estos dos puntos de anclaje relativos a la temática (qué) y a la metodología (cómo) analizamos lo acontecido para obtener conclusiones relevantes que, por una parte, pongan en valor estas prácticas significativas y, por otra, aporten nuestra experiencia para futuras propuestas de investigación en el ámbito temático y/o metodológico.

Late Holocene linkages between decade-century scale climate variability and productivity at Lake Tanganyika, Africa

Microlaminated sediment cores from the Kalya slope region of Lake Tanganyika provide a near-annually resolved paleoclimate record between similar to 2,840 and 1,420 cal. yr B.P. demonstrating strong linkages between climate variability and lacustrine productivity. Laminae couplets comprise dark, terrigenous-dominated half couplets, interpreted as low density underflows deposited from riverine sources during the rainy season, alternating with light, planktonic diatomaceous ooze, with little terrigenous component, interpreted as windy/dry season deposits. Laminated portions of the studied cores consist of conspicuous dark and light colored bundles of laminae couplets. Light and dark bundles alternate at decadal time scales. Within dark bundles, both light and dark half couplets are significantly thinner than within light bundles, implying slower sediment accumulation rates during both seasons over those intervals.