Análisis instrumental del recubrimiento de las paredes internas de dos estructuras negativas de tipo silo de la ocupación neolítica postcardial de Benàmer

Análisis instrumental mediante diferentes técnicas (ATR-IR, DRX, TG, SEM, MO, FRX, etc..) del recubrimiento de la pared interna de dos estructuras negativas (silos)del yacimiento Neolítico-Mesolítico de Cantera Benàmer (Muro d'Alcoi, Alicante).

Estudio de materiales de construcción neolíticos mediante diferentes técnicas instrumentales

Se han aplicado técnicas de análisis instrumental (FRX, DRX, ATR-IR, TG-ATD, SEM-EDX, MO) al estudio de fragmentos constructivos de época neolítica obtenidos de diferentes yacimientos de la Provincia de Alicante (España). La secuencia y el orden de aplicación de las técnicas se fija en función de las características y la cantidad disponible de cada muestra, estableciéndose con ello un protocolo de trabajo que se aplica siempre al resto de muestras, lo que nos permite comparar los resultados entre sí. El uso de dichas técnicas nos ha permitido la caracterización de los fragmentos constructivos, lo que nos ha llevado a conocer el grado de tecnología alcanzado por estas sociedades, sugiriéndonos que podíamos estar ante los inicios de la aplicación de la tecnología de la cal en esta zona de la Península Ibérica. En este trabajo se presenta una visión global de los resultados obtenidos hasta el momento.

Nueva aplicación potencial de dos técnicas instrumentales para la caracterización de materiales de construcción prehistóricos

En este trabajo se ponen de manifiesto las ventajas de la utilización de la Termogravimetría acoplada a Espectrometría de masas (TG-EM) y de la Espectrometría Infrarroja mediante Reflectancia Total atenuada (ATR-FTIR) frente a las técnicas usadas tradicionalmente de Termogravimetría (TG) y de Espectroscopia Infrarroja por Transformada de Fourier en modo transmisión (FTIR) en el estudio de materiales de construcción prehistóricos de diversos yacimientos de la Provincia de Alicante (España).

Kinetic study of thermal 1,3-dipolar cycloaddition of azomethine ylides using differential scanning calorimetry as monitoring window

Kinetics of 1,3-dipolar cycloaddition involving azomethine ylides, generated from thermal [1,2]-prototropy of the corresponding imino ester, employing differential scanning calorimetry (DSC), is surveyed. Glycine and phenylalanine derived imino esters have different behavior. The first one prefers reacting with itself at 75 ºC, rather than with the dipolarophile. However, the α-substituted imino ester gives the cycloadduct at higher temperatures. The thermal dynamic analysis by 1H NMR of the neat reaction mixture of the glycine derivative reveals the presence of signals corresponding to the dipole in very small proportion. The non-isothermal and isothermal DSC curves of the cycloaddition of phenylalaninate and diisobutyl fumarate are obtained from freshly prepared samples. The application of known kinetic models and mathematical multiple non-linear regressions (NLR) allow to determine and to compare Ea, lnA, reaction orders, and reaction enthalpy. Finally a rate equation for each different temperature can be established for this particular thermal cycloaddition.

Sulfur resistance of Pt-W catalysts

The sulfur resistance of low-loaded monometallic Pt catalysts and bimetallic Pt-W catalysts during the partial selective hydrogenation of styrene, a model compound of Pygas streams, was studied. The effect of metal impregnation sequence on the activity and selectivity was also evaluated. Catalysts were characterized by ICP, TPR, XRD, and XPS techniques. Catalytic tests with sulfur-free and sulfur-doped feeds were performed. All catalysts showed high selectivities (>98%) to ethylbenzene. Activity differences between the catalysts were mainly attributed to electronic effects due to the presence of different electron-rich species of Pt0 and electron-deficient species of Ptδ+. Pt0 promotes the cleavage of H2 while Ptδ+ the adsorption of styrene. The catalyst successively impregnated with W and Pt (WPt/Al) was more active and sulfur resistant than the catalyst prepared with an inverse impregnation order (PtW/Al). The higher poison resistance of WPt/Al was attributed to both steric and electronic effects.

Metal and precursor effect during 1-heptyne selective hydrogenation using an activated carbon as support

Palladium, platinum, and ruthenium supported on activated carbon were used as catalysts for the selective hydrogenation of 1-heptyne, a terminal alkyne. All catalysts were characterized by temperature programmed reduction, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. TPR and XPS suggest that the metal in all catalysts is reduced after the pretreatment with H2 at 673 K. The TPR trace of the PdNRX catalyst shows that the support surface groups are greatly modified as a consequence of the use of HNO3 during the catalyst preparation. During the hydrogenation of 1-heptyne, both palladium catalysts were more active and selective than the platinum and ruthenium catalysts. The activity order of the catalysts is as follows: PdClRX > PdNRX > PtClRX ≫ RuClRX. This superior performance of PdClRX was attributed in part to the total occupancy of the d electronic levels of the Pd metal that is supposed to promote the rupture of the H2 bond during the hydrogenation reaction. The activity differences between PdClRX and PdNRX catalysts could be attributed to a better accessibility of the substrate to the active sites, as a consequence of steric and electronic effects of the superficial support groups. The order for the selectivity to 1-heptene is as follows: PdClRX = PdNRX > RuClRX > PtClRX, and it can be mainly attributed to thermodynamic effects.

Innovación docente mediante recursos de investigación (GeoMar: docencia universitaria de las Geociencias Marinas)

En el contexto de los proyectos “Redes de investigación en docencia universitaria de la Universidad de Alicante” se ha establecido la red de trabajo “GeoMar: Red de investigación en docencia universitaria de las Geociencias Marinas”. En el marco esta esta red se presenta un ejemplo de innovación docente desarrollado en la asignatura “Planctología aplicada y Micropaleontología marina”. Esta actividad se fundamenta en la utilización de recursos avanzados de investigación como son el Centro de Investigación Marina de Santa Pola y los Servicios Técnicos de Investigación de la Universidad de Alicante. El plan de aprendizaje consiste esencialmente en el desarrollo de clases teórico-prácticas/tutorías grupales donde los alumnos desarrollan de forma autónoma un trabajo de iniciación a la investigación. Finalmente, se presentan los trabajos, desarrollados en comunicación tipo poster, en un mini-congreso de carácter informal denominado “Encuentro de Jóvenes Investigadores en Micropaleontología Marina”. Estos posters fueron expuestos también, como ejemplo de trabajo de iniciación a la investigación, en “III Encuentro de Investigación del Instituto Multidisciplinar para el estudio del Medio” organizado en la Facultad de Ciencias. Asimismo, esta actividad docente ha derivado en que en la actualidad dos alumnos se encuentren realizando sus trabajos fin de grado en la temática relacionada con la asignatura.

Cabezo Pardo. Análisis instrumental de materiales de construcción de barro del yacimiento argárico

Partiendo del análisis instrumental de cuatro pequeños fragmentos constructivos se intenta, en lo posible, contestar a una serie de cuestiones básicas señaladas por algunos autores (De Chazelles y Poupet, 1989: 10-11; Sánchez García, 1995: 350; 1997: 142) para poder comprender el nivel técnico de una época o cultura y la evolución de sus técnicas constructivas, en este caso aplicadas a la fase argárica del yacimiento del Cabezo Pardo.

Main ecological gradients and landscape matrix affect wild rabbit Oryctolagus cuniculus (Linnaeus, 1758) (Mammalia: Leporidae) abundance in a coastal region (South-East Spain)

Landscape analysis with transects, in the Marina Baja area (province of Alicante, Spain), has contributed to establish the influence of different landscape matrices and some environmental gradients on wild rabbit Oryctolagus cuniculus (Linnaeus, 1758) (Mammalia: Leporidae) abundance (kilometric abundance index, KAI). Transects (n = 396) were developed to estimate the abundance of this species in the study area from 2006 to 2008.Our analysis shows that rabbits have preferences for a specific land use matrix (irrigated: KAI = 3.47 ± 1.14 rabbits/km). They prefer the coastal area (KAI = 3.82 ± 1.71 rabbits/km), which coincides with thermo-Mediterranean (a bioclimatic belt with a tempered winter and a hot and dry summer with high human density), as opposed to areas in the interior (continental climate with lower human occupation). Their preference for the southern area of the region was also noted (KAI = 8.22 ± 3.90 rabbits/km), which coincides with the upper semi-arid area, as opposed to the northern and intermediate areas (the north of the region coinciding with the upper dry and the intermediate area with the lower dry). On the other hand, we found that the number of rabbits increased during the 3-year study period, with the highest abundance (KAI = 2.71 ± 1.30 rabbits/km) inMay. Thus, this study will enable more precise knowledge of the ecological factors (habitat variables) that intervene in the distribution of wild rabbit populations in a poorly studied area.

Galanet (Elche): análisis químico instrumental de los materiales de construcción

En el caso del yacimiento de Galanet sólo se han documentado 15 fragmentos de este tipo. Con estos condicionantes y a partir del análisis instrumental de tres de estos fragmentos intentaremos, dentro de los posible, responder a una serie de cuestiones que algunos autores (De Chazelles, Poupet, 1989, 10-11; Sánchez García, 1995, 350, Sánchez García, 1997, 142) han señalado como básicas para poder comprender el nivel técnico de una época o cultura y la evolución de sus técnicas constructivas, en este caso aplicadas al yacimiento de Galanet: -Determinar la procedencia del material utilizado. -Saber si la elección del material utilizado se debe a imperativos geológicos o prima en ella una decisión antrópica. -Si el material se ha usado en bruto o ha sufrido algún tratamiento previo. -Si la mayoría de las estructuras analizadas presentan una misma composición o por el contrario se utilizan diferentes composiciones en función del tipo de estructura. -Si la técnica utilizada es propia de una cronología, etapa cultural o área geográfica determinada con lo que se constituiría en un indicador cultural o por el contrario es inespecífica. -Si las soluciones técnicas empleadas son fruto del desarrollo interno de las fuerzas productivas o se deben a influencias foráneas. Es evidente que parte de estas cuestiones no se podrán contestar dado que solo contamos con unos pequeños fragmentos de material constructivo de apenas unos pocos centímetros y, sobre todo, que desconocemos cualquier detalle sobre el área de habitación del poblado de Galanet. Pero, al menos, intentaremos contribuir a conocerlo mejor.

Nanoparticles of tungsten as low-cost monometallic catalyst for selective hydrogenation of 3-hexyne

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Technical Services vs. Public Service

Regarding this issue, it seems appropriate to quote Gorman who says: And it came to pass that when Kutta, assistant God made the first library, she noted that it was good. So he called together all librarians and divided as a shepherd divides the sheep and goats. The first group spoke to him saying: you will dwell in the clarity and serve the readers and their glory will be great. Then he turned to the second group and spoke to him saying: you will dwell in the darkness. Secret must be hidden effort and work. You do not know the reader nor shall you know them. Go away and sort ... and has been up to these days (1979, p. 435).

Influence of alkylphosphonic acid grafting on the electronic and magnetic properties of La2/3Sr1/3MnO3 surfaces

Self-assembled monolayers (SAMs) are highly promising materials for molecular engineering of electronic and spintronics devices thanks to their surface functionalization properties. In this direction, alkylphosphonic acids have been used to functionalize the most common ferromagnetic electrode in organic spintronics: La2/3Sr1/3MnO3 (LSMO). However, a study on the influence of SAMs grafting on LSMO electronic and magnetic properties is still missing. In this letter, we probe the influence of alkylphosphonic acids-based SAMs on the electronic and magnetic properties of the LSMO surface using different spectroscopies. We observe by X-ray photoemission and X-ray absorption that the grafting of the molecules on the LSMO surface induces a reduction of the Mn oxidation state. Ultraviolet photoelectron spectroscopy measurements also show that the LSMO work function can be modified by surface dipoles opening the door to both tune the charge and spin injection efficiencies in organic devices such as organic light-emitting diodes.

Selective hydrogenation by novel composite supported Pd egg-shell catalysts

Two organic–inorganic mixed phase supports were prepared, comprising an alumina filler and polymers of different chemical nature. Four low loaded Pd catalysts were prepared. Good activities and selectivities were obtained during the hydrogenations of styrene, 1-heptyne and 2,3-butanedione. The catalysts were found to have excellent mechanical properties and could be used in applications needing high attrition resistance and crushing strength. In this sense, processes for fine chemicals using slurry reactors or processes for commodities using long packed beds could advantageously use them.

Platinum supported on highly-dispersed ceria on activated carbon for the total oxidation of VOCs

Catalysts consisting in platinum supported on cerium oxide highly dispersed on activated carbon, with a Pt loading of 1 wt.% and ceria loadings of 5, 10 and 20 wt.% have been prepared by impregnation method and characterized by several techniques (N2 adsorption at 77 K, ICP, XRD, H2-TPR and XPS). Their catalytic behavior has been evaluated in the total oxidation of ethanol and toluene after reduction at 473 K. The obtained results show that the prepared catalysts have better performances than platinum supported on bulk CeO2. The best catalytic performance was obtained for 10 wt.% ceria loading, likely due to an optimum synergistic interaction between highly dispersed cerium oxide and platinum particles. Pt-10Ce/C achieves total conversion of ethanol and toluene to CO2 at 433 K and 453 K, respectively, and shows no deactivation during a test for 100 h. Under humid conditions (relative humidity, RH, of 40 and 80%), the activity was only slightly influenced due to the hydrophobic character of the activated carbon support, which prevents the adsorption of water.