Improving the activity of gold nanoparticles for the water-gas shift reaction using TiO2–Y2O3: an example of catalyst design

In the last ten years, there has been an acceleration in the pace at which new catalysts for the watergas shift reaction are designed and synthesized. Pt-based catalysts remain the best solution when only activity is considered. However, cost, operation temperature, and deactivation phenomena are important variables when these catalysts are scaled in industry. Here, a new catalyst, Au/TiO2–Y2O3, is presented as an alternative to the less selective Pt/oxide systems. Experimental and theoretical techniques are combined to design, synthesize, characterize and analyze the performance of this system. The mixed oxide demonstrates a synergistic effect, improving the activity of the catalyst not only at large-to-medium temperatures but also at low temperatures. This effect is related to the homogeneous dispersion of the vacancies that act both as nucleation centers for smaller and more active gold nanoparticles and as dissociation sites for water molecules. The calculated reaction path points to carboxyl formation as the rate-limiting step with an activation energy of 6.9 kcal mol 1, which is in quantitative agreement with experimental measurements and, to the best of our knowledge, it is the lowest activation energy reported for the water-gas shift reaction. This discovery demonstrates the importance of combining experimental and theoretical techniques to model and understand catalytic processes and opens the door to new improvements to reduce the operating temperature and the deactivation of the catalyst.Ministerio de Economía y Competitividad (CTQ2015-64669-P and ENE2015-66975- C3-2-R)Junta de Andalucía (FQM-132 and TEP-106)European Union (HT-PHOTO-DB No. 752608

Gold Nanoparticles on Yttrium Modified Titania: Support Properties and Catalytic Activity

A series of titanium oxide catalysts modified with yttrium has been prepared by sol¿gel method and their structural properties have been studied. The incorporation of yttrium in the titania lattice favors the formation of oxygen vacancies while at low Y loadings the anatase structure is preserved. The catalytic activity of these solids for CO oxidation is found to be significantly dependent on their physical properties. In particular the amount of dopant controls the number of surface oxygen vacancies created as well as the gold particle size, which directly affects the catalytic activity. Also, a linear relationship between the catalytic activity and the band gap values, which depend on the Y loading, is observed. Density functional theory based calculations show that Y atoms are incorporated at the TiO2 surface at substitutional positions only, while the preferred oxygen vacancies arise by removing the bridge surface oxygen atoms. These O-vacancies are the preferential adsorption sites for Au atoms and nanoparticles, acting as nucleation centers that favor the dispersion of the catalyst active phase over the support surface. In agreement with experiment, Y doping is found to decrease the band gap of the support due to a destabilization of the valence band of the oxide.Ministerio de Ciencia e Innovación ENE2009-14522-C05-01, MAT2008-04918, CSD-00023Junta de Andalucía P08-FQM-0366

4,5-Dibromo-2,7-di-tert-butyl-9,9-dimethyl-9H-thioxanthene

In the title compound, C23H28Br2S, the thioxanthene unit is twisted, showing a dihedral angle of 29.3 (5)° between the benzene rings. When projected along [001], the packing shows two types of channels. The crystal studied was a racemic twin

Life history baseline of unexploited populations: The case of Beryx splendens from the Sierra Leone Rise

This study examines for the first time the biology of alfonsino (Beryx splendens) from three small seamounts of the Sierra Leone Rise (SLR), an unexploited and fragile ecosystem in the Atlantic, using data from an experimental survey carried out in 2001 by Spanish longliners. In general, the lack of rigorous baseline data limits the implementation of efficient management and conservation plans in fisheries strategies. Therefore, the main aim of present study was to provide baseline information on basic biological parameters of the alfonsino population associated with an unexploited ecosystem. A total of 17296 individuals of alfonsino were sampled from SLR. Alfonsino is gonochoric and presented an unbalanced sex ratio, there were significantly more females than males. Taking into account the results in stage of maturity of alfonsino and the gonadosomatic index values during studied period, we can conclude that at least one reproductive period in these seamounts was in the late spring and early summer. The spawning stage was attained at a minimum fork length of 23 and 25 cm for males and females, respectively. The size at which 50% of the population attains sexual maturity was approximately 28 and 27 cm for males and females, respectively. The stock structure of alfonsino showed a segregation of the size with the depth, as they increase in size they move into the deeper water.Versión del edito

La interpersonalidad discursiva: una alternativa al metadiscurso interpersonal

El propósito de este artículo es proponer un nuevo concepto, interpersonalidad discursiva, como forma de flexibilizar el modelo del metadiscurso interpersonal (MI). Partimos de la probada validez del MI (Hyland, 2005a, 2005b) como marco de análisis de las relaciones interpersonales entre emisores y receptores en textos escritos y hablados. Nuestra argumentación se basa en nuestras investigaciones en diferentes géneros académicos y profesionales, con el foco en la interpersonalidad. Puesto que el MI está condicionado por diferentes variables contextuales, tal como sugieren diversos trabajos (Dahl, 2004; Sala, 2006; Yakhontova, 2006; Giannoni, 2007; Mapelli, 2008; Crismore y Abdollazadeh, 2010; Gotti, 2010; Lorés-Sanz 2011a; Ivorra Pérez, 2015, 2016; Suau-Jiménez 2016; Mattiello, 2018; Turiman y otros, 2018; Herrando-Rodrigo, 2019), este tendría que redefinirse o readaptarse para dar cuenta de nuevos marcadores y nuevas realizaciones léxico- gramaticales. Como resultado y de forma muy importante, se incluiría la proposicionalidad como rasgo teórico integrante de la interpersonalidad, que las definiciones tradicionales del MI no aceptan como tal. Por tanto, un nuevo concepto necesitaría ser acuñado, que incluyera estos nuevos aspectos esenciales. Partiendo de cómo ha sido definido el MI convencionalmente (Mauranen, 1993a, 1993b; Hyland, 2005a, 2017), proponemos dos conceptos integradores: giro discursivo (Jaworski y Pritchard, 2005), no en su sentido general filosófico/ideológico sino centrándose en el discurso particular de cada texto como eje identitario o punto de partida para el análisis, e interpersonalidad (Lorés-Sanz y otros, 2010), como un concepto-paraguas más amplio que el MI. Así, una nueva perspectiva llamada interpersonalidad discursiva podría hacer posible investigaciones más satisfactorias en géneros, dominios y lenguas diversos. The purpose of this paper is to propose a new concept, discursive interpersonality, as a flexibilized model of interpersonal metadiscourse (IM). Departing from the proven validity of IM (Hyland, 2005) as a framework to analyse interpersonal relations between writers/speakers and readers/listeners, our argumentation is grounded on our research results, stemming from the study of different academic and professional genres. Since interpersonal metadiscourse is conditioned by contextual variables, such as genre, discipline, language and corpus, as an array of authors suggest (Dahl, 2004; Sala, 2006; Yakhontova, 2006; Giannoni, 2007; Mapelli, 2008; Crismore & Abdollazadeh, 2010; Gotti, 2010; Lor s-Sanz, 2011a; Ivorra P rez, 2015, 2016; Suau-Jim nez, 2016; Mattiello, 2018; Turiman et al., 2018; Herrando-Rodrigo, 2019), IM would need to be redefined or readapted, including new markers, new lexico-grammatical realizations. As a result and very importantly, propositionality should be considered a theoretical central feature that contributes to interpersonal interactions but that traditional approaches of IM do not accept as such. So, a new, more encompassing concept needs to be coined that accounts for all these essential aspects. Assuming how interpersonal metadiscourse has been defined conventionally (Mauranen, 1993; Hyland, 2005a, 2017), we propose two integrative concepts: discursive turn (Jaworski & Pritchard, 2005), not in its philosophical sense but in one that sees discourse as an identity axis or departure point for analysis, and interpersonality (Lor s-Sanz et al., 2010), considered as an umbrella term broader than IM. Discursive interpersonality might thus open more satisfactory paths for further research in a variety of genres, domains and languages

Synthesis of the BCDE Molecular Fragment of Azadiradione Mediated by Titanocene(III)

[EN]A practical, short, and diastereoselective synthesis of the azadiradione BCDE fragment from a readily available starting material is described. The key step was the titanocene(III)-promoted tandem cyclization of unsaturated epoxy nitrile

El burnout en los profesores

p. 251-256Este estudio incluye una revisión de artículos empíricos internacionales sobre el burnout en los profesores. Se han encontrado nueve artículos sobre este tema. En primer lugar se hará referencia al diseño, así como a los instrumentos aplicados y al contexto educativo y finalmente se tendrán en cuenta las diferentes variables que pueden influir en la aparición de este síndromeS

La interpersonalidad discursiva como alternativa al metadiscurso interpersonal

El propósito de este artículo es proponer un nuevo concepto, interpersonalidad discursiva, como forma de flexibilizar el modelo del metadiscurso interpersonal (MI). Partimos de la probada validez del MI (Hyland, 2005a, 2005b) como marco de análisis de las relaciones interpersonales entre emisores y receptores en textos escritos y hablados. Nuestra argumentación se basa en nuestras investigaciones en diferentes géneros académicos y profesionales, con el foco en la interpersonalidad. Puesto que el MI está condicionado por diferentes variables contextuales, tal como sugieren diversos trabajos (Dahl, 2004; Sala, 2006; Yakhontova, 2006; Giannoni, 2007; Mapelli, 2008; Crismore y Abdollazadeh, 2010; Gotti, 2010; Lorés-Sanz 2011a; Ivorra Pérez, 2015, 2016; Suau-Jiménez, 2016; Mattiello, 2018; Turiman y otros, 2018; Herrando- Rodrigo, 2019), este tendría que redefinirse o readaptarse para dar cuenta de nuevos marcadores y nuevas realizaciones léxico-gramaticales. Como resultado y de forma muy importante, se incluir a la proposicionalidad como rasgo teórico integrante de la interpersonalidad, que las definiciones tradicionales del MI no aceptan como tal. Por tanto, un nuevo concepto necesitar a ser acuñado, que incluyera estos nuevos aspectos esenciales. Partiendo de cómo ha sido definido el MI convencionalmente (Mauranen, 1993a, 1993b; Hyland, 2005a, 2017), proponemos dos conceptos integradores: giro discursivo (Jaworski y Pritchard, 2005), no en su sentido general filosófico/ideológico sino centrándose en el discurso particular de cada texto como eje identitario o punto de partida para el análisis, e interpersonalidad (Lorés-Sanz y otros, 2010), como un concepto-paraguas más amplio que el MI. Así, una nueva perspectiva llamada interpersonalidad discursiva podría hacer posible investigaciones más satisfactorias en géneros, dominios y lenguas diversos. The purpose of this paper is to propose a new concept, discursive interpersonality, as a flexibilized model of interpersonal metadiscourse (IM). Departing from the proven validity of IM (Hyland, 2005a, 2005b) as a framework to analyse interpersonal relations between writers/speakers and readers/listeners, our argumentation is grounded on our research results, stemming from the study of different academic and professional genres. Since interpersonal metadiscourse is conditioned by contextual variables, such as genre, discipline, language and corpus, as an array of authors suggest (Dahl, 2004; Sala, 2006; Yakhontova, 2006; Giannoni, 2007; Mapelli, 2008; Crismore & Abdollazadeh, 2010; Gotti, 2010; Lorés-Sanz, 2011a; Ivorra Pérez, 2015, 2016; Suau-Jiménez, 2016; Mattiello, 2018; Turiman et al., 2018; Herrando-Rodrigo, 2019), IM would need to be redefined or readapted, including new markers, new lexico-grammatical realizations. As a result and very importantly, propositionality should be considered a theoretical central feature that contributes to interpersonal interactions but that traditional approaches of IM do not accept as such. So, a new, more encompassing concept needs to be coined that accounts for all these essential aspects. Assuming how interpersonal metadiscourse has been defined conventionally (Mauranen, 1993a, 1993b; Hyland, 2005a, 2017), we propose two integrative concepts: discursive turn (Jaworski & Pritchard, 2005), not in its philosophical sense but in one that sees discourse as an identity axis or departure point for analysis, and interpersonality (Lorés-Sanz et al., 2010), considered as an umbrella term broader than IM. Discursive interpersonality might thus open more satisfactory paths for further research in a variety of genres, domains and languages

Estudio interprofesional de variables psicoeducativas

p. 455-464El constructo burnout es considerado como una patología derivada más que factores genéticos, de las características del ambiente físico, de las demandas del puesto de trabajo, pero sobre todo de las relaciones interpersonales. Afecta principalmente a aquellos profesionales cuyos destinatarios principales de su labor profesional son las personas, incidiendo en diferentes aspectos de la calidad de vida afectando negativamente al desempeño de las tareas y funciones laborales, manifestándose también en un descenso de la motivación laboral de los profesionales La muestra está compuesta por (N= 594) profesionales españoles pertenecientes a diferentes sectores profesionales. A todos ellos se les pidió que cumplimentaran los siguientes cuestionarios e instrumentos: un cuestionario de variables sociodemográficas (VGS), el Cuestionario de Ambigüedad y Conflicto de Rol (CACR), el Maslach Burnout Inventory General Survey (MBI-GS) para evaluar el burnout, la Escala de Estrés Percibido (PSS-14) para evaluar el estrés, el Cuestionario de Personalidad (NEO-FFI), El cuestionario de Autoeficacia General Percibida (AEG) y la Escala de Motivación (ESCMOT). Los profesores de Educación Infantil obtienen altas puntuaciones en ambigüedad de rol poniéndose de manifiesto que tienen claras sus atribuciones, competencias, objetivos, responsabilidades, tareas y contenidos del trabajo, cómo hacerlo y lo que se espera de ellos. Con respecto al conflicto de rol, los bomberos son los que obtienen las puntuaciones más elevadas señalándose la incompatibilidad entre las tareas o con el tiempo del que se dispone, o procedentes de diferentes personas. Sin embargo en cuanto a la eficacia profesional, cabe señalarse que los profesores de Educación Infantil son los que obtienen las mayores puntuaciones poniéndose de relieve que son eficaces en su trabajo. Se discuten los resultados en relación con la utilidad para el consejo y asesoramiento psicoeducativoS

Pentachlorophenol Removal from Water by Soybean Peroxidase and Iron(II) Salts Concerted Action

[EN] Soybean peroxidase (SBP) has been employed for the treatment of aqueous solutions containing pentachlorophenol (PCP) in the presence of hydrogen peroxide at pH range 5-7. Reaction carried out with 1mg/L of PCP, 4mg/L of H2O2, and 1.3x10(-9)M of SBP showed a fast initial elimination of PCP (ca. 30% in 20min), but the reaction does not go beyond the removal of 50% of the initial concentration of PCP. Modification in SBP and PCP amounts did not change the reaction profile and higher amounts of H2O2 were detrimental for the reaction. Addition of Fe(II) to the system resulted in an acceleration of the process to reach nearly complete PCP removal at pH 5 or 6; this is more probably due to a synergetic effect of the enzymatic process and Fenton reaction. However, experiments developed in tap water resulted in a lower PCP elimination, but this inconvenience can be partly overcome by leaving the tap water overnight in an open vessel before reaction.We want to acknowledge Davide Mainero from Acea Pinerolese for his collaboration in this research. The authors want to thank the financial support of the European Union (PIRSES-GA-2010-269128, EnvironBOS and Marie Sklodowska-Curie Research and Innovation Staff Exchange projectH2020-MSCA-RISE-2014, Mat4treaT-project number: 645551) and Spanish Ministerio de Educacion y Ciencia (CTQ2015-69832-C4-4-R). Sara Garcia-Ballesteros would like to thank the Spanish Ministerio de Economia y Competitividad for her fellowship (BES-2013-066201).Tolardo, V.; García-Ballesteros, S.; Santos-Juanes Jordá, L.; Vercher Pérez, RF.; Amat Payá, AM.; Arqués Sanz, A.; Laurenti, E. (2019). Pentachlorophenol Removal from Water by Soybean Peroxidase and Iron(II) Salts Concerted Action. 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Pergamon. https://doi.org/10.1016/j.envint.2011.04.014