Estudio de la evolución temporal de los caracteres madurativos de las cepas listán negro, listán blanco y negramoll en la denominación de origen Tacoronte-Acentejo

Dado que en la actualidad el sector vitivinícola en Canarias ha sufrido un gran crecimiento cuantitativo y cualitativo, el Departamento de Ingeniería Química y Tecnología Farmacéutica, en colaboración con distintos organismos oficiales se ha propuesto el estudio físico-químico de las variedades de uva más abundantes en la Denominación de Orígen Tacoronte-Acentejo, con el fin de proporcionar al bodeguero y enólogo datos analíticos y fiables que sirvan para conocer el potencial enológico de sus variedades, y que esto contribuya a una mejora de la calidad final de los vinos. Se estudian las influencias de los diferentes parámetros físico-químicos anlizados de los factores externos (clima, situación, prácticas de cultivo, etc.), así como la caracterización de cada variedad en el momento de la vendimia. Se establecen relaciones enológicas que determinan con una gran fiabilidad la fecha óptima de la vendimi

Turbulence Transport in Rotor-Stator and Stator-Rotor Stages of Axial Flow Fans

Turbulence analysis in turbomachines is a complex task. The combination of different turbulence sources and transport mechanisms poses the question of determining adequate metrics to quantify turbulence levels and provide insight into the flow structure and its evolution. Apart from experimental measurement techniques, numerical techniques arise as a useful tool to characterize this type of flow, especially hybrid LES techniques that allow a highly accurate description of the transport of turbulent structures, while turbulence generation at solid boundaries is addressed using RANS schemes. In this chapter, recent developments concerning numerical simulation of rotor-stator and stator-rotor interactions in low-speed axial fans using LES techniques are presented. A post-processing framework is introduced to segregate the deterministic and turbulent components of the unsteady flow, allowing an accurate description of both phenomena. Hence, turbulent transport over the different stage rows of the axial fan can be accurately addressed. Following, LES capacities to simulate turbulence transport mechanisms such as breaking-up of turbulent eddies, stretching and dissipation of vorticity or identification and convection of coherent vortices are discussed. The ability of LES computations to disclose flow turbulence in rotor-stator environments at off-design conditions is specially illustrated

Reacciones de cicloadición y cicloisomerización catalizadas por oro en compuestos "Push-pull" : síntesis regioselectiva de heterociclos

INTRODUCCIÓN. La presente memoria describe los resultados obtenidos en el estudio de la reactividad de sistemas alquinílicos funcionalizados en presencia de complejos de metales de transición, sobretodo especies de oro (I), como catalizadores. Se discuten, a modo de introducción, los aspectos generales de la activación carbofílica por oro1 y la capacidad de este metal para promover reacciones de cicloadición y cicloisomerización en presencia de nucleófilos. PARTE A. Objetivo. El objetivo de esta parte es el desarrollo de nuevos procesos hetero-deshidro-Diels-Alder en los que intervengan sistemas insaturados como eninófilos, tales como aldehídos, iminas, sililiminas, (E)-estirilpirrolidina o acetilenos electrónicamente ricos; frente a sistemas dienínicos ¿push-pull¿. Metodología empleada. Se han utilizado diversos catalizadores metálicos para promover reacciones de cicloadición, entre sistemas dienínicos ¿push-pull¿2 y diferentes sistemas insaturados. Conclusiones. Se ha desarrollado una nueva reacción de síntesis totalmente regio- y diasteroselectiva de dihidropiridonas N-sustituidas con rendimientos moderados. Esta transformación transcurre a través de una reacción hetero-deshidro-Diels-Alder3 catalizada por metales de transición, principalmente por oro, en la que intervienen dieninos ¿push-pull¿ y aldiminas (Sección A.3.3.). Por otra parte, la reacción con sililiminas genera, tras hidrólisis, 5,6-dihidropiridonas N-no sustituidas también de forma regio- y diasteroselectiva con rendimientos moderados (Sección A.3.4.). Consideradas en su conjunto, las reacciones de dieninos ¿push-pull¿ y aldiminas o sililiminas permiten acceder a dihidropiridonas polisustituidas que presentan tres puntos de diversidad de forma totalmente regio y diastereoselectiva.4 Además, se han llevado a cabo estudios preliminares usando otros nucleófilos insaturados como aldehídos, enaminas y alcoxiacetilenos, que indican que: El empleo de aldehídos como eninófilos frente a dieninos ¿push-pull¿ da lugar a la formación de sistemas triénicos con rendimientos moderados mediante una secuencia ciclación [2+2] / retro [2+2] (Sección A.3.2.). Cuando se utiliza una enamina se accede a estirenos polisustituidos (Sección A.3.7.). El empleo de alcoxiacetilenos internos genera trienos carbobicíclicos[4.2.0] en un proceso novedoso de ciclación [6+2] (Sección A.3.8.). PARTE B. Objetivo. Teniendo en cuenta la presencia del anillo de oxepinona en varios productos naturales para los que no existen muchos modos de síntesis, se propone como objetivo la optimización de las condiciones de reacción y la generalización para la formación de este tipo de compuestos a partir de ácidos alquinilciclopropano carboxílicos. Asimismo, se plantea como objetivo el análisis de los requerimientos electrónicos en el anillo de ciclopropano necesarios para que el proceso tenga lugar. Metodología empleada. En la parte B se desarrollan diferentes procesos de cicloisomerización de derivados de alquinilciclopropanos "push-pull" promovidos por catalizadores de oro (I) para la síntesis de heterociclos. Conclusiones. Se han descrito nuevos procesos de cicloisomerización catalizados por oro de derivados de alquinilciclopropanos. Cuando estos alquinilciclopropanos tienen carácter ¿push-pull¿ se produce un proceso en cascada que consistiría probablemente en un ataque nucleófilo seguido de una apertura de anillo, y que ha permitido la síntesis de anillos de siete eslabones más difícilmente accesibles que los anillos de cinco o seis eslabones debido a su menor estabilidad. De este modo, cuando se han utilizado derivados ácidos o amidas se han sintetizado de manera regioselectiva oxepinonas o azepinonas, que son heterociclos presentes en el esqueleto de diversos productos naturales. (Secciones B.4.2. y B.4.4.) Por otra parte los derivados alcoholes o amina de estos alquinilciclopropanos, que carecen de un sustituyente aceptor de densidad electrónica, no experimentan el proceso en cascada teniendo lugar solo el ataque nucleófilo, de forma regioselectiva en la mayoría de los casos, y dando lugar a biciclos [4.1.0] en los que no ha tenido lugar la apertura del ciclopropano. (Secciones B.4.3. y B.4.5.) Los alcoholes permiten la síntesis de dihidropiranonas cuando se calientan en presencia de catalizadores de oro (I). Estos resultados unidos a los descritos en el párrafo anterior ponen de manifiesto la posibilidad de dirigir térmicamente la reactividad de los alcoholes hacia unos u otros productos de reacción: biciclos[4.1.0] o piranonas.(Sección B.4.3.). BIBLIOGRAFÍA DESTACADA. 1 Para revisiones recientes de catálisis de oro en síntesis orgánica, ver: [a] A. S. K. Hashmi, Gold Bull. 2004, 37, 51. [b] A. Hoffman-Röder, N. Krause, Org. Biomol. Chem. 2005, 3, 387. [c] A. S. K. Hashmi, G. J. Hutchings, Angew. Chem. Int. Ed. 2006, 45, 7896. [d] D. J. Gorin, F. D. Toste, Nature 2007, 446, 395. [e] A. Fürstner, P. W. Davies, Angew. Chem. Int. Ed. 2007, 46, 3410. [f] E. Jiménez-Núñez, A. M. Echavarren, Chem. Commun. 2007, 43, 333. [g] A. S. K. Hashmi, Chem. Rev. 2007, 107, 3180. [h] D. J. Gorin, B. D. Sherry, F. D. Toste, Chem. Rev. 2008, 108, 3351. [i] Z. Li, C. Brouwer, C. He, Chem. Rev. 2008, 108, 3239. [j] A. Arcadi, Chem. Rev. 2008, 108, 3266. [k] R. A. Widenhoefer, Chem. Eur. J. 2008, 14, 5382. [l] A. Fürstner, Chem. Soc. Rev. 2009, 38, 3208. [m] A. Corma, A. Leyva-Pérez, M. J. Sabater, Chem. Rev. 2011, 111, 1657. [n] N. Krause, C. Winter, Chem. Rev. 2011, 111, 1994. [o] F. López, J. L. Mascareñas, Beilstein J. Org. Chem. 2011, 7, 1075. [p] B. Alcaide, P. Almendros, J. M. Alonso, Org. Biomol. Chem. 2011, 9, 4405. [q] L.-P. Liu, G. B. Hammond, Chem. Soc. Rev. 2012, 41, 3129. [r] D. Garayalde, C. Nevado, ACS Catalysis 2012, 2, 1462. [s] M. Rudolph, A. S. K. Hashmi, Chem. Soc. Rev. 2012, 41, 2256. 2 [a] J. Barluenga, P. García-García, D. de Sáa, M. A. Fernández-Rodríguez, R. Bernardo de la Rúa, A. Ballesteros, E. Aguilar, M. Tomás, Angew. Chem. Int. Ed. 2007, 46, 2610. [b] J. Barluenga, M. A. Fernández-Rodríguez, P. García-García, E. Aguilar, J. Am. Chem. Soc. 2008, 130, 2764. [c] P. García-García, M. A. Fernández-Rodríguez, E. Aguilar, Angew. Chem. Int. Ed. 2009, 48, 5534. 3 P. Wessig, G. Müller, Chem. Rev. 2008, 108, 2051. 4 J. M Fernández-García, M. A. Fernández-Rodríguez, E. Aguilar, Org. Lett. 2011, 13, 5172

Methods for autonomous wristband placement with a search-and-rescue aerial manipulator

A new robotic system for Search And Rescue (SAR) operations based on the automatic wristband placement on the victims’ arm, which may provide identification, beaconing and remote sensor readings for continuous health monitoring. This paper focuses on the development of the automatic target localization and the device placement using an unmanned aerial manipulator. The automatic wrist detection and localization system uses an RGB-D camera and a convolutional neural network based on the region faster method (Faster R-CNN). A lightweight parallel delta manipulator with a large workspace has been built, and a new design of a wristband in the form of a passive detachable gripper, is presented, which under contact, automatically attaches to the human, while disengages from the manipulator. A new trajectory planning method has been used to minimize the torques caused by the external forces during contact, which cause attitude perturbations. Experiments have been done to evaluate the machine learning method for detection and location, and for the assessment of the performance of the trajectory planning method. The results show how the VGG-16 neural network provides a detection accuracy of 67.99%. Moreover, simulation experiments have been done to show that the new trajectories minimize the perturbations to the aerial platform.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

A DFTand TD-DFTApproach to the Understanding of Statistical Kinetics in Substitution Reactions of M3Q4 (M=Mo, W; Q=S, Se) Cuboidal Clusters

For many years it has been known that the nine water molecules in [M3Q4(H2O)9]4+ cuboidal clusters (M= Mo, W; Q=S, Se) can be replaced by entering ligands, such as chloride or thiocyanate, and kinetic studies carried out mainly on the substitution of the first water molecule at each metal centre reveal that the reaction at the three metal centres occurs with statistical kinetics; that is, a single exponential with a rate constant corresponding to the reaction at the third centre is observed instead of the expected threeexponential kinetic trace. Such simplification of the kinetic equations requires the simultaneous fulfilment of two conditions: first that the three consecutive rate constants are in statistical ratio, and second that the metal centres behave as independent chromophores. The validity of those simplifications has been checked for the case of the reaction of [Mo3S4(H2O)9]4+ with Cl by using DFT and TD-DFT theoretical calculations. The results of those calculations are in agreement with the available experimental information, which indicates that the H2O ligands trans to the m-S undergo substitution much faster than those trans to the m3-S. Moreover, the energy barriers for the substitution of the first water molecule at the three metal centres are close to each other, the differences being compatible with the small changes in the numerical values of the rate constants required for observation of statistical kinetics. TD-DFT calculations lead to calculated electronic spectra, which are in reasonable agreement with those experimentally measured, but the calculations do not indicate that the three metal centres behave as independent chromophores, although the mathematical conditions required for simplification of the kinetic traces to a single exponential are reasonably well fulfilled at certain wavelengths. A re-examination of the kinetics of the reaction by using global fitting procedures yields results, which are compatible with statistical kinetics, although an alternative interpretation in which substitution only occurs at a single metal centre under reversible conditions is also possible

Structural effects of steel reinforcement corrosion on statically indeterminate reinforced concrete members

The final publication is available at Springer via http://dx.doi.org/10.1617/s11527-016-0836-2Steel corrosion in reinforced concrete structures produces loss of reinforcement area and damage in the surrounding concrete. As a consequence, increases in deflections, crack widths and stresses may take place, as well as a reduction of the bearing capacity, which depends on the structural scheme and redundancy. In this paper an experimental study of twelve statically indeterminate beams subjected to different levels of forced reinforcement corrosion is presented. Different sustained loads were applied during the corrosion phase to assess their influence on the effects of corrosion. An important increase in deflections was registered in all corroded beams, especially in those subject to higher load levels. It was also found that the rate of corrosion was affected by the load level. Internal forces redistributions due to induced damage were measured. Finally, the experimental results were compared with those predicted by a non-linear time-dependent segmental analysis model developed by the authors, obtaining in general good agreement.Peer ReviewedPostprint (author's final draft

Educate Virtuality

El presente artículo está basado en una parte de una Tesis Doctoral centrada en la validación de un Modelo Educativo Holístico para el desarrollo de la autonomía, la responsabilidad y el compromiso social de las nuevas generaciones, y en la que se analizaba, entre otras actitudes, capacidades y competencias, el uso habitual de las nuevas tecnologías por los jóvenes. Las técnicas de recogida de datos fueron tanto cuantitativas como cualitativas. Utilizando una escala tipo Likert con alumnos de 4º de ESO y Focus Group con equipos directivos y profesorado. Algunas de las conclusiones hacen referencia al uso habitual de las nuevas tecnologías por el alumnado, con el despliegue de una gran habilidad en el uso de dichos dispositivos y plataformas por parte de los jóvenes, pero también la dependencia que esta tecnología está desarrollando en ellos, al tiempo que se recababa información sobre el grado de autonomía y responsabilidad de los jóvenes, así como su sentido crítico para discriminar la información que les llega

The Merit-Order Effect of Energy Efficiency

The integration of certain amount of renewable generation in the wholesale market right-shifted the merit-order generation curve, which produces a noticeable reduction of the clearing price while slightly increases the traded energy (almost inelastic demand curve). The downward pressure on the clearing price is mainly due to the fact that the introduction of renewable generation bids with very low (even null) marginal cost, displaces to the right all kinds of conventional technologies (with higher marginal cost), including the technology which would otherwise have set the clearing market price. This right-shifted displacement of the merit-order generation curve leads to a lower wholesale clearing price, a small increment of the traded energy and a reduction of the total cost of the traded energy in the wholesale market. This is the key mechanism and its main effects on the market of the very well-known meritorder effect of the renewables. The promotion of energy-efficiency plans (industry and domestic) by policy-makers is expected to yield a reduction of the demand. As a result of the reduction of demand bids, the merit-order demand curve would experience a left-sifted displacement, which would produce a reduction of both the clearing price and the amount of traded energy. Consequently, the total cost of the traded energy also would diminish. As can be seen, the parallelism of the main effects on the market between the integration of renewable and energy efficiency evidences the existence of what can be called the merit-order effect of energy efficiency. To analyze the characteristics of this merit-order effect of the energy efficiency, a simplified model, based on the linearization of the market around the clearing point, is developed. This simplified model is also used to compare the merit-order effect of energy efficiency and renewables. A set of scenarios with energy efficiency and renewables have been generated in order to quantify the main effects on the Spanish/Iberian market for the year 2014

Renewables versus efficiency. A comparison for Spain

Along the last decades, renewable energy (especially wind) in Spain has undergone a significant development (lead by a small group of renewable promoters supported by institutional policies), contributing significantly to electric generation mix (42.8% renewable in 2014). On the contrary, the promotion of energy efficiency actions (accomplished by a large number of industrial and domestic consumers that are very poorly supported by energy policies), are still little explored. According to ODYSSEE-MURE, energy efficiency at the EU-28 level improved by 1.2%/year on average from 2000 to 2013, while for the case of Spain, the rate of improvement was only 0.6 %/year on average throughout that period (the lowest rate of energy efficiency improvement in the EU-28). This work seeks to compare the integration of renewable production with energy efficiency plans, in order to advance their potential economic impact in the wholesale market and consumers. To reach that goal, the hourly market data retrieved from the Spanish/Iberian Market Operator (OMIE) for 2014 will be used as a base. Then, a set of pseudoheuristic scenarios with integration of renewable production and energy efficiency (load saving) will be elaborated and analyzed to quantify what are expected to be the main effects on the Spanish electricity market and consumers. The results will show that energy efficiency exhibits the best performance in terms of economic efficiency (less cost of the traded energy) and environmental sustainability (greater replacement of fossil fuels).Ministerio de Economía y Competitividad PCIN-2015-043Ministerio de Economía y Competitividad ENE2015-69597-RMinisterio de Economía y Competitividad ENE2014-54115-