11 resultados para polarity

em Universidad Politécnica de Madrid


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he composition, strain and surface morphology of (0001)InGaN layers are investigated as a function of growth temperature (460–645 °C) and impinging In flux. Three different growth regimes: nitrogen-rich, metal-rich and intermediate metal-rich, are clearly identified and found to be in correlation with surface morphology and strain relaxation. Best epilayers’ quality is obtained when growing under intermediate metal-rich conditions, with 1–2 monolayers thick In ad-coverage. For a given In flux, the In incorporation decreases with increasing growth temperature due to InN thermal decomposition that follows an Arrhenius behavior with 1.84±0.12 eV activation energy.

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Plant trichomes play important protective functions and may have a major influence on leaf surface wettability. With the aim of gaining insight into trichome structure, composition and function in relation to water-plant surface interactions, we analyzed the adaxial and abaxial leaf surface of Quercus ilex L. (holm oak) as model. By measuring the leaf water potential 24 h after the deposition of water drops on to abaxial and adaxial surfaces, evidence for water penetration through the upper leaf side was gained in young and mature leaves. The structure and chemical composition of the abaxial (always present) and adaxial (occurring only in young leaves) trichomes were analyzed by various microscopic and analytical procedures. The adaxial surfaces were wettable and had a high degree of water drop adhesion in contrast to the highly unwettable and water repellent abaxial holm oak leaf sides. The surface free energy, polarity and solubility parameter decreased with leaf age, with generally higher values determined for the abaxial sides. All holm oak leaf trichomes were covered with a cuticle. The abaxial trichomes were composed of 8% soluble waxes, 49% cutin, and 43% polysaccharides. For the adaxial side, it is concluded that trichomes and the scars after trichome shedding contribute to water uptake, while the abaxial leaf side is highly hydrophobic due to its high degree of pubescence and different trichome structure, composition and density. Results are interpreted in terms of water-plant surface interactions, plant surface physical-chemistry, and plant ecophysiology.

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This paper presents an approach to compare two types of data, subjective data (Polarity of Pan American Games 2011 event by country) and objective data (the number of medals won by each participating country), based on the Pearson corre- lation. When dealing with events described by people, knowledge acquisition is difficult because their structure is heterogeneous and subjective. A first step towards knowing the polarity of the information provided by people consists in automatically classifying the posts into clusters according to their polarity. The authors carried out a set of experiments using a corpus that consists of 5600 posts extracted from 168 Internet resources related to a specific event: the 2011 Pan American games. The approach is based on four components: a crawler, a filter, a synthesizer and a polarity analyzer. The PanAmerican approach automatically classifies the polarity of the event into clusters with the following results: 588 positive, 336 neutral, and 76 negative. Our work found out that the polarity of the content produced was strongly influenced by the results of the event with a correlation of .74. Thus, it is possible to conclude that the polarity of content is strongly affected by the results of the event. Finally, the accuracy of the PanAmerican approach is: .87, .90, and .80 according to the precision of the three classes of polarity evaluated.

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The microstructural evolution of an AZ31 rolled sheet during dynamic deformation at strain rates of ∼103 s−1 has been investigated by electron backscatter diffraction, X-ray and neutron diffraction. The influence of orientation on the predominant deformation mechanisms and on the recovery processes taking place during deformation has been systematically examined. The results have been compared with those corresponding to the same alloy tested quasi-statically under equivalent conditions. It has been found that strain rate enhances the activation of extension twinning dramatically, while contraction and secondary twinning are not significantly influenced. The polarity of extension twinning is even reversed in some grains under selected testing conditions. Significant grain subdivision by the formation of geometrically necessary boundaries (GNBs) takes place during both quasi-static and dynamic deformation of this AZ31 alloy. It is remarkable that GNBs of high misorientations form even at the highest strain rates. The phenomenon of recovery has been found to be orientation dependent

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Background Most aerial plant parts are covered with a hydrophobic lipid-rich cuticle, which is the interface between the plant organs and the surrounding environment. Plant surfaces may have a high degree of hydrophobicity because of the combined effects of surface chemistry and roughness. The physical and chemical complexity of the plant cuticle limits the development of models that explain its internal structure and interactions with surface-applied agrochemicals. In this article we introduce a thermodynamic method for estimating the solubilities of model plant surface constituents and relating them to the effects of agrochemicals. Results Following the van Krevelen and Hoftyzer method, we calculated the solubility parameters of three model plant species and eight compounds that differ in hydrophobicity and polarity. In addition, intact tissues were examined by scanning electron microscopy and the surface free energy, polarity, solubility parameter and work of adhesion of each were calculated from contact angle measurements of three liquids with different polarities. By comparing the affinities between plant surface constituents and agrochemicals derived from (a) theoretical calculations and (b) contact angle measurements we were able to distinguish the physical effect of surface roughness from the effect of the chemical nature of the epicuticular waxes. A solubility parameter model for plant surfaces is proposed on the basis of an increasing gradient from the cuticular surface towards the underlying cell wall. Conclusions The procedure enabled us to predict the interactions among agrochemicals, plant surfaces, and cuticular and cell wall components, and promises to be a useful tool for improving our understanding of biological surface interactions.

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Background Most aerial plant parts are covered with a hydrophobic lipid-rich cuticle, which is the interface between the plant organs and the surrounding environment. Plant surfaces may have a high degree of hydrophobicity because of the combined effects of surface chemistry and roughness. The physical and chemical complexity of the plant cuticle limits the development of models that explain its internal structure and interactions with surface-applied agrochemicals. In this article we introduce a thermodynamic method for estimating the solubilities of model plant surface constituents and relating them to the effects of agrochemicals. Results Following the van Krevelen and Hoftyzer method, we calculated the solubility parameters of three model plant species and eight compounds that differ in hydrophobicity and polarity. In addition, intact tissues were examined by scanning electron microscopy and the surface free energy, polarity, solubility parameter and work of adhesion of each were calculated from contact angle measurements of three liquids with different polarities. By comparing the affinities between plant surface constituents and agrochemicals derived from (a) theoretical calculations and (b) contact angle measurements we were able to distinguish the physical effect of surface roughness from the effect of the chemical nature of the epicuticular waxes. A solubility parameter model for plant surfaces is proposed on the basis of an increasing gradient from the cuticular surface towards the underlying cell wall. Conclusions The procedure enabled us to predict the interactions among agrochemicals, plant surfaces, and cuticular and cell wall components, and promises to be a useful tool for improving our understanding of biological surface interactions.

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Esta memoria está basada en el crecimiento y caracterización de heteroestructuras Al(Ga)N/GaN y nanocolumnas ordenadas de GaN, y su aplicación en sensores químicos. El método de crecimiento ha sido la epitaxia de haces moleculares asistida por plasma (PAMBE). En el caso de las heteroestructuras Al(Ga)N/GaN, se han crecido barreras de distinto espesor y composición, desde AlN de 5 nm, hasta AlGaN de 35 nm. Además de una caracterización morfológica, estructural y eléctrica básica de las capas, también se han fabricado a partir de ellas dispositivos tipo HEMTs. La caracterización eléctrica de dichos dispositivos (carga y movilidad de en el canal bidimensional) indica que las mejores heteroestructuras son aquellas con un espesor de barrera intermedio (alrededor de 20 nm). Sin embargo, un objetivo importante de esta Tesis ha sido verificar las ventajas que podían tener los sensores basados en heteroestructuras AlN/GaN (frente a los típicos basados en AlGaN/GaN), con espesores de barrera muy finos (alrededor de 5 nm), ya que el canal de conducción que se modula por efecto de cambios químicos está más cerca de la superficie en donde ocurren dichos cambios químicos. De esta manera, se han utilizado los dispositivos tipo HEMTs como sensores químicos de pH (ISFETs), y se ha comprobado la mayor sensibilidad (variación de corriente frente a cambios de pH, Ids/pH) en los sensores basados en AlN/GaN frente a los basados en AlGaN/GaN. La mayor sensibilidad es incluso más patente en aplicaciones en las que no se utiliza un electrodo de referencia. Se han fabricado y caracterizado dispositivos ISFET similares utilizando capas compactas de InN. Estos sensores presentan peor estabilidad que los basados en Al(Ga)N/GaN, aunque la sensibilidad superficial al pH era la misma (Vgs/pH), y su sensibilidad en terminos de corriente de canal (Ids/pH) arroja valores intermedios entre los ISFET basados en AlN/GaN y los valores de los basados en AlGaN/GaN. Para continuar con la comparación entre dispositivos basados en Al(Ga)N/GaN, se fabricaron ISFETs con el área sensible más pequeña (35 x 35 m2), de tamaño similar a los dispositivos destinados a las medidas de actividad celular. Sometiendo los dispositivos a pulsos de voltaje en su área sensible, la respuesta de los dispositivos de AlN presentaron menor ruido que los basados en AlGaN. El ruido en la corriente para dispositivos de AlN, donde el encapsulado no ha sido optimizado, fue tan bajo como 8.9 nA (valor rms), y el ruido equivalente en el potencial superficial 38.7 V. Estos valores son más bajos que los encontrados en los dispositivos típicos para la detección de actividad celular (basados en Si), y del orden de los mejores resultados encontrados en la literatura sobre AlGaN/GaN. Desde el punto de vista de la caracterización electro-química de las superficies de GaN e InN, se ha determinado su punto isoeléctrico. Dicho valor no había sido reportado en la literatura hasta el momento. El valor, determinado por medidas de “streaming potential”, es de 4.4 y 4 respectivamente. Este valor es una importante característica a tener en cuenta en sensores, en inmovilización electrostática o en la litografía coloidal. Esta última técnica se discute en esta memoria, y se aplica en el último bloque de investigación de esta Tesis (i.e. crecimiento ordenado). El último apartado de resultados experimentales de esta Tesis analiza el crecimiento selectivo de nanocolumnas ordenadas de GaN por MBE, utilizando mascaras de Ti con nanoagujeros. Se ha estudiado como los distintos parámetros de crecimiento (i.e. flujos de los elementos Ga y N, temperatura de crecimiento y diseño de la máscara) afectan a la selectividad y a la morfología de las nanocolumnas. Se ha conseguido con éxito el crecimiento selectivo sobre pseudosustratos de GaN con distinta orientación cristalina o polaridad; templates de GaN(0001)/zafiro, GaN(0001)/AlN/Si, GaN(000-1)/Si y GaN(11-20)/zafiro. Se ha verificado experimentalmente la alta calidad cristalina de las nanocolumnas ordenadas, y su mayor estabilidad térmica comparada con las capas compactas del mismo material. Las nanocolumnas ordenadas de nitruros del grupo III tienen una clara aplicación en el campo de la optoelectrónica, principalmente para nanoemisores de luz blanca. Sin embargo, en esta Tesis se proponen como alternativa a la utilización de capas compactas o nanocolumnas auto-ensambladas en sensores. Las nanocolumnas auto-ensambladas de GaN, debido a su alta razón superficie/volumen, son muy prometedoras en el campo de los sensores, pero su amplia dispersión en dimensiones (altura y diámetro) supone un problema para el procesado y funcionamiento de dispositivos reales. En ese aspecto, las nanocolumnas ordenadas son más robustas y homogéneas, manteniendo una alta relación superficie/volumen. Como primer experimento en el ámbito de los sensores, se ha estudiado como se ve afectada la emisión de fotoluminiscencia de las NCs ordenadas al estar expuestas al aire o al vacio. Se observa una fuerte caída en la intensidad de la fotoluminiscencia cuando las nanocolumnas están expuestas al aire (probablemente por la foto-adsorción de oxigeno en la superficie), como ya había sido documentado anteriormente en nanocolumnas auto-ensambladas. Este experimento abre el camino para futuros sensores basados en nanocolumnas ordenadas. Abstract This manuscript deals with the growth and characterization of Al(Ga)N/GaN heterostructures and GaN ordered nanocolumns, and their application in chemical sensors. The growth technique has been the plasma-assisted molecular beam epitaxy (PAMBE). In the case of Al(Ga)N/GaN heterostructures, barriers of different thickness and composition, from AlN (5 nm) to AlGaN (35 nm) have been grown. Besides the basic morphological, structural and electrical characterization of the layers, HEMT devices have been fabricated based on these layers. The best electrical characteristics (larger carriers concentration and mobility in the two dimensional electron gas) are those in AlGaN/GaN heterostructures with a medium thickness (around 20 nm). However, one of the goals of this Thesis has been to verify the advantages that sensors based on AlN/GaN (thickness around 7 nm) have compared to standard AlGaN/GaN, because the conduction channel to be modulated by chemical changes is closer to the sensitive area. In this way, HEMT devices have been used as chemical pH sensors (ISFETs), and the higher sensitivity (conductance change related to pH changes, Ids/pH) of AlN/GaN based sensors has been proved. The higher sensibility is even more obvious in application without reference electrode. Similar ISFETs devices have been fabricated based on InN compact layers. These devices show a poor stability, but its surface sensitivity to pH (Vgs/pH) and its sensibility (Ids/pH) yield values between the corresponding ones of AlN/GaN and AlGaN/GaN heterostructures. In order to a further comparison between Al(Ga)N/GaN based devices, ISFETs with smaller sensitive area (35 x 35 m2), similar to the ones used in cellular activity record, were fabricated and characterized. When the devices are subjected to a voltage pulse through the sensitive area, the response of AlN based devices shows lower noise than the ones based on AlGaN. The noise in the current of such a AlN based device, where the encapsulation has not been optimized, is as low as 8.9 nA (rms value), and the equivalent noise to the surface potential is 38.7 V. These values are lower than the found in typical devices used for cellular activity recording (based on Si), and in the range of the best published results on AlGaN/GaN. From the point of view of the electrochemical characterization of GaN and InN surfaces, their isoelectric point has been experimentally determined. Such a value is the first time reported for GaN and InN surfaces. These values are determined by “streaming potential”, being pH 4.4 and 4, respectively. Isoelectric point value is an important characteristic in sensors, electrostatic immobilization or in colloidal lithography. In particular, colloidal lithography has been optimized in this Thesis for GaN surfaces, and applied in the last part of experimental results (i.e. ordered growth). The last block of this Thesis is focused on the selective area growth of GaN nanocolumns by MBE, using Ti masks decorated with nanoholes. The effect of the different growth parameters (Ga and N fluxes, growth temperature and mask design) is studied, in particular their impact in the selectivity and in the morphology of the nanocolumns. Selective area growth has been successful performed on GaN templates with different orientation or polarity; GaN(0001)/sapphire, GaN(0001)/AlN/Si, GaN(000- 1)/Si and GaN(11-20)/sapphire. Ordered nanocolumns exhibit a high crystal quality, and a higher thermal stability (lower thermal decomposition) than the compact layers of the same material. Ordered nanocolumns based on III nitrides have a clear application in optoelectronics, mainly for white light nanoemitters. However, this Thesis proposes them as an alternative to compact layers and self-assembled nanocolumns in sensor applications. Self-assembled GaN nanocolumns are very appealing for sensor applications, due to their large surface/volume ratio. However, their large dispersion in heights and diameters are a problem in terms of processing and operation of real devices. In this aspect, ordered nanocolumns are more robust and homogeneous, keeping the large surface/volume ratio. As first experimental evidence of their sensor capabilities, ordered nanocolumns have been studied regarding their photoluminiscence on air and vacuum ambient. A big drop in the intensity is observed when the nanocolumns are exposed to air (probably because of the oxygen photo-adsortion), as was already reported in the case of self-assembled nanocolumns. This opens the way to future sensors based on ordered III nitrides nanocolumns.

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Resumen: El maar de Fuentillejo está localizado en la Región Volcánica Central de Campo de Calatrava (Ciudad Real). Desde su inicio se ha comportado como un sistema cerrado y presenta una potencia total de 142 m de sedimentos lacustres, organizados en 23 unidades sedimentarias. Se ha realizado un estudio de la susceptibilidad magnética y densidad aparente de los sedimentos, mediante un equipo de testificación multisensor Geotek. Para obtener la edad del registro se han efectuado dataciones absolutas mediante radiocarbono, U-Th y con el estudio de polaridad magnética, obteniéndose un modelo de edad que permite datar el sondeo FUENT-1 en torno a los 350 ka. Los datos del registro de susceptibilidad magnética, junto con las dataciones efectuadas, permiten identificar una secuencia de eventos erosivos relacionados con los últimos estadios glaciares (LGM: Ultimo Máximo Glaciar y los estadios isotópicos MIS 6 y 8). El registro de susceptibilidad magnética se encuentra atenuado por procesos de disolución de los óxidos de Fe-Ti. Abstract: The Fuentillejo maar is located in the Central Spanish Volcanic Field of Campo de Calatrava (Ciudad Real). Fuentillejo maar-lake was a closed system where up to 142 m depth of lacustrine sediments were deposited. Magnetic susceptibility and bulk density were measured by a GEOTEK multisensor core logger. The chronological framework was constructed based on radiocarbon and U-Th methods, as well as a detailed study of magnetic polarity, yielding an age model that covers last 350 ka. Intervals with terrigenous sediments correspond to high magnetic susceptibility values. These intervals were correlated with erosive events during the Last Glacial Maximum and the MIS 6 and 8 isotopic stages. The record of magnetic susceptibility is attenuated by disolution processes of Fe-Ti oxides.

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Axonal outgrowth and the formation of the axon initial segment (AIS) are early events in the acquisition of neuronal polarity. The AIS is characterized by a high concentration of voltage-dependent sodium and potassium channels. However, the specific ion channel subunits present and their precise localization in this axonal subdomain vary both during development and among the types of neurons, probably determining their firing characteristics in response to stimulation. Here, we characterize the developmental expression of different subfamilies of voltage-gated potassium channels in the AISs of cultured mouse hippocampal neurons, including subunits Kv1.2, Kv2.2 and Kv7.2. In contrast to the early appearance of voltage-gated sodium channels and the Kv7.2 subunit at the AIS, Kv1.2 and Kv2.2 subunits were tethered at the AIS only after 10 days in vitro. Interestingly, we observed different patterns of Kv1.2 and Kv2.2 subunit expression, with each confined to distinct neuronal populations. The accumulation of Kv1.2 and Kv2.2 subunits at the AIS was dependent on ankyrin G tethering, it was not affected by disruption of the actin cytoskeleton and it was resistant to detergent extraction, as described previously for other AIS proteins. This distribution of potassium channels in the AIS further emphasizes the heterogeneity of this structure in different neuronal populations, as proposed previously, and suggests corresponding differences in action potential regulation.

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In the intricate maturation process of [NiFe]-hydrogenases, the Fe(CN)2CO cofactor is first assembled in a HypCD complex with iron coordinated by cysteines from both proteins and CO is added after ligation of cyanides. The small accessory protein HypC is known to play a role in delivering the cofactor needed for assembling the hydrogenase active site. However, the chemical nature of the Fe(CN)2CO moiety and the stability of the cofactor–HypC complex are open questions. In this work, we address geometries, properties, and the nature of bonding of all chemical species involved in formation and binding of the cofactor by means of quantum calculations. We also study the influence of environmental effects and binding to cysteines on vibrational frequencies of stretching modes of CO and CN used to detect the presence of Fe(CN)2CO. Carbon monoxide is found to be much more sensitive to sulfur binding and the polarity of the medium than cyanides. The stability of the HypC–cofactor complex is analyzed by means of molecular dynamics simulation of cofactor-free and cofactor-bound forms of HypC. The results show that HypC is stable enough to carry the cofactor, but since its binding cysteine is located at the N-terminal unstructured tail, it presents large motions in solution, which suggests the need for a guiding interaction to achieve delivery of the cofactor.

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This paper presents a proposal for a recognition model for the appraisal value of sentences. It is based on splitting the text into independent sentences (full stops) and then analysing the appraisal elements contained in each sentence according to the previous value in the appraisal lexicon. In this lexicon, positive words are assigned a positive coefficient (+1) and negative words a negative coefficient (-1). We take into account word such as ?too?, ?little? (when it is not ?a bit?), ?less?, and ?nothing? than can modify the polarity degree of lexical unit when appear in the nearby environment. If any of these elements are present, then the previous coefficient will be multiplied by (-1), that is, they will change their sign. Our results show a nearly theoretical effectiveness of 90%, despite not achieving the recognition (or misrecognition) of implicit elements. These elements represent approximately 4% of the total of sentences analysed for appraisal and include the errors in the recognition of coordinated sentences. On the one hand, we found that 3.6 % of the sentences could not be recognized because they use different connectors than those included in the model; on the other hand, we found that in 8.6% of the sentences despite using some of the described connectors could not be applied the rules we have developed. The percentage relative to the whole group of appraisal sentences in the corpus was approximately of 5%.