Oligodeoxynucleotide Duplexes Containing (5′S)-5′-C-Alkyl-Modified 2′-Deoxynucleosides: Can an Alkyl Zipper across the DNA Minor-Groove Enhance Duplex Stability?

10.1002/hlca.200390311.abs A series of oligonucleotides containing (5′S)-5′-C-butyl- and (5′S)-5′-C-isopentyl-substituted 2′-deoxyribonucleosides were designed, prepared, and characterized with the intention to explore alkyl-zipper formation between opposing alkyl chains across the minor groove of oligonucleotide duplexes as a means to modulate DNA-duplex stability. From four possible arrangements of the alkyl groups that differ in the density of packing of the alkyl chains across the minor groove, three (duplex types I–III, Fig. 2) could experimentally be realized and their duplex-forming properties analyzed by UV-melting curves, CD spectroscopy, and isothermal titration calorimetry (ITC), as well as by molecular modeling. The results show that all arrangements of alkyl residues within the minor groove of DNA are thermally destabilizing by 1.5–3°/modification in Tm. We found that, within the proposed duplexes with more loosely packed alkyl groups (type-III duplexes), accommodation of alkyl residues without extended distorsion of the helical parameters of B-DNA is possible but does not lead to higher thermodynamic stability. The more densely packed and more unevenly distributed arrangement (type-II duplexes) seems to suffer from ecliptic positioning of opposite alkyl groups, which might account for a systematic negative contribution to stability due to steric interactions. The decreased stability in the type-III duplexes described here may be due either to missing hydrophobic interactions of the alkyl groups (not bulky enough to make close contacts), or to an overcompensation of favorable alkyl-zipper formation presumably by loss of structured H2O in the minor groove.

Antisense properties of tricyclo-DNA.

Tricyclo (tc)-DNA belongs to the class of conformationally constrained DNA analogs that show enhanced binding properties to DNA and RNA. We prepared tc-oligonucleotides up to 17 nt in length, and evaluated their binding efficiency and selectivity towards complementary RNA, their biological stability in serum, their RNase H inducing potential and their antisense activity in a cellular assay. Relative to RNA or 2'-O-Me-phosphorothioate (PS)-RNA, fully modified tc-oligodeoxynucleotides, 10-17 nt in length, show enhanced selectivity and enhanced thermal stability by approximately 1 degrees C/modification in binding to RNA targets. Tricyclodeoxyoligonucleotides are completely stable in heat-deactivated fetal calf serum at 37 degree C. Moreover, tc-DNA-RNA duplexes are not substrates for RNase H. To test for antisense effects in vivo, we used HeLa cell lines stably expressing the human beta-globin gene with two different point mutations in the second intron. These mutations lead to the inclusion of an aberrant exon in beta-globin mRNA. Lipofectamine-mediated delivery of a 17mer tc-oligodeoxynucleotide complementary to the 3'-cryptic splice site results in correction of aberrant splicing already at nanomolar concentrations with up to 100-fold enhanced efficiency relative to a 2'-O-Me-PS-RNA oligonucleotide of the same length and sequence. In contrast to 2'-O-Me-PS-RNA, tc-DNA shows antisense activity even in the absence of lipofectamine, albeit only at much higher oligonucleotide concentrations.

Oxygen isotope record of oceanic and high-pressure metasomatism: a P-T-time-fluid path for the Monviso eclogites (Italy)

Fluids are considered a fundamental agent for chemical exchanges between different rock types in the subduction system. Constraints on the sources and pathways of subduction fluids thus provide crucial information to reconstruct subduction processes. The Monviso ophiolitic sequence is composed of mafic, ultramafic and minor sediments that have been subducted to ~80 km depth. In this sequence, both localized fluid flow and channelized fluids along major shear zones have been documented. We investigate the timing and source of the fluids that affected the dominant mafic rocks using microscale U-Pb dating of zircon and oxygen isotope analysis of mineral zones (garnet, zircon and antigorite) in high pressure rocks with variable degree of metasomatic modification. In mafic eclogites, Jurassic zircon cores are the only mineralogical relicts of the protolith gabbros and retain δ18O values of 4.5–6 ‰, typical of mantle melts. Garnet and metamorphic zircon that grew during prograde to peak metamorphism display low δ18O values between 0.2 and 3.8 ‰, which are likely inherited from high-temperature alteration of the protolith on the sea floor. This is corroborated by δ18O values of 3.0 and 3.6 ‰ in antigorite from surrounding serpentinites. In metasomatised eclogites within the Lower Shear Zone, garnet rim formed at the metamorphic peak shows a shift to higher δ18O up to 6‰. The age of zircons in high-pressure veins and metasomatised eclogites constrains the timing of fluid flow at high pressure at around 45–46 Ma. Although the oxygen data do not contradict previous reports of interaction with serpentinite-derived fluids, the shift to isotopically heavier oxygen compositions requires contribution from sediment-derived fluids. The scarcity of metasediments in the Monviso sequence suggests that such fluids were concentrated and fluxed along the Lower Shear Zone in a sufficient amount to modify the oxygen composition of the eclogitic minerals.

(Table 2) Organic residue at DSDP Hole 76-534A

The kind, sedimentation rate, and diagenesis of organic particles delivered to the North Atlantic seafloor during the Middle Jurassic-Early Cretaceous were responsible for the presence of carbonaceous sediments in Hole 534A. Organic-rich black clays formed from the rapid supply of organic matter; this organic matter was composed of either abundant, well-preserved, and poorly sorted particles of land plants deposited in clays and silty clays within terrigenous turbiditic sequences (tracheal facies) or abundant amorphous debris (xenomorphic facies) generated through the digestive tracts of marine zooplankton and sedimented as fecal pellets. Evidence for the fecal-pellet origin of xenomorphic debris is illustrated. Black clays were also produced in sediments containing less organic matter as a result of the black color of carbonized particles composing all or most of the residues (micrinitic facies). Slowly sedimented hematitic Aptian clays contain very little carbonized, organic debris that survived diagenetic oxidation. In the red calcareous clay sequence of the Late Jurassic, larger amounts of this oxidized debris turned several clay layers black or blackish red. Carbonized debris also dominates the residues recovered in interbedded black and green Albian clays. Carbonization of organic matter in these sediments either turned them black or provided the diagenetic environment for reduced iron. Carbonized debris is also appreciable in burrow-mottled black-green Kimmeridgian clay. The study of Hole 534A organic matter indicates that during the middle Callovian there was a rapid supply of terrigenous organic matter, followed by a late Callovian episode of rapidly supplied xenomorphic debris deposited as fecal pellets. The Late Jurassic-Berriasian was a time of slower sedimentation of organic matter, primarily of a marine dinoflagellate flora in a poorly preserved xenomorphic facies variously affected by diagenetic oxidation. Several intervals of carbonized tracheal tissue in the Oxfordian and Kimmeridgian suggest episodes of oxidized terrigenous matter. The same sequence of Callovian organic events is evident in much of the Early Cretaceous

Entre la esfera doméstica y la vida pública : los cambios en la posición de las mujeres

Si bien la participación de las mujeres en el ámbito público ha sido tradicionalmente muy inferior a la de los varones, esta situación ha cambiado en los últimos años, intensificándose la participación femenina en distintas instituciones. Simultáneamente está aumentando la presencia masculina en el ámbito doméstico. El objetivo de este trabajo es describir la actividad de las mujeres en las esferas pública y privada, teniendo en cuenta la complementariedad de estos dos ámbitos. Se ha trabajado para ello con los datos provenientes de una encuesta domiciliaria estructurada aplicada a la población del Gran Mendoza comprendida en la franja etárea de 18 a 71 años. La muestra se estratificó teniendo en cuenta sexo, edad, y nivel socio económico. El número total de casos fue de 300 e incluye, en proporciones iguales, a varones, mujeres activas y amas de casa. Esta última segmentación se debe a que numerosas investigaciones han corroborado que la práctica desarrollada por las mujeres en el mundo público modifica sustancialmente su posición respecto de las mujeres que permanecen constreñidas al ámbito de su hogar. Los hallazgos principales que se exponen están vinculados a la visión diferencial que los integrantes de las tres categorías expresan en relación al mundo público y al privado. Se discute sobre las causas de la participación en uno u otro, señalando que el cambio en la situación de la mujer implica también una modificación en la posición del varón y en la dinámica familiar y social. Se sostiene, en conclusión, que las trabas a la participación política femenina deben ser buscadas mas allá de su interés o vocación por la cosa pública, en las características propias de la práctica política y en la tensión entre los ámbitos público y privado, con la persistente responsabilidad de la mujer sobre este último.

(Table 1) Trace element/Ca ratios of Orbulina universa shells from late Neogene Mediterranean samples

A Mediterranean composite sedimentary record was analyzed for Ba/Ca ratios on carbonate shells of Orbulina universa planktonic foraminifer (Ba/Ca)carb providing the opportunity to study and assess the extent of freshwater inputs on the basin and possible impacts on its dynamics during the Tortonian to Recent period. A number of scanning electron microscope analyses and auxiliary trace element measurements (Mn, Sr, and Mg), obtained from the same samples, exclude important diagenetic effects on the studied biogenic carbonates and corroborate the reliability of (Ba/Ca)carb ratios in foraminifera calcite as indicators of seawater source components during the studied interval. A long-term trend with (Ba/Ca)carb values shifting from ~7 to 3 µmol/mol from the base of the Tortonian to the top of the Messinian is observed. The interval of the late Messinian salinity crisis, where biogenic carbonates are missing or strongly diagenized, represents a crucial passage not monitored in our record. At the base of the Pliocene, up to about 4.7 Ma, the (Ba/Ca)carb record shows a decreasing trend from ~4 µmol/mol stabilizing itself to an about constant value of 0.9 ± 0.3 µmol/mol for the whole Plio-Pleistocene interval. These results suggest a dramatic change in the continental runoff values, up to ~3-16 times higher during part of the late Neogene (Tortonian-early Pliocene), with a possible profound modification in the physical dynamics of the Mediterranean basin. First-order mass balance equations used to estimate barium and salinity budgets in the Mediterranean Sea during the late Miocene-early Pliocene interval support the hypothesis of an active connection of the basin with the Paratethys region and of a definitive restriction at the base of the Pliocene after about 0.7 Ma from the well-known Messinian Lagomare phase. They also open intriguing scenarios on possible circulation shifts during the Neogene.

Mineral, chemical and isotopic compositions of hydrothermally altered sediments from the Middle Valley (Juan de Fuca Ridge), ODP Site 139-858

Li and Li isotopes have been measured in the clay fraction of sediments recovered from the Middle Valley hydrothermal site on the Juan De Fuca Ridge. The Li content of pure detrital clays is 51 ppm while hydrothermal clays and carbonates have lower Li (22+/-11 ppm). However, there is no clear relationship between the mineralogy of the hydrothermal alteration products and their Li content. The d7Li value of the detrital clays is +5.8?. Hydrothermal clays and carbonates have d7Li in the range of -3.9? to +7.8?; these values do not seem to be dependent on the temperature at which they formed. Modelling of the Li and Li isotope systematics indicates that the fluid from which the alteration products form is significantly enriched in Li (higher than 10000 µmol/kg) relative to pore fluids recovered from within the sediments (up to 589 µmol/kg; [Wheat, C.G., M.J. Mottl, 1994. Data report: trace metal composition of pore water from Sites 855 through 858, Middle valley, Juan De Fuca Ridge. In Mottl, M.J., Davis, E.E., Fisher, A.T., Slack, J.F. (Eds.), Proc. ODP, Sci. Res. 139: 749-755; doi:10.2973/odp.proc.sr.139.269.1994]), and that this Li is derived from sediment. Thus, the alteration products are not in equilibrium with their conjugate pore fluids; rather, the alteration minerals formed at lower water/sediment ratios. This suggests that fluid flow pathways at Middle Valley were more diffuse in the past than they are today.

Morphological plasticity of the coral skeleton under CO2-driven seawater acidification

Ocean acidification causes corals to calcify at reduced rates, but current understanding of the underlying processes is limited. Here, we conduct a mechanistic study into how seawater acidification alters skeletal growth of the coral Stylophora pistillata. Reductions in colony calcification rates are manifested as increases in skeletal porosity at lower pH, while linear extension of skeletons remains unchanged. Inspection of the microstructure of skeletons and measurements of pH at the site of calcification indicate that dissolution is not responsible for changes in skeletal porosity. Instead, changes occur by enlargement of corallite-calyxes and thinning of associated skeletal elements, constituting a modification in skeleton architecture. We also detect increases in the organic matrix protein content of skeletons formed under lower pH. Overall, our study reveals that seawater acidification not only causes decreases in calcification, but can also cause morphological change of the coral skeleton to a more porous and potentially fragile phenotype.

Desarrollo de un modelo de formación del valor inmobiliario en áreas de crecimiento suburbano. Aplicación a la comarca de la Vega Baja del Segura en el litoral alicantino

Una de las principales líneas de investigación de la economía urbana es el comportamiento del mercado inmobiliario y sus relaciones con la estructura territorial. Dentro de este contexto, la reflexión sobre el significado del valor urbano, y abordar su variabilidad, constituye un tema de especial importancia, dada la relevancia que ha supuesto y supone la actividad inmobiliaria en España. El presente estudio ha planteado como principal objetivo la identificación de aquellos factores, ligados a la localización que explican la formación del valor inmobiliario y justifican su variabilidad. Definir este proceso precisa de una evaluación a escala territorial estableciendo aquellos factores de carácter socioeconómico, medioambiental y urbanístico que estructuran el desarrollo urbano, condicionan la demanda de inmuebles y, por tanto, los procesos de formación de su valor. El análisis se centra en valores inmobiliarios residenciales localizados en áreas litorales donde la presión del sector turístico ha impulsado un amplio. Para ello, el ámbito territorial seleccionado como objeto de estudio se sitúa en la costa mediterránea española, al sur de la provincia de Alicante, la comarca de la Vega Baja del Segura. La zona, con una amplia diversidad ecológica y paisajística, ha mantenido históricamente una clara distinción entre espacio urbano y espacio rural. Esta dicotomía ha cambiado drásticamente en las últimas décadas, experimentándose un fuerte crecimiento demográfico y económico ligado a los sectores turístico e inmobiliario, aspectos que han tenido un claro reflejo en los valores inmobiliarios. Este desarrollo de la comarca es un claro ejemplo de la política expansionista de los mercados de suelo que ha tenido lugar en la costa española en las dos últimas décadas y que derivado en la regeneración de un amplio tejido suburbano. El conocimiento del marco territorial ha posibilitado realizar un análisis de variabilidad espacial mediante un tratamiento masivo de datos, así como un análisis econométrico que determina los factores que se valoran positivamente y negativamente por el potencial comprador. Estas relaciones permiten establecer diferentes estructuras matemáticas basadas en los modelos de precios hedónicos, que permiten identificar rasgos diferenciales en los ámbitos económico, social y espacial y su incidencia en el valor inmobiliario. También se ha sistematizado un proceso de valoración territorial a través del análisis del concepto de vulnerabilidad estructural, entendido como una situación de fragilidad debida a circunstancias tanto sociales como económicas, tanto actual como de tendencia en el futuro. Actualmente, esta estructura de demanda de segunda residencia y servicios ha mostrado su fragilidad y ha bloqueado el desarrollo económico de la zona al caer drásticamente la inversión en el sector inmobiliario por la crisis global de la deuda. El proceso se ha agravado al existir un tejido industrial marginal al que no se ha derivado inversiones importantes y un abandono progresivo de las explotaciones agropecuarias. El modelo turístico no sería en sí mismo la causa del bloqueo del desarrollo económico comarcal, sino la forma en que se ha implantado en la Costa Blanca, con un consumo del territorio basado en el corto plazo, poco respetuoso con aspectos paisajísticos y medioambientales, y sin una organización territorial global. Se observa cómo la vinculación entre índices de vulnerabilidad y valor inmobiliario no es especialmente significativa, lo que denota que las tendencias futuras de fragilidad no han sido incorporadas a la hora de establecer los precios de venta del producto inmobiliario analizado. El valor muestra una clara dependencia del sistema de asentamiento y conservación de las áreas medioambientales y un claro reconocimiento de tipologías propias del medio rural aunque vinculadas al sector turístico. En la actualidad, el continuo descenso de la demanda turística ha provocado una clara modificación en la estructura poblacional y económica. Al incorporar estas modificaciones a los modelos especificados podemos comprobar un verdadero desmoronamiento de los valores. Es posible que el remanente de vivienda construida actualmente vaya dirigido a un potencial comprador que se encuentra en retroceso y que se vincula a unos rasgos territoriales ya no existentes. Encontrar soluciones adaptables a la oferta existente, implica la viabilidad de renovación del sistema poblacional o modificaciones a nivel económico. La búsqueda de respuestas a estas cuestiones señala la necesidad de recanalizar el desarrollo, sin obviar la potencialidad del ámbito. SUMMARY One of the main lines of research regarding the urban economy focuses on the behavior of the real estate market and its relationship to territorial structure. Within this context, one of the most important themes involves considering the significance of urban property value and dealing with its variability, particularly given the significant role of the real estate market in Spain, both in the past and present. The main objective of this study is to identify those factors linked to location, which explain the formation of property values and justify their variability. Defining this process requires carrying out an evaluation on a territorial scale, establishing the socioeconomic, environmental and urban planning factors that constitute urban development and influence the demand for housing, thereby defining the processes by which their value is established. The analysis targets residential real estate values in coastal areas where pressure from the tourism industry has prompted large-scale transformations. Therefore, the focal point of this study is an area known as Vega Baja del Segura, which is located on the Spanish Mediterranean coast in southern Alicante (province). Characterized by its scenic and ecological diversity, this area has historically maintained a clear distinction between urban and rural spaces. This dichotomy has drastically changed in past decades due to the large increase in population attributed to the tourism and real estate markets – factors which have had a direct effect on property values. The development of this area provides a clear example of the expansionary policies which have affected the housing market on the coast of Spain during the past two decades, resulting in a large increase in suburban development. Understanding the territorial framework has made it possible to carry out a spatial variability analysis through massive data processing, as well as an econometric analysis that determines the factors that are evaluated positively and negatively by potential buyers. These relationships enable us to establish different mathematical systems based on hedonic pricing models that facilitate the identification of differential features in the economic, social and spatial spheres, and their impact on property values. Additionally, a process for land valuation was established through an analysis of the concept of structural vulnerability, which is understood to be a fragile situation resulting from either social or economic circumstances. Currently, this demand structure for second homes and services has demonstrated its fragility and has inhibited the area’s economic development as a result of the drastic fall in investment in the real estate market, due to the global debt crisis. This process has been worsened by the existence of a marginal industrial base into which no important investments have been channeled, combined with the progressive abandonment of agricultural and fishing operations. In and of itself, the tourism model did not inhibit the area’s economic development, rather it is the result of the manner in which it was implemented on the Costa Brava, with a land consumption based on the short-term, lacking respect for landscape and environmental aspects and without a comprehensive organization of the territory. It is clear that the link between vulnerability indexes and property values is not particularly significant, thereby indicating that future fragility trends have not been incorporated into the problem in terms of establishing the sale prices of the analyzed real estate product in question. Urban property values are clearly dependent on the system of development and environmental conservation, as well as on a clear recognition of the typologies that characterize rural areas, even those linked to the tourism industry. Today, the continued drop in tourism demand has provoked an obvious modification in the populational and economic structures. By incorporating these changes into the specified models, we can confirm a real collapse in values. It’s possible that the surplus of already-built homes is currently being marketed to a potential buyer who is in recession and linked to certain territorial characteristics that no longer exist. Finding solutions that can be adapted to the existing offer implies the viability of renewing the population system or carrying out modifications on an economic level. The search for answers to these questions suggests the need to reform the development model, without leaving out an area’s potentiality.

Flow and fracture behaviour of high performance alloys

Based on our needs, that is to say, through precise simulation of the impact phenomena that may occur inside a jet engine turbine with an explicit non-linear finite element code, four new material models are postulated. Each one of is calibrated for four high-performance alloys that can be encountered in a modern jet engine. A new uncoupled material model for high strain and ballistic is proposed. Based on a Johnson-Cook type model, the proposed formulation introduces the effect of the third deviatoric invariant by means of three different Lode angle dependent functions. The Lode dependent functions are added to both plasticity and failure models. The postulated model is calibrated for a 6061-T651 aluminium alloy with data taken from the literature. The fracture pattern predictability of the JCX material model is shown performing numerical simulations of various quasi-static and dynamic tests. As an extension of the above-mentioned model, a modification in the thermal softening behaviour due to phase transformation temperatures is developed (JCXt). Additionally, a Lode angle dependent flow stress is defined. Analysing the phase diagram and high temperature tests performed, phase transformation temperatures of the FV535 stainless steel are determined. The postulated material model constants for the FV535 stainless steel are calibrated. A coupled elastoplastic-damage material model for high strain and ballistic applications is presented (JCXd). A Lode angle dependent function is added to the equivalent plastic strain to failure definition of the Johnson-Cook failure criterion. The weakening in the elastic law and in the Johnson-Cook type constitutive relation implicitly introduces the Lode angle dependency in the elastoplastic behaviour. The material model is calibrated for precipitation hardened Inconel 718 nickel-base superalloy. The combination of a Lode angle dependent failure criterion with weakened constitutive equations is proven to predict fracture patterns of the mechanical tests performed and provide reliable results. A transversely isotropic material model for directionally solidified alloys is presented. The proposed yield function is based a single linear transformation of the stress tensor. The linear operator weighs the degree of anisotropy of the yield function. The elastic behaviour, as well as the hardening, are considered isotropic. To model the hardening, a Johnson-Cook type relation is adopted. A material vector is included in the model implementation. The failure is modelled with the Cockroft-Latham failure criterion. The material vector allows orienting the reference orientation in any other that the user may need. The model is calibrated for the MAR-M 247 directionally solidified nickel-base superalloy.

Significado empírico de la multifractalidad de la precipitación

El objetivo central de la presente investigación es profundizar la interpretación de los parámetros multifractales en el caso de las series de precipitación. Para ello se aborda, en primer lugar, la objetivación de la selección de la parte lineal de las curvas log-log que se encuentra en la base de los métodos de análisis fractal y multifractal; y, en segundo lugar, la generación de series artificiales de precipitación, con características similares a las reales, que permitan manipular los datos y evaluar la influencia de las modificaciones controladas de las series en los resultados de los parámetros multifractales derivados. En cuanto al problema de la selección de la parte lineal de las curvas log-log se desarrollaron dos métodos: a. Cambio de tendencia, que consiste en analizar el cambio de pendiente de las rectas ajustadas a dos subconjuntos consecutivos de los datos. b. Eliminación de casos, que analiza la mejora en el p-valor asociado al coeficiente de correlación al eliminar secuencialmente los puntos finales de la regresión. Los resultados obtenidos respecto a la regresión lineal establecen las siguientes conclusiones: - La metodología estadística de la regresión muestra la dificultad para encontrar el valor de la pendiente de tramos rectos de curvas en el procedimiento base del análisis fractal, indicando que la toma de decisión de los puntos a considerar redunda en diferencias significativas de las pendientes encontradas. - La utilización conjunta de los dos métodos propuestos ayuda a objetivar la toma de decisión sobre la parte lineal de las familias de curvas en el análisis fractal, pero su utilidad sigue dependiendo del número de datos de que se dispone y de las altas significaciones que se obtienen. En cuanto al significado empírico de los parámetros multifratales de la precipitación, se han generado 19 series de precipitación por medio de un simulador de datos diarios en cascada a partir de estimaciones anuales y mensuales, y en base a estadísticos reales de 4 estaciones meteorológicas españolas localizadas en un gradiente de NW a SE. Para todas las series generadas, se calculan los parámetros multifractales siguiendo la técnica de estimación de la DTM (Double Trace Moments - Momentos de Doble Traza) desarrollado por Lavalle et al. (1993) y se observan las modificaciones producidas. Los resultados obtenidos arrojaron las siguientes conclusiones: - La intermitencia, C1, aumenta al concentrar las precipitaciones en menos días, al hacerla más variable, o al incrementar su concentración en los días de máxima, mientras no se ve afectado por la modificación en la variabilidad del número de días de lluvia. - La multifractalidad, α, se ve incrementada con el número de días de lluvia y la variabilidad de la precipitación, tanto anual como mensual, así como también con la concentración de precipitación en el día de máxima. - La singularidad probable máxima, γs, se ve incrementada con la concentración de la lluvia en el día de precipitación máxima mensual y la variabilidad a nivel anual y mensual. - El grado no- conservativo, H, depende del número de los días de lluvia que aparezcan en la serie y secundariamente de la variabilidad general de la lluvia. - El índice de Hurst generalizado se halla muy ligado a la singularidad probable máxima. ABSTRACT The main objective of this research is to interpret the multifractal parameters in the case of precipitation series from an empirical approach. In order to do so the first proposed task was to objectify the selection of the linear part of the log-log curves that is a fundamental step of the fractal and multifractal analysis methods. A second task was to generate precipitation series, with real like features, which allow evaluating the influence of controlled series modifications on the values of the multifractal parameters estimated. Two methods are developed for selecting the linear part of the log-log curves in the fractal and multifractal analysis: A) Tendency change, which means analyzing the change in slope of the fitted lines to two consecutive subsets of data. B) Point elimination, which analyzes the improvement in the p- value associated to the coefficient of correlation when the final regression points are sequentially eliminated. The results indicate the following conclusions: - Statistical methodology of the regression shows the difficulty of finding the slope value of straight sections of curves in the base procedure of the fractal analysis, pointing that the decision on the points to be considered yield significant differences in slopes values. - The simultaneous use of the two proposed methods helps to objectify the decision about the lineal part of a family of curves in fractal analysis, but its usefulness are still depending on the number of data and the statistical significances obtained. Respect to the empiric meaning of the precipitation multifractal parameters, nineteen precipitation series were generated with a daily precipitation simulator derived from year and month estimations and considering statistics from actual data of four Spanish rain gauges located in a gradient from NW to SE. For all generated series the multifractal parameters were estimated following the technique DTM (Double Trace Moments) developed by Lavalle et al. (1993) and the variations produced considered. The results show the following conclusions: 1. The intermittency, C1, increases when precipitation is concentrating for fewer days, making it more variable, or when increasing its concentration on maximum monthly precipitation days, while it is not affected due to the modification in the variability in the number of days it rained. 2. Multifractility, α, increases with the number of rainy days and the variability of the precipitation, yearly as well as monthly, as well as with the concentration of precipitation on the maximum monthly precipitation day. 3. The maximum probable singularity, γs, increases with the concentration of rain on the day of the maximum monthly precipitation and the variability in yearly and monthly level. 4. The non-conservative degree, H’, depends on the number of rainy days that appear on the series and secondly on the general variability of the rain. 5. The general Hurst index is linked to the maximum probable singularity.

Monitoring leafy vegetables through packaging films with

Fresh-cut or minimally processed fruit and vegetables have been physically modified from its original form (by peeling, trimming, washing and cutting) to obtain a 100% edible product that is subsequently packaged (usually under modified atmosphere packaging –MAP) and kept in refrigerated storage. In fresh-cut products, physiological activity and microbiological spoilage, determine their deterioration and shelf-life. The major preservation techniques applied to delay spoilage are chilling storage and MAP, combined with chemical treatments antimicrobial solutions antibrowning, acidulants, antioxidants, etc.). The industry looks for safer alternatives. Consequently, the sector is asking for innovative, fast, cheap and objective techniques to evaluate the overall quality and safety of fresh-cut products in order to obtain decision tools for implementing new packaging materials and procedures. In recent years, hyperspectral imaging technique has been regarded as a tool for analyses conducted for quality evaluation of food products in research, control and industries. The hyperspectral imaging system allows integrating spectroscopic and imaging techniques to enable direct identification of different components or quality characteristics and their spatial distribution in the tested sample. The objective of this work is to develop hyperspectral image processing methods for the supervision through plastic films of changes related to quality deterioration in packed readyto-use leafy vegetables during shelf life. The evolutions of ready-to-use spinach and watercress samples covered with three different common transparent plastic films were studied. Samples were stored at 4 ºC during the monitoring period (until 21 days). More than 60 hyperspectral images (from 400 to 1000 nm) per species were analyzed using ad hoc routines and commercial toolboxes of MatLab®. Besides common spectral treatments for removing additive and multiplicative effects, additional correction, previously to any other correction, was performed in the images of leaves in order to avoid the modification in their spectra due to the presence of the plastic transparent film. Findings from this study suggest that the developed images analysis system is able to deal with the effects caused in the images by the presence of plastic films in the supervision of shelf-life in leafy vegetables, in which different stages of quality has been identified.

Incorporating Group Recommendations to Recommender Systems: Alternatives and Performance

La importancia de los sistemas de recomendación ha experimentado un crecimiento exponencial como consecuencia del auge de las redes sociales. En esta tesis doctoral presentaré una amplia visión sobre el estado del arte de los sistemas de recomendación. Incialmente, estos estaba basados en fitrado demográfico, basado en contendio o colaborativo. En la actualidad, estos sistemas incorporan alguna información social al proceso de recomendación. En el futuro utilizarán información implicita, local y personal proveniente del Internet de las cosas. Los sistemas de recomendación basados en filtrado colaborativo se pueden modificar con el fin de realizar recomendaciones a grupos de usuarios. Existen trabajos previos que han incluido estas modificaciones en diferentes etapas del algoritmo de filtrado colaborativo: búsqueda de los vecinos, predicción de las votaciones y elección de las recomendaciones. En esta tesis doctoral proporcionaré un nuevo método que realizar el proceso de unficación (pasar de varios usuarios a un grupo) en el primer paso del algoritmo de filtrado colaborativo: cálculo de la métrica de similaridad. Proporcionaré una formalización completa del método propuesto. Explicaré cómo obtener el conjunto de k vecinos del grupo de usuarios y mostraré cómo obtener recomendaciones usando dichos vecinos. Asimismo, incluiré un ejemplo detallando cada paso del método propuesto en un sistema de recomendación compuesto por 8 usuarios y 10 items. Las principales características del método propuesto son: (a) es más rápido (más eficiente) que las alternativas proporcionadas por otros autores, y (b) es al menos tan exacto y preciso como otras soluciones estudiadas. Para contrastar esta hipótesis realizaré varios experimentos que miden la precisión, la exactitud y el rendimiento del método. Los resultados obtenidos se compararán con los resultados de otras alternativas utilizadas en la recomendación de grupos. Los experimentos se realizarán con las bases de datos de MovieLens y Netflix. ABSTRACT The importance of recommender systems has grown exponentially with the advent of social networks. In this PhD thesis I will provide a wide vision about the state of the art of recommender systems. They were initially based on demographic, contentbased and collaborative filtering. Currently, these systems incorporate some social information to the recommendation process. In the future, they will use implicit, local and personal information from the Internet of Things. As we will see here, recommender systems based on collaborative filtering can be used to perform recommendations to group of users. Previous works have made this modification in different stages of the collaborative filtering algorithm: establishing the neighborhood, prediction phase and determination of recommended items. In this PhD thesis I will provide a new method that carry out the unification process (many users to one group) in the first stage of the collaborative filtering algorithm: similarity metric computation. I will provide a full formalization of the proposed method. I will explain how to obtain the k nearest neighbors of the group of users and I will show how to get recommendations using those users. I will also include a running example of a recommender system with 8 users and 10 items detailing all the steps of the method I will present. The main highlights of the proposed method are: (a) it will be faster (more efficient) that the alternatives provided by other authors, and (b) it will be at least as precise and accurate as other studied solutions. To check this hypothesis I will conduct several experiments measuring the accuracy, the precision and the performance of my method. I will compare these results with the results generated by other methods of group recommendation. The experiments will be carried out using MovieLens and Netflix datasets.

Capacidad y comportamiento de la adsorción de fenol en caolines naturales y modificados

En la actualidad las industrias químicas, farmacéuticas y clínicas, originan contaminantes en aguas superficiales, aguas subterráneas y suelos de nuestro país, como es el caso del fenol, contaminante orgánico común y altamente dañino para los organismos, incluso a bajas concentraciones. Existen en el mercado diferentes metodologías para minimizar la contaminación pero muchos de estos procesos tienen un alto coste, generación de contaminantes, etc. La adsorción de contaminantes por medio de arcillas es un método ampliamente utilizado, encontrándose eficaz y económico. Pero la dificultad de adsorber un contaminante orgánico como el fenol motiva la creación de un material llamado organoarcillas. Las organoarcillas son arcillas modificadas con un surfactante, a su vez, los surfactantes son moléculas orgánicas que confieren a la superficie de la arcilla carga catiónica en lugar de aniónica, haciendo más fácil la adsorción de fenol. Para esta tesis se ha elegido el caolín como material adsorbente, fácilmente disponible y relativamente de bajo coste. Se ha trabajado con: arenas de caolín, material directo de la extracción, y caolín lavado, originado del proceso de lavado de las arenas de caolín. Ambos grupos se diferencian fundamentalmente por su contenido en cuarzo, ampliamente mayor en las arenas de caolín. Con el objetivo de desarrollar un material a partir del caolín y arenas de éste con capacidad de retención de contaminates, en concreto, fenol, se procedió a modificar los materiales de partida mediante tratamientos térmicos, mecánicos y/o químicos, dando lugar a compuestos con mayor superficie química reactiva. Para ello se sometió el caolín y las arenas caoliníferas a temperaturas de 750ºC durante 3h, a moliendas hasta alcanzar su amorfización, y/o a activaciones con HCl 6M o con NaOH 5M durante 3h a 90ºC. En total se obtuvieron 18 muestras, en las que se estudiaron las características físico-químicas, mineralógicas y morfológicas de cada una de ellas con el fin de caracterizarlas después de haber sufrido los tratamientos y/o activaciones químicas. Los cambios producidos fueron estudiados mediante pH, capacidad de intercambio catiónico (CEC), capacidad de adsorción de agua (WCU y CWC), distribución de tamaño de partícula (PSD), área de superficie específica (SBET), difracción de rayos X (XRD), espectroscopía infrarroja por transformada de Fourier (FTIR), métodos térmicos (TG, DTG y DTA), y microscopía electrónica de transmisión y barrido (SEM y TEM). Además se analizó los cambios producidos por los tratamientos en función de las pérdidas de Al y Si que acontece en las 18 muestras. Los resultados para los materiales derivados de la arenas caoliníferas fueron similares a los obtenidos para los caolines lavados, la diferencia radica en la cantidad de contenido de caolinita en los diferente grupos de muestras. Apoyándonos en las técnicas de caracterización se puede observar que los tratamientos térmico y molienda produce materiales amorfos, este cambio en la estructura inicial sumado a las activaciones ácida y alcalina dan lugar a pérdidas de Si y Al, ocasionando que sus propiedades físico-químicas, mineralógicas y morfológicas se vean alteradas. Un fuerte aumento es observado en las áreas superficiales y en la CEC en determinadas muestras, además entre los cambios producidos se encuentra la producción de diferentes zeolitas en porcentajes distintos con el tratamiento alcalino. Para la obtención de las organoarcillas, las 18 muestras se sometieron a la surfactación con hexadeciltrimetil amonio (HDTMA) 20 mM durante 24h a 60ºC, esta concentración de tensioactivo fue más alta que la CEC de cada muestra. Los camext bios anteriormente producidos por los tratamientos y activaciones, afectan de forma diferente en la adsorción de HDTMA, variando por tanto la adsorción del surfactante en la superficie de las muestras. Se determinó el tensioactivo en superficie por FTIR, además se realizó un análisis de componentes principales (PCA) para examinar la dependencia entre las relaciones Si/Al de las muestras en la capacidad de adsorción de tensioactivo, y para el estudio de la adsorción de HDTMA en las muestras se realizaron además del análisis termogravimétrico, aproximaciones con los modelos de Freundllich y Langmuir. Se persigue conocer las diferentes formas y maneras que tiene el tensioactivo de fijarse en la superficie de las muestras. En las organoarcillas resultantes se cuantificó el fenol adsorbido cuando éstas fueron puestas en contacto con diferentes concentraciones de fenol: 50, 500, 1000, 2000, y 2500 mg/l durante 24h. El contaminante sorbido se calculó por medio de cromatografía de gases, y se realizaron aproximaciones con los modelos de Freundllich y Langmuir. El comportamiento de adsorción de fenol en arcillas orgánicas es regido por las características de las muestras. De forma general se puede decir que las muestras de caolines lavados tienen más capacidad de adsorción de fenol que las muestras de arenas de caolín y que la activación alcalina ha proporcionado una mejora en la adsorción de fenol en los dos grupos. En consecuencia se han obtenido materiales adsorbentes heterogéneos y por tanto, con propiedades diferentes. Se ha evaluado el comportamiento global de las arenas de caolín por un lado y del caolín lavado por otro. Las arenas de caolín presentan altos niveles de cuarzo y su uso para ciertos tipos de industrias no son recomendados en ocasiones por el alto costo que el proceso de limpieza y purificación implicaría. Por ello es importante reseñar en este proyecto las aplicaciones que ofrecen algunas muestras de este grupo. Los ensayos acontecidos en esta tesis han dado lugar a las siguientes publicaciones: • Pérdida de Al y Si en caolines modificados térmica- o mecánicamente y activados por tratamientos químicos. A. G. San Cristóbal, C Vizcayno, R. Castelló. Macla 9, 113-114. (2008). • Acid activation of mechanically and thermally modfied kaolins. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Mater. Res. Bull. 44 (2009) 2103-2111. • Zeolites prepared from calcined and mechanically modified kaolins. A comparative study. A. G San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Applied Clay Science 49 (2010) 239-246. • Study comparative of the sorption of HDTMA on natural and modified kaolin. A. G San Cristóbal, R. Castelló, J. M. Castillejo, C Vizcayno. Aceptada en Clays and Clay minerals. • Capacity of modified kaolin sand and washed kaolin to adsorb phenol. A. G San Cristóbal, R. Castelló, C Vizcayno. Envío a revista sujeto a la publicación del artículo anterior. ABSTRACT Today’s chemical, pharmaceutical and clinical industries generate pollutants that affect the soils and surface and ground waters of our country. Among these, phenol is a common organic pollutant that is extremely harmful to living organisms, even at low concentrations. Several protocols exist to minimize the effects of pollutants, but most are costly procedures or even generate other pollutants. The adsorption of hazardous materials onto clays is perhaps the most used, efficient and cost-saving method available. However, organic compounds such as phenol are difficult to adsorb and this has led to the development of materials known as organoclays, which are much better at remediating organic compounds. Organoclays are clays that have been modified using a surfactant. In turn, surfactants are organic molecules that confer a cationic rather than anionic charge to the clay surface, improving it’s capacity to adsorb phenol. For this doctorate project, kaolin was selected as an adsorbent material for the removal of phenol given its easy sourcing and relatively low cost. The materials investigated were kaolin sand, a directly extracted material, and washed kaolin, which is the byproduct of the kaolin sand washing process. The main difference between the materials is their quartz content, which is much higher in the kaolin sands. To generate a product from kaolin or kaolin sand capable of retaining organic pollutants such as phenol, both materials were subjected to several heat, chemical and/or mechanical treatments to give rise to compounds with a greater reactive surface area. To this end the two starting materials underwent heating at 750ºC for 3 h, grinding to the point of amorphization and/or activation with HCl 6M or NaOH 5M for 3 h at 90ºC. These treatments gave rise to 18 processed samples, which were characterized in terms of their morphological, mineralogical, and physical-chemical properties. The behaviour of these new materials was examined in terms of their pH, cation exchange capacity (CEC), water adsorption capacity (WCU and WCC), particle size distribution (PSD), specific surface area (SBET), and their X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermal (DTG, DTA) and scanning and transmission electron microscopy (SEM and TEM) properties. The changes conferred by the different treatments were also examined in terms of Al and Si losses. Results for the materials derived from kaolin sands and washed kaolin were similar, with differences attributable to the kaolinite contents of the samples. The treatments heat and grinding produced amorphous materials, which when subjected to acid or alkali activation gave rise to Si and Al losses. This in turn led to a change in physico- chemical, mineralogical and morphological properties. Some samples showed a highly increased surface area and CEC. Further, among the changes produced, alkali treatment led to the generation of zeolites in different proportions depending on the sample. To produce the organoclays, the 18 samples were surfacted with hexadecyltrimethylammonium (HDTMA) 20 mM for 24 h at 60ºC. This surfactant concentration is higher than the CEC of each sample. The amount of HDTMA adsorbed onto the surface of each sample determined by FTIR varied according to treatment. A principle components analysis (PCA) was performed to examine correlations between sample Si/Al ratios and surfactant adsorption capacity. In addition, to explore HDTMA adsorption by the samples, DTG and DTA data were fitted to Freundllich and Langmuir models. The mechanisms of surfactant attachment to the sample surface were also addressed. The amount of phenol adsorbed by the resultant organoclays was determined when exposed to different phenol concentrations: 50, 500, 1000, 2000, and 2500 mg/l for 24 h. The quantity of adsorbed pollutant was estimated by gas chromatography and the data fitted to the models of Freundllich and Langmuir. Results indicate that the phenol adsorption capacity of the surfacted samples is dependent on the sample’s characteristics. In general, the washed kaolin samples showed a greater phenol adsorption capacity than the kaolon sands and alkali activation improved this capacity in the two types of sample. In conclusion, the treatments used gave rise to adsorbent materials with varying properties. Kaolin sands showed high quartz levels and their use in some industries is not recommended due to the costs involved in their washing and purification. The applications suggested by the data obtained for some of the kaolin sand samples indicate the added value of this industrial by-product. The results of this research project have led to the following publications: • Pérdida de Al y Si en caolines modificados térmica- o mecánicamente y activados por tratamientos químicos. A. G. San Cristóbal, C Vizcayno, R. Castelló. Macla 9, 113-114. (2008). • Acid activation of mechanically and thermally modfied kaolins. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Mater. Res. Bull. 44 (2009) 2103-2111. • Zeolites prepared from calcined and mechanically modified kaolins. A comparative study. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Applied Clay Science 49 (2010) 239-246. • Study comparative of the sorption of HDTMA on natural and modified kaolin. A. G. San Cristóbal, R. Castelló, J. M. Castillejo, C Vizcayno Accepted in Clays and Clay minerals. • Capacity of modified kaolin sand and washed kaolin to adsorb phenol. A. G San Cristóbal, R. Castelló, C Vizcayno. Shipment postponed, subject to the publication of the previous article.

MAIA: an event-based modular architecture for intelligent agents

Online services are no longer isolated. The release of public APIs and technologies such as web hooks are allowing users and developers to access their information easily. Intelligent agents could use this information to provide a better user experience across services, connecting services with smart automatic. behaviours or actions. However, agent platforms are not prepared to easily add external sources such as web services, which hinders the usage of agents in the so-called Evented or Live Web. As a solution, this paper introduces an event-based architecture for agent systems, in accordance with the new tendencies in web programming. In particular, it is focused on personal agents that interact with several web services. With this architecture, called MAIA, connecting to new web services does not involve any modification in the platform.