Disolventes supramoleculares funcionales utilizando agua como agente coacervante: modelado, caracterización y aplicaciones analíticas

The content of this Doctoral Thesis has been structured in four chapters preceded by a general Introduction in which the theoretical and practical aspects related to the synthesis, modeling possibilities and application of supramolecular solvents (SUPRAS) as well as the encapsulation of lipophilic bioactive substances in nanostructured lipid carriers are discussed. Below, the content of each chapter is described: Chapter I: Volatile amphiphile-based supramolecular solvents for reducing phospholipid-based matrix effects in LC-MS/MS The research presented in this chapter has focused on the synthesis and characterization of volatile SUPRAS with restricted access properties for the elimination of matrix effects in the analysis of biological samples by LC-MS/MS. For this purpose, a SUPRAS has been synthetized from hexanol in THF solutions by the addition of water as coacervating agent. The phase diagram for this ternary mixture was constructed, delimiting the SUPRAS region, and its composition was investigated according to the environmental conditions established for the self-assembly of hexanol. The equation predicting the volume of SUPRAS formed as a function of environmental conditions was established. As in the case of other alkanols, hexanol aggregates in the SUPRAS as inverse hexagonal structures in which the alcohol groups surround aqueous cavities while the hydrocarbon chains are dispersed in THF. The ability of the SUPRAS synthesized for the removal of matrix effects in bioanalysis was investigated by the determination of bisphenol A (BPA) in urine. The insitu formation of SUPRAS in this matrix and the removal of proteins and phospholipids were investigated. It was demonstrated that supramolecular extracts can be analyzed directly by LC-MS/MS avoiding matrix effects, which allowed the quantification of BPA via external calibration. BPA was quantitatively extracted in the SUPRAS (recoveries in the 96-107% range). The limit of quantification of the method for BPA was 0.025 ng/mL. The method was applied to the quantification of BPA in urine samples. Chapter II: Supramolecular solvents formed by oligomeric surfactants to reduce surfactant losses in the equilibrium solution The research carried out in this chapter has focused on the synthesis and characterization of SUPRAS obtained from solutions of poly-undecylenic acid (an oligomeric surfactant) in THF or ethanol, using water as coacervating agent. A comparative study of both ternary mixtures has been performed in terms of phase diagrams, the chemical composition of SUPRAS generated from different environmental conditions, the volume of SUPRAS formed and structural characteristics. Different equations have been derived, generated as a function of the composition of the synthetical solution, for predicting the volume and chemical composition of these SUPRAS. The hypothesis of the oligomer being completely incorporated into the SUPRAS was fully demonstrated. This property will make possible the application of this novel SUPRAS to wastewater treatment and to the analysis of pollutants when the use of high volumes of water is required. Chapter III: High thermally stable supramolecular solvents applicable to headspace gas chromatography The research described in this chapter is focused on the synthesis of SUPRAS from solutions of the oligomer poly-undecylenic acid in tetraglyme via the addition of water as coacervating agent. The phase diagram from this ternary mixture was constructed, delimiting the SUPRAS formation region, that was also characterized in terms of chemical composition and physical properties such as thermal stability. The applicability of these SUPRAS in headspace gas chromatography (HS-GC) was investigated by the direct analysis of the extracts obtained from the extraction of residual solvents in pharmaceutical products. The methodology developed allowed the quantitative extraction of the different legislated classes of residual solvents (37 solvents belonging to classes 1, 2A, 2B and 2C) and their determination by HS-GC-MS. The determination of the 2C class solvents by previously described procedures is very complex due to their high boiling points. It was demonstrated that the method can be applied to a wide variety of pharmaceutical products. The method was also validated according to the criteria established in the relevant legislation [ICH Q2 R1]. Chapter IV: Multifunctional supramolecular solvents for the combination of the extraction and encapsulation of lipophilic bioactive components The research described in this chapter has been developed in the ―lnstitut National de la Santé et de la Recherche Médicale Unit 1148" in Paris, during the stay of the PhD student in this center. This research has aimed at the combination of SUPRAS and nanostructured lipid carriers (NLCs) for the effective extraction, stabilization and encapsulation of lipophilic bioactive compounds. For this purpose, SUPRAS previously described by the SAC research group for the extraction of astaxanthin from Haematococcus pluvialis and formed by octanoic acid in ethanol-water have been used. In previous research, the SAC group has demonstrated that these SUPRAS with restricted access properties quantitatively extract astaxanthin and are able to produce oleoresins that show the same composition as those obtained by extraction with supercritical fluids (SFE), but at a much lower cost. The oleoresins thus obtained were used as the liquid lipid fraction to get SUPRAS-NLCs. The synthetized nanoparticles were characterized by several different techniques: DLS, AFM and Cryo-SEM microscopy, indicating that spherical particles with an approximate size of 100 nm were formed. Their antioxidant activity was determined by ORAC and α-TEAC and its ability to inhibit ROS in vitro was assessed by the DHE probe. The results showed that the SUPRAS-NLCs here synthetized exhibit an exceptional stability (at least 6 months at 4ºC) when compared to previous research. This Report also includes a section in which the main conclusions derived from the obtained results are discussed. Finally, appendix A lists the scientific papers published in specialized international journals derived for this Thesis and, appendix B, the contributions made to national and international conferences

Path planning for contact based safe human-robot cooperation

Bachelor thesis by José Carlos González Dorado presented at Karlsruher Institut für Technologie (KIT) Institut für Prozessrechentechnik, Automation und Robotik (IPR) der Fakultät für InformatikThis work improves a human-robot cooperation system using the research framework MAROCO. There are already implemented many essential parts needed to provide this cooperation, but some of them work independently of each other. The main goal is to join all these parts to conform a system that allows contact based cooperation

Inspección y análisis científico de las torres atalaya que defendieron el último reino islámico de la Península Ibérica

The Islamic Nasrid kingdom of Granada occupied the mountainous areas of the south-eastern area of the Iberian Peninsula. The Baetic mountain range worked as a natural frontier between the Nasrid kingdom and the Christian kingdom of Castile from 1232 to 1492. An extensive network of watchtowers was built by Nasrid to control this frontier stablishing visual communication between them and the Nasrid centre at the Alhambra citadel. Many of them are still standing, disperse through the provinces of Granada, Malaga, Almeria and the eastern parts of Jaen, Cordoba and Cadiz. Even being this military architecture protected by Spanish Heritage law, many of these medieval towers and their cultural landscapes are in severe risk. There are studies of individual towers, but any global comparative study has been developed. For this reason, within the framework of the R&D project called ‘Las atalayas que defendieron el reino nazarí de Granada. Análisis y documentación científica (Nazalaya)” (HAR2016-79689-P) financed by the Ministry of Economy, Industry and Competitiveness of Spain, the towers are being studied as individual exemplars as well as components of the same typological group. This generates a complete documentation constituted by a homogenous and exhaustively planimetry which supplements the existing information and enabling comparative analysis. Furthermore complete architectural surveys are being carried out using techniques as photogrammetry. In addition to the analysis of construction systems, the structural safety of these towers is evaluated formulating guidelines for its restoration.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. Proyecto del Plan Nacional I+D+i (Programa Estatal de Fomento de la Investigación Científica y Técnica de Excelencia) entitled ‘Las atalayas que defendieron el reino nazarí de Granada. Análisis y documentación científica (Nazalaya)’ (HAR2016-79689-P) Proyecto de Investigación Precompetitivo (mod. A) del Plan Propio de la Universidad de Málaga ‘La construcción de un paisaje: arquitectura de tapial en la Alta Andalucía en el siglo XIII. Estudio y análisis del sistema de torres andalusíes en el valle de Segura de la Sierra’ X Convocatoria de Proyectos de Investigación de la Fundación Pública Andaluza Centro de Estudios Andaluces en la modalidad de proyectos individuales, PRY/259/17 ‘Torres medievales y modernas conservadas en Andalucía. Documentación gráfica, análisis científico e interrelaciones

La matemática como herramienta de modelización para dar respuesta a situaciones problema

Se presenta un avance de un proyecto de trabajo docente que tiene como objetivo implementar un recorrido de estudio e investigación en la carrera de químico biológicas. Se abordan algunas modificaciones que se han propuesto a los procesos de enseñanza y aprendizaje desde la perspectiva de la resolución de situaciones problema. Se plantea lo útil que puede ser la modelización para resolver problemas del área de ciencias químico-biológicas, mediante el uso del cálculo, en la Universidad de Sonora. Se resalta la importancia de contar con la teoría antropológica de lo didáctico como el marco teórico de referencia, al mismo tiempo, se recomienda iniciar la transformación del proceso pedagógico, para darle respuesta a uno de los problemas mayores de la matemática planteado por Freudenthal

Diseño y desarrollo de una experiencia interactiva que trata el tema del comportamiento de edificaciones frente a sismos, para la sala Colombia Geodiversa del Parque Explora

Se desarrolla una Experiencia interactiva para el Parque Explora. Ésta se compone principalmente de: una mesa vibradora, que cumple la función de simular sismos y un set de módulos, que permite al usuario simular edificaciones. El proyecto inicia con una exploración de diversas áreas: museografía, pedagogía, sismología, simulación de sismos, teoría de vibraciones, ingeniería sismorresistente y técnicas de construcción local. Posteriormente se analiza y selecciona la información más relevante para el proyecto.xvii, 148 p.Contenido parcial: Museografía, lúdica y pedagogía -- Sismos y vibración -- Sismorresistencia y construcciones -- Información relevante para el desarrollo de la mesa vibradora -- Desarrollo de la mesa vibradora -- Integración de la experiencia interactiva

Flow-concurrence and bandwidth ratio on the Internet

The relevance of flow-based monitoring in tasks such as the detection of anomalies and denial of use attacks, traffic reporting, performance evaluation, software routing among others motivates the study of the Internet traffic in terms of flows. However, by the time a network manager or practitioner start any of these tasks, they face the challenge of planning probes’ capacities, which depends on the number of concurrent flows. Unfortunately, while the bandwidth of a network or link, both in operation and in future deployments, can be known, or at least estimated in advance, nothing is known about the load in terms of concurrent flows. We aimed at filling this gap by studying the concurrence of flows with respect to the bandwidth normalized by factors such as protocol shares, timeouts, applications, time and years among others. As a result, we provide the research community with several models, based on lognormal distributions, and parameter estimates in such a way that any player in the Internet arena can estimate the number of concurrent flows in their own infrastructure. Moreover, such results emerge from a diverse set of network traces so making the extrapolation of conclusions viableThis work was partially funded by the Spanish Ministry of Economyand Competitiveness through the research project TRAFICA(MINECO/FEDER TEC2015-69417-C2-1-R

Identidades nacionales y estados plurinacionales: una perspectiva psicosociológica

Depto. de Antropología Social y Psicología SocialFac. de Ciencias Políticas y SociologíaTRUEpu

Juan Martínez Montañés and the ‘Guzmanes’: The Virgin and Child of the Cathedral of Huelva (1616)

El objetivo de este trabajo es dar a conocer la libranza que documenta la Virgen con el Niño que preside el altar mayor de la catedral de Huelva como obra del escultor Juan Martínez Montañés (1568-1649), pues hasta ahora se trataba de una obra atribuida. Asimismo, se aporta la cronología exacta de dicha escultura, que se revela como un nuevo ejemplo del fecundo patrocinio artístico ejercido por el VIII duque de Medina Sidonia, don Manuel de Guzmán y Silva.The aim of this work is to make known a document that proves that the sculptor Juan Martínez Montañés (1568-1649) was the author of the Virgin and Child that presides the cathedral of Huelva. Formerly, this sculpture had been attributed to the aforementioned artist because of stylistic reasons, but now we have the documentary evidence. This document provides us the exact chronology of the work and the name of the nobleman who commissioned the sculpture, who was the 8th Duke of Medina Sidonia

Psicosociología de las relaciones internacionales

Depto. de Antropología Social y Psicología SocialFac. de Ciencias Políticas y SociologíaTRUEpu