CHEMISTRY, 3

Author: LÓPEZ GONZÁLEZ FRANCISCO JAVIER.
Year: 2004.
University: GRANADA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: This thesis has developed a platform instrumental, simple user-friendly and based on mitigating measures luminescence dynamics, which allows us to the determination of gas. This has been prepared and characterized by instrumentation unit membranes sensor for O2 using different polymers and form preparation; sensor properties exhibiting such membranes were prepared in a way that is consistent with the requirements of portable instrumentation that has developed in As for compatibility with excitation source LED and optical sensors within the visible spectrum, high light intensity, long lifetime and good stability. The median prototypes that have been developed is based on a novel which uses an element photodetector with binary output that allows measurements on the basis of a temporary parameter in which both intensity as the lifetime of the emission of light . In the prototypes have been developed including membrane sensor manufactured and has also used a direct approach coating photodetector with the substance sensor that has been successful in terms of strength and alignment possibility of rapid replacement of the sensor area. We have characterized the response to oxygen of different prototypes developed, we have studied the effect dela temperature, the effect of possible interfering gases and have the calibration of a prototype using a single point empirical equation. Finally, we have validated the system with a reference meter. We have set different strategies for the formation of membranes sensitive to CO2 in a way that could be measured with the type portable optical instrumentation that has developed. The relationship between luminance and CO2 concentration has been done through an indicator of acid base through energy transfer (ROT) and filtrointerno (EF). We have prepared nanoparticles with the material luminóforo entrapado inside it with what we have achieved the same approach earlier in the case of the determination of CO2.

Author: Pérez García Susana.
Year: 2004.
University: ALMERÍA.
Place of defense: F.Ciencias Experimentales.
Place of preparation: Facultad de Ciencias Experimentales.

Summary: In the thesis presented has been dealt with the preparation, characterization and evaluation of systems controlled release of pesticides and fertilizers, using biodegradable matrix, in order to try to reduce both water pollution subterránaeas in the area (factor condicionante- given scarce aquifers province Almería- for the continuation of this thriving farming), as the soil and atmosphere of the greenhouse, the latter with a direct impact on the health of people who work there. They have investigated the following aspects: 1-Review bibiográfica of implementing systems liberation cointrolada in different fields (medicine, agriculture, etc..). Systematic Study of pesticides and fertilizer use more widespread in horticulture from the provinvia Almeria, and their physicochemical characteristics and ways of implementation, could be capable of reaching the underground aquifers. 2-Design of analytical methods for the analysis of pesticides (cloridazona and metribuzina) and fertilizer (ammonium nitrate) selected, tested in parallel alignment of the same at various formulations for use in controlled release systems. It has chosen the high performance liquid chromatography for the analysis of pesticides and capillary electrophoresis for the analysis of fertilizer. 3-Completing the study process adsorción - desorción of pesticides on samples used modifiers (bentonite, activated charcoal and anthracite) controlled release systems. 4-Design, preparation and characterization of the formulations selected, both of pesticides and fertilizer. - Have been prepared pesticide formulations using two different techniques: an encapsulation of the active ingredient with alginate, added modifiers, and a merger of the active ingredient with lignin, the latter varying size made. In the case of fertilizer have been prepared some formulated coatings consisting of ammonium nitrate pellets with ethylcellulose, adding two kinds of plasticizers. 5-Evaluation of formulated, considering the release of the active ingredient in aqueous solution:-Nature of formulated after immersion in water. - Assessment of the influence of the composition of the formulated in the release of the active ingredient. - Implementation of different theoretical and empirical models for establishing the kinetics and mechanism of release of pesticides and fertilizer in water from the corresponding formulations. 6-Assessment formulations obtained by studying the release of pesticides and fertilizer in the soil:-Making static adsorption studies, in order to obtain the corresponding soil adsorption isotherm. - Characterization of the kinetics of release of pesticides and fertilizers made from the soil. - Characterization of the kinetics of release of pesticides from the soil into raised under conditions of leaching and comparison of mobility with respect to technical product. - Correlation of the results of soil parameters studios release of pesticides from the water in different formulations to obtain an equation that represents reliably release of the pesticide in the soil.

Author: LÓPEZ SANTOS LAURA.
Year: 2004.
University: SEVILLA.
Place of defense: INSTITUTO DE INVESTIGACIONES QUÍMICAS.
Place of preparation: INSTITUTO DE INVESTIGACIONES QUÍMICAS.

Summary: This Doctoral Thesis contains the results of the study of the activation of different ethers and amines by iridium complexes with the ligand hidrotris (3,5-dimetilpirazolil) borate. We have studied ethers of different kinds including: ethers aliphatic, aromatic ethers and vinyl ethers. In these activations generated complexes type alquilideno, in which the ligand carbeno may or may not satisfy a heteroátomo (mostly containing an oxygen atom as a replacement), but all of them are characterized by lectrofília fragment carbénico and can be considered type Fischer . The complex carbénico resulting from the selective rupture of two (and sometimes three) CH links, but also in many of the changes that are discussed paralos ethers, the rupture occurs unusual for a link OC and the formation of a link CC. It has also demonstrated the existence of equilibria cuasitermoneutros between complex nature Ir-alquilideno. They are real tradeoffs to be accessed from either of the two species, which are of great interest from the point of view crucial, because although the transformation M-alquilideno/M-alqueno is well known, the opposite has very few precedents bibiliográficos , and the observation of balance between the two types of compounds is even less common.

Author: MORA OJEDA ANTONIO.
Year: 2004.
University: SEVILLA.
Place of defense: INSTITUTO DE RECURSOS NATURALES Y AGROBIOLOGÍA DE SEVILLA. CSIC.
Place of preparation: INSTITUTO DE RECURSOS NATURALES Y AGROBIOLOGÍA.

Summary: The heavy use of xenobiotics in agriculture leads to the need to know their dynamics in the environment in order to anticipate the likely environmental impacts of these compounds. In this regard has been studying the dynamics of two herbicides, a uracilo and triazine in four soils representing a wide region. Extending the sorption and desorption, as well as the kinetics of the processes, and the process of mobility within these soils have been characterized both qualitatively and quantitatively. This has also served to establish relationships between different processes. The work, presented in parallel, a way of approaching the study of the dynamics of pesticides in the soil from a general perspective and integrators of the main processes that determine the fate of these products in the soil.

Author: Junquera Hernández José Miguel.
Year: 2005.
University: VALENCIA.
Place of defense: Facultat de Química.
Place of preparation: Facultat de Química (Universitat de Valencia).

Summary: It has studied the role of the method (SC) 2 in the study of porpiedades molecular consistent with the size. It has developed a software capable of performing calculations of this kind of electronic properties using the method of interest. This software has been applied and this method to studying different molecular systems test, the method concluyéndose (SC) 2 is capable of providing electronic properties consistent with the size and posed a significant improvement with respect to those obtained when CI methods not covered. It has been determined that the best set of basis for the calculation of this type of property is one type d-aug-cc-pVTZ and that the increase in the size of active space has a small effect on the quality of the properties obtained with this method. Finally, it has successfully implemented the method described studying several real systems for which there were discrepancies between experimental values or they were strangers.

Author: CANTÓ VALLVERDÚ MARIA.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: AUTONOMA DE BARCELONA.
Place of preparation: AUTONOMA DE BARCELONA.

Summary: In this Doctoral Thesis have addressed the synthesis of a series of natural products that contain its skeleton in a unit ciclohexánica and in all cases has been used as a substrate of departure common monoacetal of p-benzoquinona enantiopuro derived from (R, R) -hidrobenzoà ¯ na. First have addressed the synthesis of analogs of bromoxona. Subsequently, it has been determined the absolute configuration of the rengiolona. Finally, we have completed the synthesis of aquilegiolida, dihidromensidaurilida and dihidroaquilegiolida, the last two in the form enantiopura i of the alosecurinina.

Author: GUIMET VILA EUGENI.
Year: 2005.
University: ROVIRA I VIRGILI.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Author: ROEN MARTIN ALFREDO MIGUEL.
Year: 2005.
University: LA LAGUNA.
Place of defense: INSTITUTO UNIVERSITARIO DE BIO ORGÁNICA ANTONIO GONZÁLEZ.
Place of preparation: INSTITUTO UNIVERSITARIO DE BIO ORGANICA ANTONIO GONZALEZ (UNIVERSIDAD DE LA LAGUNA).

Summary: In this thesis is synthesis and study in different disacardios of stocks rotational group hidroximetilo and its dependence on the type of union glicosidica and different agliconas attached.

Author: SALLA CABAU ISABEL.
Year: 2005.
University: ROVIRA I VIRGILI.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Author: JUNQUERA HERNÁNDEZ JOSÉ MIGUEL.
Year: 2005.
University: VALENCIA.
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA (UNIVERSITAT DE VALENCIA).

Summary: It has studied the role of the method (SC) 2 in the study of molecular properties consistent with the size. It has developed a software capable of performing calculations of this kind of electronic properties using the method of interest. This software has been applied this method and the study of different molecular systems test, the method concluyéndose (SC) 2 is capable of providing electronic properties consistent with the size and posed a significant improvement with respect to those obtained when methods Cl not clothed. It has been determined that the best set of basis for the calculation of this type of property is one type d-aug-cc-pVTZ and that the increase in the size of active space has a small effect on the quality of the properties obtained with this method. Lastly been implemented satisfactorily described the method to the study of several real systems for which there were discrepancies between experimental values or they were strangers.

Author: GARCÍA VEGA MANUEL.
Year: 2005.
University: SANTIAGO DE COMPOSTELA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE FARMACIA.

Summary: In this paper we summarize and characterize complex of Zn (II), Cd (II), Hg (II) and PhHg (II) with ligands 3-aril-sulfanilpropenoicos. Using techniques for characterization of elemental analysis, X-ray diffraction, IR and Raman spectroscopy, Magnetic Resonance of 1HC, 13C, 113Cd and 199Hg. We studied the potential activity antidótica of complexes of the type [HQ] 2 [Zn (L) 2] compared to the acute Cd (II) in two cell lines derived from organs affected by the highly toxic, liver and kidney, using cell lines HepG2 and LLC-PK1 respectively. Incluyéndose addition, a study of simetrización of monofenilmercurio in solution.

Author: ALEIXOS ALAPONT SANTIAGO.
Year: 2005.
University: VALENCIA.
Place of defense: FACULTAD DE GEOGRAFIA E HISTORIA.
Place of preparation: FACULTAD DE GEOGRAFIA E HISTORIA.

Summary: The dissertation focuses, as the title indicates, in providing D. Gregory Mayans (1699-1781) to the knowledge of the figure and work of D. Antonio Agustin (1517-1586), as well as its importance in the recognition of the prelate Aragonese as one of the great humanist Europe. Seen from a higher plane this thesis shows and discusses issues such as collateral footprint of humanistic Mayans, a connection with the whole Europe Illustrated and the strong will of the Valencian in publicizing the great works of Hispanic culture. As for the specific approach of the thesis, noting that deliberately shown that the knowledge of Mayans on the illustrious prelate been broadened with the passage of time, mainly on their own willingness to do so, as evidence the many notes and warnings mayansianas that have been added in appendix documentary. In line with his thinking, the scholar did not keep their own benefit his discourses and discoveries, on the contrary, strove to transmit to the whole of Europe. Similarly, studies the evolution of thought of how many Mayans matters addressed in this thesis (epigraphs, numismatics, knowledge of humanism, history, opening for European flows, and so on.). With regard to its structure into three parts; Study of the Figure of Augustine's work, and the epistolary, noting that it meets the intent of providing a complete overview of the areas of action in which Mayans focused to claim as Augustine one of the greatest humanists Spaniards and Europeans. Finally, note that we have tried to go to the original sources, they have given us pleasant surprises, as is the case with Anton Augustins lebens, Mantissa book rarissimo Antonio Augustini, the discovery of these bridges between Patiño and the family Augustine, and so on. It is conducting a study and comparison of various editions of works by Antonio Augustine. Finally, as also with regard to the Mayans epistolary Augustine, it goes to epistolary Mayansiano, both unpublished and published as a source documentary of the first magnitude, to know what Don Gregorio worked documentary sources.

Author: Izquierdo Salado Sandra.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: Departamento de Química.
Place of preparation: Departamento de Química de la Universidad Autónoma de Barcelona.

Summary: The beta-aminoácidos ciclobutánicos are in the nature both as part of isolated peptides. In addition, on many occasions, the embodiment of the ring ciclobutánico in peptidomiméticos conformacionalmente restrigidos has allowed the preparation of biologically active products that show greater resistance to enzymatic hydrolysis, such as the analogue of Tufsina Thr- [Mom2] -Pro - Arg. Thus, in recent years, oligomers of beta-aminoácidos carbocíclicos have shown a strong tendency towards the formation of conformations preferred lead to secondary structures. In this PhD thesis describes the preparation of beta-aminoácidos ciclobutánicos enantioméricamente cigars, as well as their incorporation in different peptide chains. With beta-péptidos obtained is a study in structural solution, basically using Nuclear Magnetic Resonance techniques, and in the solid state by X-Ray Diffraction This study is complemented by different types of calculations, such as the method of Density Functional (DFT) and Molecular Dynamics. Thus, consideration should be given to whether this kind of molecules are some conformation preferential unduzca some sort of folding.

Author: TRISTANY SOLER MARIA DEL MAR.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: FACULTAD DE CIENCIAS. EDIFICIO C..
Place of preparation: FACULTAD DE CIENCIAS. EDIFICIO C.

Summary: For some years, the metallic nanoparticles are attracting great interest in the scientific community for their electronic properties, catalytic, magnetic and optical level nanotecnólogico. They are isolated particle size between 1 and 100 nm, clusters of atoms wrapped in a layer that prevents agglomeration stabilizing. In our research group had discovered that compounds polifluorados simple, such as: 1,5-bis (4.4 'bis (perfluorooctil) phenyl) -1.4 -pentadien-3-ona (dba-2RF) 2 , 4.6-tris (perfluorooctil) aniline, 1,4-bis (perfluorooctil) benzene, 11H, 11H, 12 H, 12 H, 13H, 13H, 14H, 14H, 15H, 15H, 16H, 16H-hexahidroperfluorohexacosano (tribloc ) or 1H, 1H-perfluorooctilamina, stabilized nanoparticles palladium (0) and in the case of dba-2RF, the nanoparticles were active in reactions Suzuki and Mizoroki-Heck under conditions of catalysis biphasic fluoridated, retrievable and reuse . The precedents described herein led us to consider as objective of the first part of this Doctoral Thesis improved method perfluoroalquilación of aromatic compounds to prepare stabilizers polifluorados. The method consists of perfluoroalquilación direct anilinas with iodide perfluorooctilo in the presence of copper oxide (I) in DMSO at 130Â ° C, where the oxide serving as promoter and neutralizing basis. But it is a unique method for anilinas and presents limitations with phenols, anisoles and metilendiaminas. So, try the same reaction perfluoroalquilación of anilinas with other species as promoters of the reaction, including: soluble salts of copper (I) and oxides of silver (I) and lead (II). The species tested promoted reaction perfluoroalquilación, in the presence of potassium carbonate, but in any case improving yields and conversions were obtained with oxide copper (I). Nor was achieved generalize the method to other substrates. As a second goal we set out to study and improve the method of preparing nanoparticles palladium (0) stabilized by compounds polifluorados previously appointed, as well as extending the use of these compounds to stabilize nanoparticles other metals (gold (0), ruthenium (0 ) and platinum (0)). First, sintetizamos stabilizers by the methods described. We note that the synthesis of 1,5-bis (4.4 'bis (perfluorooctil) phenyl) -1.4 -pentadien-3-ona had problems reproducibility. Alternative routes were tested for their preparation nor resolved the problem. The preparation of nanoparticles palladium (0) was carried out by reducing the complex formed between chloride palladium (II) and the sodium chloride with methanol to 60Â ° C in the presence of stabilizers polifluorados. The addition of sodium acetate produces its haste without agglomerate. We have managed to obtain smaller nanoparticles using isopropanol as a reductant. There have also been studies of the materials Solid polifluorados used by X-ray diffraction powder and molecular mechanics preliminary calculations, reaching the assumption of a stabilization of nanoparticles by entrapment by compounds polifluorados with orderly crystalline structure. Then our stabilizers were tested with ruthenium (0) by the method of reduction and separation of ligand complex organometálico, breaking the complex Ru (COD) (TOC) with hydrogen in the presence of the compounds polifluorados in an appropriate solvent. With 2,4,6-tris (perfluorooctil) aniline and 1H, 1H, 2H, 2H-tetrahidroperfluorodecilamina were obtained nanoparticles very small (3 nm), monodispersas without agglomeration and, surprisingly, in the case of the amine they autoorganizaron in regular spherical aggregates approximately 70 nm. In the case of platinum (0), were also very nanoparticles peq 8 ueñas is 4cd tabilizadas for the same products fluorinated via approximate organometálica from Pt2 (dba) 3 as a precursor. Tubular autoorganización was observed in the case of self-organization and spherical aromatic amine in the case of the amine alifática. In short, the thesis describes the preparation and characterization exhaustive (TEM, HRTEM, SEM-FEG, SAXS, WAXS, microanalysis, IR, UV-Vis, NMR, ED, p-XRD, TGA) nanoparticles different metals (Pd, Au, Ru, Pt) stabilized by compounds polifluorados simple.

Author: GARCÍA SEGOVIA ANA BELÉN.
Year: 2005.
University: VALENCIA.
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: UNIVERSITAT DE VALÈNCIA.

Summary: Both espongianos as escalaranos are two families terpenos are isolated from marine organisms such as sponges and some nudibranquios. Both have been shown to have an interesting biological activity and it has been made various synthetic approaches to the training of their respective skeletons, with the objective of achieving greater quantity of these products which are obtained from natural sources. Both routes are still parallel synthesis, starting from the carvone as product aprtida chiral allowing introduce estereoquímica suitable for obtaining the corresponding natural products. In the case of espongianos, part of the R - (-) -carvona as synthetic equivalent of ring B skeleton espongiano and follow a sequence of construction of the ring-type B> AB-> ABC-> ABCD, which employs a reaction Diels-Alder intramolecular as a key step in the synthesis for the formation of ring C with the estereoqumica desired. Through this route has come to get the preparation of espongiano natural DORISENONA C equivalent furanoespongiano, as well as other intermediate with the skeleton of espongiano with an oxygenated at position C-7. In the case of escalaranos is part of S (+) -carvona as synthetic equivalent of ring C skeleton escalarano and follow a sequence of construction lso ring type C-> CD-> ABCD-> ABCDE, which employ two reactions Diels-Alder intramolecular for preparing lso rings CD and AB. Through this route has managed to obtain the complete skeleton of escalarano with estereoquímica identical to that of natural products in all centers estereogénicos. Significantly, this is the first synthesis described giving the skeleton escalarano with an oxygenated in the position C-12. Additionally has been done assessing the activiadad antitumor some of the intermediate espongiano prepared by the National Institute of Cácer United States, having obtained an antiproliferative activity to moderate some of them with a degree of selectivity versus some specific cell lines.

Author: GALLARDO OÑA JORDI.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: FACULTAT DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Author: MUNTEANU CRISTIAN ROBERT.
Year: 2005.
University: SANTIAGO DE COMPOSTELA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: The objective of this thesis is to study d in considerable number of complex van der Waals and check the accuracy of the method CCSD (T) and the bases Dunning augmented with a series of functions "mib bond" in obtaining energy surfaces potential for interaction accurate. So, we correct some areas previously obtained by assessing their spectra accurately. In this work demonstrates the importance of choosing a base and a number of functions "mib bond" appropriate.

Author: RAMOS MARCOS M. JESUS.
Year: 2005.
University: CASTILLA-LA MANCHA.
Place of defense: FACULTAD DE CIENCIAS QUIMICAS, CIUDAD REAL.
Place of preparation: FACULTAD DE CIENCIAS QUIMICAS.

Summary: The refining industry is being changed by the various requirements imposed by the market and environmental legislation. The biggest concern for the environment has led to prohibit the sale of petrol with lead throughout the national territory and to reduce the content of aromatic compounds, among others, which negatively affects the octane number to be offset by other less harmful components. The isomerization of alcanos has been used industrially for decades to increase the octane number gasoline delas. This process makes components parafínicos normal low octane number, isomers of branched chain and high octane for reorganization of the links between atoms. This research has been carried out by the process hidroisomerización of n-octano on catalysts based on zeolites mordenite, beta and ZSM-5. As a function metal palladium has been used and / or platinum. In addition, the majority of industrial catalysts required to be bonded any kind or binder that enables particles get more resilient and prevents an excessive pressure drop in industrial fixed-bed reactors. The presence of the binder can affect wings acidic properties of the zeolite, thus the study of the influence of binder in the presence of catalysts zeolíticos, it is also of great interest. Other aspects estudidos have been content métalico, the ratio Si / Al of the zeolite, the study of the influence delas reaction conditions, development of a kinetic model for the reaction of hidroisomerización of n-octano and hidroisomerización a fraacción hydrocarbon source a naphtha refinery.

Author: OCHANDO PARDO MONTSERRAT.
Year: 2005.
University: VALENCIA.
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA.

Summary: This thesis provides a description of the mechanisms of the kinetics of some reaccionesw interest tropospheric. Currently emissions antropogéncias into the atmosphere are growing at a steady pace, making necesria a review of the impact that human activities have on our environment. To understand and prevent atmospheric phenomena, creating modlos which includes a maximum of variables. The theoretical studies such as those presented in this thesis, provide information about the mechanisms of reaction and kinetic data, such as the constant speed, which can later help to bring predictive models. One aspect common to all the reactions studied is the fact that relate to processes of oxidation of volatile organic compounds (VOCs) by the OH radical. Specifically, it has worked with alquellos (eteno, propene, isobuteno and cloreteno) and partially oxygenated compounds (glicolaldehído, vinyl methyl ketone and metacroleína). The main objectives in this thesis are: 1. Explain, by the theory of conventional state of transition. The onset of activation energies in the case of reaccciones between diverse alquenos and radial OH, aÂ'si as determining regioselectividad for those replaced. 2. Provide, in the case of system glicolaldehído + OH, the rate constant at different temperatures for a reaction multiwell and multichannel through the theory of canonical variational transition state, with multidimensional tunnel where necessary. 3. Provide a description of theoretical performance with the pressure and temperature d elas constates speed systems vinyl methyl ketone and metacroleína + + OH OH, by the theory of state of transition microcanonica conventional and resolution of the master equation. 4. Get the entalpías theoretical training and bond dissociation energies for the vinyl methyl ketone and metacroleína, as well as for their oxidation products, to provide information about the strength of the various links that form or cracks in the oxidation the radical OH.

Author: GIMÉNEZ PEDRÓS MARTA.
Year: 2005.
University: ROVIRA I VIRGILI.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.