CHEMISTRY, 5

Author: Gurauskis Jonas.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: Instituto de Cerámica y Vidrio (CSIC).
Place of preparation: Instituto de Cerámica y Vidrio (CSIC).

Summary: The traditional materials could not meet the demands imposed by current technologies. It therefore requires the development of new materials with well-defined characteristics and properties, as well as processing techniques that enable their achievement. The main objective of this work has been the development and characterization of ceramic materials with structural applications, which are designed new structures that lead to strengthening mechanisms. These mechanisms depart to materials behavior fragile for the fracture. Materials that were proposed to combine strengthening microstructural scales and macroestructural, deciding to implement the design of a laminated structure. This paper proposes the development of composite materials rolled alumina (Al2O3) / YTZP (t-ZrO2 stabilized with 3% mol. Y2O3). We have used two compositions, alumina with 5% vol. YTZP and alumina with 40% vol. YTZP. Strengthening microstructural level is obtained by the presence of YTZP as a second phase in the alumina matrix while strengthening at macroestructural stems from the residual tensions compression developed in the external layers. To process and rolled monolithic structures has developed a new method of processing. It has studied the process of rolling low pressure and room temperature for the union ceramic green tape, made from aqueous suspensions and using small additions as an emulsion polymer binder. The optimization process has enabled rolling obtaining ceramic materials free from defects related to the prosecution. To prevent defects arising from the differential sintering of the tapes must be used with tape density levels similar green. Parts monolithic underwent an extensive microstructural analysis and mechanical. The microscopic observation and the results obtained from testing of fracture and bi-axial bending and Vickers indentation in the cross section, confirmed the effectiveness of the new method of processing, since the pieces are optimized only detected flaws inherent in the ceramic materials. The trials of neutron diffraction showed no residual stress level macroestructural. Tensions were identified residual microstructural scale, caused by differences between the coefficient of thermal expansion of the constituent phases of the monolithic. Since trials bending test tubes with indentaciones and observations fractográficas found that the presence of YTZP in materials improves its mechanical behavior due to the activation mechanism of reinforcement. Proportions senior YTZP lead to greater increases in the values of the stress fracture and fracture toughness and also to conduct R curve more pronounced. Two structures were designed rolled (L1 and L2) with different levels of residual stress. Various methods were applied to evaluate the magnitude and distribution of residual stress: finite element calculation and determination pilot through piezo-espectroscopía fluorescence. Tensions show some residual effect of the presence of surface, ie are not constant and increase depending on the depth of the outer layers to the interface layers under tension. It has analyzed the influence of residual stress on the mechanical behavior of materials laminates obtained. The compressive residual stress in the external layers of the laminated structures significantly increase the value 8 is you 4bd nsión fracture and fracture toughness. The magnitude of the residual stress directly affects the absolute values of these properties, as the highest values were obtained in structure laminated L2, with the values of residual tensions higher than in L1. The results show that the R curve behavior observed in these structures is rolled activated not only by the presence of residual stress and behavior R curve of the outer layer, but also by the distribution of residual stress in the layer external.

Author: PICÓ MORÓN FERNANDO.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: INST.DE CIEN. DE MATER.DE MADRID (CSIC).
Place of preparation: INST.DE CIEN. DE MATER.DE MADRID (CSIC).

Summary: This thesis has been prepared electrode active materials based on ruthenium oxide for use in supercondensadores. The supercondensadores are devices that associated with fuel cells or batteries, have an interest in applications such as uninterrupted power systems or electric vehicles. In this paper we understand how target ranges specific capacity of composite materials based on ruthenium oxide depending on the content of RuO2 xH2O (or RuO2). This composite materials have been prepared using three media: i) a carbon mesoporoso with high specific surface area and pore volume of high ii) carbon nanofibres with specific surface and pore volume moderates, but with a very accessible to the surface of ruthenium oxide iii) a nickel oxide with specific surface and high porosity. In composite materials RuO2 xH2O/Cmesoporoso, the impregnation with ruthenium oxide does not improve the ability of the material specific carbon mesoporoso used as a support. It has been shown that the RuO2 maintains a high specific capacity in the composite material. Therefore, the decrease in the specific capacity is because impregnation with ruthenium oxide markedly reduces the surface of the material specific carbon mesoporoso by blocking a large amount of pores in the sample. The reduction in specific surface makes the contribution of carbon material to the ability of specific composite material is lower than expected for a law of mixtures. In composite materials RuO2 xH2O/nanofibras carbon impregnation with ruthenium oxide has enhanced the ability of carbon nanofibres from 30 F / g to values of 200 F / g for samples with a 35% by weight of RuO2. For transmission electron microscopy has shown that the ruthenium oxide particles are located on the surface of carbon nanofibres. The ability of specific materials increases linearly with increasing the content of RuO2, meaning that the specific capacity of the composite materials RuO2 xH2O/nanofibras carbon is governed by a law of mixtures. In composite materials RuO2 xH2O/NiO, the specific capabilities of composite materials RuO2 xH2O/NiO are higher than expected for a law of mixtures. From an applied perspective, the investigation has shown that is possible to produce composite materials with a low content of oxide ruthenium (20%), thus significantly cheaper, without loss of the specific expertise. The observed behavior can be explained because in the compositional range of 0-20% by weight of RuO2 the specific surface (300 m2 / g) did not differ significantly despite an increase in the content of ruthenium oxide. However, in RuO2 greater of 20%, increased the content is accompanied by a sharp decline in the specific surface. It has been found that the specific surface is a parameter that modulates the contribution of RuO2 xH2O the specific capacity of the composite materials. We have identified the most significant electrochemical parameters of supercondensadores assembled with composite materials synthesized. The values of specific energy and power are obtained in the range 0.5-10 Wh / kg and 50-2000 W / kg, respectively. The loss of 50% of capacity in 24h observed for the composite materials RuO2 xH2O/nanofibras carbon and RuO2 xH2O/NiO indicates that the auto-discharge when using these materials is moderate. In all supercondensadores studied were found response times around 5 s. Finally, the composite material RuO2 xH2O (30% by weight) / carbon nanofibres presents an excellent ciclabilidad, diminishing their capacity only a 7% after 10000 cycle 8 s of car 27th Ga / unloading.

Author: Fernández Martín Raúl.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: Escuela politécnica superior.
Place of preparation: Universidad Autónoma de Madrid.

Summary: In this thesis evaluates the behavior of mortar cemento-bentonita (relevant in a Deep Geologic Storage of Radioactive Waste High Activity) using experimental techniques and geochemical simulation codes. A column of compacted bentonite contacted with a cement mortar. Two alkaline solutions (Ca (OH) 2 saturated and NaOH 0.25 M) were injected from the side of cement mortar at 25, 60 and 120 Â ° C for one year. The dissolution of Ca (OH) 2 saturated does not alter the mineralogy in the time scale pilot. The dissolution of NaOH produced minor changes to 60-25 Â ° C, but at 120 Â ° C there is a disruption heterogeneous distributed throughout the sample of bentonite. The transport codes reagent PHREEQC and CRUNCHFLOW reproduce the experimentally observed reactivity at the interface mortar cement-bentonite, however, are not yet capable of properly represent some of the processes occurring in the system.

Author: GARCÍA APARICIO VÍCTOR.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: FACULTAD DE INFÓRMATICA.
Place of preparation: CENTRO DE INVESTIGACIONES BIOLÓGICAS (C.S.I.C.).

Summary: During recent years it has been shown that carbohydrates are widely distributed in nature and play a large number of functions bilológicas. Clearly the major biological role of carbohydrates is to be points especifícos of molecular recognition with lectin, enzymes, antibodies, hormones and viruses .. To be produza recognition molecular structures tridimensionalers of carbohydrate and receptor plays a major role. Whereas carbohydrates (or its synthetic analogues of glicomiméticos) as potential drugs, it is clear that knowledge of its structure in a free state as a partner to the receiver is important. Knowledge of the structure 3D a carbohydrate solutions can be obtained only through Nuclear Magnetic Resonance (NMR). In turn NMR can provide information on the conformation of the ligand recognition in the center of the protein, ie on the possible formation bioactiva. It measures the effect nuclear Overhausser transferred (tr-NOE), STD and relaxation time measurements, it is possible to determine the conformation of the receptor and ligand partner capable of detecting conformational changes in the move from free associated state. In this report we have focused on the study of the interaction between synthetic analogues (glicomiméticos) from various natural ligands, such as Ty Tn antigen, and its biological receptor as lectina of muerdago and galectina 1 huamna using a multidisciplinary approach NMR and molecular modeling. Work performed in the laboratory of Jesus Jimenez Barber in Madrid has been developed under the project by the Ministry of Science and Technology, BQU2003-03550-C03-01, in which the candidate Victor Garcia Aparicio, has been hired as a trainee Predoctoral , in the laboratory in Madrid since November 2002.

Author: RAMÍREZ MORENO CARLOS.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: FAC.DE CIEN. DEP. DE BIOL.MOL..
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The disease alzheimer sporadic (SEA) are implicated both genetic factors as environmental factors. Among these factors are advanced age, female gender, the allele e4 gene of the apolipoprotein E (APOE), the levels of APOE and a factor hitherto unknown environmental transmissible involving up to 60% of the total variance disease. In recent years it has been proposed that the herpes simplex virus type 1 (HSV-1) could be implicated in the etiology of EAE. In epidemiological studies has been described as the combination of the presence of HSV-1 in the brain and to be the bearer of APOE allele e4 of promoting an increased risk to suffer from the disease. This dissertation presents results demonstrating that the factors discussed above that have been associated with the SEA, also involved in infection by HSV-1 in mice, both during the acute phase and during dormancy. It has also been described Hematogenous vertical transmission of HSV-1 in mice, which can be avoided by therapy admisnistración oral acyclovir. This vertical transmission induces colonization by the virus brain of the offspring, invading neurons in the hippocampus from where it can be reactivated by stress stimuli. In parallel it has been shown that age, female gender, isoform human APOE4 and dose APOE gene are involved in the colonization of the brain of the offspring through this type of infection, leading to more viral load in this body .

Author: Pita Martínez Marcos.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: Instituto de Catálisis y Petroleoquímica, CSIC.
Place of preparation: Instituto de Catálisis y Petroleoquímica, CSIC.

Summary: The wide control of the synthesis of nano materials has meant one of the aims of science in recent decades, thanks to progress in characterization and visualization techniques that allow such control. Likewise, the interest attractiveness of nanostructured materials is very high, since the downsizing to levels only one or two orders of magnitude higher than the atomic size implies the emergence of new properties, opening up the range of possibilities. Thus, the metal nanoparticles, in particular gold and silver, presented a series of optical properties (resonance plasmón surface), electrical (conductivity) and physical (ability to quimisorber organic molecules) represent an ideal material to develop techniques for tying oriented already developed for gold macroscopic surfaces. Moreover, the nanoparticles superparamagnéticas represent excellent material for the development of nanostructured systems because of its stability in the absence of magnetic fields, but their reaction to an external magnetic field, which allows ownership advantages such as sample preconcentration of a point Localized; can be avoided stages in a long process of chemical synthesis, such as centrifugation. Two methods were developed for the synthesis of nanoparticles of gold, using one of them (through reverse micelles) for derivatization with topcoat Self-thiol. On these topcoat was developed to build an organizational structure that gives rise to a cause of union specifically for the immobilization of proteins through histidinas. Thus, through these amino acids by introducing genetic engineering in the area of a desired enzyme in particular, get a grounding oriented. Moreover were synthesized and characterized two types of ferrofluidos, selecting one for the coating of magnetic nanoparticles with a metal outer layer; well either gold or silver and gold. These nanoparticles were used for immobilization of antibodies directed through Self topcoat, and the development of a sensor of DNA through the complementary union with a compound biomimético, NAPA. It also developed two methods for detecting the signal, a built based on the detection by infrared spectroscopy transmission of the reasons different spectral between DNA and PNA (bands symmetric and antisymmetric tension of the phosphate groups), and another method consisting of the fluorescence detection of an external developer, Rodamina 6G. PUBLICATIONS IN THESIS Jose M. Abbot, Mark Pita et al. "Functionalization of Thioctic Acid-Capped Gold Nanoparticles for Specific Immobilization of Histidine-Tagged Proteins." J.Am.Chem.Soc., 2005, 127, 5689-5694. Jose M. Abbot, Mark Pita, and Victor M. Fernandez. "Immobilization of Proteins on Gold Surfaces." Methods in Biotechnology 22, p. 229-238, 2006. JM Guisan (ed), Humana Press Inc.., Totowa, NJ. Mark Pita et al. "Direct heterogeneous electron transfer reactions of fungal laccases at bare and thiol-modified gold electrodes." Electrochem Commun 8 (2006) 747-753. Mark Pita, Victor Manuel Fernandez Lopez, Jose Angel Martin Gago, Jose Carlos Pereda Serna, Cristina Vaz Dominguez, Carlos Briones Llorente, Eva Matthew Marti. "Nanopartícula Biosensora, Procedures Development and Applications". Invention Patent number 200502269, September 16, 2005. Ana Beloqui, Mark Pita et al. "Novel Polyphenol Oxidase Mined From A Metagenome Expression Library Of Bovine Rumen: Biochemical Properties, Structural Analysis And Phylogenetic Relationships", J. Biol. Chem. In press. Sergey Shleev, Mark Pita, et al. "Direct heterogeneous electron transfer reactions of Trametes hirsuta laccase at bare and thiol-modified gold electrodes." Electroanal. In press.

Author: GÓMEZ-HORTIGÒELA SAINZ LUIS.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: FACULTAD DE CIENCIAS (U.A.M.).
Place of preparation: INSTITUTO DE CATÁLISIS Y PETROLEOQUÍMICA.

Summary: This research work has been carried out a study on the ability of organic molecules to direct the synthesis of structures microporosas crystal, trying to understand, from a combination of experimental and theoretical studies, the mechanisms involved. The synthesis of materials microporosos crystalline both zeolites as aluminofosfatos is often employ organic molecules that act as templates structures during the synthesis process. These materials crystallize around these organic molecules, and therefore have an effect director structure, which is called the agents managers structure (ADE). The ability of these ADEs to lead structures microporosas depends critically on the interactions of no-enlace establish with them. So far, the major molecules used as ADEs were amines or quaternary ammonium salts, where these interactions occur via the hydrogen atoms in the molecules. This article has attempted to modify the chemical nature of these interactions, introducing fluorine atoms in ADEs. The methodology of work consists of two types of approaches. First, we studied from an experimental point of view, the ability of these molecules to direct synthesis of aluminofosfatos microporosos crystalline. We have employed molecules containing aromatic rings. The molecules were synthesized ADE both fluorinated derivatives in various positions of the aromatic rings, as no-fluorado so as to establish the effect of fluoride, and then were tested as ADEs in the synthesis of aluminofosfatos microporosos in different compositions. The solid obtained were characterized by various physicochemical techniques. Once experimentally determined the influence of fluorine on the ability of individual molecules to direct the synthesis of these structures were used theoretical methods of calculation to explain these effects. It used a combination of simulation techniques based on the molecular mechanics methods. This was achieved understand the effect of fluoride on the ability of organic molecules to direct the synthesis of structures microporosas. We studied mainly three types of molecules: bencilpirrolidina (bp), dibencildimetilamonio (dbdm) and (S) -1-bencil-2-pirrolidinmetanol (bpm), and fluorinated compounds in ortho positions, and aim for the aromatic ring. All of them led to the crystallization of the material AlPO-5 (structural AEF), which is composed of unidirectional channels cylindrical 7.3 Ã, although differences were found when using fluoride molecules. Theoretical calculations indicate a strong tendency of these molecules to be added within the channel structures zeolíticas as supramolecular structures, either as dimers (molecules with a single aromatic ring, and bp bpm) or chains (dbdm). There is a coupling of two rings bencénicos parallel to each other, thereby maximizing the molecular density in the system microporoso. We have found various effects that can exert fluoride in ADEs. On the one hand, the presence of liaison CF increases electrostatic interactions with the network that establishes inorganic, and thus improve the leadership structure of the same. However, the presence of fluoride also significantly affects the ability of packaging these molecules inside the structures. Thus, the fluoride in certain positions can cause repulsiones interest or intramoleculares to prevent a compact packaging of the molecules inside the channel. The presence of fluoride can also involve the establishment of strong interactions ADE with other molecules, such as water, giving rise to an effect director of the cooperative structure of the two. The third molecule, bpm, was designed rationally in an attempt to induce a long-range ordering of molecules ADE. From a theoretical point of view, the most stable of these molecules inside the microporous structure comprises an order helic 8 oidal (q 406 uiral) of the same. This quiralidad in supramolecular provision of ADEs could lead eventually to a character chiral solid. Materials are doparon with silicon and magnesium, to get active acid sites, and to evaluate the catalytic activity of the same. We found that fluoride in ortho positions and target of ADEs greatly improves the activity of the materials.

Author: Pozueta Larios Julio.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: Departamento de Biología Molecular.
Place of preparation: Universidad Autonoma de Madrid, Facultad de ciencias.

Summary: In 1907 Añois Alzheimer public description of the first neuropathological syndrome, characterized by progressive loss of memory and the deterioration of cognitive abilities. The two key characteristics that define Alzheimer's disease (AD) are training about acumulos extracellular called senile plaques and some acumulos intracellular are called neurofibrillary tangles. The beta-amyloid peptide is a key component of the senile plaques and is a derivative of precursor protein beta-amyloid peptide, or PDB. Since that 1991 will be generated by the first transgenic this protein has been made, a variety of transgenic animals that can reproduce partially some of the symptoms, although most of them have been designed for estúdio of EE family, minority variant of the disease. We have created a new model for studying the disease using a yeast artificial chromosome (YAC) with a size of 520 Kb, which has been modified mediane homologous recombination in yeast gene to maintain the PDB complete with all its regions but regulators eliminating the presence of other genes, such as the transcription factor GABPA present in the YAC departure. Using the method of transgenesis mediated by intracytoplasmic injection of sperm heads, we have been able to generate several lines of transgenic mice. In two of these lines, the 35 and 64, the YAC has been integrated completely. The analysis of gene expression and protein, has resultada greatly similar to the endogenous gene in mice.

Author: Mauleón Pérez Pablo.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: Facultad de Ciencias UAM.
Place of preparation: Facultad de Ciencias, UAM.

Summary: BACKGROUND AND OBJECTIVES OF THE QUESTION PROPOSED Continuing studies developed by the group of Professor John C. Carretero on applications of synthetic vinyl and vinyl sulfóxidos sulfones in mediated reactions of transition metals, (1) was raised as a project for this Doctoral Thesis development of catalytic processes directed towards funcionalización stereoselective the position of sulfones -insaturadas by reaction Heck and the addition of acids borónicos catalysed by rhodium, two reactions interconnected through a common reaction intermediate. In case of formation of a center estereogénico in position (adding catalysed by rhodium) would be of great interest to developing processes highly enantioselectivos. Both goals (Heck intermolecular reaction and addition of acid borónicos to vinyl sulfones) presents a major component innovative, there being no precedent for this in the literature prior to the start of this dissertation. Moreover, the outputs should have a great potential in organic synthesis because of the great versatility of synthetic group sulfonilo. DEVELOPMENT OF WORK AND METHODOLOGY 1. Heck Reaction: arilación intermolecular cascading As a first target was raised preparing vinyl sulfones, b b'-disustituidas through a reaction Heck. However, this thesis has been found that in the case of the usual phenyl vinyl sulfones reaction with yodobenceno (or yodoarenos p-sustituidos) catalysed passes through a cascade of four components in which makes four CC links in a single phase reaction, resulting in the formation of 9,10-dihidrofenantrenos. This kind of reaction multicomponent was known only in the case of alquenos cyclical who can not undergo reactions b-eliminación hydrogen (eg norborneno), but not from olefins acíclicas. Under the same experimental conditions, vinyl sulfones with the group potentially coordinating 2 - (N, N-dimetilamino) phenyl it led only to the product Heck suggesting that the reaction of arilación cascade involves highly electrófilas of palladium. In this thesis has shown that both processes catalyzed by palladium (arilación cascade and Heck reaction of vinyl sulfones) have a great general, irrespective of the position b replacement of the vinyl sulfota or estereoquímica Eo Z. Both experimental results and theoretical calculations support the participation of paladaciclos trans-sustituidos as a key intermediate in the reaction of poliarilación. Compared with other olefins, these results indicate the great uniqueness of sulfones, a b-insaturadas in reactions catalyzed by palladium. 2. Adding conjugate acid borónicos catalyzed asymmetric rhodium has been developed by a general method for adding conjugated to a sulfones, b-insaturadas, unknown process so far. While the phenyl sulfones were inert under the reaction conditions tested, piridil sulfones, a b-insaturadas experience a clean reaction adding acids borónicos lag with excellent yields and good enantioselectividades, stressing the importance of the group coordinating piridilo. The piridil sulfones b-sustituidas thus obtained can be used in a reaction olefinación of Julia-Kocienski providing alquenos alílicos with excellent yields. This sequence of two stages (adding conjugate / olefinación of Julia-Kocienski) is a very attractive alternative and complementary to the replacement alílica catalyzed by palladium derivatives alcohols alílicos. An example of the high potential of synthetic methodology developed shown in its application to the reaction of acidic saw 8 nil boró e98 nicos with vinyl sulfones, b b'-disustituidas. In the usual conditions of reaction, are generated quaternary carbons with moderate to good yields and excellent enantioselectividades. It is important to stress that at the beginning of this dissertation, there was no process known generation quaternary carbon catalytic processes by adding conjugate enantioselectiva. (1) Using the group sulfinilo as chiral auxiliary in reactions Pauson-Khand: (a) J. Adrio, J. C. Carretero, J. Am. Chem. Soc. 1999, 121, 7411. (B) J. C. Carretero, J. Adrio, Synthesis 2001, 1888. (C) M. Rodriguez Rivero, J. C. De la Rosa, J. C. Carretero, J. Am. Chem. Soc. 2003, 125, 14992. (E) M. Rodriguez Rivero, I. Alonso, J. C. Carretero, Chem. Eur. J. 2004, 10, 5443. Vinil sulfones funcionalizadas in reactions Pauson-Khand intramoleculares: (f) J. Adrio, M. Rodriguez Rivero, J. C. Carretero, Angew. Chem. Int. Ed. 2000, 39, 2906. (G) J. Adrio, M. Rodriguez Rivero, J. C. Carretero, Chem. Eur. J. 2001, 7, 2435. G-Hidroxi vinyl sulfones funcionalizadas and derivatives in replacement alílica catalyzed reactions by Pd: (h) I. Alonso, J. C. Carretero, J. L. Garrido, V. Magro, C. Pedregal, J. Org. Chem. 1997, 62, 5682. (I) J. L. Garrido, I. Alonso, J. C. Carretero, J. Org. Chem. 1998, 63, 9406. Using the group sulfinilo as chiral auxiliary reactions Heck: (j) N. Diaz Buezo, I. Alonso, J. C. Carretero, J. Am. Chem. Soc. 1998, 120, 7129. (K) J. Priego, J. C. Carretero, Synlett 1999, 1603. (L) M. M. Segorbe, J. Adrio, J. C. Carretero, Tetrahedron Lett. 2000, 41, 1983. (M) N. Diaz Buezo, O. Garcia Mancheño, J. C. Carretero, Org. Lett. 2000, 2, 1451. (N) J. C. De la Rosa, N. Diaz Buezo, J. C. Carretero, Tetrahedron Lett. 2000, 41, 4107. (O) N. Diaz Buezo, J. C. De la Rosa, J. Priego, I. Alonso, J. C. Carretero, Chem. Eur. J. 2001, 7, 3890. Through the reactivity own group sulfonilo the previous sulfones have been transformed easily and with excellent yields in other compounds with quaternary carbons and varied funcionalización (ketones, esters and 1,4-dienos 3-sustituidos). Ultimately, the development of this thesis has been achieved four major milestones for which there was no precedent in the literature and present a strong interest synthetic: a) The reaction arilación multi a alqueno acyclic with yodoarenos with training dihidrofenantrenos (formation of 4 or more links in a single phase DC synthetic). B) The reaction Heck diastereoselectiva of sulfones -insaturadas whenever it uses a group of coordinating palladium joined the group sulfonilo. C) The addition reaction of conjugated highly enantioselectiva acid borónicos to sulfones -insaturadas catalysed by rhodium. In this case it is imperative the use of the group 2-piridilsulfonilo as assistant group coordinating the atom rhodium. D) The generation highly enantioselectiva of quaternary carbon reactions by adding acids alquenil borónicos to sulfones -insaturadas -disustituidas.

Author: CABRERA HERRANZ SILVIA.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The project started in the year 2000 by the group of Professor John C. Carretero on the development and applications of new chiral ligands based tioéteres in asymmetric catalysis processes, was raised as a target for this Doctoral Thesis implementation of the family of ligands Fesulphos (1-sulfenil-2-fosfinoferroenos) in two types of reactions different opening alquilativa of alquenos heterobicíclicos with reagents dialquilcinc catalysed by Pd and the reaction of cicloadición 1,3-dipolar of iluros of azometino catalyzed by metal complexes of the ligands Fesulphos. Both transformations asymmetrical presents an important and novel synthetic interest because prior to the start of this doctoral thesis there were few precedents bibliographic. 1. Opening alquilativa of alquenos heterobicíclicos. As a first target was raised evaluation of the family of ligands Fesulphos at the opening alquilativa of alquenos heterobicíclicos with organocíncicos catalysed by Pd. This thesis has been found that the use of cationic complexes of metilpaladio (II) of the ligands Fesulphos are extremely efficient catalysts in this reaction, providing levels of reactivity and enantioselectividad much higher than those described in the literature for a wide variety of substrates . Only 0.5 mol% of catalyst cationic [Pd (1g) (I)] + induces desimetrización of oxabenzonorbornadienos differently replaced with Me2Zn, Et2Zn and Bu2Zn with good yields (61-99%) and excellent enantioselectividades (94-> 99% ee). Likewise, the opening of substrates less reactive as alquenos [2.2.1] oxabicíclicos and azabenzonorbornadienos N-sustituidos in the presence of complex metilpaladio (II) ligand Fesulphos (formed in situ or preformed, respectively) took place at room temperature or lower , isolated the goods opening with good yields and excellent enantioselectividades (90-> 99% ee). Unlike the preceding previously described for these substrates requiring reflux DCE and / or catalytic amounts of Lewis acid, in this thesis has shown that the excellent effectiveness of cationic complexes [(Fesulphos) Pd (I)] + permits to carry out this transformation in a very mild reaction conditions. 2. Cycloaddition 1,3-dipolar of iluros of azometino. Despite that have been described for this effective systems catalytic reaction prior to the development of this goal, the applicability of these catalytic system was limited to a small number of iluros of azometino replaced and dipolarófilos. In this regard, the second objective of this Doctoral Thesis has studied the effectiveness of metal complexes of the ligands Fesulphos as chiral Lewis acids in the reaction 1,3-dipolar enantioselectiva. It has been shown that the combination Fesulphos-CuClO4 is an excellent Lewis acid for this cicloadición obtained the enantioselectividades higher described this reaction and for presenting a wide-ranging structural both with respect to the replacement of iluro of azometino as to the nature of dipolarófilo. Get exceptional enantioselectividades (80-> 99% ee) and complete diastereoselectividades in the reaction of the N-fenilmaleimida with iminoésteres derivatives glycinate methyl, or leucinato methyl and even cetiminoésteres. The latter, which allows generation centers quaternary estereogénicos C-5, are the first examples described synthesis enantioselectiva such pirrolidinas. The structural scope of this methodology has been extended to a wide range of dipolarófilos both diactivados (maleimidas, maleatos Dimethyl, fumarate dime 8 Linden f 842 umarodinitrilo) as monoactivados (acrylates, lactones, -insaturadas, aldehydes and nitroderivados, -insaturados) . In general, yields the corresponding pirrolidinas with high enantioselectividades (69-> 99% ee) and moderate to excellent endo-selectividades, with the exception of nitroderivado, -insaturado and fumarodinitrilo who provided mostly corresponding exo adducts. Importantly, the cicloadición with metacroleina, which generates a pirrolidina with a quaternary center in c-4, fenilnitroestireno and furan-2-ona are the first examples described reaction 1,3-dipolar catalytic asymmetric with iluros of azometino. 3. Opening alkylating of alquenos heterobicíclicos with Grignard reagents. It has developed a new method of opening alkylating of alquenos heterobicíclicos with Grignard reagents catalyzed by Cu (I). Most of the reactions of opening these substrates previously described the development of this project were taking place with estereoselectividad without. Against this background, the opening of alquenos oxa- and azabicíclicos with Grignard reagents, both arílicos as alquílicos, catalysed by sales of Cu (I) leads to the corresponding products of openness with good yields and complete anti-estereocontrol. At the opening of alquenos azabicíclicos the choice of the group (2-piridil) sulfonilo joined the nitrogen was essential for the reaction to take place.

Author: BARRAJON CATALAN ENRIQUE.
Year: 2005.
University: MIGUEL HERNÁNDEZ DE ELCHE.
Place of defense: INST.DE BIOLOGIA MOLECULAR Y CELULAR.
Place of preparation: INSTITUTO DE BIOLOGIA MOLECULAR Y CELULAR.

Summary: The work presented in this Doctoral Thesis stems from the need to identify the molecular mechanisms involved in the transition from a phenotype hormonodependiente another hormonoindependiente in human breast carcinoma. Specifically, the overall objective of this study is to clarify the relationship between kinase Src, the ERalpha and acquisition of a phenotype hormonindependiente within the context of breast tumors. This would have raised the following specific objectives: 1.Generar and characterize a model of proper study from cell carcinoma human MCF7 2.Estudiar the breast expression and activity of ERalpha as chief regulator of the response to both hormones the new model cell like cells MCF7. 3. Discovering possible mechanisms to explain the phenomena encountered. 4. Study proliferation on the basis of the dependence of the different models of estrogen cell. As a model study has created a new cell line using stable transfection of cells MCF7 parent with a constitutively active mutant of the kinase Src. This cell line, called MCF7src, to evaluate the role of the kinase Src in the acquisition of a phenotype hormonoindependiente, as well as their effect in regulating the expression and activity of the estrogen receptor alpha. Such a situation, in which the kinase is present in a constitutively active, but not overly sobreexpresada, is a typical of the conditions under which presents breast cancer. The results and conclusions obtained in this study are:-cell line MCF7src expressed in a stable isoform the constitutively active Y534F the kinase Src. This line-present activity of ERalpha diminished. - The expression of the kinase leads to an accumulation of protein ERalpha in cells MCF7src. This effect comes from an accumulation in levels of mRNA. - To cumulación of mRNA of ERalpha in cells MCF7src is due to the effect of the kinase on its half-life, which is enhanced more than twice. - Kinase Src causes an increase in the phosphorylation of tyrosine residues in the ERalpha in cells MCF7src. - This phosphorylation and / or their accumulation is the result of the decreased activity of ERalpha. - The presence of the kinase endows / provides cells MCF7src a degree of hormonoindependencia their predecessors, the cells MCF7 not possess. - The acquisition of hormonoindependencia allows cells MCF7src grow in the absence of estrogen. - The cells MCF7src, for its resemblance to actual tumors, are a model study applies to the search for new therapies against cancer of the breast.

Author: Arroyo Máñez Pau.
Year: 2005.
University: VALENCIA.
Place of defense: Facultad de Farmacia.
Place of preparation: Facultad de Química.

Summary: There have been various studies notably those for the study of molecular mechanisms of reactions cicloadición [4 +2] or reactions Diels-Alder, and [3 +2] or cicloadiciones 1,3-dipolar. It has studied the mechanism of the reaction of 4,6-dinitrobenzofuroxano with ciclopentadieno, the reaction of 4-aza-6-nitrobenzofuroxano with ciclopentadieno, the reaction hetero Diels-Alder of nitrosoalquenos and enaminas and cicloadición 1,3-dipolar between N-óxidos of benzonitrilo and metilenftaliminas. Besides, the thesis presents 2 collaborations with the experimental group of Professor José Sepulveda: the study of the transformation regio-and stereoselective trans aziridinas 1,2,3-trisustituidas in trans oxazolidin-2-onas, and the study of new examples Effect N-metilo in the acceleration of reactions ciclación.

Author: Cháfer Pericás Consuelo.
Year: 2005.
University: VALENCIA.
Place of defense: Facultad de Química.
Place of preparation: Facultad de Química.

Summary: This thesis is directed to the study of coupling microextracción in solid phase (SPME) -cromatografía. It covers aspects little treated in the literature as the coupling SPME-cromatografía liquid (LL) and conventional resulting in the formation of the fiber. The first specific objective is to study the configuration SPME on fibers and conventional LC, the analytes were elected aliphatic amines and amphetamines. It demonstrated the usefulness of reactive FMOC for their determination in aqueous matrices and air, as well as urine samples. We studied different options coupling SPME-derivatización. In determining amphetamines, devoted a part to the determination enantiomeric using the reagent chiral OPA-NAC. The second objective is specific coupling SPME-cromatografía gas (CG) for the determination of the main volatile organic compounds in water legislated. The sampling procedure was performed using SPME in the space of head of the sample as an alternative to the direct injection, in order to avoid some of the drawbacks associated with the liquid-liquid extraction, such as low sensitivity and selectivity. The third specific objective raised was the coupling SPME in tubo-CL capillary. The first section compares the advantages and disadvantages of this link to the configuration of the SPME over fiber and conventional LC for determining triazinas. In the second paragraph proposes a procedure based on the configuration SPME tube column with open testing hair with two different internal diameter and thickness stage, to carry out the screening of triazinas and organophosphorus pesticides. To summarize, this thesis contributes to the reduction in sample handling during the extraction and derivatización.Los work developed have made a significant contribution to implementing the derivatization with different methodologies and different sample analytes. It also contributes to the miniaturization of systems, the development of links SPME-CL, knowledge of the methods of screening samples and improved sensitivity for determining triazinas and organophosphorus pesticides by SPME in LC and capillary tube.

Author: Lloret Fillol Julio.
Year: 2005.
University: VALENCIA.
Place of defense: Facultat de Química.
Place of preparation: Universidad de Valencia, Facultad de Química, Dept. Química Inorgánica..

Summary: INTRODUCTION. Compounds bis-ciclometalados of rhodium (II) with fosfinas arílicas have been active catalysts estereo-selectivos in reactions transformation of alfa-diazo compounds (> 95% yield,> 90% ee) (Ref. 1.2) . In order to expand the family of catalysts bis-ciclometalados of rhodium (II) and diversify the electronic properties and estéricas, has studied the reactivity of rhodium acetate (II) with fosfolanos chiral and tienilfosfinas. In light of the preliminary results will study in detail the reactivity of the compounds bis-ciclometalados with tienilfosfinas. DISCUSSION AND RESULTS 1 .- Study of metalación of fosfolanos chiral and ciclopropanación catalytic intermediate and intra-molecular by transferring carbeno.La synthesis of catalysts bis-ciclometalados with fosfolanos chiral is achieved by modifying the conditions of reaction, with high diastereoselectividad for both diastereoisomeros. From the study of the reaction catalyzed, ciclopropanación international and intra-molecular through compounds obtained, the following conclusions are drawn: a) more favorable conditions for induction are chiral pentane reflux (> 95% R.;> ; 75% ee). b) catalysts with bridges trifluoroacetatos induce greater ee that bridges acetate. C) The quiralidad more influence on the structure, which the methyl groups of fosfolano in inducing quiral.d) monometalados also can give reactions enantioselectividad.Estos results have been published (Ref. 3). 2 .- Study metalación of fosfinas heteroaromatic with Rh2 (AcO) 4.Se has explored the reactivity of fosfinas tris (2-tienil) phosphine (Ref. 4, 5), tris (3-tienil) phosphine, tris (5 - metil-2-tienil) phosphine, tris (benzo) tienilfosfina and fosfinas mixed phenyl / thienyl derivatives with rhodium acetate (II). A) compounds mono-ciclometalados and bis-ciclometalados with configuration cabeza-cola and cabeza-cabeza have been obtained. All compounds have been well characterized through 1D NMR 1H and 31P, 2D NMR COZY and 2D HMBC 1H-31P. Most of the compounds have been analyzed using diffraction rayos-Xb) compound derived from (2-tienil) fosfinas per share thermal acetic acid presents an unusual reunion ring metalado obtaining a new compound with the ring metalado regrouped. The S atom moves to the position ortho to ring metalado. Kinetic experiments, marking isotopic and theoretical calculations of density functional (DFT) have been conducted to analyze the reagrupamiento.3 .- In addition, we have studied the interaction metal-carbeno, compounds bis-ciclometalados with triarilfosfinas and bridges acetates. BIBLIOGRAFIA.1 .- Barberis, M.; Pérez-Prieto, J.; Herbst, K.; Lahuerta, P. Organometallics 2002, 21, 1667.2 - Taber, D. F. Malcolm, S. C.; Bieger, K.; Lahuerta, P.; Sanaú, M.; Stiriba, SE; Pérez-Prieto, J.; Monge, MA J. Am. Chem. Soc., 1999, 121, 860. 3 .- Estevan, F.; Lahuerta, P.; Lloret, J.; Pérez-Prieto, Werner H. Organometallics, 2004, 23, 1369. 4 .- Bieger, K.; Estevan, F.; Lahuerta, P.; Lloret, J.; Pérez-Prieto, J.; Sanaú, M.; Siguiero, N.; Stiriba, SE Organometallics, 2003, 22, 1799. 5 .- Lloret, J.; Estevan, F.; Lahuerta, P.; Pérez-Prieto, J.; Sanaú, M. Organometallics, 2006, 25, 3156.

Author: DIAZ GAVILAN MONICA.
Year: 2005.
University: GRANADA.
Place of defense: Facultad de Farmacia.
Place of preparation: FACULTAD DE FARMACIA.

Author: GIMÉNEZ LÓPEZ MARÍA DEL CARMEN.
Year: 2005.
University: VALENCIA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: It deals with the study of the magnetic modulation in Prussian blue analogs under a disturbance external physical or chemical. We have studied the properties piezomagnéticas and isomería liaison crystals of a hexacianocromato (III), iron (II). This compound is ordered ferromagnéticamente below 19 K. By applying pressure, the system isomeriza and part of the centers of iron pass to the low-spin state, which translates into a decrease in magnetization and the critical temperature. The phenomenon has been characterized by spectroscopic measures (IR, Raman, MÃ ¶ ssbauer) and magnetic. It has also studied the thermal treatment through modulation of the magnetic properties of the material fotomagnético hexacyanoferrate cobalt. In a second part, deals with the synthesis and structural characterization of a series of magnetic iron salts (II), which presents transition from spin-based cations [Fe (bpp) 2] 2 + (bpp = 2, 6-bis- (pirazol-3-il) -piridina) and anions paramagnetic. In these compounds has been observed that the transition from spin is related to processes solvatación-desolvatación, allowing modular their magnetic properties by reversible adsorption of different solvents.

Author: Yusà Pelechà Vicent Anfós.
Year: 2005.
University: VALENCIA.
Place of defense: Facultad de Química.
Place of preparation: Facultad de Química.

Summary: This study, based on six original works (I-VI), describes various procedures microwave assisted extraction (MAE) and pressurized fluid extraction (PFE) from different families of contaminants in food and environmental matrices. The MAE has been used for the extraction of polycyclic aromatic hydrocarbons (PAHs), and substances polihalogenadas as OCPs, PBDEs, PCNs and PBBs, devices semipermeable membranes (SPMDs) and sediments. On the other hand, the EDP has been used for the extraction of PAHs in ambient air particles (PM10) and mussels, as well as Acrylamide in food. For each of the six test procedures developed has been optimized extraction process, using either a conventional system optimization "becoming a factor" (I, IV, V) or by the design of experiments (DOE) (II III, VI). In general, the optimization parameters have been subjected to the type of solvent, extraction time, volume of solvent, temperature and pressure. In all cases the new extraction procedure has been compared with conventional extraction procedure most commonly used, such as Soxhlet, dialysis or sonication. In five of the six working (IV) has been used a stage of purification (clean) based on by gel permeation chromatography (GPC), to eliminate substances coextraidas of the matrix such as fat, polyethylene or oligomers sulfur that may interfere with the analytical stage. This technique allows the automation of this stage, and achieves a high efficiency and productivity. The work on identification of Acrylamide (VI) purification employee has been based on the precipitation through an appropriate reagent (positions). The gas chromatography (GC) detector coupled to a mass spectrometry (MS) in tandem (MS-MS) has been used for the identification of substances polihalogenadas (I, II, III). The PHAs have been determined either through GC-MS, SIM mode, or high-resolution liquid chromatography (HPLC) with fluorescence detector (Fl). In the case of Acrylamide has been used liquid chromatography coupled with mass detector triple cuadrupolo mode SRM (LC-MS-MS). The values of the parameters which have a greater impact on the effectiveness of the response analytical MS-MS, both coupled with gas chromatography (II, III, IV) and liquid chromatography (V), have been optimized through the use of DOE. In order to improve the limits of detection (LOD) of the substances polihalogenadas or PAHs, present at trace levels in the environmental matrix has been used injecting large volumes (up to 70 L) through an injector vaporization temperature programmed (PTV ) (II, III, IV). The injection through PTV-LV has been optimized for each family of analytes using DOE. For different methods developed have identified their most important quality characteristics (LOD, linearity, accuracy, precision), and methods have been applied to real samples. In the case of Acrylamide has been carried out in Spain the first evaluation of their levels in different foods from cereals.

Author: CHAMMAA TÓRTOLA SAMY.
Year: 2005.
University: MÁLAGA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS, UNIVERSIDAD DE MÁLAGA.

Summary: Describes a new synthetic methodology oriented obtaining these new natural products and analogs. As a first approximation, it was possible to obtain the estevastelinas of 13-miembros through reaction macrolactonización Yamaguchi. He then proceeded to the preparation of the corresponding 2,3-epoxianálogos cyclical through a study ciclación all the resources possible acyclic. Once obtained these 2,3-epoxianálogos, which in themselves represent interesting similar proceeded to the opening of oxirane ring, but unfortunately, the opening failed. Thus, openness decanillo of oxirane was conducted in stages prior to the reaction ciclación, can be obtained in this manner, estevastelinas of 15-miembros (Estevastelina B). It also allowed for the reaction of translactonización of estevastelinas of 15-miembros toward the 13-miembros (Estevastelina B3). Next was summarized the estevastelina C3 reactions transesterificación. Once the sequence summarizes proceeded to the preparation of analogues. Thus he could get two similar modified C-2 by opening with oxirane ring hydride and Ethyl. The following similar, modified amino acids, could be obtained by the incorporation of different amino acid or synthetic peptides in the sequence described for obtaining natural products, as well, we were able to get four other similar. A similar additional resulted from the preparation of the corresponding natural product in which the side chain lipid nature was eliminated.

Author: SAMARANCH CLARAMUNT BÁRBARA.
Year: 2005.
University: BARCELONA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA (UB).

Summary: In this Doctoral Thesis new materials have been developed based systems binary oxides (MoO3-ZrO2 and Ta2O5-ZrO2) by the method of coprecipitación. These materials have been characterized by chemical and physical techniques are chemical analysis, determining the specific area by the BET method, X-ray diffraction, and espectroscopias Infrared, Raman and Ultravioleta-visible mode reflactancia diffuse sound. In addition they have used three methods to determine the acidity of surface materials, two by adsorption of molecules probe followed by FTIR, as probe molecules have been used lutidina (2,6-dimetilpiridina) and CO, and a method in the past that was followed in the reaction of continuous dewatering 2-propanol. Subsequently, these materials have been used as carriers of monkey catalysts (Pt) and bimetálicos (Pt-Sn) and have been characterized by spectroscopy fotoelectrónica of rayos-Xy through monitoring the adsorption of CO by FTIR. Finally, the catalysts have been tested in the reaction of hidro-isomerización of hexane (typical reaction of catalytic reformed naphthas) concluded that the materials developed in this work are valid for use as catalysts dual-purpose.

Author: SABIDO ESPÍN MARTA.
Year: 2005.
University: BARCELONA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA, UNIVERSITAT DE BARCELONA.

Summary: The memory of the doctoral thesis was essentially experimental, including, in addition, a theoretical study of structural or dynamic estimate, which is intended to provide a qualitative interpretation of the experimental facts. With regard to the experimental memory has two pairs well defined. The first section presents the results obtained using the technique of molecular beams crossed, the study of systems Mg + ion alkali (sodium, potassium, rubidio and cesium) which explores different processes excitation of the atom and Mg charge transfer excitation with alkaline ion. As for the type of theoretical studies are presented ab initio results obtained at the level of calculation CSID (Interaction Configurations Singles and Doubles) and using the technique of pseudopotenciales for different states electronic singulete and hat-trick of the different states diátomicos Mg alkali - Ion obtained all of them with great accuracy compared to the experimental values. Moreover, with the aim of initially qualitative links have been calculated not adiabéticos between states singulete which makes possible a qualitative interpretation of the experimental results. The second part is intended to describe the development, assembly and tuning up the state of current configuration of a new team for the pilot study of reactions between ions and molecules at low energy. The new apparatus utilizala technical beam guided by oscillating electric fields and caracterizalos different ionic products by mass spectrometry. All the experimental system has been computerized for monitoring, and data processing takes. The report shows the first results obtained from sections effective with the new apparatus on the formation of the adduct Li-acetona.