CHEMISTRY, 7

Author: BALCELLS BADIA DAVID.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: UNIVERSIDAD AUTONOMA DE BARCELONA.
Place of preparation: UNIVERSIDAD AUTÓNOMA DE BARCELONA.

Summary: The synthesis of chiral sulfóxidos has been investigated theoretically considering two of the more advanced methods: asymmetric oxidation of sulphides with hydrogen peroxide catalyzed by vanadium and method DAG. The mechanism of these reactions was explored at DFT (Functional Theory of Gravity) system models. The origin of the enantioselectividad in the actual system was investigated using hybrid QM / MM (Quantum Mechanics / Molecular Mechanics). The study DFT on the sulfoxidación asymmetric catalysed by vanadium revealed that this process remains a mechanism for direct transfer of oxygen in which the substrate is oxidized in a single stage concert. The catalyst is a complex of vanadium (V +), in which the oxidant is coordinated to the metal mode hidroperoxo. This complex catalyzes the oxidation process by reducing the energy barrier from 40.4 to 26.7 kcal / mol. The study QM / MM in the real system showed that there are two diastereómeros catalyst, labeled A and B, which catolizan oxidation promoting enantisolectividades opposite. The coexistence of A and B in solution allowed explain the influence of the structure of the ligand quieral on enantioselectividad. The study DFT method DAG revealed that the resolution kinetic dynamics involved in this reaction follows a mechanism for adding / deleting. The key step is in addition to that alcohol reacts directly with chloride sulfinilo. This process involves a transfer of hydrogen which is assisted by a foundation. The trimethylamine reduces the barrier of this process from 26.8 to 12.2 kcal / mol. The base also catalyses the racemisation chloride sulfinilo lowering the barrier on your investment pyramid from 63.4 to 22.3 kcal / mol. The initial movement of chloride on the part of the database was discarded. The study QM / MM of real system confirmed that the enantioselectividad process can be easily reversed using different bases not chiral, as pyridine or colidina, as experimentally observed. Our study revealed that the role estérico of the database is critical when the pyridine is changed by colidina. This change involves an investment basis of the distribution of chiral volume estérico around the sulfur that causes the change in the meaning of enantioselectividad.

Author: BALLESTEROS PÉREZ BELEN.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: INSTITU DE CIENCIA DE MATERIALS DE BARCELONA.
Place of preparation: INSTITUT DE CIENCIA DE MATRIALS DE BARCELONA.

Summary: Fuel cells provide new key pieces in the already complex puzzle of energy. But first, several scientific and technological challenges must be addressed and overcome. On the one hand, technological achievements should contribute to lower costs and improve efficiencies. At the same time, revolutionary scientific discoveries could lead to solving key problems and limits you. This thesis is our contribution to these great challenges. With it, we have tried to integrate scientific and technological aspects of fuel cells solid oxide cells (SOFCs, the English Solid Oxide Fuel Cells). The technological aspect of this work focuses on the processing of materials and manufacturing SOFCs supported in the anode by tape casting, a technique that is simple, economical and easily implementable industry-wide. A variation of this technique, the double-casting tape, has enabled us to prosecute bicapas electrolito-ánodo, to which is added to the cathode sprayed or painted. In sta will get electrolyte cells with thicknesses of YSZ (zircona stabilized with yttria) reduced, about 20 microns, so that these cells can be applied to intermediate temperatures (600-800Â ° C). Measures of the performance of the cells have shown that these show good current densities and power, reached 3.7Acm-2 and 700mWcm-2. As regards the most fundamental aspect, we have conducted studies into alternative materials to conventional anode, cermets of Ni-YSZ. The materials studied are perovsquitas based titanato calcium replaced with elements of the rare earths in position A and with vacancy in that position. In this manuscript detailing the synthesis, structural characterization and electrochemical characterization of these oxides. In addition, we have carried out measures of the benefits of these materials as anodes in fuel cell. Studies show low atmospheric methane benefits relatively poor, but these oxides have high catalytic ability to break bonds CH, very interesting property. Moreover, the benefits of these materials as anode using hydrogen as a fuel are good.

Author: ALCALA BERNARDEZ MANEL.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS DE LA UNIVERSIDAD AUTONOMA DE BARCELONA.

Summary: There will always be a study of the application of NIR spectroscopy for the determination of parameters of interest in the pharmaceutical industry with the aim of proposing new methodologies faster and effective sena real alternatives to conventional methods. Studies develop a wide variety of methods ranging from the determination of active ingredients in samples of the finished product or process until physical properties of these samples in different matrices and concentration levels. Have been developing new methods for determining NIR five principias assets in a formulation consisting of a granular solid, with concentrations ranging from the 6% to 0.04%; this method demonstrates the ability of the technique in identifying multiple and his remarkable sensitivity. Another example of the ability of the technique is the determination of active ingredients and preservatives prepared kind of gel that presents itself as remarkably strong absorption characteristics of the matrix and the low concentration of preservatives. Similarly has been established methods for determining the active ingredient in intact tablets, which enables the study of the uniformity of content of unit dose preparation. The methods have been developed and validated by following the guidelines that allow EMEA ICH and its implementation methods of sufficient quality for the analytical control of a production process. Another aspect of the study is the establishment of stuffed to determine physical parameters of finished products such as pressure and compaction testing dissolution closely related to the previous one. The NIR method allows the determination of the full profile of the dissolution of a tablet from its spectrum, which provides information very fast (less than 1 second) that the method conveniconal need more than 1 hour. The determination of the pressure compaction of the tablets has resulted in a new method of identifying active ingredients in tablets based solely on individual laboratory samples, which allows for simpler and more robust models that the methods developed so far NIR . The application of new methods quimiométricos treatment spectra (MCR-ALS) has revealed changes in polymorphic form (crystalline to morfa) which occurs during the wet granulation process, which is a frequent stage of the manufacturing process pharmacist. This transformation Polymorphic can have influence on the bioavailability of the active ingredient.

Author: NOGUERA JULIÁN MARC.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: FACULTAT DE CIÉNCIES.
Place of preparation: UNIVERSITAT AUTÓNOMA DE BARCELONA.

Author: HERNANDEZ PEREZ JUAN CARLOS.
Year: 2005.
University: LA LAGUNA.
Place of defense: INSTITUTO DE BIOORGNICA ANTONIO GONZALEZ.
Place of preparation: INSTITUTO DE DE BIOORGANICA ANTONIO GONZALEZ.

Summary: HE MAKES A REVISION BIBLIOGRAFICA ON THE CHEMISTRY OF GENDER DRACAENA. SE AISLAN AND IDENTIFY A TOTAL OF 53 METABOLITOS SIDE OF THE SPECIES DRACENA DRACO, IDENTIFIED FROM DIFFERENT PARTS OF THE FLOOR. HE MAKES A STUDY BY HPLC EXCERPTS FROM DIFFERENT KIND OF THIS WITH OR WITHOUT TREATMENT WITH INSECTICIDE. HE IS THE SUMMARY OF VARIOUS OF SIMILAR IN THE SAPONINAS ESTEROIDALES AISLADAS PLANT. AND ESTUDIA ACTIVITY OF VARIOUS SAPONINAS ESTEROIDALES HOME NATURAL OR SINTÉTICO FACE OF ONLINE LEUCÉMICA HL-60.

Author: PÉREZ HERNÁNDEZ NATALIA.
Year: 2005.
University: SEVILLA.
Place of defense: INSTITUTO DE INVESTIGACIONES QUÍMICAS (CSIC).
Place of preparation: INSTITUTO DE INVESTIGACIONES QUÍMICAS (CSIC) SEVILLA.

Summary: The work is a study of the factors involved in the possible incorporation of water molecules in crystalline structures formed by organic monomers bind to each other through hydrogen bond, in order to determine their impact in the hidrofilia and hydrophobicity of autoensamblado result. This is discussed in a series of crystal structures obtained from various systems in the chemical characteristics as they change their size and polarity. It has come to establish certain relationships between molecular structure, the balances that must take place in solution and the resulting crystalline structures, which in some cases generate organizations porous hydrophilic or hidrofobias. The analysis of the structures has been used, in addition to the X-ray crystallography, nuclear magnetic resonance techniques of solids and calorimetric techniques. Finally there has developed a synthetic route for new hidroxi-ácidos interest for further structural studies.

Author: ROS LAÓ ABEL.
Year: 2005.
University: SEVILLA.
Place of defense: CENTRO DE INVESTIGACIONES CIENTÍFICAS ISLA DE LA CARTUJA, CSIC-USE.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: Within this general framework, and as a result of a collaboration with BayerCropScience GmbH, in this Doctoral Thesis have developed new methodologies synthesis specifically aimed at obtaining product families with special relevance as intermediates for the synthesis of the latest generation of herbicides. The results harvested are organized into two main chapters: Chapter II: Synthesis of derivatives 4,5-dihidroisoxazoles. Herbicides Safeners chiral. Chapter III: Summaries enantioselectiva of cicloalcanoles and cicloalquilaminas through hydrogenation transfer. Herbicides of the family of Triazinas.

Author: SAYAGO GARCÍA FRANCISCO JAVIER.
Year: 2005.
University: SEVILLA.
Place of defense: FACULTAD DE BIOLOGÍA.
Place of preparation: DEPARTAMENTO DE QUÍMICA ORGÁNICA. UNIVERSIDAD DE SEVILLA.

Summary: The doctoral thesis falls within the broader work on the study and conformacional of synthetic derivatives of sugars with biological properties. Within this framework focuses on the synthesis of iminoespiroazúcares compounds which can also be considered esprio-C-nucleósidos. Both types of compounds are considered of great interest because of its potential biological and pharmacological activity. In regard to the synthesis of iminociclitoles can be distinguished in this thesis two different methodologies to reach them. On the one hand, the use of 1.6 and 1.45 anhidroazaazúcares as chiral intermediates key rings can reach seven vertices (azepanos) and five vertices (polihidroxipirrolidinas) respectively. If 1,4-anhidroazaazúcares these compounds also react with etanotiol leading after adding etanotiol and ciclación intramolecular to etiltiooxopirrolizidinas. These substances are thioglycosides of iminociclitoles and thus presents many potential uses, not only from the point of view pharmacological and biological but also from the point of view as synthetic donors glicosilo and inductors chiral. On the other hand, are used nitronas cyclical derived from carbohydrates as chiral intermediates in the achievement by adding compounds Grignard, pirrolidinas with substituents lipofílicos at position 2. This part of the doctoral thesis took place in Stuttgart under the direction of Proffesor Volker JÃ ¤ ger. Compounds obtained tested for enzyme inhibition and proved to be potent inhibitors of fucosidasa. With regard to the preparation of iminoespiroazúcares used the addition of cyanide trimetilsililo to espiroacetales derived from D-fructosa followed by reduction, mesilación and ciclación to get N-mesilglicoespiroazetidinas soluble in water. These compounds are completely novel and a potential biological interest due to the properties they exhibit the azetidinas and compounds derived from them. Finally, it uses a variant of the methodology described above in obtaining azaazúcares with ether bridges, substances that present a high rigidity conformacional vary their biological properties with regards iminociclitoles conformacionalmente flexible.

Author: RINCÓN LLORENTE BÁRBARA MARÍA.
Year: 2005.
University: SEVILLA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: INSTITUTO DE LA GRASA (CSIC).

Summary: 4,000,000 t alperujo / yr. Given the high organic load which has -150 to 190 g / L expressed as DQO-, is a serious environmental problem. The anaerobic digestion can be an alternative for treatment, as through the action of three key groups of microorganisms that act in a coordinated manner and interdependent, organic matter is transformed into a mixture CH4 (60-70%) -CO2 (30 - 40%) of high energy (20.833-25.000 kJ/m3). The digested sludge resulting are stable and can be used in composting to contribute to sustainable agriculture. The objective of this paper is the comparative study of the process of anaerobic digestion mesóflia (a35Â ° C) within one two stages of "wet pomace. Initially operating with a single lead, with all the microbial populations working together (one stage). In a second experiment is divided into stages hidroítica-acidogéncia and metanogénica in two working reactors in series, favors the terms of cooperation of the microorganisms responsible for each stage. Previously, it evaluates the feasibility of treatment using different dilutions alperujo. We checked the reactor methanogenic process works in two stages so that the more stable phase in a process, relations with volatile fatty acids / Total Alkalinity very low, reaching VCO up to 20 g COD / Ld This VCO is obtained by the maximum speed of production métano (3.2 L CH4/Lreactor.día) doubled over that achieved in the reactor at a stage (1.7 L CH4/Lreactor.día for a VCO = 9.18 g COD / Ld). The coefficients of performance on methane obtained for both processes are 0244 +-0005 and 0268 +-0005 L CH4 in normal / g DQOeliminado for trials 1 and 2 stages respectively, which represents an increase of 10% for the process two stages. The effluent output of the process in two stages and have a volatile acid content DQObiodegradable minors, bringing its membership is more favorable with a view to a post for biological purification comprehensive. VCO; speed organic load and COD: Chemical Oxygen Demand). With the introduction of two phases for the development of olive oil (campaign 1991-1992), thereby decreasing the volumes of the liquid waste generated in a 80% (wash water and olive oil), constituting the fraction semisolid ( marc wet or alperujo) residue majority. With more moisture and sugar content, this pomace, presents problems of transport, drying and extraction. Whereas 90% of the mills and Spanish using this system (800 kg alperujo / t olive molturada), the volumes generated are estimated at 2.000.000-4.000.000 t alperujo / yr. Given the high organic load which has 150 to 190 g / L as expressed or DQO-, is a serious environmental problem. The anaerobic digestion can be an alternative for treatment, as through the action of three key groups of microorganism acting in a coordinated manner and interdependent, organic matter is transformed from a mixture CH4 (60-70%) CO2 (30-40 %) of high energy (20.8335-25.000 Kj/m3). The digested sludge resulting are stable and can be used in composting to contribute to sustainable agriculture. The objective of this paper is the comparative study of the process of anaerobic digestion mesophyll (35Â ° C) within one two stages of "wet pomace. Initially operating with a single reactor, with all the microbial populations working together (one stage). In a second experiment is divided into stages hidrlítica-acidogénica and metanogénica in two working reactors in series, favors operating conditions of the microorganisms responsible for each stage. Previously, it evaluates the feasibility of treatment using different dilutions alperujo. We checked the reactor methanogenic process works in two stages so that the more stable phase in a process, relations with volatile fatty acids / Total Alkalinity very low, reaching VCO ha 8 sta 20g 1f4a COD / L. This VCO is obtained by the maximum speed of methane production (3.2 L CH4/Lreactor.día) doubled over that achieved in the reactor at a stage (1.7 L CH4/Lreactor.día for a VCO = 9.18 g COD / Ld). The coefficients of performance on methane obtained for both processes are 0244 +-0005 and 0268 +-0005 L CH4 in normal / g DQOeliminado to process 1 and 2 stages respectively, which represents an increase of 10% for the process in two stages. The effluent from the departure process into two stages and have a volatile acid content DQObiodegradable minors, bringing its membership is more favorable with a view to a post for biological purification comprehensive. (VCO: organic loading speed and COD: Chemical Oxygen Demand). WCon the introduction of two phases for the development of olive oil (campaign 1991-1992), thereby decreasing the volumes of the liquid waste generated in a 80% (wash water and olive oil), constituting the fraction semisolid ( marc wet or alperujo) residue majority. With more moisture and sugar content, this pomace, presents problems of transport, drying and extraction. Conmiserando that 90% of the mills and Spanish using this system (800 kg alperujo / t olive molturada), the volumes generated are estimated at 2.000.000-4.000.000 t alperujo / yr. Given the high organic load which has -150 to 190 g / L expressed cook DQO-representa a serious environmental problem. The anaerobic digestion can be an alternative for treatment, as through the action of three key groups of microorganisms that majority. With more moisture and sugar content, this pomace, presents problems of transport, drying and extraction. Whereas 90% of the mills and Spanish using this system (800 kg alperujo / t olive molturada), the volumes generated are estimated at 2.000.000-4.000.000t of laperujo / yr. Given the high organic load which has -150 to 190 g / L expressed as DQO-, is a serious problem medioambietnal. The anaerobic digestion can be an alternative for treatment, as through the action of three key groups of microorganisms that act in a coordinated manner and interdependent, organic matter is transformed into a mixture CH4 (60-70%) -CO2 (30 - 40%) of high energy (20.833-25.000 Kj/m3). The digested sludge resulting are stable and can be used in composting to contribute to sustainable agriculture. The objective of this paper is the comparative study of the process of anaerobic digestion mesófila (35Â ° C) within one two stages of 'wet pomace. Initially operating with a single reactor, with all the microbial populations working together (one stage). In a second experiment is divided into stages hidrolítica-acidogénica and metanogénica in two working reactors in series, favors operating conditions of the microorganisms responsible for each stage. Previously, it evaluates the variability of treatment using different dilutions alperujo. We checked the reactor methanogenic process works in two stages so that the more stable phase in a process, relations with volatile fatty acids / Total Alkalinity very low, reaching VCO up 20g COD / Ld This VCO is obtained by the maximum speed of methane production (3.2 L CH4 / L reactor.día) doubled over that achieved in the reactor at a stage (1.7 L CH4/Lreactor.día for a VCO COD = 9.18 g / Ld). The coefficients of performance on methane obtained for both processes are 0244 +-0005 and 0268 +-0005 L CH4 in normal / g DQOeliminado paralos processes in 1 and 2 stages respectively, which represents an increase of 10% for the process two stages. The effluent output of the process in two stages and have a volatile acid content DQObiodegradable minors, bringing its membership is more favorable with a view to a post for biological purification comprehensive. (VCO: organic loading speed and COD: Chemical Oxygen Demand). With the introduction of two phases for producing olive oil (Campaign 1991-1992), thereby decreasing the volumes of the liquid waste generated in a 80% (wash water and olive oil), constituting the fraction semisolid ( marc and humid or alperujo) residue majority. With more moisture and sugar content, this pomace, presents problems of transport, drying and extraction. Whereas 90% of the mills and Spanish using this system (800 kg alperujo / t olive molturada), the volumes gernados are estimated at 2,000,000 - 4,000,000 t alperujo / yr. Given the high organic load which has -150 to 190 g / L expressed as DQO-, is a serious environmental problem. The anaerobic digestion can be an alternative for treatment, as through the action of three key groups of micro-organisms which act in a coordinated manner and interdependent, organic matter is transformed and a mixture CH4 (60-70%) -CO2 (30 - 40%) of high energy (20.833-25.000 kJ/m3). The digested sludge resulting are stable and can be used in composting to contribute to sustainable agriculture. The objective of this paper is the comparative study of the process of anaerobic digestion mesófila (35Â ° C) within one two stages of 'wet pomace. Initially operating with a single reactor, with all the microbial populations working together (one stage). In a second experiment is divided into stages hidrolítica-acidogénica and metanogénica in two working reactors in series, favors operating conditions of the microorganisms responsible for each stage. Previously, it evaluates the feasibility of treatment using different dilutions alperujo. We checked the reactor methanogenic process works in two stages so that the more stable phase in a process, relations with volatile fatty acids / Total Alkalinity very low, reaching VCO up 20g COD / Ld This VCO is obteien the maximum production rate of methane (3.2 L CH4/Lreactor.día) doubled over that achieved in the reactor at a stage (1.7 L CH4/Lreactor.día for a VCO = 9.18 g COD / Ld). The coefficients of performance on methane obtained for both processes are 0244 +-0005 and 0268 +-0005 L CH4 in normal / g DQOeliminado for processes in 1 and 2 stages respectively, which represents a umento of 10% for the process in two stages. The effluent output of the process in two stages and have a volatile acid content DQObiodegradable minors, conlo which its membership is more favorable with a view to a post for biological purification comprehensive. (VCO: organic loading speed and COD: Chemical Oxygen Demand) With the introduction of two phases for the development of olive oil (campaign 1991-1992), thereby decreasing the volumes of the liquid waste generated in a 80% (wash water and olive oil), constituting the fraction semisolid (wet pomace or alperujo) residue majority. With more moisture and sugar content, this pomace, presents problems of transport, drying and extraction. Whereas 90% of the mills Spanish uitlizan and this system (800 kg alperujo / t olive molturada), the volumes generated are estimated at 2,000,000 - 4,000,000.

Author: PRADO FERNÁNDEZ CÉSAR.
Year: 2005.
University: SEVILLA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE FARMACIA.

Summary: We have studied aspects of the kinetic phase transitions experienced adenine to form condensed phases on mercury concentrations above 1mM to neutral pH, on the basis dela Classical Theory of Nucleación and Growth. THE takeover of adenine on monocrystalline gold electrodes has been characterized by cyclic voltammetry and measures impedance electrodes on the guidelines (111_), (100) and (110). It has been shown that the chemical adsorption is dependent not only on the crystallographic orientation of the structure but also rebuilt or no-reconstruida the surface electródica. The results show that the adsorbed adenine promotes the elimination of reconstruction. The thermodynamic aspects of the adsorption have been studied, taking into account the results of the conduct of adenine on gold. The experimental conditions and the procedure for obtaining curves burden had to be modified to avoid overlapping with the adsorption and electrochemical processes of reconstruction with the evolution of hydrogen. The results showed a chemical adsorption with a concentration in the surface region of saturation is not compatible with a flat file of the molecule. It has also been able to deduce that the molecule is absorbed in a provision that does not vary with the electric field. The kinetics of the absorption process has been studied through analysis of the dependence of capacity with the frequency. According to the model Paijkossy and can relate to the thermodynamic and kinetic parameters of the process of adsorption with the scattering of data impedance with frequency, from the expression of the speed Net adsorption and diffusion linear semi-infinita. This model leads to an expression that can be represented as a circuit equivalent to two parallel branches, with a condenser capacity Cd and with the other three elements of adsorption resistance, Ta, an element of Warburg, Oa, and capacity Ch. Of the relationships between these elements have been able to obtain the kinetic parameters of the process of adsorption, which show a mixed regime of adsorption and transport of material. The apparent rate constant decreases with the adsorption potential, indicating that the role of adsorption varies more important that the adsorption rate constant. The structural aspects of adsorption was studied by IR reflection techniques situ, in internal and external configuration. The spectra do not see modified their bands with the potential, which indicates a single file independent of the electric field. These results confirm the deductions made from you thermodynamic data. The two studies combined with spectroscopic techniques, together with allocations of gangs active in the denina adsorbed, made from the theoretical and experimental spectra of vibration of the molecule and its derivatives, suggest an interaction through metal adenine the amino group of the molecule, after deformation thereof, and participation in the position N7.

Author: IBARZ ESTEVA MARÍA JESÚS.
Year: 2005.
University: ZARAGOZA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The overall objective of the work has been the study of the effect exerted by the contents of amino acids in wine and other precursors in the composition of aromatic wine. The memory is divided into two blocks. The first has studied the influence of the art of wine nitrogen, amino acids and ammonium mainly in the aroma of wine obtained. To that end, it develops an analytical method for the determination of free amino acids in musts that allows quantifying 21 amino acids present in musts and wines in the order of fentomoles avoiding interferences due to other amino compounds. It has proven to be sufficiently accurate and precise to be considered as a good method of analysis. It explores the relationship between the profile aminoacídico of wine and the formation of certain aromas fermentativos with different yeasts. It was determined the evolution of formation of volatile compounds during alcoholic fermentation and it was noted that his training depended on the concentration of nitrogen must. It was determined the effect of adding different concentrations and other nitrogen sources on the content flavorings fermentativos and in the sensory profile of the wines. Through various statistical treatments was observed that the rate of nitrogen added and the same amount of influence significantly on the amount of flavorings formed. Besides these differences were remarkable sensory level. Finally, it was determined the importance of sensory aromatic compounds generated during alcoholic fermentation directly related to the metabolism of amino acids, corroborating the results previously obtained. We studied both red wines as whites. The study has shown that variations in the composition aromatic caused by the different profiles aminoacídicos have an important sensory impact. The second part of the report focuses on the development of analytical methods for determining the flavor potential of the grapes, given the need to generate analytical methodologies for the determination of such compounds and to evaluate the quality of the grape. We considered three types of precursors: carotenoids, derived from cysteine, and finally glicosídicos. For the determination of carotenoids proposed a method based on the intrinsic absorption properties of the analytes using HPLC-UV as separation technology analysis. In the case of derivatives of cysteine, it was necessary for the synthesis patterns and the resulting development of a method to control these reactions by HPLC-UV. The development of the method included optimizing the management of the sample (comparison of different sorbents for separation) as well as enzymatic hydrolysis of these precursors. We developed a method of analysis based on HPLC- Fluorescence after derivatization with AQC. Finally, in the case of precursors glicosídicos developed a method of indirect analysis, which included the SPE of the analytes from a maceration of skins, acid hydrolysis, SPE of flavorings and GC-MS for its determination.

Author: BELOSO GONZÁLEZ INMACULADA.
Year: 2005.
University: VIGO.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: The Doctoral Thesis deals with the synthesis and characterization of new metal complex Co (II), Ni (II), Cu (II), Ag (I), Zn (II) and Cd (II) on c ligands derived from sulfonamide, which characterized by introducing nitrogen atoms and oxygen atoms giving. These compounds are of great interest because among its main applications include: bioinorgánica and medicine (as simple models of interactions metal-proteínas and in the prevention and treatment of infections); extractantes metal; catalytic processes; severance of links and NN in the synthesis of macrociclos. Once synthesized and characterized the ligands, the synthesis of the metal complex was carried out following an electrochemical procedure. In addition to the synthesis of the complex homolépticos in all cases were also carried out following the same procedure for the synthesis of complexes with mixed ligands additional 2.2 '-bipiridina and 1,10-fenantrolina. Different complex preparations have been characterized, in addition to using elemental analysis, infrared spectroscopy, ultraviolet, measurements of magnetic susceptibility, RPA, mass spectrometry and NMR 1H. In cases where it was possible to obtain adequate monocrystals, these were also studied by X-ray diffraction

Author: GARCÍA MAZARÍO MARTA.
Year: 2005.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS, UNIVERSIDAD COMPLUTENSE DE MADRID.

Summary: Segregation in the border grain is a phenomenon that is the diffusion of atoms from the inside towards the edges of grain resulting in local changes in the microquímica of them. This can produce significant changes in the mechanical properties of the material, which affect their behavior in operation. It is known that lso processes segregation induced by temperature and / or radiation change the behavior of structural materials for the light water reactors presently available, it is expected these processes affect the service life of the materials will be used in future nuclear systems. In this thesis is the study of the microquímica the edges of grain in materials technology such as austenitic stainless steels, martensitic steels and nickel-based alloys, with the objective of contributing to the understanding of the mechanisms of aging and degradation suffered by materials as a result of its operation. To achieve this objective, the study has been divided into four parts, each of which provides for a nuclear system, the type of materials used in the same and the problems that may occur during their lives in service. * Austenitic stainless steels of internal components of light water reactors. These materials are suffering under stress corrosion processes assisted by irradiation (IASCC) during the operation. Therefore, the objectives of this first part of the work have been, firstly, to determine lso induced changes in the microquímica of grain edges you in austenitic stainless steels, simulating the effects of irradiation using varying and different cold work heat treatments, and moreover, to determine which of the conditions studied more faithfully reproduced the changes induced by neutron irradiation in lso grain edges of these materials. * Martensitic steels for fusion reactors. The structural materials for future nuclear fusion systems will be subject, among other factors, long periods at high temperatures. These conditions produced interfacial segregation of alloy elements and impurities that may affect significantly the tenacity and susceptibility to intergranular cracking of martensitic steels. The aim of this part of the work has been to study the effect of thermal aging, in simulated conditions of service operation, in microquimica the edges of grain steels candidates as structural materials for these systems of energy production. * Martensitic steels for systems transmutation ADS. Given the conditions so severe that they will be subjected whites spallation (irradiation with protons and neutrons), the structural strength of genetic material in them is critical, unique to this type of system and seen as the limiting factor of life these components. The aim of this part of the thesis study the effect of the production elements spallation in microquímica the edges grain of candidate materials for window spallation target of genetic systems transmutation ADS. * Materials spallation sources. In the latter part of the thesis deals with the effect of irradiation in three different materials from a source of estalación, an austenitic steel, a zero martensítico and nickel base alloy with the aim of understanding the changes induced in the microquímica of the edges of grain in the real conditions of operation of these systems, new and little-known. The characterization of the microquímica in all materials and conditions has been carried out by AUGER spectroscopy, which is a technique for analyzing surface considered as a fundamental tool in the study of segregation in edge grain. The findings of this thesis allow purchase criteria for estimating changes in the behavior of materials 8 is the 30e s in service conditions and thus contribute to the management of the life and specification of materials substitution in the case of light water reactors, as well as establishing and operating margins withstand the design of new materials in the case of fusion reactors, systems transmutation ADS and the Generation IV reactors.

Author: RAMOS LIMA FRANCISCO JAVIER.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: UNIVERSIDAD AUTÓNOMA DE MADRID.

Summary: Cisplatin is one of the drugs most commonly used in clinical tumor. But cis-DDP presents a number of limitations such as its low solubility, limited range of action, toxic effects and acquired resistance. For these reasons are still looking for new platinum complexes that do address these barriers. In 1992 were published several platinum complexes with trans geometry presenting activity citotoxica even in tumor cells resistant to cisplatin. The aim of this thesis has been the synthesis and characterization of new platinum complexes trans geometry for studies of cytotoxic activity in cálulas tumor and non-tumor, and establish new structure activity relationships depending on the size of the ligands and their carcterísticas lipophilic or hydrophilic. The complex which have submitted better antitumor activity have been selected for studies of interaction with DNA, influence of the protein p53 in response to cytotoxicity, changes in the cell cycle by flow cytometry and confocal microscopy.

Author: MARTÍNEZ CRESPIERA SANDRA.
Year: 2006.
University: AUTÓNOMA DE BARCELONA.
Place of defense: UNIVERSIDAD AUTÓNOMA DE BARCELONA.
Place of preparation: UNIVERSIDAD AUTÓNOMA DE BARCELONA.

Author: CANO ÒDENA ÀNGELS.
Year: 2006.
University: AUTÓNOMA DE BARCELONA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: At present, the processes aimed at reducing waste and the production of high added value are presented as a promising target with expectations. In this thesis are designed polymeric membranes targeted for the treatment of waste biomass plant, specifically lignocellulosic material. The enzyme endo-1, 4-? -xilanasa II, which hydrolyzed links 1.4-? -glicosídicos In skeleton xilano, it ties in membranes through a covalent bond with the aim of recovering from the oligosaccharides hydrolysis of this polymer xilano. The interest of the immobilization of enzymes in polymeric media lies in reducing the cost and simplifying the overall process, as a result of the possibility of reusing the immobilized enzyme while retaining its catalytic activity. We have investigated two types of polymer membranes as well as methods of restraint by covalent bond between functional groups of the enzyme and support. The first consists of membranes acrylate polysulphone (ACPS). The immobilization of the protein was confirmed by amino acid analysis by HPLC and by comparison with the analysis of the protein in solution. The other type of membrane (N25) are comprised of polymers monolithic. The physical and chemical properties of these materials depend on the proper selection and the amount of the components of dissolution precursor membrane. This has been optimized composition of the precursor dissolution with the objective of obtaining the best results of enzymatic activity. We have compared different procedures and conditions of detention for the two membranes to assess their capacity for restraint. Membranes ACPS retain more enzyme that the N25 though this data is not associated with greater enzymatic activity, as this depends on the stability of the immobilized protein in each case. The proposed use of molecular biology techniques to carry out a detention directed, and thus avoid blocking center of the active enzyme molecules by direct binding of the center with support. The influence of process parameters immobilization in enzymatic activity (pH and temperature) are studied and compared with the optimal parameters for the enzyme solutions. As well as kinetic parameter values as found in Michaelis.Menten, which neither differs significantly between free and immobilized enzyme, which means that the affinity of catalyst for substrates considered remains totally unaffected once immobilized. For the physical characterization of the membranes have been used different techniques for characterization, as microsopía scanning electron (SEM), from which there are differences in terms of porosity and symmetry between the two types of polymeric membrane. From as images of atomic force microscopy (AFM), there are no differences in the same type of membrane according to whether or not immobilized enzyme. In the determination of pure water flows, the higher values are obtained with the membrane N25. Since measures adsorción - desorción gas shows that the membranes N25 have a greater surface area and pore distributions with greater pore diameter medium. The measures contact angle of an increased hydrophilic character of the membranes N25 than for ACPS, and the hydrophilic nature increases as increasing the amount of enzyme in the membranes. In terms of implementation, the membranes have been used in the treatment of biomass, using two different membrane modules. In any event only have been obtained separation of the products with respect to the initial substrate in the case of using a filtration module front and applying pressure. The largest concentration of hydrolysis products were obtained with the membrane N25 in the case of substrate hydrolysis of Birchwood xylan, although it is not possible reutilizarlas in a second consecutive hydrolysis with dissolution of new substrate. By contrast, in the treatment of substrates that comes from direct treatment of corn husks, the membranes ACPS can be 8 No reutil 598 fly, but the concentration of products is lower than in the first hydrolysis. The products obtained were analyzed by a colorimetric method, and by capillary electrophoresis, chromatography and gel permeation by ionization with matrix-assisted laser analyzer flight time and detection by mass spectrometry (MALDI-TOF-MS). Finally, it conducts a comprehensive assessment process and presented proposals for improvements to carry out in a continuation of this research.

Author: Tamayo Haro Abel.
Year: 2006.
University: AUTÓNOMA DE BARCELONA.
Place of defense: Univerdad Autónoma de Barcelona.
Place of preparation: Universidad Autónoma de Barcelona.

Summary: The Doctoral thesis entitled: "Nous Desenvolupament of Mono i Bimacrocicles Funcionalitzats amb Grups Luminescents or Electroquímicament Actius," summarizes the main results obtained during the investigation period Predoctoral. The work lies in the field of inorganic chemistry, although ventures into organic chemistry and eventually, in fotofísica. Both ligands macrocíclicos possess a secondary amine likely to be funcionalizada. Through these amines have been funcionalizado the macrociclos groups luminescent (anthracene and cumarina343), or with groups electroquímicamente assets (ferroceno). The properties of the Coordinating ligands macricíclicos synthesized, have been studied against the metallic cations Pd (II), Ni (II) and Co (II), Cu (II).

Author: GIL MESTRES ADRIÁN.
Year: 2006.
University: AUTÓNOMA DE BARCELONA.
Place of defense: CENTRE NACIONAL DE MICROELECTRÒNICA.
Place of preparation: DEPARTAMENT DE QUÍMICA / FACULTAT DE CIÈNCIES / UNIVERSITAT AUTÒNOMA DE BARCELONA.

Summary: This work analyses the effects of ionisation on the structure and reactivity of different kind of systems, which can be involved in biological oxidative or mass spectrometry processes, by means of quantum chemical methods. In the first part of the work we focus on the changes induced on the binding energies of AHn systems ( A = Li-F and Na-Cl), along with their behaviour when interacting with H2O. The second part of this work includes an exhaustive theoretical study on the influence of ionisation in amino acids and peptides, the basic structural units of proteins. A crucial point observed in this work is the large increase of acidity induced in a system upon removal of one electron. Moreover, ionisation can change the acidity relative order of different functional groups present in biological molecules. As a consequence, ionisation largely affects the hydrogen bonds in amino acids and peptides in such a way that important reorganisations such as isomerisations or proton-transfer processes, leading to distonic radical cations, are often observed. In addition, for amino acids and peptides, it is observed that the site of ionisation and subsequent rearrangements and reactivity largely depend on the nature of the side-chain and on the initial intramolecular hydrogen bonds. Finally, this work shows that for open-shell systems, (case of radical cations) the most popular DFT method in the bibliography (B3LYP) may fail to predict the lowest energy ionised structure due to its tendency to overstabilise delocalised spin densities. It is observed that using the recent developed meta-hybrid MPWB1K functional with more percentage of exact exchange than B3LYP these problems are corrected.

Author: Bernaus Darbra Anna.
Year: 2006.
University: AUTÓNOMA DE BARCELONA.
Place of defense: Universidad Autónoma de Barcelona.
Place of preparation: Universidad Autónoma de Barcelona.

Summary: The toxicity of mercury is determined by their likelihood of exposure, the geochemical and environmental factors influencing its development and migration within the environment, and in particular by the chemical species in which it finds itself. However, the number and accuracy of analytical techniques capable of recognizing several species of mercury remains very limited. Therefore, the techniques of X-ray absorption spectroscopic (XAS) based on synchrotron radiation, have been promised interesting and readily available tools to overcome in the field of speciation. Examples of the most common techniques are XANES (Near Edge X-ray Absorption Spectroscopy) and EXAFS (Extended X-ray Absorption Fine Structure). Further advances in this field are based on the union of the absorption techniques with a high spatial resolution micro level, using techniques  µ -XRF (microscopic X-ray Fluorescence) or  µ -XAS. The understanding of the environmental hazard posed by methylmercury (CH3HgCl and CH3HgOH) adsorbed on typical components of the soil has been achieved by a combination of techniques and sensors XAS luminescent (Escherichia coli MC1061, pmerBRBSluc). The amount of adsorbed Hg has proved to be pH dependent, whereas the nature of the link independent of pH. When comparing the interaction between metilmercuri and clay or humic materials, the first have resulted in a higher ionic character and thus a chance to mobilize the largest mercury. Furthermore, this interaction has proven to be more stable by the CH3HgOH that by the CH3HgCl due to the reactivity extra hydroxyl group. The district Almadén in Ciudad Real has resulted in one of the most impacted by the environment Hg anywhere in the world. In this context, techniques XAS (supplemented with analysis of SES, XRD and SEM - EDS) has been used to study the behavior of mercury in this region. The cinnabar has been found which is the main species in minerals and soils, while the metacinabrio is the main species in the slag. In all samples have also been found more soluble salts of mercury (HgCl2, HgSO4 and schuetteite). Las técnicas de microsonda también han revelado correlaciones elementales entre el Hg y el Pb, Ni y S, indicando un posible acoplamiento geoquímico de estos elementos. Correlations have been identified between Hg and Fe / Mn, which has been attributed to the absorption of mercury on oxihidróxidos of Fe and Mn. On the other hand, the chlor-alkali industry with cathode mercury has been one of the most important industrial uses of mercury in Western Europe, and have become one of the most important sources of contamination of this item. The charge of the conduct of mercury in these environments has been driven by the techniques XAS attached to SES. Information speciation has shown that inorganic mercury dominate in all soil samples considered, as cinnabar and corderoite the main species. However, there have also been identified phases slightly soluble (HgO and HgSO4) in proportions of lesser importance. Moreover, the analysis  µ -XRF has shown a correlation geochemistry Hg, Cu and Ni suggest that the formation of solid solutions of these elements within the same crystalline structure. Finally, techniques microprobe with synchrotron radiation have been proposed for the direct observation of mercury and other elements present in human teeth restored with amalgam of mercury. Analysis has shown a minimum of Hg spread through the tooth, with the identification of a linear correlation between Hg and Cu. Moreover, it has identified 8 do a d 40e ifusión significant Cu and Zn of the amalgam to the region of dentine, suggesting a possible exchange of Ca2 + with Cu2 + / Zn2 + in crystals of hydroxyapatite (Ca10 (PO4) 6 (OH) 2). Moreover,  µ -EXAFS has determined that the atmosphere molecular initial Hg in the region of the amalgam is limited by the phase Ag2Hg3 formed during the process of amalgamation.

Author: ORENES MARTÍNEZ RAÚL ÁNGEL.
Year: 2006.
University: MURCIA.
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: FACULTAD DE QUÍMICA, UNIVERSIDAD DE MURCIA.

Summary: The results compiled in this report demonstrate that certain species containing fragment structural tribencilamina such as tris (2-ureidobencil) amines and tris (3-ureidobencil) amine, can act as modules in supramolecular chemistry despite its high flexibility . These molecules are autoensamblan in solid state and solvents uncompetitive forming aggregates diméricos capsular. Some structural features of these dimers are propeller type topology in which provides the skeleton of tribencilamina and the presence of an internal cavity. In such dimers ortho cavity possesses some very restricted dimensions, as this is something greater in dimers goal, which allows the encapsulation of certain solvents and other guests inside the same. Other features of these processes of self-assembly is a high degree of molecular recognition and the ability to control them by varying pH. Predictably processes dimerización processes are controlled by the enthalpy due to an unfavorable change in entropy caused by the loss of degrees of freedom for the corresponding monomers in the process of self-assembly. The affinity between different hosts and the cavity of dimers goal is determined by their complementarity both electronic and geometric and is independent of the solvent used. The thermodynamic analysis of the data for the encapsulation of some guests representative demonstrates compensation entálpica-entrópica. The analysis of the kinetic parameters of the same points to a type gating mechanism for the input / output of these guests. The self-assembly of tris (2-and 3-uridobencil) amines Cs symmetry produces a mixture dissolution of all possible regioisomers in equal proportion in most cases. This distribution of isomers is independent of the host, temperature and solvent. By contrast, solid-state has been detected only one of the possible regioisomers, namely regioisómero aquiral. Perhaps more interesting is the process of self-assembly of a racemic mixture of triureas chiral methyl group containing an alpha in the nitrogen pivotal in one of the branches of the tripod. In dissolving the formation of the corresponding dimers occurs so diastereoselectiva. In addition, this process autoensamblje can be seen that elapses with autodiscriminación chirality. In solid state the self-assembly of these triureas is also regioselectivo. The pattern of association of the tris (ureidobencil) amine is so strong that allows replacement, in one of the branches of radical ureidobencilo joined the nitrogen atom pivotal for ureidopropilo even more flexible. These triureas is autoensamblan in CDCl3. The hexaureas resulting from the coupling through a bridge hexametilénico two molecules tris (2 - or 3-ureidobencil) amine was autoensamblan in dissolution but with different patterns of association. The first form aggregates diméricos bicapsulares coexisting in harmony with monomers without join. Rather second unspecified form partnerships that evolve to the appropriate organogeles. This behavior suggests that these modules are autoensamblan to the corresponding aggregates capsular polymer. Eliminating ground characteristic of the species listed assembled so far, the belt six groupings associated urea hydrogen bridge so cooperative supposed lack of self-assembly processes and in the tritioureas, triamidas or tetraureas prepared.