MACROMOLECULES

Author: TORRE GURUTZEALDE FRANCISCO JAVIER.
Year: 2004.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE QUÍMICA (SAN SEBASTIÁN).
Place of preparation: FACULTAD DE QUÍMICA - SAN SEBASTIÁN.

Summary: This thesis examines the mixing behavior of a liquid crystal polymer, Vectra A950, with polypropylene isotáctico, which is a thermoplastic industry. In particular, this paper analyzes the effect of Vectra A950 in the process of crystallization and melting of morphology and crystalline polypropylene also determined the barrier properties of mixtures obtained. The samples were prepared using various methods of mixing. The polypropylene used in the form of pellets and liquid crystal polymer in the form of pellets, short-fiber and fiber-long, which resulted in different morphologies. The main experimental techniques have been used, in addition to the traditional in these subjects (differential scanning calorimetry, termomicroscopía optical, scanning electron microscopy, X-ray diffraction, gravimetry of sorption), a more innovative as synchrotron radiation and microscopy atomic force. It has studied the crystallization, both as a dynamic isothermal, as well as the behavior of melting polypropylene isotáctico after the isothermal crystallization, the materials obtained by mixing the polymer polypropylene with the liquid crystal in the form of pellets. The detailed analysis of the process of crystallization, as both dynamic isothermal, has revealed that the liquid crystal polymer is able to promote nucleation polypropylene isotáctico, obtaining different crystalline forms of the same in terms of percentage of Vectra A950 entered. On the other hand, it also has studied the effect of Vectra in the secondary crystallization of polypropylene. In addition, it has analyzed the influence of polímenro liquid crystal on the morphological changes taking place during the heating process, following the isothermal crystallization until the full merger, depending on the heating rate. Subsequently has studied the morphology presenting crystalline materials obtained by mixing polypropylene isotáctico fiber and stretched and unstretched of Vectra A950, having conducted the study so that only melted thermoplastic matrix and not the liquid crystal polymer. Finally, we have analyzed the transport properties of polypropylene films and their blends with the liquid crystal polymer, used as a penetrating propylene, ethylene and carbon dioxide, for each of which has been given the dependence of their coefficients and solubility dissemination pressure.

Author: ARRESE IGOR IRIGOYEN SILVIA.
Year: 2004.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE CIENCIAS QUIMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUIMICAS.

Summary: The working thesis includes exhaustive study of the dynamics of the phenylene rings below the glass transition temperature in a range of engineering thermoplastic derived from the group bisfenol-A 8BPA) using neutron techniques. The deuteración selective samples and the use of different types of spectrometers (flight time and backscattering) allows isolate the dynamics of specific groups within the molecule, and cover a wide range of time. Thus responded to a double motivation, basic knowledge of the movements in molecular systems trainers glass, and the supposed interest technological know that ultimately the factors which determine the macroscopic properties of polymers, as they are directly or indirectly related to the dynamic processes that occur at the molecular level. The macromolecules of different samples used are formed in each case by repeating units BPA spacers groups united by more or less large and flexible. In addition to the dynamic and geometric characterization of the movement of the phenylene rings in the units BPA, he examines the influence of the spacer group interactions and intra-and inter-in that movement and the relationship of that with the origin of the molecular relaxation secondary observed through spectroscopic techniques in these materials.

Author: MH ALHENDAWI HUSSEIN.
Year: 2004.
University: AUTÓNOMA DE MADRID [www.uam.es].
Place of defense: DEPARTAMENTO DE QUÍMICA ORGANICA.
Place of preparation: DEPARTAMENTO DE QUÍMICA ORGANICA.

Summary: We have prepared materials microcristalinos organo-inorgánicos based on the structure of the lamellar phase range of zirconium phosphate, with pillars organic derivatives of polyethylene, and glycidol tartarico acid on the one hand, and polifenileno by another. To that end, there are difosfonatos chiral, optically pure, in various lengths, which have been incorporated in the inorganic matrix with different levels of trade. This has been very variable-porous materials, suitable for producing catalysis processes and molecular recognition in the midst of building three-dimensional. The materials obtinidos, both from difosfonatos chiral as derivatives polyphenyl, with levels nariables of incorporation of organic chain, has been subjected to a second round of exchange, in which phosphates interchangeable remnants had been replaced with success group hipofosfito, polarity much smaller. The double reaction of inte'rcambio not described in the literature previously, and tuning in our laboratory, allows you to adjust the components of the material organo-inorgánico and ownership of this global total accuracy. The materials derived from difosfonatos chiral show some structural features and chemical behavior very different from those containing bisphosphonates alquilicos described previously. Its main caracteistica is that the chains chiral present a movímiento Reversible helical winding which is induced by a mere change of the pH of the medium. Materials with pillars derivatives difosfonatos chiral cambián enórmemente its interlaminar distance and therefore its porosity, depending on intercalation other espacies as amines chain logitud vaiable. Materials and interspersed show optical properties of activity that does not depend on the intrinsic quiralidad but from the shackles of their organization supramolecular level. This property has been revealed for the first time in this type of malteriales in this Doctoral Thesis. Materials with pillars derivatives difosfonatos chain polyphenyl have shown in some cases uria high porosity and surface values comprehensive specific, especially when they have been treated with ácído hipofosforoso to replace phosphates inorganic surface of the foils. The resulting material, highly apolar are able to retain a high volume of inert gases and are strong candidates for use in the storage of combustible gases under normal conditions of pressure and temperature.

Author: GONZÁLEZ HORRILLO MIREN NEKANE.
Year: 2004.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE QUÍMICA SAN SEBASTIAN.
Place of preparation: FACULTAD DE QUÍMICA SAN SEBASTIÁN.

Summary: This thesis is focused on the study of polymeric systems based on poly vinyl chloride by the technique of infrared spectroscopy Fourier transform (Ftir). In Chapter 1 is an introduction to the systems studied and the experimental techniques that are used primarily differential scanning calorimetry (DSC), thermogravimetry high resolution (Hi-Res TGA) spectroscopy and infrared Fourier transform . In chapter 2, a study of the compatibility resin / plasticizer by analyzing vibration band voltage infrared link C-Cl. The most visible results indicate that the compatibility increases with increasing ramification of plasticizers and decreases with increasing length of the hydrocarbon chain. In Chapter 3 discusses the degradation processes termooxidativa. To highlight shown that the introduction to the degradation occurs in the sequence heterotácticas polymer. When it comes to plastic samples, the highest rate of degradation is obtained for samples containing plasticizers more compatible. In Chapter 4 discusses the processes fotooxidación. It follows that the level of fotooxidación of samples is independent of the estereoregularidad polymer base. Samples plastic degrade more than the base polymer. The final chapter focuses on the behavior of samples based on PVC in a specific application which is the plasticultura. It is proposed that at the time of making a film should be taken into account the specific climatic conditions of the place of application.

Author: MIGUEL CABRERA MANUEL DE.
Year: 2005.
University: AUTÓNOMA DE BARCELONA [www.uab.es].
Place of defense: FACULTAT DE CIENCIES.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: HE HAS MADE THE SUMMARY OF NEW COMPOUNDS MACTOCÍCLICOS WITH SETS ÁTOMOS DADORES MIXED nitrogen, sulfur and phosphorous. HAS BEEN ENSAYADO CAPACITY COORDINANTE OF THESE METAL ION FACE OF TRANSITION AS Ni (II), Cu (II), Rh (R) O Ru (II). BY COMPARISON OF ITS CAPACITY COORDINANTE WITH OTHER LIGANDOS LIKE FEW HAVE TRIED TO ESTABLISH GUIDELINES REACTIVITY RELATING TO THE EXTENT OF THE CAVITY MACROCÍCLICA AND THE NATURE OF ÁTOMOS DADORES.

Author: GONZÁLEZ BELLOSO IÑIGO.
Year: 2005.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS Y SAN SEBASTIÁN.
Place of preparation: FACULTAD DE QUIMICAS DE SAN SEBASTIÁN.

Summary: The properties of polymers synthesized through emulsion polymerization are defined by the conditions of the process. Therefore, the knowledge of how these conditions affect the process to end properties is of great significance. One possibility is the use of strategies based on knowledge of the microstructure in order to relate the conditions of process with the properties end. This paper applies this methodology of work to a particular case, the synthesis of a latex algutinante for the coating of metals in water based. The latex is composed of a copolymer of butyl acrylate, methyl methacrylate, methacrylic acid, methacrylate acetoacetatoy SIPOMER PAM 100. Given the presence of 5 monomers different, the investigation has been divided into parties growth complexity. The study began by investigating the effects of transfer to the polymer chain, both intra-and intermolecular, in the polymerization of butyl acrylate. It was noted that these processes significantly affect a number of both the kinetics of polymerization and the microstructure increasing the formation of the gel and ramifications. Then we studied the copolymerization of MMA / n-BA / MAA in which it was stated that the incorporation of MMA fell transfer processes chain so that both the formation of gel and branches decreased significantly. The next step involved the incorporation of agent reticulable AAEMA, after which it was observed that protection against hydrolysis of the functionality acetoacetoxy (AcAc) had a great impact on the microstructure, achacando an addition Michael groups AcAc and double bonds in terminals the system increased intersecting observed. The presence of double bonds was demonstrated by MRI and Michael supported by the reaction modeling. Additionally, it was observed that cross generated by this reaction affected the subsequent reaction of intersecting with diaminas. The trial of resistance to solvents entrecruzados films revealed a major weakness compared with polar solvents, which was related to the burial of groups AcAc in particle and the use of tiaminas soluble in the aqueous phase. In addition, the non-existence of an intersecting uniform throughout the particle also produced a certain sensitivity to solvents. Adding promoter of accession phosphate SIPOMER PAM100 was estudiad and noted that adherence of the coating on metallic surfaces was increased. Furthermore, it was noted the importance of cure the SIPOMER PAM 100 closer to the surface of the particles. Finally, part of the latexes synthesized were evaluated as part of an actual formulation of a painting and developed a primer for metal surfaces with excellent anticorrosive properties using a copolymer containing a 5% ed AAEMA and a 5% SIPOMER PAM100 in the formulation.

Author: GONZÁLEZ URANGA OSCAR.
Year: 2005.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE QUÍMICA DE SAN SEBASTIÁN.
Place of preparation: FACULTAD DE QUÍMICA DE SAN SEBASTIÁN.

Summary: The bitumen used in asphalt paving roads for more than a century. However, in recent decades, the classic problems that caused the destruction of the pavement (extreme weather conditions, due to traffic loads, etc.). They had been joined by others as the biggest step of vehicles, and the resulting traffic jams the continuous increase of vehicles in circulation. All these factors as a whole increases the speed of deterioration of roads, which entails an increase in the work of reconstruction and maintenance of the pavements. The objective of this thesis is to study the modification of bitumen from the distillation of petroleum, by adding polymers virgin and recycled in order to improve the properties viscoelásticas and durability of these materials. This will work with two groups of different polymer modifiers: * Polyethylenes virgin synthesized through catalysis conveniconal and metalocénica. * Políomeros recycled from agricultural covered.

Author: Pamies Porras Ramón Francisco.
Year: 2006.
University: MURCIA [www.um.es].
Place of defense: Facultad de Química.
Place of preparation: Facultad de Química.

Summary: The physical chemistry of macromolecules in solution or polymers is of great interest because it allows the characterization conformacional of macromolecular chains. Moreover, when these solutions are subjected to flow, macromolecules vary their formation, which gives the fluid properties different from those of balance, being especialmene remarkable variation of the viscosity with the gradient flow implemented. This type of study is part of ámito of Rheology, science that studies the deformation and flow of matter. A very useful tool for understanding and predicting the behavior of macromolecules in flux is the computational simulation. This thesis has been studied, both through experimental techniques such as simulation of the formation and dynamics of various polymeric systems, both in solution diluted as concentrated. The techniques were used Monte Carlo simulation and dynamic Browniana, where the Group Polymers Murcia possesses extensive experience. With regard to experimental techniques have been used primarily viscosimetría rotational and capillary and light scattering. The mathematical model used to represent the polymer chain was the ball and docks [Bird et al. Dynamics of polymeric liquids, Kinetic Theory, and sons Wiley, New York, 1987] that have been included realistic effects such as hydrodynamic interaction, the volume excluded and extensibility finite. This would have evaluated the influence that has an effect on the viscosity of the dissolution under increasing intensity in a shear flow, found that high intensities appears Region clearance shear or shear thinning as a result of the finite extensibility, but at intermediate values of the gradient performance curve viscosity is the result of competition from the effects of hydrodynamic interaction and volume excluded. To study through a polymer actual simulation has proposed a strategy of parameterization of the chain of balls and springs from the length and turning radius pilot of the macromolecule [Pamies et al. Macromolecules, 38 (2005) 1371]. With this method of parameterization has been made to reproduce experimental curves viscosity of polymers and vinyl derived from cellulose from other authors. It has also been studied computationally behavior of dilute solutions of polymers with non-linear topology, including rings and stars regularly subjected to shear flows and elongacional. In shear flow behavior appears similar to that of linear chains, although stars illustrates the influence of functionality or number of arms in the same values of the viscosity. On the other hand, flow elongacional uniaxial appears the phenomenon known as transition coil-stretch, whereby a certain amount of gradient elongacional or critical gradient, the macromolecule stretches sharply leading to the surge in the value of conformational properties and dynamics of the same. It has studied the dependence of critical gradient with the molecular weight observed the emergence of a power law exponent in which depends on the inclusion or otherwise of the hydrodynamic interaction in the calculations. In the case of stars is emphasize that the dependence of critical gradient is rather with the molecular weight of the arm [Hernandez Code et al. Polymer 46 (2005) 6756]. Other systems studied in the thesis is related solutions polielectrolitos, macromolecules with loads along the chain. Computacionalmente has studied the evolution of polyelectrolyte in shear flow. To represent the influence of the ionic strength of the medium in the chain 8 poly 88c electrolyte using a potential Debye-HÃ ¼ ckel. It is found that a high ionic strength behavior is similar to a string neutral excluded volume while a small ionic strength behavior that tends to present a rigid rod. Experimentally have characterized various samples of sodium alginate, finding that the ratio of Parls-Hermans and characterize, from, the rigidity of the chains. It has also studied the formation of gels by adding sodium alginate and calcium ions have been performed its curves fluently. Lastly, another polymeric system studied was the formation of polymeric mesh reversible hydroxyethyl cellulose amended hidrofóbicamente HM-HEC [Behesti et al. J. Chem. Phys. B 110 (2006) 6601]. The formation of these meshes is influenced by the presence of the additive cyclodextrin, which is capable of blocking groups hidrofóbiocos forming unions reversible between different chains HM-HEC. Computacionalmente has proposed a model based on the simulation of ball chains and springs which do not interact with each other but whose elements are associated to a certain probability that at each instant of time move from being confined in mesh free, and vice versa . Through our strategy of parameterization and using the model proposed balls and springs have been achieved reproduce experimental curves viscosity of this kind of mesh reversible HM-HEC in the presence of cyclodextrin.

Author: HERNÁNDEZ ARAMBURU LIDIA.
Year: 2006.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE QUÍMICA DE SAN SEBASTIÁN.
Place of preparation: FACULTAD DE QUÍMICA DE SAN SEBASTIÁN.

Summary: The acrylic bone cement have evolved in order to adapt to new techniques for minimally invasive surgery such as verebroplastia percutaneous or cifoplastia. This development stems from the need to inject the cement through needles long and narrow, visulizando injection through fluoroscópica guide. The objective of this thesis is the development of new formulations of acrylic bone cement injections. In addition to possessing a high radiopacidad, is intended to cement possesses a fluidity suitable for use in these new techniques. On the other hand, together with the strengthening spine, which was looking for cement provide an additional therapeutic action. To do so, agents that can be used to intervene in the healing process as antibiotics, anti-inflammatories or components osteo-regeneradores.

Author: TOLOSA BARRILERO JUAN.
Year: 2006.
University: CASTILLA-LA MANCHA [www.uclm.es].
Place of defense: FACULTAD DE CIENCIAS QUMICAS DE CIUDAD REAL.
Place of preparation: FACULTAD DE CIENCIAS QUIMICAS.

Summary: The present work shows the synthesis and study of different structures dendrímericas of a different nature. In a first section conducts the preparation of derivatives dendriméricos based poliariléteres with various peripheral functions. Among them, those containing vinyl groups in outlying areas have been used as cross-linkers catalysis supported, observándo an increase in the degree of funcionalización of ligands that make up support for the metal. Later addressing the asymmetric synthesis of conjugated systems. From discrete molecules with useful in the field of sensors until dendrímeros where it gets a thorough control of each group peripherals. This methodology has been prepared dendrímeros up to the third generation with 8 different groups on the periphery (all). Lastly was conducted by the synthesis of oligomers dendronizados helical in which it has studied the influence of the branches dendriméricas in the aggregation of different oligomers in helical structures stabilized by hydrogen bridges.

Author: PASTOR DEL COMPO ISABEL.
Year: 2006.
University: MIGUEL HERNÁNDEZ DE ELCHE [www.umh.es].
Place of defense: INSTITUTO DE BIOLOGIA MOLECULAR Y CELULAR.
Place of preparation: INSTITUTO DE BIOLOGIA MOLECULAR Y CELULAR.

Summary: Usually the immobilization of proteins in sol-gel matrix has been used as a tool in biotechnology, mainly for the design and development of biosensors, studying for it, the enzymatic activity of immobilized proteins, and its variation with time. However, very little is known about how to affect the process of immobilization in a sol-gel matrix proteins. Thus this thesis has two objectives: immobilization and characterization of proteins in sol-gel matrices and their use for the development of fluorescent biosensors. This thesis is based on two major independent blocks, the first of which described the development of a system for immobilization of proteins in sol-gel matrices and characterization of two enzymes, superoxide dismutase and lysozyme, which have been immobilized by this methodology. The first one was selected as a protein highly studied, the structure and properties in solution are well known. And the second because of its catalytic properties, which were used in the design and development of one of biosensors. This work is intended to find common behavioral patterns in the two species stranded contributing light on how proteins are found in the interior of the pores of sol-gel. The methodology used in this study has been fundamentally fluorescence spectroscopy at steady state and time-resolved. It used the intrinsic fluorescence of the protein: tryptophan in the case of lysozyme and tyrosine in the case of SOD. Using fluorescence in this study is possible thanks to the transparency of the sol-gel matrix that enables the use of optical techniques. In the case of lysozyme, as a protein whose distortion is controlled thermodynamic also conducted a detailed analysis of its stability, using complementary techniques of differential scanning calorimetry. The second section describes the application of the methodology of immobilization earlier in the design and development of two Biosensors: a biosensor for uric acid and a biosensor for radio superoxide. Both are based on a common mechanism, which includes the use of a fluorescent indicator coupled to a system multienzimático. For each case are described, in addition, different applications.