We have measured the optical properties of films of the organic semiconductors PTCDA (3,4:9,10-perylene-tetracarboxylic dianhydride) and HBC (peri-hexabenzocoronene), prepared by Organic Molecular Beam Expitaxy (OMBE), on different substrates by means of Differential Reflectance Spectroscopy (DRS). The optical setup enables us to directly follow the thickness dependent optical properties of the organic films, starting from submonolayer coverage up to thicker films on the order of 20 monolayers (ML) film thickness. Due to the different optical nature of the different substrates used, i.e., mica, glass, Au(111), and HOPG, the direct interpretation of the DRS signal is not feasible. Therefore, we have proposed a method by which the calculation of the optical constants n (index of refraction) and k (absorption index) of thin films on arbitrary substrates from just one spectral measurement (in our case the DRS) becomes possible. The results fulfill a priori a Kramers-Kronig consistency and no specific model is needed to express the spectral behavior of the optical constants. Based on our method, we have successfully calculated the optical constants, and therefore the absorption behavior, of films of different thickness of PTCDA on mica, glass, Au(111), and HOPG, as well as of HBC on mica, glass, and HOPG. Extrinsic effects due to island growth or the presence of a polarizable substrate (screening) have been accounted for. We have introduced a finite dipole model which considers the extended geometry and anisotropy of the organic molecules. The calculated absorption behavior is discussed in great detail in terms of spectral changes with varying film thickness, different growth modes, degree of ordering of the films, interactions with the substrates and oscillator strength. A direct observation of a monomer-dimer transition in solid films could be observed for the first time. Our results indicate an exciton delocalization over about 4 molecules for both molecules.

The 2-aryl-6,8-dibromoquinazolin-4(3H)-ones were prepared in a single-pot operation by condensing 6,8-dibromoanthranilamide and aryl aldehydes in the presence of molecular iodine in ethanol. Treatment of the 2-aryl-6,8-dibromoquinazolin-4(3H)-ones with thionylchloride in the presence of dimethylformamide afforded the corresponding 2-aryl-4-chloro-6,8-dibromoquinazolines. Palladium(0)-copper iodide catalysed Sonogashira cross-coupling reaction of 2-aryl-4-chloro-6,8-dibromoquinazolines with terminal alkynes at room temperature afforded series of 2-aryl-6,8-dibromo-4-(alkynyl)quinazolines. Further transformation of the 2-aryl-6,8-dibromo-4-(phenylethynyl)quinazolines via Suzuki-Miyaura cross-coupling with arylboronic acids occurred without selectivity to afford the corresponding 2,6,8-triaryl-4-(phenylethynyl)quinazolines. The compounds were characterized using a combination of NMR (1H and 13C) and IR spectroscopic techniques as well as mass spectrometry. The absorption and emission properties of 2,6,8-triaryl-4-(phenylethynyl)quinazolines were determined in solution. / Chemistry / M.Sc. (Chemistry)

Les principaux objets étudiés dans cette thèse sont les équations décrivant le morphisme de groupe sur une variété abélienne, plongée dans un espace projectif, et leurs applications en cryptographie. Notons g sa dimension et k son corps de définition. Ce mémoire est composé de deux parties. La première porte sur l'étude des courbes d'Edwards, un modèle pour les courbes elliptiques possédant un sous-groupe de points k-rationnels cyclique d'ordre 4, connues en cryptographie pour l'efficacité de leur loi d'addition et la possibilité qu'elle soit définie pour toute paire de points k-rationnels (loi d'addition k-complète). Nous en donnons une interprétation géométrique et en déduisons des formules explicites pour le calcul du couplage de Tate réduit sur courbes d'Edwards tordues, dont l'efficacité rivalise avec les modèles elliptiques couramment utilisés. Cette partie se conclut par la génération, spécifique au calcul de couplages, de courbes d'Edwards dont les tailles correspondent aux standards cryptographiques actuellement en vigueur. Dans la seconde partie nous nous intéressons à la notion de complétude introduite ci-dessus. Cette propriété est cryptographiquement importante car elle permet d'éviter des attaques physiques, comme les attaques par canaux cachés, sur des cryptosystèmes basés sur les courbes elliptiques ou hyperelliptiques. Un précédent travail de Lange et Ruppert, basé sur la cohomologie des fibrés en droite, permet une approche théorique des lois d'addition. Nous présentons trois résultats importants : tout d'abord nous généralisons un résultat de Bosma et Lenstra en démontrant que le morphisme de groupe ne peut être décrit par strictement moins de g+1 lois d'addition sur la clôture algébrique de k. Ensuite nous démontrons que si le groupe de Galois absolu de k est infini, alors toute variété abélienne peut être plongée dans un espace projectif de manière à ce qu'il existe une loi d'addition k-complète. De plus, l'utilisation des variétés abéliennes nous limitant à celles de dimension un ou deux, nous démontrons qu'une telle loi existe pour leur plongement projectif usuel. Finalement, nous développons un algorithme, basé sur la théorie des fonctions thêta, calculant celle-ci dans P^15 sur la jacobienne d'une courbe de genre deux donnée par sa forme de Rosenhain. Il est désormais intégré au package AVIsogenies de Magma. / The main objects we study in this PhD thesis are the equations describing the group morphism on an abelian variety, embedded in a projective space, and their applications in cryptograhy. We denote by g its dimension and k its field of definition. This thesis is built in two parts. The first one is concerned by the study of Edwards curves, a model for elliptic curves having a cyclic subgroup of k-rational points of order 4, known in cryptography for the efficiency of their addition law and the fact that it can be defined for any couple of k-rational points (k-complete addition law). We give the corresponding geometric interpretation and deduce explicit formulae to calculate the reduced Tate pairing on twisted Edwards curves, whose efficiency compete with currently used elliptic models. The part ends with the generation, specific to pairing computation, of Edwards curves with today's cryptographic standard sizes. In the second part, we are interested in the notion of completeness introduced above. This property is cryptographically significant, indeed it permits to avoid physical attacks as side channel attacks, on elliptic -- or hyperelliptic -- curves cryptosystems. A preceeding work of Lange and Ruppert, based on cohomology of line bundles, brings a theoretic approach of addition laws. We present three important results: first of all we generalize a result of Bosma and Lenstra by proving that the group morphism can not be described by less than g+1 addition laws on the algebraic closure of k. Next, we prove that if the absolute Galois group of k is infinite, then any abelian variety can be projectively embedded together with a k-complete addition law. Moreover, a cryptographic use of abelian varieties restricting us to the dimension one and two cases, we prove that such a law exists for their classical projective embedding. Finally, we develop an algorithm, based on the theory of theta functions, computing this addition law in P^15 on the Jacobian of a genus two curve given in Rosenhain form. It is now included in AVIsogenies, a Magma package.

The thesis is focused on the synthesis and characterization of novel Mn2+ complexes as alternative to Gd3+ chelates which are wide-spread contrast agents in Magnetic Resonance Imaging (MRI). In the perspective to find suitable chelators of Mn2+ , three groups of pentadentate ligands with different size of macrocylic cavity, different donor atoms and number of pendant arms containing various functional groups have been investigated. Coordination numbers of 6 or 7 were found in the crystal structure of the Mn2+ complexes enabling binding of one or two water molecules in the first coordination sphere. The direct water coordination causes a decrease in the complex stability and thus, the thermodynamic stability of investigated chelates is lower than that of polyaminocarboxylate complexes and their dissociation is very fast in comparison to [Mn(nota)] and [Mn(dota)]2- . The studied Mn2+ complexes do not undergo oxidation in air except for complexes with 12-membered ligands which are oxidized to Mn3+ species. The proton relaxivities of the bishydrated complexes are two times higher than those for monohydrated complexes and are comparable to those of commercial contrast agents based on Gd3+ complexes. Variable-temperature 17 O NMR data revealed that the water exchange varies from slow to intermediate or...

Ce mémoire est divisé en deux parties : Partie 1 : Nous obtenons des résultats d'existence pour des problèmes au limite mettant en jeu des opérateurs polyharmoniques conformément invariants. Nous nous plaçons indifféremment dans le cas d'une variété riemannienne avec ou sans bord. En particulier, nous montrons que la meilleure constante de Sobolev sur les variétés est exactement la constante euclidienne. En conséquence, nous montrons l'existence d'une solution d'énergie minimale lorsque la fonctionnelle descend en-dessous d'un seuil quantifié. Puis nous montrons l'existence de solutions de haute énergie en utilisant la méthode topologique de Coron. Nous généralisons la décomposition des suites de Palais-Smale comme somme de bulles sur une variété avec ou sans bord : il s'agit d'un résultat dans l'esprit du célèbre théorème de Struwe en 1984. Nous obtenons aussi une version du lemme de compacité-concentration de Pierre-Louis Lions sur les variétés. Partie 2 : Dans cette partie, nous effectuons une analyse de blow-up pour une équation de Hardy-Sobolev à croissance critique et à singularité évanescente au bord. En supposant que l'équation limite n'admet pas de solution minimisante, nous étudions le comportement asymptotique d’une suite de solutions de l'équation perturbée. Ici, la perturbation est la singularité à l'origine. Dans un premier temps, nous obtenons un contrôle ponctuel optimal de la suite de solutions. Dans un second temps, nous obtenons des informations précises sur le point d'explosion en utilisant une identité de Pohozaev / This memoir can be divided into two parts: Part 1: In this part we obtain some existence results for conformally invariant polyharmonic boundary value problems on a compact Riemannian manifold with or without boundary. In particular we show that the best constant of the Sobolev embedding on manifolds is same as the euclidean one, and as a consequence prove the existence of minimum energy solutions when the energy functionnal goes below a quantified threshold. Next we show the existence of high energy solution using the topological method of Coron. We generalize the decomposition of Palais Smale sequences as a sum of bubble on manifolds with or without boundary, a result in the spirit of Struwe's celebrated 1984 result and also an extension of PL Lions concentration compactness result on manifolds. Part2: In this part we do a blow-up analysis of the nonlinear elliptic Hardy-Sobolev equation with critical growth and vanishing boundary singularity. We assume that our equation does not admit minimising solutions, and study the asymptotic behaviour of a sequence of solution to the perturbed equation. Here the perturbation is the singularity at the origin. First we obtain optimal pointwise controlon the sequence and then obtain more precise informations on the localization of the blow-up point using the Pohozaev identity

分析具有巢狀誤差結構的迴歸模式時，惹忽略隨機誤差項之間的相關性，而採用最小平方(OLS)估計量所導出的標準 F 統計量（以 F^S表之）進行檢定，會導致過大的型 I 錯誤機率；若將隨機誤差項之間的相關性納入考量，而採用廣義最小平方(GLS)估計量所導出的 F 統計量 （以 F^GLS表之），則計算上會較為繁雜。因此我們藉由轉換方式，將模式轉換成隨機誤差項之間彼此獨立的新模式後，再以 F^S 進行檢定，其結果與直接以 F^GLS 檢定相同，且可使計算較為方便。由於模式轉換所需的轉換矩陣為母體變異數的函數，因此當母體變異數未知時，我們以 Henderson 的常數配適 （fitting-of-constants）方法來估計之。藉由模擬結果得知，若各段的觀察個數相等，則不論巢狀誤差結構為二段式(two-stage)或三段式(three-stage)，廣義最小平方估計量(GLS)均較最小平方估計量(OLS)表現穩定，且 F^GLS 在檢定力及實際顯著水準方面的表現也都比 F^S 好。 / When analyzing the regression model with nested-error structure, if the correlations between errors are ignored, and conduting the model adequacy test by the standard F statistic (F^S) led from the ordinary leastsquares estimator (OLSE) , then the type I error rate will be inflated. However, if the corrlated structure is considered and the model is tested by F^GLS led from the general least-squares estimator (GLSE) , the calculation will be more complicate. The model can be transformed to a new model with independent random errors and then, tested by F^S . The result is the same as the one by F^GLS , also it is more convenient for calculation. Since the transformation matrix is a function of variance components, we estimate variance components by Henderson's fitting-of-constants when they are unknown. Through simulation, it is concluded that if the observations in each stage of nested-error structure are the same, the GLSE is more stable than the OLSE in both two-stage and tree-stage structures. Also, the power and the sizes of F^GLS will perform better than those of F^S .

Durante la última década y paralelamente al incremento de la velocidad de computación, las técnicas de simulación molecular se han erigido como una importante herramienta para la predicción de propiedades físicas de sistemas de interés industrial. Estas propiedades resultan esenciales en las industrias química y petroquímica a la hora de diseñar, optimizar, simular o controlar procesos. El actual coste moderado de computadoras potentes hace que la simulación molecular se convierta en una excelente opción para proporcionar predicciones de dichas propiedades. En particular, la capacidad predictiva de estas técnicas resulta muy importante cuando en los sistemas de interés toman parte compuestos tóxicos o condiciones extremas de temperatura o presión debido a la dificultad que entraña la experimentación a dichas condiciones. La simulación molecular proporciona una alternativa a los modelos termofísicos utilizados habitualmente en la industria como es el caso de las ecuaciones de estado, modelos de coeficientes de actividad o teorías de estados correspondientes, que resultan inadecuados al intentar reproducir propiedades complejas de fluidos como es el caso de las de fluidos que presentan enlaces de hidrógeno, polímeros, etc. En particular, los métodos de Monte Carlo (MC) constituyen, junto a la dinámica molecular, una de las técnicas de simulación molecular más adecuadas para el cálculo de propiedades termofísicas. Aunque, por contra del caso de la dinámica molecular, los métodos de Monte Carlo no proporcionan información acerca del proceso molecular o las trayectorias moleculares, éstos se centran en el estudio de propiedades de equilibrio y constituyen una herramienta, en general, más eficiente para el cálculo del equilibrio de fases o la consideración de sistemas que presenten elevados tiempos de relajación debido a su bajos coeficientes de difusión y altas viscosidades. Los objetivos de esta tesis se centran en el desarrollo y la mejora tanto de algoritmos de simulación como de potenciales intermoleculares, factor considerado clave para el desarrollo de las técnicas de simulación de Monte Carlo. En particular, en cuanto a los algoritmos de simulación, la localización de puntos críticos de una manera precisa ha constituido un problema para los métodos habitualmente utilizados en el cálculo de equlibrio de fases, como es el método del colectivo de GIBBS. La aparición de fuertes fluctuaciones de densidad en la región crítica hace imposible obtener datos de simulación en dicha región, debido al hecho de que las simulaciones son llevadas a cabo en una caja de simulación de longitud finita que es superada por la longitud de correlación. Con el fin de proporcionar una ruta adecuada para la localización de puntos críticos tanto de componentes puros como mezclas binarias, la primera parte de esta tesis está dedicada al desarrollo y aplicación de métodos adecuados que permitan superar las dificultades encontradas en el caso de los métodos convencionales. Con este fin se combinan estudios de escalado del tamaño de sitema con técnicas de "Histogram Reweighting" (HR). La aplicación de estos métodos se ha mostrado recientemente como mucho mejor fundamentada y precisa para el cálculo de puntos críticos de sistemas sencillos como es el caso del fluido de LennardJones (LJ). En esta tesis, estas técnicas han sido combinadas con el objetivo de extender su aplicación a mezclas reales de interés industrial. Previamente a su aplicación a dichas mezclas reales, el fluido de LennardJones, capaz de reproducir el comportamiento de fluidos sencillos como es el caso de argón o metano, ha sido tomado como referencia en un paso preliminar. A partir de simulaciones realizadas en el colectivo gran canónico y recombinadas mediante la mencionada técnica de "Histogram Reweighting" se han obtenido los diagramas de fases tanto de fluidos puros como de mezclas binarias. A su vez se han localizado con una gran precisión los puntos críticos de dichos sistemas mediante las técnicas de escalado del tamaño de sistema. Con el fin de extender la aplicación de dichas técnicas a sistemas multicomponente, se han introducido modificaciones a los métodos de HR evitando la construcción de histogramas y el consecuente uso de recursos de memoria. Además, se ha introducido una metodología alternativa, conocida como el cálculo del cumulante de cuarto orden o parámetro de Binder, con el fin de hacer más directa la localización del punto crítico. En particular, se proponen dos posibilidades, en primer lugar la intersección del parámetro de Binder para dos tamaños de sistema diferentes, o la intersección del parámetro de Binder con el valor conocido de la correspondiente clase de universalidad combinado con estudios de escalado. Por otro lado, y en un segundo frente, la segunda parte de esta tesis está dedicada al desarrollo de potenciales intermoleculares capaces de describir las energías inter e intramoleculares de las moléculas involucradas en las simulaciones. En la última década se han desarrolldo diferentes modelos de potenciales para una gran variedad de compuestos. Uno de los más comunmente utilizados para representar hidrocarburos y otras moléculas flexibles es el de átomos unidos, donde cada grupo químico es representado por un potencial del tipo de LennardJones. El uso de este tipo de potencial resulta en una significativa disminución del tiempo de cálculo cuando se compara con modelos que consideran la presencia explícita de la totalidad de los átomos. En particular, el trabajo realizado en esta tesis se centra en el desarrollo de potenciales de átomos unidos anisotrópicos (AUA), que se caracterizan por la inclusión de un desplazamiento de los centros de LennardJones en dirección a los hidrógenos de cada grupo, de manera que esta distancia se convierte en un tercer parámetro ajustable junto a los dos del potencial de LennardJones.En la segunda parte de esta tesis se han desarrollado potenciales del tipo AUA4 para diferentes familias de compuesto que resultan de interés industrial como son los tiofenos, alcanoles y éteres. En el caso de los tiofenos este interés es debido a las cada vez más exigentes restricciones medioambientales que obligan a eliminar los compuestos con presencia de azufre. De aquí la creciente de necesidad de propiedades termodinámicas para esta familia de compuestos para la cual solo existe una cantidad de datos termodinámicos experimentales limitada. Con el fin de hacer posible la obtención de dichos datos a través de la simulación molecular hemos extendido el potencial intermolecular AUA4 a esta familia de compuestos. En segundo lugar, el uso de los compuestos oxigenados en el campo de los biocombustibles ha despertado un importante interés en la industria petroquímica por estos compuestos. En particular, los alcoholes más utilizados en la elaboración de los biocombustibles son el metanol y el etanol. Como en el caso de los tiofenos, hemos extendido el potencial AUA4 a esta familia de compuestos mediante la parametrización del grupo hidroxil y la inclusión de un grupo de cargas electrostáticas optimizadas de manera que reproduzcan de la mejor manera posible el potencial electrostático creado por una molecula de referencia en el vacío. Finalmente, y de manera análoga al caso de los alcanoles, el último capítulo de esta tesis la atención se centra en el desarrollo de un potencial AUA4 capaz de reproducir cuantitativamente las propiedades de coexistencia de la familia de los éteres, compuestos que son ampliamente utilizados como solventes. / Parallel with the increase of computer speed, in the last decade, molecular simulation techniques have emerged as important tools to predict physical properties of systems of industrial interest. These properties are essential in the chemical and petrochemical industries in order to perform process design, optimization, simulation and process control. The actual moderate cost of powerful computers converts molecular simulation into an excellent tool to provide predictions of such properties. In particular, the predictive capability of molecular simulation techniques becomes very important when dealing with extreme conditions of temperature and pressure as well as when toxic compounds are involved in the systems to be studied due to the fact that experimentation at such extreme conditions is difficult and expensive.Consequently, alternative processes must be considered in order to obtain the required properties. Chemical and petrochemical industries have made intensive use of thermophysical models including equations of state, activity coefficients models and corresponding state theories. These predictions present the advantage of providing good approximations with minimal computational needs. However, these models are often inadequate when only a limited amount of information is available to determine the necesary parameters, or when trying to reproduce complex fluid properties such as that of molecules which exhibit hydrogen bonding, polymers, etc. In addition, there is no way for dynamical properties to be estimated in a consistent manner.In this thesis, the HR and FSS techniques are combined with the main goal of extending the application of these methodologies to the calculation of the vaporliquid equilibrium and critical point of real mixtures. Before applying the methodologies to the real mixtures of industrial interest, the LennardJones fluid has been taken as a reference model and as a preliminary step. In this case, the predictions are affected only by the omnipresent statistical errors, but not by the accuracy of the model chosen to reproduce the behavior of the real molecules or the interatomic potential used to calculate the configurational energy of the system.The simulations have been performed in the grand canonical ensemble (GCMC)using the GIBBS code. Liquidvapor coexistences curves have been obtained from HR techniques for pure fluids and binary mixtures, while critical parameters were obtained from FSS in order to close the phase envelope of the phase diagrams. In order to extend the calculations to multicomponent systems modifications to the conventional HR techniques have been introduced in order to avoid the construction of histograms and the consequent need for large memory resources. In addition an alternative methodology known as the fourth order cumulant calculation, also known as the Binder parameter, has been implemented to make the location of the critical point more straightforward. In particular, we propose the use of the fourth order cumulant calculation considering two different possibilities: either the intersection of the Binder parameter for two different system sizes or the intersection of the Binder parameter with the known value for the system universality class combined with a FSS study. The development of transferable potential models able to describe the inter and intramolecular energies of the molecules involved in the simulations constitutes an important field in the improvement of Monte Carlo techniques. In the last decade, potential models, also referred to as force fields, have been developed for a wide range of compounds. One of the most common approaches for modeling hydrocarbons and other flexible molecules is the use of the unitedatoms model, where each chemical group is represented by one LennardJones center. This scheme results in a significant reduction of the computational time as compared to allatoms models since the number of pair interactions goes as the square of the number of sites. Improvements on the standard unitedatoms model, where typically a 612 LennardJones center of force is placed on top of the most significant atom, have been proposed. For instance, the AUA model consists of a displacement of the LennardJones centers of force towards the hydrogen atoms, converting the distance of displacement into a third adjustable parameter. In this thesis we have developed AUA 4 intermolecular potentials for three different families of compounds. The family of ethers is of great importance due to their applications as solvents. The other two families, thiophenes and alkanols, play an important roles in the oil and gas industry. Thiophene due to current and future environmental restrictions and alkanols due ever higher importance and presence of biofuels in this industry.

Zahlreiche Studien belegen, dass Maillard-Reaktionsprodukte (MRP) in vivo einen Einfluss auf den physiologischen Metallionenhaushalt haben können. Da bisher noch keine Korrelation zwischen dem Entstehen von definierten MRP und einem erhöhten Metallionenbindungsvermögen ermittelt werden konnte, war es das Ziel dieser Arbeit, die Komplexbildungseigenschaften der ausgewählten MRP Nε-Carboxymethyllysin, Isomaltol und Maltosin sowie deren Strukturanaloga Maltol, Deferipron, Mimosin und Pyridosin mit den physiologisch relevanten Metallionen Cu(II), Zn(II), Fe(III), Al(III) und Mn(II) zu untersuchen. Dazu wurden die MRP Nε-Carboxymethyllysin und Maltosin sowie die parallel untersuchten Substanzen Pyridosin, Maltosin-3-benzylether, Nα-Hippuryl- und Nα-Acetylmaltosin in ausreichender Menge und Reinheit synthetisiert. Dabei gelang es, für Maltosin und Pyridosin neue und effiziente Synthesewege zu entwickeln, bei welchen zum ersten Mal beide Substanzen gezielt aufgebaut wurden. Die Komplexbildungskonstanten der Liganden mit den Metallionen wurden pH-potentiometrisch bestimmt (I[KNO3] = 0,15 M; θ = 25 °C). Durch die Auswertung der Protonierungskonstanten der gebildeten Komplexe und das Vermessen geeigneter Derivate konnten für die untersuchten Komplexe zusätzlich die Koordinationsstellen der Liganden aufgeklärt werden. Die Untersuchungen zu den Komplexbildungseigenschaften bestätigten erstmals die Vermutung, dass MRP in der Lage sind, Metallionen zu binden. Dabei wurde weiterhin ermittelt, dass die Bindung von Cu(II) durch Nε-Carboxymethyllysin und von Fe(III), Al(III) und Cu(II) durch Maltosin durchaus von physiologischer Relevanz sind. Die Bedeutung der Ergebnisse wurde qualitativ durch Versuche mit Maltosin-derivatisiertem Rinderserumalbumin unterstrichen. Als besonderes Ergebnis der Arbeit ist herauszustellen, dass das MRP Maltosin und die Verbindung Pyridosin deutlich stabilere Komplexe mit Fe(III) bilden als das zur Fe(III)-Chelattherapie eingesetzte Medikament Deferipron. Diese festgestellte Eigenschaft bietet interessante Perspektiven für zukünftige Studien zur möglichen Anwendung von z. B. Maltosin als Pharmakon. / Several studies show that Maillard reaction products (MRP) may influence the physiological metal ion balance. But none of these studies prove a correlation between the formation of defined MRP and an enhanced metal ion binding. Therefore it was the aim of this work to investigate the complex formation characteristics of the selected MRP Nε-carboxymethyllysine, isomaltol and maltosine as well as the structural analogues maltol, deferiprone, mimosine and pyridosine with the physiological relevant metal ions Cu(II), Zn(II), Fe(III), Al(III) and Mn(II). For that purpose the MRP Nε-carboxymethyllysine and maltosine plus the parallel analysed substances pyridosine, maltosine-3-benzylether, Nα-hippuryl- and Nα-acetylmaltosine were synthesised. Thereby new and efficient syntheses for maltosine and pyridosine were developed. The stability constants of the ligands with the metal ions were determined by pH-potentiometry (I(KNO3) = 0,15 M; θ = 25 °C). Furthermore the donor atoms within the formed complexes were determined by the evaluation of the protonation constants of the formed complexes and by the analysis of adequate derivatives. The studies to the complex formation characteristics confirm for the first time the assumption, that MRP are able to form stable complexes with metal ions. Withal it was ascertained that the coordination of Cu(II) by Nε-carboxymethyllysine and of Fe(III), Al(III) and Cu(II) by maltosine may be of physiological relevance. The significance of the results was pointed out by experiments with maltosine derivatised bovine serum albumine. The fact that the MRP maltosine and the compound pyridosine form more stable complexes with Fe(III) as the medicament for the Fe(III) chelate therapy deferiprone is a particular result of this work. This property affords interesting perspectives for future studies about a possible appliance of e.g. maltosine as pharmaceutical.

Η παρούσα διατριβή ερευνητικά εντάσσεται στην περιοχή της Μη Γραμμικής Ανάλυσης και ειδικότερα στην επίλυση Μη Γραμμικών Ελλειπτικών Μερικών Διαφορικών Εξισώσεων (Μ.Δ.Ε.) με υπερκρίσιμο εκθέτη. Η μη γραμμικότητα δεν επιτρέπει την επίλυση των εξισώσεων αυτών χρησιμοποιώντας τις συμπαγείς εμφυτεύσεις. Αξιοποιώντας τις ιδιότητες συμμετρίας που παρουσιάζει η πολλαπλότητα, αφενός παρακάμπτουμε το εμπόδιο αυτό και αφετέρου επιτυγχάνουμε να επιλύσουμε εξισώσεις αυτού του τύπου με υπερκρίσιμο εκθέτη. Στο πρώτο μέρος της Διατριβής υπολογίζουμε την πρώτη βέλτιστη σταθερά στη γενική ανισότητα Sobolev και στη γενική ανισότητα Sobolev με σύνορο στον στερεό τόρο, μελετάμε το φαινόμενο της συμπύκνωσης και επιλύουμε τα προβλήματα (P1) και (P2). Στο δεύτερο μέρος υπολογίζουμε την πρώτη βέλτιστη σταθερά στη γενική ανισότητα Sobolev και στη γενική ανισότητα Sobolev με σύνορο σε μια λεία, συμπαγή, n-διάστατη, n\geq 3, πολλαπλότητα Riemann (M,g) με σύνορο, που είναι αναλλοίωτη από τη δράση μιας οποιασδήποτε συμπαγούς υποομάδας G της ομάδας των ισομετριών Is(M,g) της Μ και της οποίας όλες οι G-τροχιές έχουν άπειρο πληθάριθμο και κάνουμε μια σύντομη παρουσίαση των λύσεων των προβλημάτων (P3) και (P4). / The present Thesis is incorporated in the research area of Nonlinear Analysis, especially solvability of Nonlinear Elliptic PDE’s with supercritical exponent.The nonlinear nature of the equations makes it impossible to be solved by means of compact imbeddings. Taking advantage of the symmetry properties of the manifold we overcome the obstacle as well as we succeed in solving equations of this type possessing supercritical exponent. In the first part of the Thesis we calculate the first best constant in the general Sobolev inequality and in the general Sobolev trace inequality on the solid torus, we study the phenomenon of concentration and solve problems (P1) and (P2).In the second part we calculate the first best constant in the general Sobolev inequality and in the general Sobolev trace inequality on a smooth, compact, n−dimensional Riemannian manifold (M, g), n _ 3, with boundary, which is invariant under the action of a subgroup G of the isometry group Is(M, g) of M, the orbits of which have infinity cardinality. We also present brief solutions of problems (P3) and (P4).

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