Cette thèse est divisée en cinq parties portant sur les thèmes suivants: l’interprétation physique et algébrique de familles de fonctions orthogonales multivariées et leurs applications, les systèmes quantiques superintégrables en deux et trois dimensions faisant intervenir des opérateurs de réflexion, la caractérisation de familles de polynômes orthogonaux appartenant au tableau de Bannai-Ito et l’examen des structures algébriques qui leurs sont associées, l’étude de la relation entre le recouplage de représentations irréductibles d’algèbres et de superalgèbres et les systèmes superintégrables, ainsi que l’interprétation algébrique de familles de polynômes multi-orthogonaux matriciels. Dans la première partie, on développe l’interprétation physico-algébrique des familles de polynômes orthogonaux multivariés de Krawtchouk, de Meixner et de Charlier en tant qu’éléments de matrice des représentations unitaires des groupes SO(d+1), SO(d,1) et E(d) sur les états d’oscillateurs. On détermine les amplitudes de transition entre les états de l’oscillateur singulier associés aux bases cartésienne et polysphérique en termes des polynômes multivariés de Hahn. On examine les coefficients 9j de su(1,1) par le biais du système superintégrable générique sur la 3-sphère. On caractérise les polynômes de q-Krawtchouk comme éléments de matrices des «q-rotations» de U_q(sl_2). On conçoit un réseau de spin bidimensionnel qui permet le transfert parfait d’états quantiques à l’aide des polynômes de Krawtchouk à deux variables et on construit un modèle discret de l’oscillateur quantique dans le plan à l’aide des polynômes de Meixner bivariés. Dans la seconde partie, on étudie les systèmes superintégrables de type Dunkl, qui font intervenir des opérateurs de réflexion. On examine l’oscillateur de Dunkl en deux et trois dimensions, l’oscillateur singulier de Dunkl dans le plan et le système générique sur la 2-sphère avec réflexions. On démontre la superintégrabilité de chacun de ces systèmes. On obtient leurs constantes du mouvement, on détermine leurs algèbres de symétrie et leurs représentations, on donne leurs solutions exactes et on détaille leurs liens avec les polynômes orthogonaux du tableau de Bannai-Ito. Dans la troisième partie, on caractérise deux familles de polynômes du tableau de Bannai-Ito: les polynômes de Bannai-Ito complémentaires et les polynômes de Chihara. On montre également que les polynômes de Bannai-Ito sont les coefficients de Racah de la superalgèbre osp(1,2). On détermine l’algèbre de symétrie des polynômes duaux -1 de Hahn dans le cadre du problème de Clebsch-Gordan de osp(1,2). On propose une q - généralisation des polynômes de Bannai-Ito en examinant le problème de Racah pour la superalgèbre quantique osp_q(1,2). Finalement, on montre que la q -algèbre de Bannai-Ito sert d’algèbre de covariance à osp_q(1,2). Dans la quatrième partie, on détermine le lien entre le recouplage de représentations des algèbres su(1,1) et osp(1,2) et les systèmes superintégrables du deuxième ordre avec ou sans réflexions. On étudie également les représentations des algèbres de Racah-Wilson et de Bannai-Ito. On montre aussi que l’algèbre de Racah-Wilson sert d’algèbre de covariance quadratique à l’algèbre de Lie sl(2). Dans la cinquième partie, on construit deux familles explicites de polynômes d-orthogonaux basées sur su(2). On étudie les états cohérents et comprimés de l’oscillateur fini et on caractérise une famille de polynômes multi-orthogonaux matriciels. / This thesis is divided into five parts concerned with the following topics: the physical and algebraic interpretation of families of multivariate orthogonal functions and their applications, the study of superintegrable quantum systems in two and three dimensions involving reflection operators, the characterization of families of orthogonal polynomials of the Bannai-Ito scheme and the study of the algebraic structures associated to them, the investigation of the relationship between the recoupling of irreducible representations of algebras and superalgebras and superintegrable systems, as well as the algebraic interpretation of families of matrix multi-orthogonal polynomials. In the first part, we develop the physical and algebraic interpretation of the Krawtchouk, Meixner and Charlier families of multivariate orthogonal polynomials as matrix elements of unitary representations of the SO(d + 1), SO(d, 1) and E(d) groups on oscillator states. We determine the transition amplitudes between the states of the singular oscillator associated to the Cartesian and polyspherical bases in terms of the multivariate Hahn polynomials. We examine the 9j coefficients of su(1,1) through the generic superintegrable system on the 3-sphere. We characterize the q-Krawtchouk polynomials as matrix elements of "q-rotations" of U_q(sl_2). We show how to design a two-dimensional spin network that allows perfect state transfer using the two-variable Krawtchouk polynomials and we construct a discrete model of the two-dimensional quantum oscillator using the two-variable Meixner polynomials. In the second part, we study superintegrable systems of Dunkl type, which involve reflections. We examine the Dunkl oscillator in two and three dimensions, the singular Dunkl oscillator in the plane and the generic system on the 2-sphere with reflections. We show that each of these systems is superintegrable. We obtain their constants of motion, we find their symmetry algebras as well as their representations, we give their exact solutions and we exhibit their relationship with the orthogonal polynomials of the Bannai-Ito scheme. In the third part, we characterize two families of polynomials belonging to the Bannai-Ito scheme: the complementary Bannai-Ito polynomials and the Chihara polynomials. We also show that the Bannai–Ito polynomials arise as Racah coefficients for the osp(1,2) superalgebra. We determine the symmetry algebra associated with the dual − 1 Hahn polynomials in the context of the Clebsch-Gordan problem for osp(1,2). We introduce a q -generalization of the Bannai-Ito polynomials by examining the Racah problem for the quantum superalgebra osp_q(1,2). Finally, we show that the q-deformed Bannai-Ito algebra serves as a covariance algebra for osp_q(1,2). In the fourth part, we determine the relationship between the recoupling of representations of the su(1,1) and osp(1,2) algebras and second-order superintegrable systems with or without reflections. We also study representations of Racah–Wilson and Bannai-Ito algebras. Moreover, we show that the Racah Wilson algebra serves as a quadratic covariance algebra for sl(2). In the fifth part, we explicitly construct two families of d-orthogonal polynomials based on su(2). We investigate the squeezed/coherent states of the finite oscillator and we characterize a family of matrix multi-orthogonal polynomials.

Dans la lutte contre le cancer, la médecine personnalisée est une stratégie nécessaire et très prometteuse. En effet, il est primordial de pouvoir tester l'innocuité et l'efficacité de médicaments anticancéreux sur des échantillons provenant du patient lui-même, du fait de la diversité des réponses entre patients. Le but est d'améliorer la performance des soins et d'éviter des traitements inutiles et même parfois nocifs pour le patient. Ainsi, l'exemple de la chimiothérapie illustre parfaitement cette stratégie. Le cout élevé des molécules thérapeutiques, la nocivité de ces molécules et les réponses variées des patients face à une même molécule implique le recours aux tests de ces molécules sur un échantillon provenant du patient lui-même. Il en résulte un intérêt croissant dans le développement de tests simples, robustes et peu couteux permettant l'évaluation de la chimio sensibilité de cellules biologiques issues d'une biopsie. Les problématiques liées à la mise en place de tels tests sont la quantité de cellules disponibles dans une biopsie, la diversité des molécules thérapeutiques à tester et également le choix d'une technique de détection permettant de suivre la cinétique d'action des molécules sur les cellules biologiques. L'une des réponses à la faible quantité de cellules est le développement de tests dans des environnements microfluidiques qui nécessitent donc l'intégration et la miniaturisation d'une technique de détection. La stratégie qui sera étudiée dans cette thèse est l'utilisation de l'impedancemetrie par le biais d'électrodes inter digitées d'Oxyde d'Etain et d'Indium (ITO) pour l'analyse quantitative de l'état de cellules de cancer du sein pour des applications de criblage de médicaments anticancéreux. Ce matériau présente l'avantage d'être transparent permettant ainsi des mesures d'impédance qui pourrait être couplées à des mesures optiques dans un environnement microfluidique. Dans une première partie, nous avons caractérisé et étudié des électrodes inter digitées d'or et d'ITO pour des mesures d'impédance avec des cellules cancéreuses. Cette caractérisation par spectroscopie d'impédance réalisée dans des solutions de milieu de culture en présence et absence de cellules, ont permis de démontrer que la différence de sensibilité entre ces deux matériaux provenait à la fois d'une différence de comportement résistif mais également d'une différence d'impédance interfaciale, dans les deux cas à la défaveur de l'ITO. Après ce constat, nous avons donc poursuivi l'étude afin d'évaluer les capacités de l'ITO pour des mesures de chimio sensibilité de la molécule 5-fluorouracil et également proposé une stratégie pour améliorer la sensibilité de l'ITO tout en conservant sa transparence. La stratégie développée consiste en la modification de la surface de d'électrodes d'ITO avec de l'oxyde d'iridium pour améliorer la sensibilité de l'ITO, tout en gardant sa transparence. Cette approche est intéressante pour pouvoir concevoir un dispositif transparent et facile à coupler avec un système d'observation microscopique dans un environnement microfluidique / In the fight against cancer, personalized medicine is a necessary and very promising strategy. In fact, it is essential to be able to test the safety and effectiveness of anticancer drugs on samples from the patient, due to the diversity of responses between patients. The aim is to improve the performance of health care and avoid unnecessary and sometimes harmful treatments. Thus, chemotherapy perfectly illustrates this strategy. The high cost of therapeutic molecules, the harmfulness of these molecules and the varied responses of patients involve the use of tests with chemotherapeutic molecules on samples coming from cancer patients. This results in a growing interest in the development of simple, robust and inexpensive tests for assessing the chemo sensitivity of biological cells from a biopsy. The problems related to carrying out such tests are the quantity of cells available in a biopsy, the diversity of the therapeutic molecules to be tested and also the choice of a detection technique, able to monitor the kinetics of action of the molecules on the biological cells. One solution to the small amount of cells is to carry out the tests in microfluidic environments which therefore require the integration and miniaturization of a detection technique. The strategy that will be studied in this thesis is the use of electrical impedance with interdigitated electrodes of indium tin oxide (ITO) for the quantitative analysis of the state of breast cancer cells for screening applications of anticancer drugs. This material has the advantage of being transparent allowing impedance measurements that could be coupled to optical measurements in a microfluidic environment. In the first part, we characterized and studied interdigitated electrodes of gold and ITO for impedance measurements with cancer cells. This impedance spectroscopy characterization carried out in culture medium solutions, in the presence and absence of cells, demonstrated that the difference in sensitivity between these two materials comes from a difference in resistive behavior and also from a difference in interfacial impedance, in both cases to the disadvantage of ITO. After this, we continued the study to evaluate the capabilities of ITO for chemosensitivity measurements using the molecule 5 fluorouracil and we suggested a strategy to improve the sensitivity of ITO while maintaining its transparency. The strategy developed consists of modifying the surface of ITO electrodes with iridium oxide to improve the sensitivity of the ITO, while keeping its transparency. This approach is interesting for developing a transparent device and easy to couple with a microscopic observation system in a microfluidic environment

Made available in DSpace on 2016-06-02T20:36:36Z (GMT). No. of bitstreams: 1 4179.pdf: 5952888 bytes, checksum: b0961612c482aa701a73cb33605c06a6 (MD5) Previous issue date: 2012-02-17 / The formation of In1-xSnxO2 (ITO) nanocrystals through the conversion of radiant energy into heat has been studied by using an adapted domestic microwave oven. The formation of powder was obtained by heating the oven to 200 C using a heating rate of 50 C/min and soaking time of 30 min. The obtained powder by this method was characterized by X-ray Diffraction (XRD), Field Emission Scanning Electron Microscope (FEG-SEM), High Resolution Transmission Electron Microscope (HRTEM) and Selected Area Diffraction technique whose enable to distinguish possible crystalline phases, as well as the structure and morphology of the powder. Spherical particles with average size of 4, 8 and 12 nm were identified. This powder was characterized by sensing response against the presence or absence of oxygen gas. Finally, ITO powder was deposited on amorphous quartz or glass substrates by spin coating method. The films thus obtained were characterized by FEG-SEM, UVVIS and the electrical sheet resistance was measured using a four probe tips. Best results were obtained in the film whose particles were synthesized at pH 6,5. Optical transmittance at visible region of 98,5 % was observed and with an optical gap and resistance calculated to be 3,55 eV and 3,6.10-3 Ω.m respectively. / Utilizando um forno micro-ondas doméstico adaptado como fonte de energia, estudou-se a formação de nanocristais de In1-xSnxO2 (ITO) por meio da conversão de energia radiante em térmica. O pó do material foi formado em uma temperatura de 200 ºC por tempo de 30 minutos, a razão de aquecimento do sistema foi de 50 ºC/min. Os pós obtidos por esse método foram caracterizadas por Difratometria de raios-X (DRX), Microscopia Eletrônica de Varredura com Campo Emissor de Elétrons (FEG-SEM), Microscopia Eletrônica de Transmissão de Alta Resolução (HRTEM) e Difração em Área Selecionada (SAD), essas técnicas possibilitaram a distinção das possíveis fases bem como a estrutura e morfologia do pó. Partículas esféricas e com tamanhos médios de 4, 8 e 13 nm foram identificadas. Os pós também foram caracterizados como sensores e suas respostas foram medidas na presença e ausência do gás oxigênio. Finalmente, o pó de ITO foi depositado sobre substrato de quartzo amorfo ou vidro pelo Método Spin Coating. Os filmes assim obtidos foram caracterizados por FEG-SEM, UV-VIS e a resistência elétrica superficial de cada um dos filmes foram medidas pelo método de quatro pontas. Os melhores resultados foram apresentados pelo filme cujas partículas foram sintetizadas em pH 6,5, sua transmitância é de 98,5%, gap óptico de 3,55 eV e resistividade de 3,6 10-3Ω.m.

Moderne optoelektronische Dünnfilmapplikationen erfordern den Einsatz effizienter großflächiger Elektrodensysteme, die einerseits über sehr gute Leitfähigkeitseigenschaften verfügen und andererseits eine hohe Transparenz in einem breiten Wellenlängenspektrum aufweisen. Momentan wird für derartige Anwendungen zum Großteil der Werkstoff Indiumzinnoxid (ITO) eingesetzt, dessen Hauptbestandteil Indium nur in geringen Mengen auf der Erde vorkommt. Für die Erhaltung der Marktfähigkeit und zur Weiterentwicklung der Dünnschichtelektronik ist es nötig, dieses Ressourcenproblem zu lösen. Eine Möglichkeit zur Substitution von ITO ist die Verwendung dünner metallischer Filme als transparente Elektroden. Die vorliegende Dissertationsschrift untersucht in diesem Zusammenhang die Anwendung der Direkten Laserinterferenzstrukturierung (DLIP). Um hinreichend große optische Transparenz bei entsprechender elektrischer Leitfähigkeit zu erhalten, werden Dünnschichtensysteme aus Kupfer, Aluminium, Chrom und Silber mit verschiedenen periodischen Lochmustern zwischen 1,5-2,7 µm perforiert. Im Anschluss werden die bearbeiteten Probenkörper hinsichtlich ihrer optischen, elektrischen und topografischen Eigenschaften vermessen. Die umfangreichen gewonnenen Daten werden in einer Auswertung zusammengefasst und mit Resultaten aus numerischen Modellrechnungen verglichen. Neben den Ergebnissen zur Effizienzsteigerung der Dünnfilme untersucht die vorliegende Arbeit die laserinduzierte Ablationsdynamik metallischer Filme auf Glassubstrat zwischen 5-40 nm Schichtdicke.

Au cours des dernières décennies, les chromophores organiques “push-pull” ont vu leur intérêt grandir en raison de leurs applications potentielles dans les domaines des transistors à effet de champ, de l'optique non linéaire, des OLEDs, et du photovoltaïque. Dans le cadre de la conception de cellules photovoltaïques, ces structures moléculaires correctement organisées sur une surface devraient permettre d’améliorer l’interface donneur/accepteur, l’absorption optique, et d’augmenter le volume de la couche active. Nous avons développé une synthèse en plusieurs étapes de nouvelles molécules “push-pull” comportant une tête réactive thiol autorisant la formation de monocouches moléculaires auto-assemblées (SAM) sur surfaces d’or ou d’ITO. En variant les groupements donneur, accepteur, et l’espaceur il a été possible de moduler les propriétés optiques et électroniques.Les produits obtenus possèdent une forte absorption de lumière et peuvent donc être efficaces pour le photovoltaïque. Les monocouches moléculaires finales des chromophores avec ou sans nanoparticules d’or ont été étudiées principalement par angles de contact, techniques de spectroscopie IR, UV-Vis, XPS, et par microscopie à sonde locale (STM, AFM). Les matériaux ainsi obtenus à base de SAMs de chromophores “push-pull” et de nanoparticules de métaux nobles ont ensuite caractérisés électriquement et optiquement pour évaluer leur utilisation potentielle pour la conversion de l’énergie photovoltaïque. / During the past decades, the synthesis of organic donor-acceptor (D/A) “push-pull” chromophores has been of considerable interest because of their potential use in nonlinear optics, LEDs, field effect transistors, and photovoltaics (PV). As a part of the design of the PV cells, these molecular structures correctly arranged on a surface should improve the donor/acceptor interface, the optical absorption, and increase the volume of the active layer. We have developed a multi-step synthesis of new “push-pull” molecules bearing a thiol reactive group enabling to form self-assembled monolayers (SAM) on gold or ITO surfaces. Combining various donor, acceptor, and spacer moieties we could tune the “push-pull” optical and electronic properties. The obtained “push-pull” products exhibit a high light absorption and can thus be effective in PV applications. Final SAMs with and without nanoparticles were studied mainly by contact angles, UV-vis, IR and XPS spectroscopy, ellipsometry and near-field microscopy (STM and AFM). As-obtained organic layers were then electrically and optically characterized to assess their potential use in the field of PV energy conversion.

Information Technology Outsourcing (ITO) in terms of the replacement of the in-house production of IT activities by the use of third party suppliers had already started in the 1960s and has increased considerably. For 2013, the Gartner Group expected that the global ITO market would reach a volume of 288 bn US dollars. Until 2017, the market should grow on average about 5.4% yearly. Despite the rich set of experiences companies have already had with ITO, the chances of success are seen as at best 50:50. Currently, the dramatic growth of ITO is accompanied by backsourcing of formerly outsourced IT functions or reports about dissatisfaction and problems with ITO. Scientists put ITO failures or problems down to a lack of modelling of all the possible factors affecting ITO success and demand a specific ITO theory as a basis for better explaining and predicting successes and failures in an IT sourcing context. This thesis takes up this research gap. The aim of this thesis is to develop a novel ITO Model which aids organisations in planning and implementing ITO solutions by guiding them through the ITO process steps of preparation, selection, contract, transition, execution, and post-deal comprising a comprehensive picture of the weighted aspects relevant to ITO success and their interdependencies. In order to achieve this aim, the following objectives were established for this thesis: raising the topical level of scientific knowledge of the last decades about successinfluencing factors in the ITO field based on an extensive literature survey of 48 scientific articles deriving ITO success factors from empirical research work; structuring of this success factor knowledge by the development of two ITO taxonomies (taxonomy of success factors and taxonomy of success factor interdependencies); testing its practical applicability on the basis of 8 real long-running application outsourcing cases in the banking industry; further development of the success factor knowledge by identification of weightings and the temporal relevance of relevant success factors / success factor interdependencies within the ITO process. Design of the novel ITO Model based on the empirical knowledge gained by development of rules for relevant success factors and success factor interdependencies, by arrangement of these rules in temporal order within the ITO process and by assignment of these rules to four levels of environment.

This thesis focuses on understanding the chemistry involved in a variety of surface modification reactions, both on metal oxides and graphene. In this work, the rates of chemisorption of a prototypical phosphonic acid on ITO under several processing protocols are measured using XPS to determine the optimal procedure. UPS is used to track the dependence of the electronic structure of the system, specifically of the work function and position of the valence band maximum on coverage. Phosphonic acid monolayers with appropriate tail groups can also be used to initiate chemistry from surfaces, which has potential for building layers of organic-electronic devices, including organic solar cells and capacitors. The growth of non-conjugated polymers from BaTiO₃ nanoparticles using a facile ATRP technique is studied via solution-phase and solid-state techniques to determine its applicability to make matrix-free composites for hybrid dielectrics. In addition, the surface chemistry involved in Kumada Catalyst-Transfer to grow polythiophene derivatives from ITO is examined via XPS. Finally, the newly emerged alternative for replacement of ITO as transparent electrode, graphene, is n- and p-doped using redox-active, solution-processable metal-organics, which increased its conductivity and allowed the work function to be tuned over a range of 1.8 eV. The systems are characterized in a systematic study, and the results are promising for future applications of graphene.

De par leur excellente résolution spatiale et leurs propriétés particulières, les ultramicroélectrodes (UME) constituent des outils de choix pour l'étude de mécanismes biologiques de sécrétion à l'échelle de la cellule unique. En configuration " synapse semi-artificielle ", du fait de la faible distance qui sépare la cellule émettrice de l'UME, les molécules sont libérées dans un faible volume, induisant alors des concentrations suffisamment élevées pour être détectables par électrochimie. Ainsi, les UME offrent la possibiIité de mesurer des flux, même infimes, de molécules électroactives en temps réel. Cette technique analytique a été utilisée, complétée ou adaptée afin d'étudier deux phénomènes biologiques : l'exocytose vésiculaire et le stress oxydant cellulaire. L'analyse ampérométrique de l'exocytose, mécanisme impliqué dans la communication cellulaire, permet l'étude quantitative de la cinétique de libération des molécules intravésiculaires libérées dans le milieu extracellulaire. L'UME, placée dans le milieu extérieur, n'apporte pas d'information quant au statut des vésicules avant la fusion. Pour compléter ces informations, nous avons développé, par des techniques de microfabrication, un microsystème constitué d'électrodes conductrices et transparentes d'ITO permettant un couplage des détections ampérométrique et optique (microscopie TIRF) pour l'étude de la sécrétion des cellules BON BC21. L'ampérométrie à quatre potentiels constants, utilisée au laboratoire pour la détection des ROS/RNS libérées par les macrophages, cellules du système immunitaire, nécessite un grand nombre d'expériences pour s'affranchir de la variabilité cellulaire et des différences de sensibilité des UME. Afin de réduire considérablement le temps d'expérience, nous avons développé un microsystème constitué de quatre chambres de mesure, chacune contenant un jeu de trois électrodes. Ces quatre chambres permettront, à terme, le suivi et la détection simultanée en temps réel des variations de production de H2O2, ONOO-, NO* et NO2- libérées par une cellule.

This thesis is concerned with the deposition of nanoparticle films onto boron-doped diamond and tin-doped indium oxide (lTO) surfaces and the characterisation of the films using electron microscopy, powder diffraction methods and quartz crystal microbalance (QCM) data. The redox behaviour of the porous films was examined using cyclic voltammetry in various media to investigate potential electroanalytical applications. TiOz (anatase) mono-layer films were immobilised onto an inert boron-doped diamond substrate. Cyclic voltammetry experiments allowed two distinct steps in the reduction - protonation processes to be identified that are consistent with the formation of Ti(III) surface sites accompanied by the adsorption of protons. Preliminary data for electron transfer processes at the reduced TiOz surface such as the dihydrogen evolution process and the 2 electron - 2 proton reduction of maleic acid to succinic acid are discussed. Novel multi-layer TiOz films were deposited with a variety of organic binder molecules onto ITO substrates. The redox reactivity of Cuz+ with 1,4,7,10- tetraazacyclododecane- 1,4,7, IO-tetrayl- tetrakis (methyl-phosphonic acid) in solution and immobilised on an electrode surface are investigated. The influences of film thickness, scan rate, and pH on the electrochemistry of immobilised pyrroloquinoline quinone was investigated with two possible electron transport processes observed. The thickness of TiOz phytate films was found to change the shape of the resulting cyclic voltammograms dramatically. Computer simulation and impedance spectroscopy allowed insights into the diffusion of electrons to be obtained. 1, 1 ~Ferrocenedimethanol was employed as an adsorbing redox system to study the voltammetric characteristics of carboxymethyl-y-cyclodextrin films and evidence for two distinct binding sites is considered. The apparent transport coefficients for dopamine and Ru(NHJ)6J+ are estimated for TiOz Nafion® films. The electrochemical processes in biphasic electrode systems for the oxidation of water-insoluble N,N-didodecyl-N;N~diethyl-benzene-diamine (DDPD) pure and dissolved in di-(2-ethyl-hexyl)phosphate (HDOP) immersed in aqueous electrolyte media are described. Transfer of the anion from the aqueous electrolyte phase into the organic phase accompanies the oxidation of pure DDPD. In the presence of HOOP, oxidation is accompanied by proton exchange. The electrochemically driven proton exchange process occurs over a wide pH range. Organic microdroplet deposits of OOPD in HDOP at basal plane pyrolytic graphite electrodes are studied using voltammetric techniques and compared to the behaviour of organic microphase deposits in mesoporous Ti02 thin films. Two types of Ti02 thin film electrodes were investigated, (i) a 300-400 nm film on ITa and (ii) a 300-400 nm film on ITa sputter-coated with a 20 nm porous gold layer. The latter biphasic design is superior. Titanium carbide (TiC) nanoparticies were deposited onto ITa electrodes. Partial anodic oxidation and formation of novel core-shell TiC-Ti02 nanoparticies was observed at applied potentials positive of 0.3 V vs. SCE. Significant thermal oxidation of TiC nanoparticies by heating in air occurs at 250 °c leading to coreshell TiC-Ti02 nanoparticies, then Ti02 (anatase) at ca. 350 °c, and Ti02 (rutile) at temperatures higher than 750 °c. The electrocatalytic properties of the core-shell TiC-Ti02 nanoparticulate films were surveyed for the oxidation of hydroquinone, ascorbic acid, dopamine and nitric oxide (NO) in aqueous buffer media. Mono- and multi-layer Ce02 deposits on ITa are shown to be electrochemically active. A reduction assigned to a Ce(IV/III) process has been observed and followup chemistry in the presence of phosphate discovered. The interfacial formation of CeP04 has been proven and effects of the deposit type, pH and phosphate concentration on the process analysed. The electrochemistry of multi-layer Ce02 nanoparticulate films in organic solvent is shown to be more stable.

In the West architectural historiography, or writing on architectural history, can be considered as a modern practice. Its emergence accompanied with the development of modern nation states. Architecture’s reflection on its historical texts came to find particular expression in the search for the origins of architecture. The formation of oriental architectural history tended to follow this pattern. Oriental architectural historiography was initiated by a Japanese scholar, Chūta Itō. In his formulation, the origins of Japanese architecture were linked not only with Chinese and Indian architecture, but also with Classical Greek architecture. In addition, Itō’s theoretical formulation of architectural history was also followed by other Japanese scholars, and it informed those later scholars who studied Taiwanese architectural history. That is, the formulations and classification systems that Itō set out for Japanese architecture framed subsequent scholarship on the architecture of other parts of East Asia, including Taiwan. The system that Itō established has been widely regarded as being based on modern and scientific academic research. This thesis investigates Itō’s system, its significance for architectural scholarship in other parts of East, as well as its claimed scientific basis. The thesis pays particular attention to the architectural history of Taiwan in the Japanese colonial period. The thesis hypothesises that the historiographical tradition that Itō’s work established was based on an unbalanced colonial relationship of power and uneven structure of authority, It explores how authenticity in East Asian architecture was authorised, and how hidden ideologies and methodologies lie behind these historiographical practices. This is the first ambition of the thesis. The examination of Japanese construction of oriental and Taiwanese architectural history in this thesis pays particular attention to the context of Japanese colonialism. In doing so it draws on a range of contemporary postcolonial theoretical perspectives. In addition, the particular kind of oriental colonialism, as a materialised colonial medium, Japanese writing on oriental and Taiwanese architectural history provides an additional perspective on that current and recent postcolonial criticism expressed through such concepts as Edward Said’s orientalism, Homi Bhabha’s hybridity and Gayatri Spivak’s strategic essentialism. At a theoretical level, the thesis argues that since these concepts emerged from the colonial/anti-colonial operation and negotiation between the west and its colonies, a refined analysis is required for thinking through Japanese colonialism. To this end, the thesis supplements postcolonial theory with the idea of oriental orientalism as developed by Yuko Kikuchi. In so doing, the thesis aims to contribute to an enriched discussion of contemporary postcolonial criticism in general, and as it applies to East Asian in particular. The exploration of architectural history as the subject of a wider colonial operation and the revision of the core conceptual tools of postcolonial criticism in the context of Japanese colonialism in East Asian, and Taiwan, provides further possibilities for the the construction of identity in those formerly colonised subject in places such as Taiwan. A postcolonial reading of Japanese writing on architectural history shows both the limitation of postcolonial criticism, and to question the framework of architectural discourse in the discipline. This project has to be based on an inquiry into the way in which the other’s architecture has been formulated and constructed in the discipline of architecture in the light of postcolonial criticism. Without such an inquiry, we are unable to open the metaphorical ‘space’ to negotiate the self-writing of Taiwanese subjects on their own architecture and architectural history.