Presented diploma thesis was focused on study of biologically active compounds, especially some sugars in cereal products. In experimental part the total of 29 different cereal materials, food industry waste products and natural complex matrixes (microbial polysaccharide, honey, beer) were used. As a part of this work optimization of analytical methods suitable for analysis of simple sugars, oligo- and polysaccharides was done. In cereal samples reduced and neutral sugars were analyzed spectrophotometrically and individual sugars were detected by chromatography. For HPLC/RI analysis optimal mobile phase composition and chromatography conditions were proposed. For mono- a oligosaccharides C18-NH2 sorbent, mixture acetonitril:water 75:25 as mobile phase and flow 1 ml/min were verified as suitable separation parameters. Thin layer chromatography of mono- and oligosaccharides was optimized too. Introduced chromatography and spectrophotometry methods were then applied to analysis of cereal samples. As a model sugar natural microbial polysaccharide pullulan was used to analytical method testing. In cereal products and food matrixes total neutral and reduced sugars as well as products of their acid and enzyme hydrolysis were measured. Detailed analysis of some glycoside composition was tested too. As the most usable method for both qualitative and quantitative analysis of cereal sugars HPLC/RI method was found. To detailed identification of malto-oligosacharides tandem LC/MS/MS technique using derivatization by 1-phenyl-3-methyl-5-pyrazolon was tested too.

La caractérisation des propriétés optiques de gouttes de combustible aux alentours de la pression critique est un défi. L’objectif de la thèse est de mesurer la taille et l’indice de réfraction de fluides dans des conditions de pression élevée proche du point critique. A cet effet, une installation expérimentale d’injection de gouttes à haute pression a été conçue. La réfractométrie d’arc-en-ciel a été développée et adaptée pour travailler d’abord sur des gouttelettes d’eau et d’éthanol dans le domaine de pression 1 - 40 bar. Des évolutions de leur indice de réfraction avec la pression ont été obtenues. Pour les mesures se rapprochant d’un fluide proche du point critique, l’éthane a été sélectionné car son point critique est à 48,7 bar et 32,2°C. Des mesures de réfraction d’index sur des gouttes liquides d’éthane ont ensuite été réalisées dans le domaine 40 - 46 bar et 18 - 25°C. Une mesure de l’indice de réfraction de gouttes d’éthane donne alors une valeur de 1,255 ± 0.002. / The characterization of the optical properties of fuel drops around the critical pressure is a challenge. The aim of the thesis is to measure the size and the refractive index of fluids under high pressure conditions close to the critical point. For this purpose, an experimental installation of injection of high-pressure drops has been designed. Rainbow refractometry has been developed and adapted to work first on water and ethanol droplets in the pressure range 1 - 40 bar. Evolutions of their index of refraction with the pressure were obtained. For measurements approaching a fluid near the critical point, ethane was selected because its critical point is 48.7 bar and 32.2 ° C. Index refractive measurements on liquid drops of ethane were then carried out in the range 40 - 46 bar and 18 - 25 ° C. A measurement of the refractive index of ethane drops then gives a value of 1.255 ± 0.002.

Le procédé de photopolymérisation a été optimisé en vue de l’élaboration de matériaux composites à matrice époxyde épais (> 1 mm) via un mécanisme cationique. L’étude des cinétiques de photopolymérisation de deux résines époxydes (glycidyl éther et cycloaliphatique) a montré que l’ajout d’un renfort de microsphères de silice induit un gradient de conversion dans l’épaisseur du matériau en raison d’un phénomène d’absorption et/ou de diffusion de la lumière, ce dernier étant d’autant plus important que l’écart d’indice de réfraction entre la charge et la matrice est élevé. Cependant, cette hétérogénéité de conversion a pu être compensée par une réaction de postpolymérisation à température ambiante. Une analyse des propriétés mécaniques a ensuite montré qu’il est possible d’obtenir par photopolymérisation des matériaux composites épais réticulés de façon homogène et dont la rigidité est augmentée par la présence du renfort. Enfin, la stratégie d’égalisation des indices de réfraction de la charge et de la matrice, couplée à une photopolymérisation cationique frontale induite par voie radicalaire (RICFP), ouvre des perspectives intéressantes en vue de l’élaboration de photocomposites de plusieurs centimètres d’épaisseur en appliquant uniquement un stimulus lumineux. / The photopolymerization process has been optimized for the elaboration of thick epoxy composite materials (> 1 mm) through a cationic mechanism. The study of the photopolymerization kinetics of two epoxy resins (glycidyl ether and cycloaliphatic) has shown that the addition of a silica microsphere reinforcement induced conversion gradient in the material thickness, resulting from a light absorption and/or scattering phenomenon. The light scattering is all the more important as the refractive index gap between filler and matrix is high. However, this conversion heterogeneity has been compensated by a postpolymerization reaction at room temperature. Then, the analysis of the mechanical properties has shown that it was possible to obtain thick composite materials homogeneously crosslinked and whose rigidity was increased by the presence of the filler. In addition, the strategy of equalizing the filler and matrix refractive indices, coupled with the radical induced cationic frontal polymerization (RICFP) opens interesting perspectives for the development of photocomposites several centimeters thick using only a light stimulus.

Over the last three decades, the performance of OLEDs has been improved rapidly, however, as an important assessment for OLED, the EQE data are still quite low. As outlined in the theoretical background, the EQE is the product of out-coupling efficiency and internal quantum efficiency (IQE). Therefore, this thesis focuses on designing two types of polymers with different optical functionalities, to increase the EQE addressing the two aforementioned determining factors. Thus, the first part of the thesis addresses the light out-coupling efficiency in OLED devices. Here high refractive index (HRI) polymers are aimed for as potential material for the out-coupling layer, which are so far scarily reported for application in OLED devices, due to existing limitations, such as limited transparency, extra fluorescence, tedious synthesis, poor thermal stability and low solubility. However, if suitable polymers are becoming easily available, they will offer the unique advantage, compared to low molar mass HRI compounds, of being able to using cost-effective solution based technology for large area film preparation. In addition, polymeric materials will allow to introducing fully new concepts for increasing the light-out-coupling efficiency, like patterning allowing micro-lens preparation, or the incorporation of light scattering particles into the out-coupling layer. The approach described in this thesis is based on a previous work where HRI polymers were prepared via metal-free thiol-yne “A2+B3” polyaddition reaction, which led in an easy one-pot synthesis to hyperbranched polyvinylsulfides of high solubility and already reasonable high RI. For further increasing RI, in this work B3 as well as finally A2 monomers with high naphthalene content were chosen which should, in addition to the positive effect of the sulfur-containing units, render polymers with even higher RI, and hopefully also of high solubility due to the branching. A challenging aspect of this work was to find reaction conditions which allow the preparation of high molar mass as well as highly soluble, highly aromatic polymers by that A2+B3 approach, even so very sterically demanding monomers are used. In addition, the material properties should be fine-tuned by careful selection of the monomer ratio. It was expected that these new, easily available HRI polymers will be of high potential in OLED application. Thus, the work in this part of the thesis comprises on the one hand monomer and polymer synthesis as well as detailed characterization of the structure and the solution and thermal properties of the new materials. But on the other hand, the elucidation of the thin film preparation and the quality and optical properties of the resulting polymer films are major objectives. Finally, evaluation of the performance of the polymer films in an OLED device compared to conventionally low molar mass our-coupling layers was aimed for, which could be realized with the help of partners from the Institute of Applied Photophysics at TU Dresden. For increasing the IQE in OLEDs, this thesis focuses on the development of a new type of polymeric thermally activated delayed fluorescence (TADF) material. TADF materials have the potential of theoretical 100% IQE and are considered as key materials for the next generation of OLEDs. So far, a significant amount of low molar mass TADF molecules has been developed, however, only a limited number of design rules are reported so far for polymers, even though polymers would offer, as already outlined above, significant advantages with regard to processing cost-effectively more efficient OLEDs for large area application. The new concept described in this thesis for TADF polymers is based on a new monomer which exhibits individual promising structural units for achieving TAFD properties but does not emit TADF itself due to its large ΔEST (the energy gap between singlet S1 and triple T1 state). However, it has to be expected that once the monomer is polymerized, the resulting polymeric product will have reduced ΔEST due to the increased conjugation length and thus can be expected to emit TADF. This new concept has the potential to significantly increase the scope of polymeric materials with TADF properties. Thus the second part on the thesis focuses on the design of a new monomer based on carbazole units with a pendant benzophenone moiety and its polymerization and full structural elucidation with the help of model compounds involving intensive NMR and MALDI-TOF analysis. In addition to the expect TADF properties, the benzophenone unit will also provide the possibility for film stabilization and even photopatterning due to photo-crosslinking. Thus the study of film formation and photo-crosslinking of the new TADF polymers was a further objective of this thesis. Finally, first theoretical as well as experimental studies of the photo physical properties of the monomer, a low molar mass model compound and the polymer, again together with the partners from the Institute of Applied Photophysics, should provide evidence on the suitability of the new polymer design principle.

The temperature dependence of the refractive index and the density of aqueous binary mixtures of water and ethyl alcohol (C₂H₅OH) were measured by using a modified Michelson interferometer and a narrow glass capillary tube over the temperature range of 278≤T≤353 K for solutions of 100, 75,65, 50, 25, 10 and 0 volume percent ethyl alcohol. The temperature was cycled over both increasing and decreasing directions to explore hysteresis in the cycling. The data are discussed and compared with the Lorentz-Lorenz (LL) formula. A more accurate formula which fits the experimental data better than the LL relation was derived. An attempt was made to determine the nature of the solvent-solute interaction through any changes that were found in the refractive index for He-Ne laser light and IR diode signals and to analyze the refractive index and density results to test the accuracy of the available mixing rules in predicting the refractive index values and the density of binary systems. Conductivity measurements (d. c.) over the temperature range 278≤T≤353 K of aqueous solutions of NaCl at various concentrations were made and used to establish transport properties of ions in solution. The dynamical properties of the electrolytes were used to establish the nature of hydrogen bonding in aqueous binary mixture systems. Rate equations for ion formation and recombination were used to establish the temperature ranges in which hydrogen bonding dominated in forming polymeric species. From experimental data on the binary mixtures with water, a better understanding of water in its different functions and aggregation is possible. The water molecule itself and its response to the environment are understood when suitable studies are made of the forces in the system. In this work, some qualitative aspects of the interactions and dynamics of the water molecule have been investigated. Classical molecular dynamics simulations were tried to explain some of the thermodynamical properties of the water molecule.

Ferroelectrics are a group of advanced electronic materialswith a wide variety of properties useful in applications suchas memory devices, resonators and filters, infrared sensors,microelectromechanical systems, and optical waveguides andmodulators. Among the oxide perovskite-structured ferroelectricthin film materials sodium potassium niobate or Na0.5K0.5NbO3(NKN) has recently emerged as one of the most promisingmaterials in microwave applications due to high dielectrictunability and low dielectric loss. This licentiate thesispresents results on growth and structural, optical, andelectrical characterization of Na0.5K0.5NbO3 thin films. Thefilms were deposited by rf-magnetron sputtering of astoichiometric, high density, ceramic Na0.5K0.5NbO3 target ontosingle crystal LaAlO3 and Al2O3, and polycrystalline Pt80Ir20substrates. By x-ray diffractometry, NKN films on c-axisoriented LaAlO3 substrates were found to grow epitaxially,whereas films on hexagonal sapphire and polycrystallinePt80Ir20 substrates were found to be preferentially (00l)oriented. Optical and waveguiding properties of theNa0.5K0.5NbO3/Al2O3 heterostructure were characterized using aprism-coupling technique. Sharp and distinguishable transversemagnetic (TM) and electric (TE) propagation modes wereobserved. The extraordinary and ordinary refractive indiceswere calculated to ne = 2.216±0.003 and no =2.247±0.002 for a 2.0 μm thick film at λ = 632.8nm. This implies a birefringence Δn = ne - no =-0.031±0.003 in the film. The ferroelectric state inNKN/Pt80Ir20 films at room temperature was indicated by apolarization loop with polarization as high as 33.4 μC/cm2at 700 kV/cm, remnant polarization of 9.9 μC/cm2 andcoercive field of 91 kV/cm. Current-voltage characteristics ofvertical Au/NKN/Pt80Ir20 capacitive cells and planar Au/NKN/LaAlO3 interdigital capacitors (IDCs) showed very goodinsulating properties, with the leakage current density for anNKN IDC on the order of 30 nA/cm2 at 400 kV/cm. Rf dielectricspectroscopy demonstrated low loss, low frequency dispersion,and high voltage tunability. At 1 MHz NKN/LaAlO3 showed adissipation factor tan δ of 0.010 and a tunability of 16.5% at 200 kV/cm. For the same structure the frequencydispersion, Δεr, between 1 kHz and 1 MHz was 8.5%. <b>Key words:</b>ferroelectrics, sodium potassium niobates,thin films, rf-magnetron sputtering, waveguiding, refractiveindex, prism coupling, dielectric tunability / NR 20140805

Microphotonics has been offering a body of ideas to prospective applicationsin optics. Among those, the concept of photonic integrated circuits (PIC’s) has recently spurred a substantial excitement into the scientific community. Relisation of the PIC’s becomes feasible as the size shrinkage of the optical elements is accomplished. The elements based on photonic crystals (PCs) represent promising candidacy for manufacture of PIC’s. This thesis is devoted to tailoring of optical properties and advanced modelling of two types of photonic crystals: (Bi3Fe5O12/Sm3Ga5O12)m and (TiO2/Er2O3)m potentially applicable in the role optical isolators and optical amplifiers, respectively. Deposition conditions of titanium dioxide were first investigated to maximise refractive index and minimise absorption as well as surface roughness of titania films. It was done employing three routines: deposition at elevated substrate temperatures, regular annealing in thermodynamically equilibrium conditions and rapid thermal annealing (RTA). RTA at 500 oC was shown to provide the best optical performance giving a refractive index of 2.53, an absorption coefficient of 404 cm−1 and a root-mean-square surface roughness of 0.6 nm. Advanced modelling of transmittance and Faraday rotation for the PCs (Bi3Fe5O12/Sm3Ga5O12)5 and (TiO2/Er2O3)6 was done using the 4 × 4 matrix formalism of Višňovský. The simulations for the constituent materials in the forms of single films were performed using the Swanepoel and Višňovský formulae. This enabled generation of the dispersion relations for diagonal and off-diagonal elements of the permittivity tensors relating to the materials. These dispersion relations were utilised to produce dispersion relations for complex refractive indices of the materials. Integration of the complex refractive indices into the 4 × 4 matrix formalism allowed computation of transmittance and Faraday rotation of the PCs. The simulation results were found to be in a good agreement with the experimental ones proving such a simulation approach is an excellent means of engineering PCs.

A combination of quantum chemical calculation and molecular dynamics simulation is applied to compute refractive indices of liquid-forming silicon oils. The densities of these species are obtained from molecular dynamics simulations based on the NPT ensemble while the molecular polarizabilities are evaluated by density functional theory. This procedure is shown to yield results well compatible with available experimental data, suggesting that it represents a robust and economic route for determining the refractive indices of liquid-forming organic complexes containing silicon.

Le contrôle des polluants environnementaux présents à faible concentration a conduit à la création de détecteurs miniaturisés, à bas coûts et ultra-sensibles, capables d’identifier spécifiquement certaines substances. Dans cette thèse, la méthode de détection explorée repose sur la sensibilité de micro-lasers polymères à une variation d’indice de réfraction. Cette approche a été mise en application pour détecter des métaux lourds (mercure – Hg2+, cadmium – Cd2+ et plomb – Pb2+) dans l’eau potable. En effet les fréquences de résonance de ces micro-cavités sont particulièrement sensibles à l’indice de réfraction du milieu extérieur et se déplacent lorsque celui-ci est modifié. Ce système permet ainsi une détection sans marqueur (« label ») en recouvrant la cavité d’une couche de reconnaissance spécifique de l’espèce recherchée. L’originalité de ce travail repose sur l’utilisation de micro-cavités actives, ou micro-lasers, fabriquées avec des polymères dopés par des colorants lasers. En effet les micro-lasers permettent d’augmenter le rapport signal/bruit et de profiter de pics de résonance étroits, même pour des facteurs de qualité de l’ordre de quelques milliers seulement. Le choix de matériaux organiques comme milieu à gain a été dicté par les nombreux avantages qu’ils offrent. Contrairement aux semi-conducteurs inorganiques, les polymères peuvent être fonctionnalisés de manière relativement aisée et l’utilisation de matériaux poreux devrait augmenter la sensibilité en faisant circuler le fluide à tester à l’intérieur même du résonateur. De plus le protocole de fabrication des micro-lasers organiques reste d’un coût modéré et permet une intégration aisée en micro-fluidique. Deux voies différentes ont été explorées dans cette thèse : détection d’une variation d’indice de réfraction avec des cavités non-fonctionnalisées et détection d’ions lourds avec des cavités fonctionnalisées. Dans le premier cas, la sensibilité obtenue est comparable à ce qui est publié pour des micro-résonateurs passifs. Dans le second cas, nous avons réussi à mettre en évidence la présence d’ions mercure jusqu’à 10-6 M. Quelques approches ont été envisagées pour diminuer encore le seuil de détection dont certaines ont été vérifiées expérimentalement. Ainsi, cette étude propose un prototype de composant sur puce pour la détection d’espèces chimiques ou biologiques. / Monitoring of environmental pollutants present at low concentrations requires creation of miniature, low-cost, and highly sensitive detectors that are capable to specifically identify target substances. In this thesis, a detection approach based on refractive index sensing with polymer micro-lasers is proposed and its application to the detection of heavy metal pollutants in water (mercury – Hg2+, cadmium – Cd2+ and lead – Pb2+) is studied. The resonance frequencies of the microcavity are highly sensitive to the refractive indices of the resonator surrounding: the resonances shift by a small amount when the surface refractive index changes, resulting from the interaction of the mode evanescent field with the surrounding medium. This permits label-free detection by coating the resonator with a suitable recognition species. The originality of this work lies in the utilization of active microcavities, or microlasers, created of the dye-doped polymers. Active microcavities offer an enhanced signal/noise ratio as compared to the passive ones and very narrow resonance peaks even at moderate quality factors (Q &#8805- 6000). The choice of polymers as an active medium is connected with a number of advantages they offer: as opposite to semiconductors, polymers can be easily functionalized, integrated in microfluidic circuits and are cheaper in processing. Moreover, the use of porous polymer matrices may allow accumulation of analyte ions inside the microcavity and thus enhance the sensitivity. Two possible applications of microlasers are investigated in the thesis: refractive index variation sensing with non-functionalized cavities and heavy metal ion detection with functionalized cavities. In the first case, the sensitivity values have been obtained, comparable with the reported in literature for planar passive microresonators. In the second case, the experimental proofs of specific detection of mercury ions in liquid are presented. The ways of sensitivity improvement are discussed and verified and a foundation is layed for the creation of integrated Lab-on-Chip microfluidic biochemical detector.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20402号 / 工博第4339号 / 新制||工||1672(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 中條 善樹, 教授 澤本 光男, 教授 古賀 毅 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM