Gegenstand der vorliegenden Arbeit ist die Synthese und Charakterisierung neuer chromophorer Catecholderivate mit ausgeprägten push-pull-pi-Systemen. Die solvatochromen Eigenschaften dieser Verbindungen werden in Abhängigkeit der Wasserstoffbrückenbindungsdonor- und -akzeptorfähigkeit sowie Lösungsmitteldipolarität diskutiert. Mit entsprechenden methoxy- und dimethoxyfunktionalisierten Catecholderivaten ist es möglich, vergleichende Struktur-Eigenschaftsbeziehungen aufzustellen. Durch Untersuchungen zu den Wechselwirkungen der chromophoren Catechole mit Schwermetallionen kann gezeigt werden, dass die synthetisierten Verbindungen als Sensoren eingesetzt werden können. In der vorliegenden Arbeit wird des Weiteren die Adsorption der Catecholderivate an Metalloxide beschrieben. Mit Farbstoffen sensibilisierte Oberflächen stellen derzeit ein interessantes Forschunggebiet dar. Ferner wird über die Umsetzung der Catecholderivate mit Trialkoxysilanen zu zwitterionischen, spirozyklischen, pentakoordinierten lambda5Si-Silicaten sowie mit Tetraalkoxysilanen zu dianionischen, hexakoordinierten lambda6Si-Silicaten berichtet. Besonderes Augenmerk lag dabei auf UV/vis-spektroskopischen Untersuchungen.

Introduction Le remplacement prothétique est le traitement ultime pour la dégénérescence avancée de la hanche. Cependant, l’usure prématurée des surfaces de frottement métal contre polyéthylène conventionnel (MoPc) réduit de façon importante sa longévité chez les patients jeunes et actifs. Pour surmonter ce problème, des surfaces de frottement alternatives ont été proposées, notamment les couples métal-métal (MoM) et céramique-céramique (CoC). Le but de cette étude est d'évaluer la survie à long terme de ces surfaces d'appui lors du remplacement total de la hanche (PTH) avec une articulation de petit diamètre MoM ou CoC et du resurfaçage de la hanche (RH) MoM. Méthodes La survie des implants a été évaluée à long terme dans deux études où les sujets ont été randomisées pour une PTH MoM 28 mm (99 hanches) ou un RH (104 hanches) dans l’étude 1 ou une PTH CoC (71 hanches) ou MoPc (69 hanches) dans l’étude 2. Les mesures d’efficacité principales comparés, au dernier recul, était le taux de révision, les taux de complications, score fonctionnels validés, et les signes radiographiques anormaux. Résultats Étude 1, après un suivi moyen de 15 ans, la survie avec révision pour toutes causes était de (89,2 % pour le RH versus 94,2 % pour la PTH MoM, p=0,292). Toutefois avec une révision aseptique comme critère d'évaluation, la survie était significativement plus élevée dans les PTH (97,4 % contre 89,2 % ; p=0,033). Les deux groupes ont obtenu des scores fonctionnels similaires. Étude 2, après un suivi moyen de 21 ans, la survie était significativement plus élevée (96,9% vs 73,6%, p<0,001) pour les PTH CoC versus MoPc. À l'évaluation radiographique, 13 % des MoPc étaient considérés descellées versus aucune CoC et 61 % des MoPc versus 6 % des CoC présentaient des signes d’ostéolyse (p<0,001). Les PTHs CoC avaient des scores moyens de WOMAC significativement plus élevés que le groupe MoPc (11.0 vs 19.4; p = 0.048). Conclusion L’utilisation de couples dur-dur MoM ou CoC en PTH ou RH ont offert une excellente survie et fonction à long terme chez une clientèle de sujets jeunes et actifs. En comparaison, le taux d’échec élevé du couple MoPc confirme qu’il doit être abandonné. Les résultats de cette étude doivent être mis en perspective avec les résultats futurs des nouveaux couples métal contre polyéthylènes réticulés. / Introduction Prosthetic replacement is the ultimate treatment for advanced hip degeneration. However, premature wear of the metal-on-conventional polyethylene (MoPc) bearing surfaces significantly reduces its longevity in young and active patients. To overcome this problem, alternative bearing surfaces have been proposed including metal-on-metal (MoM) and ceramic-on-ceramic (CoC) bearings. The aim of this study is to evaluate the long-term survival of these bearing surfaces during total hip replacement (THA) with a small diameter MoM or CoC bearings and hip resurfacing (HR) MoM. Methods Long-term implant survival was assessed in two studies where subjects were randomized to 28mm MoM THA (99 hips) or HR (104 hips) in Study 1, or CoC THA (71 hips) or MoPc (69 hips) in Study 2. The main outcome measures compared, at final follow-up, were revision rate, complications’ rate, validated functional scores, and abnormal radiographic signs. Results Study I: after a mean of 15 years, survivorship with endpoint all-cause revision was 89.2% for HR versus 94.2% for MoM THA MoM (p = 0.292). However, with aseptic revision as an endpoint, survivorship was significantly higher in MoM THA (97.4%) compared to (89.2%) in HR (p = 0.033). Both groups achieved similar functional scores. Study II: after a mean follow-up of 21 years, survivorship was significantly higher in CoC (96.9%) versus (73.6%) in MoPc THAs (p<0.001). On radiographic evaluation, 13% MoPc were considered loose versus non in CoC, and 61% MoPc versus 6% CoC showed osteolytic signs (p<0.001). CoC had better mean WOMAC scores than MoPc (11.0 vs 19.4; p = 0.048). Conclusion Good long-term survival and function for HR and MoM 28-mm THA implants with similar overall rates of complications and revisions. CoC provided excellent results compared to MoPc at more than 20-year follow-up.

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Catalysis using nanostructures has been a topic of substantial interest for fundamental studies and for practical applications in energy and environmental sectors. The growing demand for production of energy and in the cleaning of polluting hazardous vehicles/industrial wastes has led to several studies in catalysis. Despite the substantial growth of heterogeneous catalytic technologies in last decade, they are still far from reaching their full potential in terms of efficiency, selectivity as well as durability. It is often difficult to simultaneously tackle all the mentioned issues with single component catalysts. Most of these challenges are being overcome with heterostructures/supported hybrid catalysts by modifying their interfaces. The properties of heterostructures hybrids arises not only from the individual contributions of the individual components but also from strong synergetic effect arising from the interface. Engineering the interfaces provides pathways to promote the catalytic performance and hence has been explored. In this regard, we have focused on the progress in investigating the active interfaces that affect the performance of metal oxide-metal, semiconductor-metal and coupled semiconductor nanocatalyst hybrids. We explored a wide spectrum of their applications in photo catalytic, electrocatalytic as well as gas-phase reactions and highlighted the importance of the interface for overall performance. The entire study reported in the thesis is organized as follows: Chapter 1 is a general introduction of hybrid nanocatalyst and their role in wide spectra of catalytic reactions in photo/electro catalysis as well as gas-phase reactions. This chapter describes the motivation behind modulating the interface between two or more nanostructures to obtain multifunctional nanocatalysts. Nan catalysts to achieve high throughput with active interfaces are elaborated while indicating the role of morphology, internal induced state, charge transfer, geometric, support, as well as electronic effect for enhanced performance. Motivation behind specific nanocatalyst hybrid, synthesis routes as well as characterization techniques are detailed in the respective chapters. Specific details for different hybrids are described in the following chapters. Chapter 2 describes the synthesis of high dense ultrathin Au wires on ZnO nanorods for electrocatalytic oxidation of ethanol, where the prerequisite step is the formation of amine-modified support. Oleylamine modification not only serves to anchor Au nanowires on ZnO but also passivates surface defects of ZnO, which in turn enhances the photocurrent. In addition to the stability, the support induces electronic effect on Au nanowires, which facilitates redox process at low potential. Most importantly, the support promotes the activity of Au nanowires upon photoirradiation, and thus leading to synergy between electro and photooxidation current. This is of immense importance for photofuel cell technologies. Moreover, the method enabled the first time electrocatalysis on these nanowires that revealed ultrathin nanowires are potentially interesting systems for catalysis applications provided they are stabilized by a suitable support. Chapter 3 deals with the growth of ultrathin Au nanowires on metal oxide (TiO2) coupled with graphene hybrid support in order to overcome the low conductivity of metal oxide. Oleylamine, used for growth of Au nanowires simultaneously functionalizes the support and leads to room temperature GO reduction. With respect to catalytic activity, we also synthesized the binary counterparts (rGO/Au, TiO2/Au ultrathin nanowires) to delineate the contribution of each of the components to the overall electrocatalytic oxidation of ethanol. Comparative analysis of photo and electrocatalytic activity between the different binary and ternary hybrids provides interesting information. Both, electronic effect of TiO2 and electrical conductivity of rGO add their specific beneficial to the nanowires, leading to superior ternary system. Chapter 4 rGO supported ultrathin Au nanowires exhibits high electrocatalytic performance for oxidation of borohydride with a lower onset potential compared to rGO/Au nanoparticles. Electrochemical impedance spectroscopy measurements display abnormal inductive behavior of the synthesized hybrids, indicative of Au surface reactivation. DFT calculations indicate that the origin of the high activity stems from the shift in the position of the Au d-band center. Chapter 5 Different aspect ratio ZnO nanostructures are obtained by varying the solvothermal reaction time. We observed a direct correlation between observed photocatalytic activity, measured photocurrent and length of the ZnO nanorods. Furthermore, photoresponse of the high aspect ratio ZnO nanorods are improved by attaching Au nanoparticles, intimate contact of two components leads to band bending. Thus, the synthesized ZnO/Au heterostructure favors for prominent separation of photogenerated charge carriers. Chapter 6 TiO2 and PbO/TiO2 hybrids are synthesized via non–hydrolytic sol–gel combustion method. Hybrid exhibits higher photocatalytic activity for the degradation of dye than TiO2. The estimated photogenerated species reveals that the origin of enhanced activity stems from the direct oxidization of dye via photogenerated hole rather than radicals. The semiconductors are matched based on their band edge positions, for the formation of energetic radicals to degrade the pollutants. Based on this study, we infer that semiconductors should not neglected (for example Si) based on calculated mismatch of their valence band edges position for photooxidation reaction via radicals. Chapter 7 describes the Pd dopant associated band engineering, a strategy for tuning the optoelectronic properties of ZnO towards enhanced photocatalytic activity. Incorporated Pd heterocation induces internal energy states within the ZnO band gap. The created energy level leads to trends mismatch between photocatalytic activity and measured photocurrent. Formed energy level arrests the photogenerated electrons, which make them not contribute for the photocurrent generation. Hence, the isolated photogenerated hole efficiently oxidizes the pollutants through hydroxyl radicals, and thus leads to enhanced photocatalytic activity. Chapter 8 employed Pd-substituted zinc stannate for CO oxidation as heterogeneous catalyst for the first time. Compared with SnO2 support, zinc stannate based materials exhibits abnormal sudden light-off profiles at selective temperatures. On the basis of DRIFT studies under relevant conditions, we find that the initially formed product gets adsorbed over the catalyst surface. It leads to the accumulation of carbonates as a consequence, both lattice oxygen mobility and further CO interactions are disabled. As soon as Sn redox nature dominates over the accumulated carbonates, this leads to sudden release of lattice oxygen, and thus leads to a sudden full conversion. Therefore, choosing the suitable support material greatly influences the nature of the light-off CO oxidation profile. Chapter 9 Although, reducible oxide supported gold nanostructures exhibits the highest CO oxidation activity; they still suffer from problems such as limited selectivity towards CO in the presence of H2. Both ex-situ and in-situ experiments demonstrate that, Au nanoparticles supported on Zn2SnO4 matrix selectively oxidizes CO. DRIFT experiments revealed that the involvement of OH groups leads to the formation of hydroxycarbonyl under PROX conditions. Chapter 10 This chapter discusses the conclusions for the previous chapters and highlights the possibilities for future scope for the developed nanocatalysts hybrids for energy and environmental applications.

L'augmentation de l'interaction lumière-matière aux échelles micro et nanométriques est un des fers de lance de la nanophotonique. En effet, le contrôle de la répartition spatiale de la lumière grâce à l'interaction résonante entre nanostructures et ondes électromagnétiques a conduit aux développements de nombreuses applications dans des domaines variés tels que les télécommunications,la spectroscopie et la détection d'objets. Le ralentissement de la lumière, sujet de la thèse, obtenue grâces à l'interférence d'ondes contre-propageantes dans des milieux périodiques ou le confinement sub-longueur d'onde dans des guides d'ondes plasmoniques, est associé à une compression des pulses lumineux et une forte augmentation du champ électrique, deux phénomènes clés pour la miniaturisation de composées optiques et l'augmentation de l'interaction lumière matière. / Enhancing light-matter interactions at micro and nanoscales is one of the spearheads of nanophotonics. Indeed, the control of the field distribution due to the resonant interaction of nanostructures with electromagnetic waves has prompted the development of numerous optical components for many applications in telecommunication, spectroscopy or sensing. A promising approach lies in the control of light speed in nanostructures. Light slowdown, obtained by wave interferences in periodic structures or subwavelength confinement in plasmonic waveguides, is associated to pulse compressions and large field enhancements,which are envisioned as key processes for the miniaturization of optical devices and the enhancement of light-matter interactions.The thesis studies both fundamental aspects and possible applications related to slow light in photonic and plasmonic nanostructures. In particular, we study the impact of periodic system sizes on the group velocity reduction and propose a novelfamily of resonators that implement slow light on very small spatial scales. We then investigate the role of fabrication disorder in slow periodic waveguides on light localization and demonstrate how modal properties influence the confinement of localized modes. Also we propose a new hollow-core photonic crystal waveguide that provides efficient and remote couplings between the waveguide and atoms thatare trapped away from it. Finally we demonstrate the important role played by slow plasmons on the emission of quantum emitters placed in nanogap plasmonic antennas and explain how large radiation efficiency can be achieved by overcoming quenching in the metal. Additionally, one part of the thesis is devoted to thederivation of a novel modal method to accurately describe the dynamics of plasmonic resonators under short pulse illumination.

Plasmonic properties and the related novel applications are studied on various types of metallic nano-structures in one, two, or three dimensions. For 1D nanostructure, the motion of free electrons in a metal-film with nanoscale thickness is confined in its normal dimension and free in the other two. Describing the free-electron motion at metal-dielectric surfaces, surface plasmon polariton (SPP) is an elementary excitation of such motions and is well known. When further perforated with periodic array of holes, periodicity will introduce degeneracy, incur energy-level splitting, and facilitate the coupling between free-space photon and SPP. We applied this concept to achieve a plasmonic perfect absorber. The experimentally observed reflection dip splitting is qualitatively explained by a perturbation theory based on the above concept. If confined in 2D, the nanostructures become nanowires that intrigue a broad range of research interests. We performed various studies on the resonance and propagation of metal nanowires with different materials, cross-sectional shapes and form factors, in passive or active medium, in support of corresponding experimental works. Finite- Difference Time-Domain (FDTD) simulations show that simulated results agrees well with experiments and makes fundamental mode analysis possible. Confined in 3D, the electron motions in a single metal nanoparticle (NP) leads to localized surface plasmon resonance (LSPR) that enables another novel and important application: plasmon-heating. By exciting the LSPR of a gold particle embedded in liquid, the excited plasmon will decay into heat in the particle and will heat up the surrounding liquid eventually. With sufficient exciting optical intensity, the heat transfer from NP to liquid will undergo an explosive process and make a vapor envelop: nanobubble. We characterized the size, pressure and temperature of the nanobubble by a simple model relying on Mie calculations and continuous medium assumption. A novel effective medium method is also developed to replace the role of Mie calculations. The characterized temperature is in excellent agreement with that by Raman scattering. If fabricated in an ordered cluster, NPs exhibit double-resonance features and the double Fano-resonant structure is demonstrated to most enhance the four-wave mixing efficiency.

In dieser Arbeit setzen wir ab-initio-Methoden zur Untersuchung einiger Oberflächensysteme und eines Bulksystems ein. Im Wesentlichen greifen wir hierbei auf die Dichtefunktionaltheorie (DFT) und die GW-Approximation (GWA) im Rahmen der Vielteilchenstörungstheorie zurück. Wir nutzen diese Methoden um die Adsorption von TMA auf der Rutil TiO2-Oberfläche zu untersuchen, optische Spektren von TiO2 zu berechnen und um die Adsorption von [7]-HCA auf der Calcit(10-14)-Oberfläche zu verstehen. Weiterhin beschäftigen wir uns intensiv mit PTCDA auf Ag(111), welches mit einer chemisch kontaktierten STM-Spitze manipuliert wird.