Materials for studies related to nanoscience and nanotechnology have gained tremendous attention owing to their unique physical, chemical and electronic properties. Among various anisotropic nanostructures, one dimensional (1D) materials have received immense interest in numerous fields ranging from catalysis to electronics. Imparting multi-functionality to nanostructures is one of the major areas of research in materials science. In this direction, use of nanosized materials in energy systems such as fuel cells has been the subject of focus to achieve improved performance. Tuning the morphology of nanostructures, alloying of catalysts, dispersing catalytic particles onto various supports (carbon nanotubes, carbon nanofibers, graphene, etc.) are some of the ways to address issues related to electrochemical energy systems. It is worth mentioning that highly stable and corrosion resistant electrodes are mandatory as electrochemical cells operate under aggressive environments. Additionally, carbon, which is often used as a support for catalysts, is prone to corrosion and is subsequently implicated in reduced performance due to poor adherence of catalyst particles and loss in electrochemically active area. Hence, there is a quest for the development of stable and durable electrocatalysts / supports for various studies including fuel cells. The present thesis is structured in exploring the multi-functional aspects of titanium carbide (TiC), an early transition metal carbide. TiC, a fascinating material, possesses many favorable properties such as extreme hardness, high melting point, good thermal and electrical conductivity. Its metal-like conductivity and extreme corrosion resistance prompted us to use this material for various electrical and electrochemical studies. The current study explores the versatility of TiC in bulk as well as nanostructured forms, in electrical and electrochemical studies towards sensing, electrocatalytic reactions and active supports. 1D TiC nanowires (TiC-NW) are prepared by simple solvothermal method without use of any template and are characterized using various physico-chemical techniques. The TiC-NW comprise of 1D nanostructures with several µm length and 40 ± 15 nm diameter (figure 1). Electrical properties of individual TiC-NW are probed by fabricating devices using focused ion beam deposition (FIB) technique. The results depict the metallic nature of TiC-NW (figure 2). Figure 1. (a) SEM, (b) TEM and (c) HRTEM images of TiC-NW prepared by solvothermal method. Figure 2. (a) SEM image and (b) I-V characteristics of TiC-NW - based device as a function of temperature. The contact pads are made of Pt. Subsequently, oxidized TiC nanowires are prepared by thermal annealing of TiC-NW, leading to carbon - doped TiO2 nanowires (C-TiO2-NW) (figure 3). Photodetectors are fabricated with isolated C-TiO2-NW and the device is found to respond to visible light (figure 3) radiation with very good responsivity (20.5 A/W) and external quantum efficiency (2.7 X 104). The characteristics are quite comparable with several reported visible light photodetectors based on chalcogenide semiconductors. Figure 3. (a) HRTEM, (b) EDAX, (c) Scanning TEM-DF images of C-TiO2-NW along with (d) Ti (e) O and (f) C mapping. (g) Current – voltage curves of single C-TiO2-NW recorded in dark (black) and in presence of visible light radiation (red) of intensity 57.7 mW/cm2 at 25oC. Inset of (g) shows the SEM image of the device (top) and schematic illustration of fabricated photodetector (bottom). The next chapter deals with the electrochemical performance of TiC demonstrated for studies involving oxygen reduction and borohydride oxidation reactions. Electrochemical oxygen reduction reaction (ORR) reveal that TiC-NW possess high activity for ORR and involves four electron process while it is a two electron reduction for bulk TiC particles (figure 4). The data has been substantiated by density functional theory (DFT) calculations that reveal different modes of adsorption of oxygen on bulk and nanowire morphologies. Stable performance is observed for several hundreds of cycles that confirm the robustness of TiC. The study also demonstrates excellent selectivity of TiC for ORR in presence of methanol and thus cross-over issue can be effectively addressed in direct methanol fuel cells. In the chapter on borohydride oxidation, bare TiC electrode is explored as a catalyst for the oxidation of borohydride. One of the major issues in direct borohydride fuel cells (DBFC) is the hydrolysis of borohydride that happens on almost all electrode materials leading to low efficiency. The present study reveals that TiC is a very good catalyst for borohydride oxidation with little or no hydrolysis of borohydride [figure 5 (a)] under the experimental conditions studied. Further, shape dependant activity of TiC has been studied and fuel cell performance is followed [figure 5 (b)]. Polarization data suggests that the performance of TiC is quite stable under fuel cell experimental conditions. Figure 4. (a) Linear sweep voltammograms for ORR recorded using (i) bulk TiC particles and (ii) TiC-NW in O2-saturated 0.5 M KOH at 1000 rpm. Scan rate used is 0.005 Vs-1. (b) Variation of number of electrons with DC bias. Black dots correspond to TiC bulk particles while red ones represent nanowires. Figure 5. (a) Cyclic voltammograms of borohydride oxidation on TiC coated GC electrode in 1 M NaOH containing 0.1 M NaBH4. Scan rate used is 0.05 Vs-1. (b) Fuel cell polarization data at 70oC for DBFC assembled with (i) bulk TiC particles and (ii) TiC-NW as anode catalysts and 40 wt% Pt/C as cathode. Anolyte is 2.1 M NaBH4 in 2.5 M NaOH, and catholyte is 2.2 M H2O2 in 1.5 M H2SO4. Anode loading is 1.5 mg cm-2 and cathode loading is 2 mg cm-2. The corrosion resistance nature of TiC lends itself amenable to be used as an active support for catalytic particles (Pt and Pd) for small molecules oxidation reactions. In the present study, electro-oxidation of methanol, ethanol and formic acid have been studied. As shown in figure 6 (a), the performance of Pd loaded TiC (Pd-TiC) is found to be higher than that of Pd loaded carbon (Pd-C) suggesting the active role of TiC. The catalytic activities of TiC-based supports are further improved by tuning their morphologies. Figure 6 (c) reveals that the activities are higher in case of Pd-TiC-NW than that of Pd-TiC. Figure 6. (a) Cyclic voltammograms of Pd-TiC and Pd-C for ethanol oxidation, (b) T EM image of Pd-TiC-NW and (c) voltammograms of Pd-TiC-NW in N2-saturated 1 M ethanol in 1 M KOH medium, scan rate used is 0.05 Vs-1. The next aspect explored, is based on the preparation of C-TiO2 and its use as a substrate for surface enhanced Raman spectroscopy (SERS). Carbon doped titanium dioxide is prepared by thermal annealing of TiC. It is observed that the amount of dopant (carbon content) is dependent on the experimental conditions used. SERS studies using 4¬mercaptobenzoic acid (4-MBA) as the analyte, indicates that C-TiO2 [figure 7 (a)] enhances Raman signals based on chemical interactions between the analyte and the substrate. Raman signal intensities can be tuned with the amount of carbon content in C¬TiO2. Enhancement factors are calculated to be (7.7 ± 1.2) x 103 (for 4-MBA) and (1.7 ± 1.2) x 103 (for 4-nitrothiophenol). The SERS substrates are found to be surface renewable using visible light, a simple strategy to re-use the substrate [figure 7 (b)]. The regeneration of SERS substrates is based on self cleaning action of TiO2 that produces highly reactive oxygen containing radicals known to degrade the molecules adsorbed on TiO2. Thus, the versatility of TiC has been demonstrated with various studies. In addition to using TiC-based materials, nanoparticles of Rh, Ir and Rh-Ir alloy structures have also been used for borohydride oxidation reaction. This is explained in the last section. In Appendix-I, preliminary studies on the preparation of TiC-polyaniline (PANI) composites using liquid-liquid interfacial polymerization is explained. Raman spectroscopy results suggest that the presence of TiC-NW makes PANI to assume preferential orientation in the polaronic (conducting) form. Appendix-II discusses the role of TiC-NW as a fluorescence quencher for CdS semiconductor nanoparticles.

The presented diploma thesis is focused on the preparation, characterization and study of membrane properties of liposomal systems which were composed of the neutral phosphatidylcholine (DPPC), cholesterol, negatively charged phosphatidylglycerol (DPPG), polyethylenglycol bounded to phosphatidylethanolamine (PEG5000–PE) and polycation N,N,N-trimethylchitosan (TMC). The influence of individual components and their concentrations on the average particle size, zeta potential and changes in the outer and inner part of the bilayer was investigated. In this matter, methods of dynamic and electrophoretic light scattering and fluorescence spectroscopy with the application of laurdan and DPH probes were used. Based on the above-mentioned parameters, concentrations of components that most suitably influence properties of liposomes in terms of the intended application were selected for the definite complex. It was managed to prepare a liposomal complex stealth liposome–N,N,N-trimethylchitosan, which, due to the optimized composition, could have suitable attributes as a drug delivery system for inhalation administration of biologically active substances.

Par rapport au système financier conventionnel qui a vécu ces dernières années des épisodes de forte instabilité liés en partie à une mauvaise gouvernance, le système financier islamique a montré des signes de robustesse et de pérennité. Sa capacité à surmonter les événements défavorables a incité plusieurs parties prenantes à proposer la finance islamique comme solutionaux déficits financiers et substitut potentiel au système bancaire actuel. Les partisans de cette finance ont fait valoir que la récente crise financière aurait pu être évitée si la finance islamique avec une bonne gouvernance et un cadre réglementaire solide avait été introduite au lieu de la finance conventionnelle. Pour ces raisons, l’objectif de cette thèse est d’une part d’examiner si la finance islamique pourrait garantir la stabilité en période de crise et être une alternative au système financier traditionnel, et d’autre part d’évaluer l’effet des mécanismes internes et externes de gouvernance bancaire sur le risque des banques islamiques par rapport à leurs homologues conventionnelles. Pour y arriver, nous avons élaboré trois chapitres avec desévidences empiriques en utilisant un échantillon de 95 banques islamiques et 130 banques conventionnelles (38 banques dont 14 banques islamiques sont exclues dans le dernier chapitre) dans 18 pays des régions MENAP et Asie du Sud-Est, durant la période 2006-2013. Le premier chapitre porte sur les spécificités et le risque de la banque dans un système financier islamiquepar rapport au système conventionnel. Les résultats trouvés indiquent que la taille et le capital de la banque ainsi que la croissance du PIB sont des facteurs clés de la solidité des deux systèmes bancaires de tous les pays étudiés, notamment des pays du Golfe. Cependant, d’autres résultats ne sont pas assez robustes pour savoir si les banques islamiques sont plus ou moins risquées que les banques conventionnelles. Par conséquent, nous concluons que le système bancaire islamique ne peut pas se substituer au système traditionnel, mais il est plutôt un complément financier qui a ses propres limites. Le deuxième chapitre examine l’effet des mécanismes internes de gouvernance bancaire, à savoir le conseil d’administration et le conseilde surveillance de la charia comme un organe de contrôle spécifique, sur le risque des banques conventionnelles par rapport aux banques islamiques. Les résultats ne montrent pas de différence significative entre les deux groupes bancaires,sauf pour les banques islamiques des pays du Golfe qui font preuve d’une plus grande solidité financière, grâce notamment auxcompétences de spécialistes en finance et en droit islamique, et au recrutement des administrateurs étrangers. En outre, nous trouvons que, dans les pays du Golfe en particulier, l'effet indésirable d'une taille importante du conseil d'administration et celui de la dualité des fonctions sur les risques des banques conventionnelles, disparaissent avec la présence d'un nombre élevé d’administrateurs indépendants. En traitant la question de la dimension externe de gouvernance bancaire dans le dernier chapitre, l’accent est mis sur l’effet probable des récentes réformes bancaires relatives aux banques conventionnelles et aux banques islamiques, à la lumière de Bâle III et du CSFI-12/15, sur le risque de ces banques. Les résultats trouvés montrent que si les exigences réglementaires de ces deux normes internationales de solvabilité avaient été appliquées durant notre période d'étude, elles auraient probablement amélioré la stabilité des deux systèmes bancaires des pays étudiés. Cependant, cet effet n’est pas uniforme pour toutes les banques, en particulier pour les banques conventionnelles des pays d’Asie du Sud-Est qui semblent moins stables et plus exposées au risque de crédit que le reste des banques.L’ensemble de ces résultats apporte une nouvelle dimension de la recherche en gouvernance dans une perspective islamique ... / Compared to the conventional financial system, which has experienced periods of high volatility in recent years partly due to poor governance, the Islamic financial system has shown signs of robustness and sustainability. Its ability to overcome the unfavorable events has encouraged several stakeholders to propose Islamic finance as a solution to financial deficits and as a potential alternative to the current banking system. The supporters of this finance argued that the recent financial crisis could have been avoided if Islamic finance with good governance and a solid regulatory framework had been introduced instead of conventional finance. For these reasons, the purpose of this thesis is twofold. First, we examine whether Islamic finance could guarantee stability in times of crisis and be a substitute for the traditional financial system. Second, we assess the effect of internal and external mechanisms of banking governance on the risk of Islamic banks compared to their conventional counterparts. To this end, we have developed three chapters with empirical evidence using a sample of 95 Islamic banks and 130 conventional banks (38 banks including 14 Islamic banks are excluded at the last chapter) in 18 MENAP and Southeast Asian countries, during the period 2006-2013. The first chapter analyzes the specificities and the risk of the bank in an Islamic financial system compared to conventional system. The results indicate that the size and capital of the bank as well as the GDP growth are crucial factors for the soundness of the two banking systems of all surveyed countries, especially of the Gulf region. However, other results are not strong enough to answer whether Islamic banks are more or less risky than their conventional counterparts. We therefore conclude that the Islamic banking system cannot replace the traditional system, but is, rather, a financial supplement that has its own limitations. The second chapter examines the effect of internal mechanisms of banking governance, such as the board of directors and the sharia supervisory board as a control organ specific to Islamic banks, on the risk of conventional banks compared to their Islamic counterparts. The findings show no significant difference between the two banking systems, except for the Islamic banks of Gulf countries, which demonstrate greater financial solidity thanks particularly to the skills of the specialists in finance and Islamic law, and the recruitment of foreign directors. In addition, we find especiallyin Gulf countries that the harmful effect of a large board size and dual functions on the risks of conventional banks disappear with the presence of a significant number of independent directors. In investigating the issue of the external dimension of banking governance, the focus is on the probable effect of recent banking reforms relating to conventional and Islamic banks, in light of Basel III and IFSB-12/15, on the risk of the two banking systems. Our findings support that if the regulatory requirements of these two international solvency standards had been applied during our sampling period, they would probably have improved the stability of the two banking systems of the surveyed countries. However, this effect is not uniform for all banks. In particular, conventional banks of Southeast Asian countries seem less stable and more exposed to credit risk than the other ones. All of these results bring a new dimension of governance research from an Islamic perspective, which could be a valuable source ofknowledge for both bankers and regulators in the banking sector.

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