In this thesis current questions regarding the functionality of liberalized electricity markets are studied addressing different topics of interest in two main directions: market power and competition policy on electricity wholesale markets, and network investments and incentive regulation. The former is studied based on the case of the German electricity market with respect to ex-post market power analysis and ex-ante remedy development. First an optimization model is designed to obtain the competitive benchmark which can be compared to the observed market outcomes between 2004 and 2006. In a second step the horizontal breaking up of dominant firms (divestiture) is simulated applying equilibrium techniques (the classical Cournot approach and the Supply Function Equilibrium approach). The later issue of transmission capacity investment is addressed by highlighting the complexity of network investments in electricity markets and by analyzing a regulatory mechanism with a two part tariff approach. The technical characteristics of power flows are combined with economic criteria and tested for different network settings.

ABSTRACT PLASMA SURFACE MODIFICATION AND CHARACTERIZATION OF PMMA FILMS &Ouml / zgen, &Ouml / zge M.Sc., Department of Polymer Science and Technology Supervisor: Prof. Dr. Nesrin Hasirci Co-supervisor: Prof. Dr. Vasif Hasirci December 2011, 114 pages Surface properties play an essential role for determining the behavior of a material for many applications such as coating, printing, adhesion and prosthesis implanting since the surface is the first part that comes in contact with the environment. Although the bulk properties of some materials are at the desired level, the surface may need to be modified for a better compatibility with its surrounding. Plasma treatment is one generally preferred technique because of its high potential to create various functional groups on the surface of the sample by changing the applied plasma parameters. Some molecules can be successfully immobilized onto these surfaces using these specific chemical functional groups created by plasma. The type of the functional group is important for intended purpose of covalent binding of different molecules on the surface of a material. Present study offers important routes for optimization of the surface functionality of (PMMA) films by changing the plasma parameters. For this purpose, solvent casted polymethylmetacrylate PMMA films were modified by, nitrogen, argon and oxygen plasma by using a radiofrequency (RF) generator / and with various powers (10W, 50W, 100W) for different periods (5min, 15min and 30min). The effects of these plasma parameters (gas type, applied power, plasma time) on hydrophilicity, surface free energy, surface chemistry, and surface topography were investigated. Also, the types of surface free radicals created with oxygen plasma treatment were analysed and the decay of these radicals were examined by Electron Spin Resonance Spectroscopy (ESR). In general, plasma treatment reduced the contact angle of PMMA films where the most hydrophilic surface was obtained for 100W 30 min argon plasma treated sample showing superhydrophilic character with the water contact angle value of ~10&deg / . Surface free energy measurements were carried out according to Geometric Mean, Harmonic Mean, Acid-Base approach and it was found that oxygen, nitrogen and argon plasma treatments increased the surface free energy for all samples by increasing the polar components and introducing functional groups on the surface. X-Ray Photoelectron Spectroscopy (XPS) analysis results revealed that free carbonyl and carbonate groups were formed by oxygen plasma treatment, whereas carboxylic acid and free carbonyl groups were formed after argon plasma treatment, and imine, primary amine, amide and nitrozo groups were formed by nitrogen plasma. Atomic Force Microscopy (AFM) analysis revealed that the roughness of the surface increased considerably from ~2 nm to ~75 nm for the 100W 30 min oxygen plasma treated samples. ESR analysis indicated the presence of peroxy radicals on the surface of the oxygen plasma treated PMMA and the intensity of these radicals increased with increasing plasma power. Decay study of the newly created radicals demonstrated that after 1 month under the atmospheric conditions there were still peroxy radicals on the surface of PMMA. This functionality is important in leading time for further process for binding of different molecules to the surface of the materials for specific purposes. As a result, RF plasma was found to be an effective tool for modification of surface properties of materials with product diversity for intended purposes.

A successful supercritical fluid extraction method includes removal of the analyte from the matrix into the bulk fluid as well as trapping or concentration of the analyte prior to analysis. In the first phase of this research, the trapping capacities of three solid-phase traps (glass beads, 50/50 (w/w) glass beads/octadecylsilica), 50/50 (w/w) Porapak Q®/glass beads) were determined as a function of trap composition for a mixture of components varying in polarity and volatility. The Porapak Q®/glass beads mixture was found to be the most successful solidphase investigated exhibiting the highest trapping capacity. The use of the Porapak Q®/glass beads as a solid-phase trap was investigated in later extraction studies in this dissertation. The extraction of highly polar, multifunctional analytes may not be completely successful with modified carbon dioxide, therefore, a secondary modifier (i.e. additive) may be added directly to the extraction fluid in hopes of improving the recoveries. In the second phase of this research, the effect of secondary modifiers in the subcritical fluid extraction of lovastatin from in-house prepared tablet powder mixtures and MEVACOR® tablets was investigated. The effect of in-line methanol-modifier percentage, additive type (acidic, basic, neutral) to the in-line methanol, and additive concentration on the extraction efficiency were examined. The extraction recoveries of lovastatin from MEVACOR® tablets were shown to be highly dependent on methanol concentration and additive type. Isopropylamine was shown to be the most successful additive investigated. An optimized and reproducible extraction method was developed. The extraction of ionic compounds with carbon dioxide may be difficult due to the high polarity of the compounds. In the third phase of this research, the addition of ion-pairing additives to the matrix in hopes of forming an ion-pair complex of reduced analyte polarity was investigated. Therefore, a screening study consisting of a fractional-factorial design was performed in order to identify the factors which contribute most to the recovery of an anionic species, triphenylphosphinetrisulfonate (TPPTS), from a spiked-sand surface employing supercritical fluid extraction with carbon dioxide. The experimental parameters investigated were: type of ion-pairing additive (i.e. tetralkylammonium hydrogen sulfates) and its concentration, carbon dioxide density, extraction temperature, static extraction time, CO₂ mass used, liquid CO₂ flow rate, and the volume of methanol spiked into the matrix prior to extraction. Of the eight factors investigated, four factors were identified as significantly affecting the recovery of the anionic species. They were: 1) ion-pairing reagent added to the spiked sand surface and its concentration; 2) static extraction time; and 3) volume of methanol present in the extraction vessel. The experimental parameters and settings identified as influential by the statistical approach were later shown in concert to yield 100% recovery of TPPTS from the spiked-sand. In the fourth phase, the extraction of a cationic species, pseudoephedrine hydrochloride, from spiked-sand and Suphedrine tablets, with pure and methanol-modified CO₂ was examined. Once the extraction was shown to feasible, several strategies were compared in terms of their effectiveness in enhancing the analyte's extractability. The first strategy involved the addition of ion-pairing additives. Several sodium salts of alkylsulfonic acids varying in lipophilicity and concentration were investigated. The addition of 1-heptanesulfonic acid, sodium salt, in methanol, in a 5:1 mole ratio of reagent to analyte was shown to be the most useful in recovering the drug from the spiked-sand. The second strategy considered the influence of acids and bases and other modifier compositions such as a methanol/water mixture with or without 1-heptanesulfonic acid, sodium salt, on the pseudoephedrine recovery. The recoveries obtained from the drug spiked-sand were shown to comparable in the presence of a methanol/water solution, a tetrabutylammonium hydroxide in methanol solution, and a methanol solution with 1-heptanesulfonic acid, sodium salt. Next the extraction of pseudoephedrine hydrochloride from Suphedrine tablets was performed with pure and modified CO₂. Similar to the sand-spike studies, the effect of the addition of the ion-pairing reagent and other in-cell modifiers were examined. Once again, the recoveries obtained when the matrix was in the presence of a methanol/water mixture and a methanol solution containing 1-heptanesulfonic acid, sodium salt were similar. Finally, the identity of the extracted analyte was determined via IR analyses, and it was shown that pseudoephedrine hydrochloride was indeed extractable from the tablets with in-line modified CO₂ in the absence of any in-cell modifier. In the last phase of this research, a supercritical fluid chromatographic separation with evaporative light scattering detection was developed for the separation of five phospholipids varying in polarity and ionic characteristics. Several parameters were investigated and shown to be influential in the separation. They were: 1) stationary phase composition, 2) addition of an acidic additive and its concentration, 3) mobile phase ramp rate, and 4) column outlet pressure. / Ph. D.

Plastics are widely used and they vary in their applicability, ranging from automobile parts, components for houses and buildings, and packaging for everything from food to electronic parts. The diverse applications of plastics, such as polystyrene, polyolefins and polyester, are credited to the incorporation of additives. Additives improve the performance of these and other polymer resins. Without the incorporation of such additives, for example Ethanox ® 330, some plastics would degrade during processing or over time. To ensure that the specified amount of an additive or combination of additives are incorporated into a polymer after the extrusion process, a rapid and accurate analytical method is required. Quantitation of additive(s) in the polymer is necessary, since the additive(s) may degrade and the amount of additive(s) can influence the physical nature of the polymer. Conventional extraction techniques for polymer additive(s), such as, Soxhlet or dissolution / precipitation are labor intensive, time consuming, expensive, and the optimal recovery is significantly less than 90 percent. In addition, a large amount of solvent , such as toluene or decalin, must be eliminated in order to concentrate the sample prior to chromatographic separation. Supercritical Fluid Extraction (SFE) has been employed as an alternative polymer preparation technique. SFE is a favorable means for various analytical sample preparation applications, credited to its short extraction times. This research employs SFE for the extraction of the antioxidant Ethanox® 330 from high density polyethylene (HDPE) followed by HPLC/UV analysis. The effects of temperature, modifier type, and modifier concentration were investigated. Once the optimal extraction conditions were determined, the extraction efficiency of Ethanox ® 330 as a single additive and in the presence of co-additives from HDPE were investigated. Recoveries of greater than 90% were obtained for Ethanox ® 330 when a secondary antioxidant was present in the HDPE. / Master of Science

Cette thèse porte sur les processus de sélection, formation et encadrement (SFE) des gestionnaires, appelés pilotes et considérés comme agents de changement dans les télécentres communautaires au Mali. Ces processus sont étudiés sous l'angle de leur contribution positive ou négative à l'implantation et au développement de ces centres. Les projets "technologies de l’information et de la communication", initiés par les partenaires techniques et financiers, répondent au besoin des autorités maliennes préoccupées par un souci de connecter les 703 communes du pays. À la suite du sommet mondial sur la société de l’information en décembre 2003 à Genève, l’UNESCO et la Coopération suisse ont décidé d’installer des centres multimédias communautaires dans trois pays d’Afrique (Mali, Mozambique, Sénégal). Ces implantations de télécentres ont été réalisées sur le modèle de ce qui avait été fait en Asie sans tenir compte des besoins réels des bénéficiaires et des conditions particulières (économiques, politiques, culturelles) des sites d’implantation. Malgré les conditions parfois difficiles de l’Afrique, les populations témoignent un enthousiasme réel pour les technologies de communication. Les TIC ont connu une croissance considérable et se sont multipliées partout en Afrique, à des degrés divers. Néanmoins, elles n’ont pas encore atteint la majorité des populations africaines, car 70% de celles-ci vivent en zones rurales souvent marginalisées par les difficultés économiques. Après l’implantation des télécentres, les sites ont donc été confrontés à la difficile tâche de sélectionner les pilotes comme agents de changement. Les responsables chargés de la mise en œuvre des projets ont choisi les pilotes dans leur réseau familial. En ce sens, la thèse met l’accent sur l’importance du rôle d’un pilote dans un télécentre et l’appui qu’il peut générer dans la population bénéficiaire. Nous proposons un modèle qui part de l’action des agents de changement, et ce, afin de potentiellement susciter une prise de conscience chez les décideurs locaux. Nous avons fait une étude de cas sur quatre sites pour mieux connaître les processus de sélection, formation et encadrement des pilotes et nous avons tenté d'identifier les facteurs qui, dans ces processus, ont pu influencer le niveau de réussite de chacun de ces centres. / This dissertation examines the processes of selecting, training, and mentoring managers, also known as "pilots," and considered as change agents in the development of community telecentres in Mali. These processes are analyzed according to their positive and negative outcomes regarding the establishment and development of telecentres. The Information and Communication Technologies (ICT) project, launched by technical and financial partners, responds to the needs of Malian authorities in their efforts to connect the country’s 703 communes. Following the World Summit on the Information Society, held in Geneva on December 2003, UNESCO and the Swiss Agency for Development and Cooperation (SDC) decided to establish multimedia community telecentres in three African countries (Mali, Mozambique, and Senegal). The setting-up of these telecentres was modeled after a similar project conducted previously in Asia, without however taking into account the primary needs of the beneficiaries, nor their specific conditions (both economic, political, and cultural). Despite the difficult conditions that sometimes characterize the African context, African populations express a genuine interest for Information and Communication Technologies. The ICT sector has witnessed a considerable and widespread growth throughout many African countries, although with various degrees of success. However, a majority of the African population has still not been connected, since 70% of the population lives in more economically marginalized rural areas. Once the telecentres were established in various locations, most of them were confronted with the difficult challenge of selecting "pilots," to serve as change agents. Those in charge of selecting the pilots favored people located within their own family networks. Therefore, the dissertation emphasizes the pilot’s decisive role in the telecentres, and the support that he is able to generate within the beneficiary population. We put forward a model starting from the actions of the change agents, hoping to stimulate awareness amongst local deciders. We conducted a case study on four different sites in order to better understand the processes of selecting, training, and mentoring pilots, with a focus on the key factors influencing, for each of those processes, the level of success in all the telecentres.

Gegenstand vorliegender Arbeit ist die Untersuchung unterschiedlicher Modellansätze zur Beschreibung der Extraktion organischer Schadstoffe aus Böden unter Verwendung von überkritischem Wasser. Dazu wurden in der Literatur vorhandene Stofftransportmodelle herangezogen und eigene Modellansätze entwickelt. Das Modell berücksichtigt die Geschwindigkeits- und Temperaturverteilung im Reaktor und berechnet daraus, in Abhängigkeit der desorptiven, diffusiven und konvektiven Stofftransportvorgänge eine Schadstoffverteilung. Zur Lösung der Modellgleichungen wurde FEMLAB 3.1 verwendet. Zur Parameterbestimmung und Modellüberprüfung wurden Extraktionsversuche an real kontaminierten Böden und an künstlich kontaminierten Modellböden durchgeführt. Einfache und komplexe chemische Gleichgewichte der organischen Schadstoffe wurden auf Basis der Gibbs Energetik mit FACTSAGE 5.2 ermittelt und dienten als weitere Inputparameter für die Modellberechnungen.

Cette thèse porte sur les processus de sélection, formation et encadrement (SFE) des gestionnaires, appelés pilotes et considérés comme agents de changement dans les télécentres communautaires au Mali. Ces processus sont étudiés sous l'angle de leur contribution positive ou négative à l'implantation et au développement de ces centres. Les projets "technologies de l’information et de la communication", initiés par les partenaires techniques et financiers, répondent au besoin des autorités maliennes préoccupées par un souci de connecter les 703 communes du pays. À la suite du sommet mondial sur la société de l’information en décembre 2003 à Genève, l’UNESCO et la Coopération suisse ont décidé d’installer des centres multimédias communautaires dans trois pays d’Afrique (Mali, Mozambique, Sénégal). Ces implantations de télécentres ont été réalisées sur le modèle de ce qui avait été fait en Asie sans tenir compte des besoins réels des bénéficiaires et des conditions particulières (économiques, politiques, culturelles) des sites d’implantation. Malgré les conditions parfois difficiles de l’Afrique, les populations témoignent un enthousiasme réel pour les technologies de communication. Les TIC ont connu une croissance considérable et se sont multipliées partout en Afrique, à des degrés divers. Néanmoins, elles n’ont pas encore atteint la majorité des populations africaines, car 70% de celles-ci vivent en zones rurales souvent marginalisées par les difficultés économiques. Après l’implantation des télécentres, les sites ont donc été confrontés à la difficile tâche de sélectionner les pilotes comme agents de changement. Les responsables chargés de la mise en œuvre des projets ont choisi les pilotes dans leur réseau familial. En ce sens, la thèse met l’accent sur l’importance du rôle d’un pilote dans un télécentre et l’appui qu’il peut générer dans la population bénéficiaire. Nous proposons un modèle qui part de l’action des agents de changement, et ce, afin de potentiellement susciter une prise de conscience chez les décideurs locaux. Nous avons fait une étude de cas sur quatre sites pour mieux connaître les processus de sélection, formation et encadrement des pilotes et nous avons tenté d'identifier les facteurs qui, dans ces processus, ont pu influencer le niveau de réussite de chacun de ces centres. / This dissertation examines the processes of selecting, training, and mentoring managers, also known as "pilots," and considered as change agents in the development of community telecentres in Mali. These processes are analyzed according to their positive and negative outcomes regarding the establishment and development of telecentres. The Information and Communication Technologies (ICT) project, launched by technical and financial partners, responds to the needs of Malian authorities in their efforts to connect the country’s 703 communes. Following the World Summit on the Information Society, held in Geneva on December 2003, UNESCO and the Swiss Agency for Development and Cooperation (SDC) decided to establish multimedia community telecentres in three African countries (Mali, Mozambique, and Senegal). The setting-up of these telecentres was modeled after a similar project conducted previously in Asia, without however taking into account the primary needs of the beneficiaries, nor their specific conditions (both economic, political, and cultural). Despite the difficult conditions that sometimes characterize the African context, African populations express a genuine interest for Information and Communication Technologies. The ICT sector has witnessed a considerable and widespread growth throughout many African countries, although with various degrees of success. However, a majority of the African population has still not been connected, since 70% of the population lives in more economically marginalized rural areas. Once the telecentres were established in various locations, most of them were confronted with the difficult challenge of selecting "pilots," to serve as change agents. Those in charge of selecting the pilots favored people located within their own family networks. Therefore, the dissertation emphasizes the pilot’s decisive role in the telecentres, and the support that he is able to generate within the beneficiary population. We put forward a model starting from the actions of the change agents, hoping to stimulate awareness amongst local deciders. We conducted a case study on four different sites in order to better understand the processes of selecting, training, and mentoring pilots, with a focus on the key factors influencing, for each of those processes, the level of success in all the telecentres.

Gegenstand vorliegender Arbeit ist die Untersuchung unterschiedlicher Modellansätze zur Beschreibung der Extraktion organischer Schadstoffe aus Böden unter Verwendung von überkritischem Wasser. Dazu wurden in der Literatur vorhandene Stofftransportmodelle herangezogen und eigene Modellansätze entwickelt. Das Modell berücksichtigt die Geschwindigkeits- und Temperaturverteilung im Reaktor und berechnet daraus, in Abhängigkeit der desorptiven, diffusiven und konvektiven Stofftransportvorgänge eine Schadstoffverteilung. Zur Lösung der Modellgleichungen wurde FEMLAB 3.1 verwendet. Zur Parameterbestimmung und Modellüberprüfung wurden Extraktionsversuche an real kontaminierten Böden und an künstlich kontaminierten Modellböden durchgeführt. Einfache und komplexe chemische Gleichgewichte der organischen Schadstoffe wurden auf Basis der Gibbs Energetik mit FACTSAGE 5.2 ermittelt und dienten als weitere Inputparameter für die Modellberechnungen.

The objective of this research was to develop new sample preparation procedures for the isolation of sulfonamides, as well as, to determine the applicability of employing on-line nitrogen selective and mass spectrometric detection methods. The first phase of this research investigated the effect of temperature and pressure on the supercritical fluid extraction (SFE) of sulfonamides from a spiked sand matrix. Temperature effects were either positive or negative with respect to extraction rate and total recovery, depending on the pressure and extraction fluid employed. The second portion of this research compared trifluoromethane (CHF3) and carbon dioxide (CO2) as fluids for the extraction of sulfonamides from spiked non-fat dry milk, beef liver, and egg yolk were found to be more selective using CHF3 than CO2. The polar trifluoromethane improved the extraction efficiency of the polar sulfonamides from the biological matrices and also reduced the amount of co-extractives. The next phase of this research considered the effect of organic modifier and CO2 in the SFE of sulfonamides from chicken liver, beef liver and egg yolk. Methanol, ethanol, acetone, acetonitrile were compared to determine optimum conditions. A SFE method employing 20% acetonitrile modified CO2 yielded quantitative recovery of sulfonamides from chicken liver, but 20% acetone modified CO2 was required to obtain quantitative recovery from beef liver. Either 20% acetone or 20% acetonitrile yielded quantitative recovery from egg yolk. The last phase of this research focused on the evaluation of selective detection methods for sulfonamide analysis. Chemiluminescence nitrogen detection (CLND) parameters were optimized for use with packed column supercritical fluid chromatography (SFC) yielding a minimum detectable quantity (MDQ) of 5 ng of sulfamethazine, on column. Improvements in the detector design decreased the MDQ to 0.5 ng, while, decreasing the column diameter further reduced the MDQ to 125 pg. The second part of this phase evaluated PLC/Atmospheric pressure chemical ionization (APCI) mass spectrometry for the detection of sulfonamides. Sensitivity in selective ion mode was found to be as low as 50 pg on column for sulfamethazine. Supercritical fluid extracts of sulfonamides spiked at 100μg/kg in chicken liver were found to be readily detected by this method. / Ph. D.

Aim:                Parkour is a relatively new action sport, which is not only popular in non-conflict regions but also in regions where armed conflict is taking place. When being featured in the media, youth from conflict regions frequently report that Parkour has helped them to deal with the consequences of armed conflict. Although Parkour is being used in psychosocial and life skills interventions in European countries, and despite the fact that action sports are used in humanitarian assistance, there is no research on the potential of Parkour as a tool in humanitarian interventions. The aim of this thesis is to analyse how Parkour can be used in humanitarian aid interventions, particularly focusing on its potential for life skills interventions. In order to do so, a mapping of Parkour teams in conflict regions is conducted. What is more, example cases highlight the importance Parkour has for youth in conflict regions. Lastly, a qualitative thematic analysis, will review the cases and academic literature, in order to discuss to what extent these characteristics coincide with the ten life skills as they were outlined by the World Health Organization (WHO). Methods:       Mapping is limited to the timeframe 2013 – 2018 and to countries which display a high amount of organized violence within said timeframe. Furthermore, qualitative thematic analysis in combination with a review of relevant literature is used, in order to understand what Parkour’s potential for life skills interventions could be. Findings:         The mapping indicates that Parkour teams and individuals are active in 16 out of the 22 countries which comply with the mapping criteria. The cases further exemplify that for many practitioners in the conflict regions, Parkour is used as a tool to deal with the consequences of armed conflict.  The qualitative thematic analysis shows that Parkour’s characteristics seem to coincide with the 10 life skills laid out by the WHO. Conclusion:    Action sports are already being used in aid interventions. Parkour’s assets in particular are multiple. It is an accessible, cost-effective and popular sport that youth globally and in conflict regions is attracted to. That, in combination with its characteristics and social media based nature, could be compelling arguments to use Parkour in humanitarian assistance.