Made available in DSpace on 2014-12-17T14:07:09Z (GMT). No. of bitstreams: 1 AmandaLM_DISSERT.pdf: 3676559 bytes, checksum: 256cb3ce22bbf3b5f114a2ff3021de96 (MD5) Previous issue date: 2013-02-06 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Fuel cells are electrochemical devices that convert chemical energy into electricity. Due to the development of new materials, fuel cells are emerging as generating clean energy generator. Among the types of fuel cells, categorized according to the electrode type, the solid oxide fuel cells (SOFC) stand out due to be the only device entirely made of solid particles. Beyond that, their operation temperature is relatively high (between 500 and 1000 ?C), allowing them to operate with high efficiency. Another aspect that promotes the use of SOFC over other cells is their ability to operate with different fuels. The CeO2 based materials doped with rare earth (TR+3) may be used as alternatives to traditional NiO-YSZ anodes as they have higher ionic conductivity and smaller ohmic losses compared to YSZ, and can operate at lower temperatures (500-800?C). In the composition of the anode, the concentration of NiO, acting as a catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, providing internal reform in the cell. In this work compounds of NiO - Ce1-xEuxO2-δ (x = 0.1, 0.2 and 0.3) were synthesized from polymeric precursor, Pechini, method of combustion and also by microwave-assisted hydrothermal method. The materials were characterized by the techniques of TG, TPR, XRD and FEG-SEM. The refinement of data obtained by X-ray diffraction showed that all powders of NiO - Cex-1EuxO2-δ crystallized in a cubic phase with fluorite structure, and also the presence of Ni. Through the characterizations can be proved that all routes of preparation used were effective for producing ceramics with characteristics suitable for application as SOFC anodes, but the microwave-assisted hydrothermal method showed a significant reduction in the average grain size and improved control of the compositions of the phases / C?lulas a combust?vel s?o dispositivos eletroqu?micos que convertem a energia qu?mica em el?trica. Em virtude do desenvolvimento de novos materiais, as c?lulas a combust?vel v?m se destacando como promissores na gera??o de energia de forma limpa. Dentre os tipos de c?lulas a combust?vel, classificadas de acordo com o tipo de eletr?lito, destacam-se as de ?xido s?lido (SOFC), por serem as ?nicas inteiramente constitu?das por s?lidos. Al?m disso, pela sua temperatura de opera??o ser relativamente elevada (entre 500 e 1000 ?C), estas c?lulas operam com alta efici?ncia. Outro aspecto que favorece o emprego de SOFC ? a sua habilidade de operar com diferentes combust?veis, como fontes de hidrog?nio.Os materiais a base de CeO2 dopados com terras raras (TR+3) podem ser utilizados como alternativas aos tradicionais anodos de NiO-YSZ. Al?m de maior condutividade i?nica maior e menores perdas ?hmicas, elas podem operar a temperaturas mais baixas (500- 800?C). Na composi??o do anodo, a concentra??o de NiO, atuando como catalisador confere alta condutividade el?trica e alta atividade eletroqu?mica das rea??es, proporcionando a reforma interna do combust?vel na c?lula. Neste trabalho compostos de NiO - Ce1-xEuxO2-δ (x = 0,1; 0,2 e 0,3), foram sintetizados a partir do m?todo dos precursores polim?ricos, Pechini, do m?todo de combust?o e, tamb?m, pelo m?todo hidrotermal assistido por micro-ondas. Os materiais obtidos foram caracterizados atrav?s das t?cnicas de TG, DRX, TPR e MEV-FEG. O refinamento dos dados obtidos pela difra??o de raios X indicou que todos os p?s de NiO - Ce1- xEuxO2-δ cristalizaram-se em uma fase c?bica com estrutura fluorita, e tamb?m a presen?a de NiO. Todas as rotas de prepara??o utilizadas mostraram-se eficientes para a produ??o de p?s com caracter?sticas adequadas para aplica??o como anodos de SOFC, por?m o m?todo hidrotermal assistido por micro-ondas apresentou significativa redu??o do tamanho m?dio de gr?os e melhor controle das composi??es das fases

Regulations with respect to the storage and handling of animal waste by livestock operations state that no person shall keep animals in a permanent confinement area unless there is a nutrient management strategy. Various studies indicate that constructed wetlands and vegetative filters are effective add-on technologies to supplement the treatment provided by conventional sedimentation pond systems in livestock operations. Seven months of data from a Pond/Wetland/Vegetative Filter system receiving cattle feedlot runoff were used to i) evaluate its efficiency removing organic matter, solids and nutrients from water, (ii) quantify constructed wetland kinetic removal rates described by the P-C-k model and examine the impact of temperature, (iii) evaluate and compare the performance of a two types of vegetative filter systems at different hydraulic loading rates; and (iv) recommend an optimum management option with design loading for beef producers. Results indicate that the effect of isolated rain events on the performance of the wetland showed to be contingent on the intensity of the event, former humidity conditions of the feedlot and the hydraulic capacity of the wetland. This experiment suggests that even relatively small VFSs or short FPs can markedly improve quality of runoff from livestock operations, and that it is possible to achieve significant mass and concentration removals if they are properly operated and maintained in conjunction with a pre-treatment system. The Pond/Wetland/Vegetative Filter system was effective at reducing Chemical Oxygen Demand COD (+92%), Total Phosphorus (+93%), Orthophosphate as P (+91%), Total Inorganic Nitrogen (+96%), Ammonia as N (+97%) and Nitrate as N (+82%) from manure and exercise yard runoff, providing a cost-effective treatment option for beef producers.

Substitution of MeCN ligands in the activated cluster Os3(CO)10(MeCN)2 by the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2 (cDPPEn) or 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) proceeds rapidly at room temperature to furnish the ligand-bridged cluster 1,2-Os3(CO)10(P-P) (P-P represents cDPPEn or bpcd). Heating 1,2-Os3(CO)10(P-P) leads to the formation of the thermodynamically more stable chelating isomer 1,1-Os3(CO)10(P-P). Each compound of Os3(CO)10(P-P) has been characterized by x-ray diffraction, IR, 31P NMR and 1H NMR. Ligand isomerization kinetics have been investigated by UV-VIS and 31P NMR (for cDPPEn) or 1H NMR (for bpcd) spectroscopies. The isomerization mechanism is discussed based on the activation parameters and CO inhibition (for cDPPEn) or ligand trapping experiments (for bpcd). Thermolysis of 1,1-Os3(CO)10(bpcd) in refluxing toluene gives the hydrido cluster HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] and the benzyne cluster HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhC=C(PPh2)C(O)CH2C(O)]. Photolysis of 1,1-Os3(CO)10(bpcd) using near UV light affords HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] as the sole product. HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhC=C(PPh2)C(O)CH2C(O)] has been characterized in solution by IR and NMR spectroscopies. Furthermore its molecular structure has been determined by X-ray crystallography. Reversible C-H bond formation in HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] is demonstrated by ligand trapping studies to give 1,1-Os3(CO)9L(bpcd) (where L = CO, phosphine) via the unsaturated intermediate 1,1-Os3(CO)9(bpcd). The kinetics for reductive coupling in HOs3(CO)9[γ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] and DOs3(CO)9[μ-(PPh2-d10)C=C{P(Ph-d5)(C6D4)}C(O)CH2C(O)] in the presence of PPh3 give rise to a kH/kD value of 0.88, whose magnitude supports the existence of a preequilibrium involving the hydride(deuteride) cluster and a transient arene-bound Os3 species that precedes the rate-limiting formation of 1,1-Os3(CO)9(bpcd). Strong proof for the proposed hydride(deuteride)/arene preequilibrium has been obtained from photochemical studies employing the isotopically labeled cluster 1,1-Os3(CO)10(bpcd-d4ortho), whose bpcd phenyl groups each contain one ortho hydrogen and deuterium atom. Equilibrium and kinetic isotope effects in the orthometallation step has been determined by 1H NMR in photochemical studies. Kinetics for the transformation from HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] to HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhC=C(PPh2)C(O)CH2C(O)] has been studied by UV-VIS spectroscopy for which the mechanism is discussed.

Die vorliegende Dissertation beschreibt die Synthese und Charakterisierung von neuartigen perferrocenylierten, cyclischen Komplexen unter Anwendung der Cobalt-vermittelten Cyclomerisierung in Kombination mit einer C-H-Bindungsaktivierung als auch die Bildung von ferrocenylierten Phosphinoalkinid-Komplexen mit Eisen- und Cobaltcarbonylen. Die elektrochemischen Eigenschaften und die Elektronentransfer-prozesse zwischen den terminalen Ferrocenyleinheiten in den unterschiedlichen cyclischen Verbindungen wurden unter Einbeziehung der Struktur/chemischen Zusammensetzung der Brückenbausteine ermittelt. Elf perferrocenylierte, cyclische Komplexe wurden mittels [2+2] bzw. [2+2+2] Cyclomerisierung von 1,4-Diferrocenylbutadiin FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) unter Verwendung von Dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2 erhalten. Diese können in drei Gruppen unterteilt werden: (i) Produkte der Cyclodimerisierung mit zusätzlicher Kettenverlängerung, welche Cyclobutadienyl-einheiten als zentrale Brückenbausteine besitzen (3a,b und 4a,b), (ii) Produkte der Cyclodimerisierung mit gleichzeitiger CO-Insertion (6a,b,c und 7), und (iii) Produkte der Cyclotrimerisierung gefolgt von einem Ringschluss durch eine C-H-Bindungsaktivierung (5a,b,c). Die Optimierung der Reaktionsbedingungen wurde zur Ausbeutemaximierung der jeweiligen Verbindungsfamilien durchgeführt. Ein weiterer Teil dieser Forschungsarbeit bezieht sich auf die verschiedenen Reaktionsmuster von (Ferrocenylethinyl)diphenylphosphan- mit zweikernigen Eisen- bzw. Cobaltcarbonylverbindungen in Form von Dieisennonacarbonyl und Dicobaltoctacarbonyl als Reagenzien. Dabei konnten sechs gemischte Carbonyl- und Ferrocenyl-funktionalisierte Phosphinoacetylid-Komplexe mit Eisen(0) und Cobalt(0) erhalten und charakterisiert werden. / The present PhD study focuses on the synthesis and characterization of novel perferrocenylated cyclic complexes utilizing cobalt - mediated cyclomerization in combination with C–H bond activation as well as formation of ferrocenylated phosphino-alkyne compounds with iron and cobalt carbonyls. Electrochemical properties and electron-transfer processes between terminal ferrocenyl units in the diverse cyclic compounds are explored in relation to the chemical composition of the building blocks connecting them. Eleven perferrocenylated cyclic compounds were obtained via [2 + 2] and [2 + 2 + 2] cyclomerization of 1,4-diferrocenylbutadiyne FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) by the reaction with dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2. They are subdivided into three groups: (i) products of cyclodimerization with additional chain extension, possessing cyclobutadienyl moieties as a central linkage unit (3a,b and 4a,b), (ii) products of cyclodimerization with consecutive CO insertion (6a,b,c and 7), and (iii) products of cyclotrimerization followed by cycle formation via C–H bond activation (5a,b,c). Optimization of the reaction conditions was made in order to maximize the amount of each group of compounds. Furthermore, another part of this research work focuses on diverse reaction patterns of (ferrocenylethynyl)diphenylphosphane with diironnonacarbonyl and dicobaltocta-carbonyl. Six mixed carbonyl and ferrocenyl-functionalized phospinoalkynyl compounds of iron(0) and cobalt(0) were obtained and characterized.

Die vorliegende Dissertation beschreibt die Synthese und Charakterisierung von neuartigen perferrocenylierten, cyclischen Komplexen unter Anwendung der Cobalt-vermittelten Cyclomerisierung in Kombination mit einer C-H-Bindungsaktivierung als auch die Bildung von ferrocenylierten Phosphinoalkinid-Komplexen mit Eisen- und Cobaltcarbonylen. Die elektrochemischen Eigenschaften und die Elektronentransfer-prozesse zwischen den terminalen Ferrocenyleinheiten in den unterschiedlichen cyclischen Verbindungen wurden unter Einbeziehung der Struktur/chemischen Zusammensetzung der Brückenbausteine ermittelt. Elf perferrocenylierte, cyclische Komplexe wurden mittels [2+2] bzw. [2+2+2] Cyclomerisierung von 1,4-Diferrocenylbutadiin FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) unter Verwendung von Dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2 erhalten. Diese können in drei Gruppen unterteilt werden: (i) Produkte der Cyclodimerisierung mit zusätzlicher Kettenverlängerung, welche Cyclobutadienyl-einheiten als zentrale Brückenbausteine besitzen (3a,b und 4a,b), (ii) Produkte der Cyclodimerisierung mit gleichzeitiger CO-Insertion (6a,b,c und 7), und (iii) Produkte der Cyclotrimerisierung gefolgt von einem Ringschluss durch eine C-H-Bindungsaktivierung (5a,b,c). Die Optimierung der Reaktionsbedingungen wurde zur Ausbeutemaximierung der jeweiligen Verbindungsfamilien durchgeführt. Ein weiterer Teil dieser Forschungsarbeit bezieht sich auf die verschiedenen Reaktionsmuster von (Ferrocenylethinyl)diphenylphosphan- mit zweikernigen Eisen- bzw. Cobaltcarbonylverbindungen in Form von Dieisennonacarbonyl und Dicobaltoctacarbonyl als Reagenzien. Dabei konnten sechs gemischte Carbonyl- und Ferrocenyl-funktionalisierte Phosphinoacetylid-Komplexe mit Eisen(0) und Cobalt(0) erhalten und charakterisiert werden.:Table of contents Bibliografische Beschreibung und Referat iii Abstract iv Ort und Zeitraum der Durchführung v Widmung vi Präambel vii List of Abbreviations xii CHAPTER A Introduction 15 References 16 CHAPTER B State of Knowledge 19 1 (Spectro)electrochemical studies of mixed-valent transition metal complexes. Theoretical background 19 1.1 Mixed-valent compounds – classification 20 1.2 Spectroelectrochemistry 21 1.3 Electrochemistry 25 2 (Di)ferrocenylalkynes – synthesis and reactions 28 2.1 1,4-Diferrocenylbutadiyne 29 2.2 Other (poly)ferrocenyl substituted alkyne derivatives 35 3 Dicarbonylcyclopentadienylcobalt – [2+2] and [2+2+2] cyclo-addition reactions 37 3.1 [2+2] and [2+2+2] cycloaddition – cyclobutadiene, cyclopentadienone, benzene and pyridine based systems 38 3.2 Mechanism of [2+2] and [2+2+2] cycloaddition/cyclization and [2+2] cycloaddition/cyclization with CO insertion mediated by CoCp(CO)2 40 4 Chelation-assisted C–H bond activation mediated by cobalt species 42 5 Phosphinoalkynes and their reaction with iron and cobalt carbonyls 44 5.1 Mechanism of the P–C(sp) bond cleavage in phosphinoalkynes 48 6 Complexes setup by (ferrocenylethynyl)diphenylphosphane 50 References 56 CHAPTER C Multiferrocenyl Cobalt-Based Sandwich Compounds 64 1 Introduction 64 2 Results and Discussion 65 2.1 Synthesis and Characterization 65 2.2 Solid-State Structures 71 2.3 Electrochemistry 73 2.4 Spectroelectrochemistry 76 3 Experimental Section 79 3.1 Instrumentation 79 3.2 General Conditions 81 3.3 Reagents 81 3.4 General Procedure - Reaction of 1 with 2 81 3.4.1 Compound 3a 82 3.4.2 Compound 3b 82 3.4.3 Compound 4b 83 3.4.4 Compound 5c 83 3.4.5 Compound 6a 84 3.4.6 Compound 6b 84 3.4.7 Compound 6c 85 3.4.8 Compound 7 85 4 Supporting information 86 5 References 86 CHAPTER D Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures 91 1 Introduction 91 2 Results and Discussion 92 3 Experimental Section (Supporting information) 98 3.1 General Information 98 3.2 Starting Materials 98 3.3 Synthesis of 3a and 3b from 2 99 3.3.1 Complex 3a: 99 3.3.2 Complex 3b: 100 3.4 Synthesis of 9a and 9b from 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 101 3.4.1 Synthesis of 1-Bromo-2-Ferrocenylethynyl Benzene (7) 101 3.4.2 Synthesis of 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 102 3.4.3 Synthesis of 9a and 9b from 8 103 3.5 Synthesis of 3a and 3b from 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105 3.5.1 Synthesis of 1,3,5-Trichloro-2,4,6-Triethynylferrocenyl Benzene (12) 105 3.5.2 Synthesis of 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105 3.5.3 Synthesis of 3a and 3b from 4 106 4 Supporting information 107 4.1 Spectroelectrochemistry of 3a,b 107 4.2 Conversion of Isomer 9a to 9b – Electrochemical and Chemical oxidation 109 4.3 Chemical oxidation experiment 110 5 References 111 CHAPTER E Coordination Behavior of (Ferrocenylethynyl)diphenyl-phosphane Towards Binuclear Iron and Cobalt Carbonyls 114 1 Introduction 114 2 Results and Discussion 115 3 Experimental Section 126 3.1 Instrumentation 126 3.2 General 128 3.3 Reagents 128 3.4 Synthesis of 4 128 3.5 Synthesis of 4, 5 and 6 129 3.6 Synthesis of 6 by reacting 4 with 2 131 3.7 Synthesis of 7 and 8 131 3.8 Synthesis of 8 from 1 with 3 132 3.9 Synthesis of 9 in the reaction of 7 with 2 133 3.10 Synthesis of 9 in the reaction of 4 with 3 133 4 Electronic Supplementary Material (Supporting information) 134 5 References 134 CHAPTER F Summary 139 1 Conclusions of Chapter C (Appendix A) 139 2 Conclusions of Chapter D (Appendix B) 141 3 Conclusions of Chapter E (Appendix C) 142 Appendix 145 1 Appendix D (Chapter C) 145 2 Appendix E (Chapter D) 146 3 Appendix F (Chapter E) 147 Curriculum Vitae 150 Publications 152 Acknowledgements 154 Selbstständigkeitserklärung 155 / The present PhD study focuses on the synthesis and characterization of novel perferrocenylated cyclic complexes utilizing cobalt - mediated cyclomerization in combination with C–H bond activation as well as formation of ferrocenylated phosphino-alkyne compounds with iron and cobalt carbonyls. Electrochemical properties and electron-transfer processes between terminal ferrocenyl units in the diverse cyclic compounds are explored in relation to the chemical composition of the building blocks connecting them. Eleven perferrocenylated cyclic compounds were obtained via [2 + 2] and [2 + 2 + 2] cyclomerization of 1,4-diferrocenylbutadiyne FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) by the reaction with dicarbonylcyclopentadienylcobalt Co(η5-C5H5)(CO)2. They are subdivided into three groups: (i) products of cyclodimerization with additional chain extension, possessing cyclobutadienyl moieties as a central linkage unit (3a,b and 4a,b), (ii) products of cyclodimerization with consecutive CO insertion (6a,b,c and 7), and (iii) products of cyclotrimerization followed by cycle formation via C–H bond activation (5a,b,c). Optimization of the reaction conditions was made in order to maximize the amount of each group of compounds. Furthermore, another part of this research work focuses on diverse reaction patterns of (ferrocenylethynyl)diphenylphosphane with diironnonacarbonyl and dicobaltocta-carbonyl. Six mixed carbonyl and ferrocenyl-functionalized phospinoalkynyl compounds of iron(0) and cobalt(0) were obtained and characterized.:Table of contents Bibliografische Beschreibung und Referat iii Abstract iv Ort und Zeitraum der Durchführung v Widmung vi Präambel vii List of Abbreviations xii CHAPTER A Introduction 15 References 16 CHAPTER B State of Knowledge 19 1 (Spectro)electrochemical studies of mixed-valent transition metal complexes. Theoretical background 19 1.1 Mixed-valent compounds – classification 20 1.2 Spectroelectrochemistry 21 1.3 Electrochemistry 25 2 (Di)ferrocenylalkynes – synthesis and reactions 28 2.1 1,4-Diferrocenylbutadiyne 29 2.2 Other (poly)ferrocenyl substituted alkyne derivatives 35 3 Dicarbonylcyclopentadienylcobalt – [2+2] and [2+2+2] cyclo-addition reactions 37 3.1 [2+2] and [2+2+2] cycloaddition – cyclobutadiene, cyclopentadienone, benzene and pyridine based systems 38 3.2 Mechanism of [2+2] and [2+2+2] cycloaddition/cyclization and [2+2] cycloaddition/cyclization with CO insertion mediated by CoCp(CO)2 40 4 Chelation-assisted C–H bond activation mediated by cobalt species 42 5 Phosphinoalkynes and their reaction with iron and cobalt carbonyls 44 5.1 Mechanism of the P–C(sp) bond cleavage in phosphinoalkynes 48 6 Complexes setup by (ferrocenylethynyl)diphenylphosphane 50 References 56 CHAPTER C Multiferrocenyl Cobalt-Based Sandwich Compounds 64 1 Introduction 64 2 Results and Discussion 65 2.1 Synthesis and Characterization 65 2.2 Solid-State Structures 71 2.3 Electrochemistry 73 2.4 Spectroelectrochemistry 76 3 Experimental Section 79 3.1 Instrumentation 79 3.2 General Conditions 81 3.3 Reagents 81 3.4 General Procedure - Reaction of 1 with 2 81 3.4.1 Compound 3a 82 3.4.2 Compound 3b 82 3.4.3 Compound 4b 83 3.4.4 Compound 5c 83 3.4.5 Compound 6a 84 3.4.6 Compound 6b 84 3.4.7 Compound 6c 85 3.4.8 Compound 7 85 4 Supporting information 86 5 References 86 CHAPTER D Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures 91 1 Introduction 91 2 Results and Discussion 92 3 Experimental Section (Supporting information) 98 3.1 General Information 98 3.2 Starting Materials 98 3.3 Synthesis of 3a and 3b from 2 99 3.3.1 Complex 3a: 99 3.3.2 Complex 3b: 100 3.4 Synthesis of 9a and 9b from 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 101 3.4.1 Synthesis of 1-Bromo-2-Ferrocenylethynyl Benzene (7) 101 3.4.2 Synthesis of 1-Ferrocenylethynyl-2-Ferrocenyl Benzene (8) 102 3.4.3 Synthesis of 9a and 9b from 8 103 3.5 Synthesis of 3a and 3b from 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105 3.5.1 Synthesis of 1,3,5-Trichloro-2,4,6-Triethynylferrocenyl Benzene (12) 105 3.5.2 Synthesis of 1,3,5-Triethynylferrocenyl-2,4,6-Triferrocenyl Benzene (4) 105 3.5.3 Synthesis of 3a and 3b from 4 106 4 Supporting information 107 4.1 Spectroelectrochemistry of 3a,b 107 4.2 Conversion of Isomer 9a to 9b – Electrochemical and Chemical oxidation 109 4.3 Chemical oxidation experiment 110 5 References 111 CHAPTER E Coordination Behavior of (Ferrocenylethynyl)diphenyl-phosphane Towards Binuclear Iron and Cobalt Carbonyls 114 1 Introduction 114 2 Results and Discussion 115 3 Experimental Section 126 3.1 Instrumentation 126 3.2 General 128 3.3 Reagents 128 3.4 Synthesis of 4 128 3.5 Synthesis of 4, 5 and 6 129 3.6 Synthesis of 6 by reacting 4 with 2 131 3.7 Synthesis of 7 and 8 131 3.8 Synthesis of 8 from 1 with 3 132 3.9 Synthesis of 9 in the reaction of 7 with 2 133 3.10 Synthesis of 9 in the reaction of 4 with 3 133 4 Electronic Supplementary Material (Supporting information) 134 5 References 134 CHAPTER F Summary 139 1 Conclusions of Chapter C (Appendix A) 139 2 Conclusions of Chapter D (Appendix B) 141 3 Conclusions of Chapter E (Appendix C) 142 Appendix 145 1 Appendix D (Chapter C) 145 2 Appendix E (Chapter D) 146 3 Appendix F (Chapter E) 147 Curriculum Vitae 150 Publications 152 Acknowledgements 154 Selbstständigkeitserklärung 155

Ο καρκίνος της ουροδόχου κύστης είναι η τέταρτη συχνότερη κακοήθεια στους άνδρες και η δέκατη στις γυναίκες και η ετήσια επίπτωσή του αυξάνει συνεχώς στις ανεπτυγμένες χώρες. Oι προγνωστικοί παράγοντες που χρησιμοποιούνται σήμερα δεν μπορούν να προβλέψουν με βεβαιότητα την μακροπρόθεσμη έκβαση του ουροθηλιακού καρκίνου και έτσι προκύπτει η ανάγκη αναγνώρισης δεικτών με δυνατότητα πρόγνωσης της συμπεριφοράς των καρκινωμάτων. Επιπλέον, δεδομένων των περιορισμένων δυνατοτήτων των σημερινών θεραπευτικών επιλογών (χειρουργική αντιμετώπιση, χημειοθεραπεία ή ανοσοθεραπεία και ακτινοθεραπεία), απαιτούνται νέες θεραπευτικές στρατηγικές. Μία τέτοια στρατηγική είναι η στόχευση σε μεταγραφικούς παράγοντες όπως οι πυρηνικοί υποδοχείς και οι upstream ενεργοποιητές τους. Η διαταραχή αυτών των μεταγραφικών παραγόντων είναι κομβικό σημείο της έναρξης και διατήρησης του κακοήθους φαινοτύπου. O πυρηνικός υποδοχέας PPARγ εμπλέκεται στον έλεγχο του μεταβολισμού, την κυτταρική ανάπτυξη, την αγγειογένεση και την ανοσολογική και φλεγμονώδη απάντηση. Επιπρόσθετα, υπάρχουν ενδείξεις ότι ρυθμίζει τους μηχανισμούς καταστολής αλλά και προαγωγής της καρκινογένεσης. Ο RXRα είναι επίσης μέλος της υπεροικογένειας των πυρηνικών υποδοχέων και ετεροδιμερίζεται με τον PPARγ προς σχηματισμό του συμπλόκου που αλληλεπιδρά με το DNA. Οι προσδέτες των RXR υποδοχέων έχουν ήδη χρησιμοποιηθεί στη χημειοπρόληψη διαφόρων μορφών καρκίνου. Ο μεταγραφικός παράγoντας AP-1, απαρτίζεται από διμερή των Fos και Jun πρωτεϊνών και η δράση του σχετίζεται με την πρόοδο της καρκινογένεσης. Υπάρχουν πάντως και ενδείξεις για προ-αποπτωτική δράση του. Η CBP είναι ένας απ’ τους σημαντικότερους ολοκληρωτές σημάτων της μεταγραφής. Ο ανταγωνισμός μεταξύ των PPARγ και AP-1 για τη CBP είναι ένας απ’ τους μηχανισμούς που εξηγούν την αρνητική «συνομιλία» (cross-talk) μεταξύ των PPARγ και AP-1. Στην παρούσα μελέτη εξετάσαμε τόσο ξεχωριστά όσο και σε συνδυασμό μεταξύ τους, την έκφραση των πέντε μοριακών παραγόντων (PPARγ, RXRα, p-c-Jun, c-Fos, CBP) στο φυσιολογικό ουροθήλιο, τις προκαρκινικές αλλοιώσεις και τα ουροθηλιακά καρκινώματα (ΟΚ). Τα ιστικά δείγματα προήλθαν από 88 ασθενείς οι οποίοι υπέστησαν διαγνωστική βιοψία ή θεραπευτική κυστεκτομή, νεφρεκτομή ή ουρητηρεκτομή. Εφαρμόστηκε η ανοσοϊστοχημική μέθοδος σε τομές παραφίνης και εκτιμήθηκε η σχετική έκφραση των μελετώμενων παραγόντων στα ενδοκυττάρια διαμερίσματα, τις ενδοεπιθηλιακές στιβάδες και τις φυσιολογικές ή παθολογικές ιστολογικές βαθμίδες. Όλοι οι παράγοντες παρουσίασαν κυρίως πυρηνική εντόπιση. Η έκφραση του p-c-Jun ελαττώνεται στους ασθενείς άνω των 70 ετών σε σχέση με τους νεώτερους, ενώ κανένα άλλο απ’ τα μελετώμενα μόρια δε φαίνεται να επηρεάζεται από την ηλικία. Η έκφραση των PPARγ, CBP, p-c-Jun και c-Fos σημειώνει αύξηση κατά την πορεία προς τον καρκίνο. Όσο αφορά στα ΟΚ, οι PPARγ και CBP παρουσιάζουν αρνητική συσχέτιση με την αποδιαφοροποίηση. Επιπλέον ο PPARγ συσχετίζεται αρνητικά με την απόκτηση χαρακτήρων διήθησης στα ΟΚ. Αντιθέτως, η έκφραση του RXRα δεν διακυμαίνεται στατιστικώς σημαντικά σε όλη την πορεία της καρκινογένεσης. Η ανάλυση της συνδυασμένης έκφρασης των πέντε παραγόντων έγινε με σκοπό την αποκάλυψη ενδεχόμενων αλληλεπιδράσεων μεταξύ τους. Η προστατευτική δράση του PPARγ στο ουροθήλιο συνοδεύεται από ταυτόχρονη μέτρια ή ισχυρή έκφραση των RXRα, p-c-Jun και c-Fos. Αναλυτικά, η αυξανόμενη έκφραση του p-c-Jun συμπίπτει με ενίσχυση της θετικής συσχέτισης του PPARγ με καλύτερα διαφοροποιημένους, λιγότερο διηθητικούς όγκους, ενώ ο c-Fos φαίνεται να εξασθενίζει ήπια την ευνοϊκή δράση του PPARγ στη διαφοροποίηση του ουροθηλίου. Η αυξανόμενη έκφραση της CBP έδειξε να εξασθενίζει και τελικά να εκμηδενίζει τη στατιστικά σημαντική αύξηση του PPARγ στην πορεία προς τον καρκίνο και την επαγωγή του στους μη διηθητικούς όγκους σε σύγκριση με τους διηθητικούς. Ταυτόχρονα, η αρνητική σχέση της CBP με την αποδιαφοροποίηση και την αύξηση της κακοήθειας των ΟΚ επηρεάζεται από την παρουσία των PPARγ και AP-1, επιβεβαιώνοντας την υπόθεση της συνομιλίας αυτών των μοριακών παραγόντων. Ενδιαφέρουσα είναι η παρατήρηση ότι οι περισσότερες από τις αναφερθείσες πιο πάνω συσχτίσεις μεταξύ των μοριακών παραγόντων ίσχυαν για μεγαλύτερους των 70 ετών αλλά όχι πάντα για τους νεώτερους ασθενείς. Τα αποτελέσματα της παρούσας μελέτης μπορούν πιθανόν να οδηγήσουν σε συμπεράσματα με εφαρμογή σε χημειοπροληπτικές και θεραπευτικές στρατηγικές για τον ουροθηλιακό καρκίνο. / Bladder cancer is the fourth and tenth most common malignancy in men and women, respectively, and its incidence is increasing annually in the developed countries. Current prognostic parameters cannot predict with certainty the long-term outcome of bladder cancer and as a result there is a need to identify markers that may predict tumor behavior. Furthermore, given the limitations of current therapeutic options (surgery, chemotherapy or immunotherapy and radiotherapy), novel treatment strategies are very much needed. One such strategy targets transcription factors such as nuclear receptors and their upstream activators. Disruption of these transcription factors is a key element in the initiation and maintenance of a malignant phenotype. The nuclear receptor PPARγ is involved in controlling metabolism, cell growth, angiogenesis, and immune and inflammatory responses. In addition, it has also been suggested that it regulates tumor suppression as well as tumor promotion. RXRα is another member of the nuclear receptor superfamily, that partners PPARγ to form the DNA-binding complex. RXR ligands are already being used as chemopreventive agents in various types of cancer. The transcription factor AP-1 is formed by dimerization of Jun and Fos proteins and its activity is often associated with tumor progression. On the other hand, there is also evidence that AP-1 may enhance apoptosis. CBP is one of the most important transcriptional integrators. The competition of PPARγ and AP-1 for CBP is one of the multiple mechanisms that explain the negative PPARγ/AP-1 cross-talk. In the present study, we assessed separate and concurrent expression of the five factors (PPARγ, RXRα, p-c-Jun, c-Fos, CBP) in normal urothelium, precancerous lesions and urothelial carcinomas (UC). Clinical samples were derived from 88 patients who had undergone diagnostic biopsy or therapeutic excision of the bladder, the kidney or the ureter. Parafin section immunohistochemistry was utilized and relative expression was estimated in intracellular compartments, intraepithelial layers and histologic categories of urothelium. All five factors had mainly nuclear pattern of expression. P-c-jun was downregulated in patients older than 70 years old compared to younger ones, whereas age did not affect the expression of the rest four factors. PPARγ, CBP, p-c-Jun and c-Fos were upregulated towards tumorigenesis. PPARγ and CBP showed an inverse relationship with carcinoma level of differentiation. Moreover, PPARγ expression downregulated significantly in invasive tumors compared to non-invasive ones. On the contrary, RXRα expression did not vary significantly along the carcinogenesis course. The following correlations were based on coexpression analysis to reveal molecular interactions between the five factors. The established protective effect of PPARγ on urothelium was accompanied by concomitant RXRα, p-c-Jun and c-Fos moderate or strong expression. In detail, p-c-Jun’s increasing expression strengthened the positive relation of PPARγ with better differentiated, less invasive tumors, whereas c-Fos seemed to mildly lessen PPARγ’s favourable effect in urothelium differentiation. Statistically significant PPARγ upregulation in malignant tissues compared to normal urothelium and in non-invasive tumors compared to invasive ones is suppressed and finally cancelled by CBP’s increasing expression. PPARγ and AP-1 seemed to influence the negative relation of CBP with loss of differentiation and increase of malignant potential in UC, an observation that denotes a cross-talk between these molecular factors. Interestingly, most of the aforementioned correlations were noticed in patients older than 70 years old, but not all of them were plausible in younger patients. The results from the present study could lead to conclusions possibly applicable in chemoprevention and therapy strategies for urothelial carcinomas.

Cette thèse porte sur l’adaptation des étudiants en période de transition. Elle repose sur une comparaison franco-canadienne entre étudiants primo-entrants et étudiants internationaux vietnamiens. Dans l’objectif d’apporter un éclairage nouveau sur les processus de leur adaptation, nous avons intégré deux modèles théoriques permettant de distinguer deux niveaux d’adaptation, l’un dit « local » commun à tous les étudiants, l’autre dit « international » spécifique aux Vietnamiens (Black, Mendenhall & Oddou, 1991), dans lesquels viennent s’imbriquer deux dimensions du processus : l’adaptation psychologique et l’adaptation socioculturelle (Ward & Searle, 1991). La personnalité anxieuse, suivie de l’attachement adulte et des tracas quotidiens, apparaissent comme le fondement explicatif de l’adaptation des étudiants, quels qu’ils soient, tant à un niveau psychologique que socioculturel. A ces aspects « locaux » pour les Vietnamiens, s’ajoutent deux enjeux interculturels : l’identification à la culture d’origine et les différents réseaux de socialisation. Les résultats soulignent également pour les différents groupes d’étudiants une fragilisation des modèles internes de l’attachement, des différences culturelles dans leurs potentialités à former un corps étudiant et à se socialiser au sein de l’université ainsi que la présence d’individus à risques : ces derniers seraient dans l’incapacité de faire face efficacement au stress induit par la période de transition. / This dissertation focuses on students’ adaptation in transition. It is based on a French-Canadian comparison between freshmen students and international Vietnamese students. With the aim to shed a new light on the process of their adaptation, we integrated two theoretical models which allowed us to distinguish two levels of adaptation, one considered as “local” and common to all students, the other as “international” and specific to Vietnamese students (Black, Mendenhall & Oddou, 1991), in which are embedded two dimensions: psychological adaptation and sociocultural adaptation (Ward & Searle, 1991). Anxious personality, followed by adult attachment and daily hassles, appeared as the root of students’ adaptation both at a psychological and sociocultural level. In addition to these “local” aspects, Vietnamese have to deal with two cross-cultural issues: their identification with culture of origin and the different social networks in their environment. Results also highlighted for all students a weakening in their working models of attachment, cultural differences in their potential to form a student body and to socialize within the university and, the existence of individuals “at risk”: these students appeared to be unable to cope effectively with the stress induced by the transition. / Lu?n án này d? c?p d?n s? h?i nh?p c?a sinh viên trong quá trình chuy?n d?i. Lu?n án du?c th?c hi?n d?a trên m?t so sánh Pháp và Canada gi?a nh?ng sinh viên m?i vào d?i h?c và sinh viên qu?c t? Vi?t Nam. V?i mong mu?n dem l?i m?t cái nhìn m?i m? v? qúa trình h?i nh?p c?a h?, chúng tôi dã trình bày hai mô hình lý thuy?t nh?m phân bi?t hai m?c d? h?i nh?p, m?t « mô hình c?c b? » chung cho m?i sinh viên và m?t « mô hình qu?c t? » d?c trung cho sinh viên Vi?t Nam (Black, Mendenhall & Oddou, 1991). Trong hai mô hình này, hai m?t c?a quá trình dan xen l?n nhau : s? h?i nh?p tâm lý và s? h?i nh?p van hóa xã h?i (Ward & Searle, 1991). Tính cách hay lo, ti?p d?n là s? g?n bó sâu s?c và nh?ng khó khan trong cu?c s?ng thu?ng ngày là co s? lý gi?i cho s? h?i nh?p c?a sinh viên c? v? m?t tâm lý và van hóa xã h?i. ? khía c?nh « c?c b?», sinh viên Vi?t Nam còn ph?i d?i phó v?i hai v?n d? mang tính ch?t liên van hóa : s? d?ng nh?t v?i n?n van hóa g?c và các m?ng xa h?i khác nhau. K?t qu? c?a lu?n án dã nh?n m?nh r?ng d?i v?i nh?ng nhóm sinh viên khác nhau, có s? không b?n v?ng c?a các m?u bên trong c?a các m?i liên h? (working models of attachment), c?a s? khác bi?t v? van hóa trong xu hu?ng hình thành m?t t?p th? sinh viên (student body) và xu hu?ng xã h?i hóa trong tru?ng d?i h?c cung nhu là s? t?n t?i nh?ng cá nhân thu?ng xuyên có v?n d?, nhi?u tâm : nh?ng sinh viên này du?ng nhu không th? d?i phó m?t cách hi?u qu? v?i nh?ng cang th?ng trong quá trình chuy?n d?i này.

本研究有系統地收集了2003年8月12日到2005年9月30日止共495個交易日的台指期貨、選擇權市場裡P/C量、P/C倉、隱含波動率(AIV)、不同天數的歷史波動率等收盤資料，進行這些因素與行情走勢間的關係，以及因素彼此的互動性。結果證實分析台指選擇權指標是需要區分金融重大衝擊前後期間，以及區分漲勢、跌勢、盤整的各期間，各期間的選擇權指標均會有不同意涵。 本論文證實使用結構轉換的Chow-ARMA(2,1)模型可能比較符合模擬指數 實況，且GARCH(1,1) 模型也很適合描述台期指貨波動度預測力。在選擇權指標方面：P/C量與AIV與台指期貨呈現負相關，P/C倉與台指期貨正相關。其中以P/C倉對指數漲跌的影響程度最大、P/C量的影響程度次之、AIV影響程度最小。若把隱含波動率區分成買權與賣權之各個波動率更有效地預測行情走勢，在大跌期間的買賣權隱含波動率更能表現出優越的預測能力，其中前兩期的賣權隱含波動率(PIV)更是效率性指標， 實證結果使用20天的歷史波動率比較能貼近選擇權市場的變化，跟過去教 科書慣用的90天不同。若比較歷史波動率與隱含波動率間的關係，結論是當「大跌期」歷史波動率大於買權隱含波動率(CIV)時，買權是會被低估的，其他的各種假設條件均不成立。理由有二：一是市場效率性決定了是否可使用隱含波動率與歷史波動率之間的高低關係。二是「大跌時期」相對於「大漲時期」的市場資訊被反應的更敏銳，而在「大跌時期」的賣權價格反應比買權價格反應更快速敏銳。 本研究推論的Chow-ARMA(2,1) 台指期貨模型、GARCH(1,1) 波動率模型、P/C量-P/C倉-AIV的多變數模型、FMA20/XIV模型等等在研判指數變化上具有參考價值，進一步均可以做為選擇權操作策略參考依據之一。

This item contains the agenda, minutes, and attachments for the Faculty Senate meeting on this date. There may be additional materials from the meeting available at the Faculty Center.