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Amphiphilic Fullerenes for Biomedical and Optoelectronical Applications”

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Amphiphilic Fullerenes for Biomedical and Optoelectronical Applications” AMPHIPHILIC FULLERENES FOR BIOMEDICAL AND OPTOELECTRONICAL APPLICATIONS Den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades vorgelegt von Patrick Witte aus Nürnberg Als Dissertation genehmigt von den Naturwissenschaftlichen Fakultäten der Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 25.04.2008 Vorsitzender der Prüfungskommission: Prof. Dr. Eberhard Bänsch Erstberichterstatter: Prof. Dr. Andreas Hirsch Zweitberichterstatter: Prof. Dr. Tim Clark Meinem Doktorvater, Prof. Dr. A. Hirsch, gilt mein besonderer Dank für sein reges Interesse am Fortgang dieser Arbeit sowie für seine Anregungen und die Diskussionen mit ihm. Die vorliegende Arbeit wurde in der Zeit zwischen Dezember 2003 bis Dezember 2007 am Institut für Organische Chemie der Friedrich-Alexander-Universität Erlangen- Nürnberg durchgeführt. Dedication FormyParentsandKati -Scienceisfacts; justashousesaremadeofstones,soissciencemadeoffacts; butapileofstonesisnotahouseandacollectionoffactsisnotnecessarilyscience HenriPoincare(1854-1912) Index of Abbreviations t Bu ................. tert-Butyl BAM . Brewster Angle Microscopy Boc ................ tert-Butoxycarbonyl CV ................. Cyclic Voltammetry DBU . 1,8-Diaza-bicyclo[5.4.0]undecen-7-en DCE . 1,2-Dichloroethane DCU ............... Dicyclohexylurea DMA . 9,10-Dimethylanthracene DMAP . 4-Dimethylaminopyridine DMSO . Dimethyl Sulfoxide dpf . Days Post Fertilization EA . Elemental Analysis EDC . 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Hydrochloride eq . Equivalent FAB . Fast Atom Bombardment FC . Flash Column Chromatography HOBt . 1-Hydroxybenzotriazole hpf . Hours Post Fertilization HPLC . High Performance Liquid Chromatography IPR . Isolated Pentagon Rule IR .................. Infrared Spectroscopy LB . Langmuir-Blodgett I MW . Molecular Weight NBA . 3-Nitrobenzylalcohol NMR . Nuclear Magnetic Resonance PBS . Phosphate Buffered Saline PCBM . [6,6]-Phenyl-C61 Butyric Acid Methyl Ester pf .................. Post Fertilization ppm . Parts per Million ROS ............... Reactive Oxygen Species RT . Room Temperature STM . Scanning Tunneling Microscopy SWCNT . Single Walled Carbon Nanotube TFA . Trifluoroacetic Acid THF . Tetrahydrofuran TLC . Thin Layer Chromatography UV/Vis . Ultraviolet-Visible Spectroscopy XPS . X-ray Photoelectron Spectroscopy II Table of Contents 1 Introduction 1 1.1 NanostructuredMaterials . 1 1.2 TheDiscoveryofFullerenes. 4 1.3 TheStructureofFullerenes . 5 1.4 PhysicalProperties.. .. .. .. .. .. .. .. .. .. .. .. .. .. 7 1.4.1 Thermodynamic and Kinetic Stability of C60 ............ 7 1.4.2 Solubility of C60 ............................ 7 1.5 SpectroscopicProperties . 9 1.5.1 UV/Vis-Spectroscopy . 9 1.5.2 MassSpectroscopy . .. .. .. .. .. .. .. .. .. .. .. 10 1.5.3 NMRSpectroscopy ......................... 11 1.5.3.1 3He and 1HSpectroscopy. 11 1.5.3.2 13CSpectroscopy ..................... 13 1.6 Electronic Structure and Reactivity of Fullerenes . ......... 14 1.7 Spherical Aromaticity of C60 ......................... 15 1.8 Chemistry of C60 ............................... 16 2 Proposal 20 3 Results and Discussion 22 3.1 Water-soluble Amphiphilic Fullerene-Monoadducts . ......... 22 3.1.1 Synthesis of Anionic Amphiphilic Monoadducts . 24 III Table of Contents 3.1.2 Synthesis of an Anionic Amphiphilic Monoadduct Carrying an UnsaturatedFattyAcid. 33 3.1.3 Synthesis of a Cationic Amphiphilic Monoadduct . 39 3.1.4 Amphiphilic Fullerenes as Potential Drug Candidates ....... 44 3.1.4.1 Introduction and Background . 44 3.1.4.2 Antioxidant Activity . 47 3.1.4.3 Cytochrome C Binding . 52 3.1.4.4 In vivo Studies of the Amphiphilic Fullerenes using Ze- brafish (Danio Rerio) Embryos as Model System . 57 3.1.5 Mechanistic Aspects of the Reaction of Fullerenes with Superoxide 69 3.1.5.1 Cyclic Voltammetry Measurements of Amphiphilic Mono- adducts........................... 70 3.1.5.2 Kinetic Measurements of Amphiphilic Monoadducts . 73 3.1.6 Amphiphilic Fullerenes in Material Science Applications . 77 3.1.6.1 Formation of LANGMUIR-Films with Amphiphilic Fullerene- Monoadducts........................ 79 3.1.6.2 Incorporation of the Amphiphilic Fullerene-Monoadducts in Organic Solar Cell Devices . 85 3.2 Triazole Dendrimers Based Fullerenes via "Click Chemistry" . 89 3.2.1 Synthesis of Novel Dendritic Triazol-Fullerenes . ....... 92 3.3 Synthesis of Novel Fullerene-SWCNT Hybrids . 102 3.3.1 Covalent Sidewall Functionalization of SWCNT’s with a Fullerene- Monocarboxylic Acid Derivative . 103 3.3.2 Non-Covalent Functionalization of SWCNT’s with a Fullerene- PyreneDyad ............................. 106 3.4 Supramolecular Approach for the Formation of C60-Bisadducts . 116 3.4.1 Metallomacrocycles as Tethers for Regioselective Cyclopropana- tion .................................. 117 3.4.2 Hydrogen-bonded Dimers as Tethers for Regioselective Cyclo- propanation.............................. 120 IV Table of Contents 3.5 Synthesis of Novel Multiple Fullerene Arrays Consisting of Mixed C60- HexakisadductUnits . 125 3.5.1 Synthesis of Bisfunctionalized Janus-Type Fullerene-Dimers . 127 3.5.2 Synthesis of a Fullerene-Rich Nanocluster . 137 4 Summary 142 4 Zusammenfassung 146 5 Experimental Part 151 5.1 ChemicalsandInstrumentation . 151 5.2 Synthetic Procedures and Spectroscopic Data . 154 Appendices 224 A Materials and Methods for the Determination of Biological Activity in vivo 224 B Materials and Methods for the Preparation and Examination of SWCNT- Fullerene-Hybrid ............................... 229 References 231 V CHAPTER 1 1 Introduction 1.1 Nanostructured Materials Although the idea of carrying on manipulations at smaller and smaller scales has been around for quite some time the birth of nanotechnology, at least on an ideological level, is usually traced back to a speech by RICHARD FEYNMAN at the December 1959 meet- ing of the American Physical Society. In his speech, he challenged his fellow scientists to find ways by which to create manufacturing, storage, and retrieval systems that are as efficient as DNA and to contain such systems in a submicroscopic, self-contained unit with the size of a cell. It would be over two decades before the first recognized paper on molecular nanotechnology was published.[1] The challenge in nanoscience is to understand how materials behave when sample sizes are close to atomic dimensions. Figure 1.1 for example shows an overview of artificial nanostructures, being of the same size as biological entities, which allows them to interact with biomolecules on the surface of the cell and inside it. When the characteristic length scale of the structure is in the 1- 100 nm range, it becomes com- parable with the critical length scales of physical phenomena, resulting in the so-called "size and shape effects". This leads to unique properties and the opportunity to use 1 Chapter 1 Introduction Figure 1.1: Artificial (top) and biological (bottom) nanostructures. such nanostructured materials in novel applications and devices. Phenomena occur- ring on this length scale are of interest to chemists, physicists, biologists, electrical and mechanical engineers, and computer scientists, making research in nanotech- nology a frontier activity in materials science. Nanomaterials, which can be classi- fied as carbon-based nanomaterials, nanocomposites, biological nanomaterials, nano- polymers, nano-glasses and nano-ceramics find and promise applications in a wide range of fields such as medicine (therapeutic agent, sensors, labelling), device tech- nology (nanophotonics, solar energy conversion, opto-electronics) and chemical syn- thesis (catalysis). This thesis deals with the design and synthesis of functionalized carbon-based nanomaterials, to get more insight in structure-function relationships and 2 Chapter 1 Introduction to provide a predictive mechanism that will allow chemists to efficiently design nano- materials that perform exactly as desired. 3 Chapter 1 Introduction 1.2 The Discovery of Fullerenes The discovery of C60 has a long and very in- teresting history.[3] The structure of truncated icosahedron was already known about more than 500 years ago. ARCHIMEDES is credited for discovering the structure and LEONARDO DA VINCI included it in one of his drawings. At the end of 1960’s, scientists were increas- ingly interested in non-planar aromatic struc- ture, and thereafter the bowl-shaped corannu- lene was synthesized.[4] In 1970, EIJI OSAWA realized that a molecule made up of sp2 hy- bridized carbons could have a spherical struc- ture. He therefore made the first proposal for [5] C60. Then, a group of Russian scientists in- dependently proposed the C60 structure, the Figure 1.2: Leonardo da Vinci‘s paper published by BOCHVAR and GAL’PERN "Truncated Icosahedron".[2] in 1973 not only predicted some properties of [6] C60, but also of C20 (the smallest fullerene) as well. The first spectroscopic evidence [7] for C60 and other fullerenes was published in 1984 by ROHLFING and coworkers. Eventually in 1985 ROBERT CURL and RICHARD SMALLEY from Rice University, and HAROLD KROTO from the University of Sussex discovered the fullerenes while doing experiments with a laser-vaporization supersonic cluster beam apparatus developed by SMALLEY. Upon vaporizing graphite from the disk with high-power laser pulses, they found in their data, to their surprise, an indication of what appeared to be a cluster con- sisting of 60 carbon atoms. After furiously debating, building models, and consulting the literature, they theorized
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