DNA hybrid materials consisting of oligonucleotides and organic molecules: synthesis, characterization and applications

The goal of this thesis was to increase the functionality of pristine DNA scaffolds by functionalizing them with fluorescent dyes and hydrophobic moieties. Two important steps were necessary to realize this aim successfully. First, nucleic acids needed to be synthesized making use of multidisciplinary toolbox for the generation and manipulation of polynucleic acids. The most important techniques were the solid phase synthesis involving the incorporation of standard and modified phosphoramidite building blocks as well as molecular biology procedures like the polymerase chain reaction, the bacterial amplification of plasmids and the enzymatic digestion of circular vectors. Second, and evenly important, was the characterization of the novel bioorganic hybrid structures by a multitude of techniques, especially optical measurements. For studying DNA-dye conjugates methods like UV/Vis and photoluminescence spectroscopy as well as time resolved luminescence spectroscopy were utilized. While these measurements characterized the bulk behavior of an ensemble of DNA-dye hybrids it was necessary for a complete understanding of the systems to look at single structures. This was done by single-molecule fluorescence spectroscopy and fluorescence correlation spectroscopy. For complete analysis the optical experiments were complemented by direct visualization techniques, i.e. high resolution transmission electron microscopy and scanning force microscopy.

Amidverknüpfte Ferrocene - schaltbare molekulare Drähte und Sensoren

In dieser Arbeit werden Synthesen und Eigenschaften von Verbindungen mit einer oder mehreren Ferrocen- bzw. Biferroceneinheiten beschrieben, die über Amid-, Anhydrid- oder Harnstoff-Funktionen verknüpft oder mittels Amidfunktion an α-Aminosäurederivate gebunden sind. Als Zentralbausteine dienen die künstlichen Aminosäuren 1’-Aminoferrocen-1-carbonsäure (Fca) bzw. 1’-Aminobiferrocen-1-carbonsäure (Bfca). Die Ferroceneinheit agiert als redoxschaltbares Gelenk, die Amidfunktion ermöglicht die Ausbildung von Sekundärstrukturen und die Bindung von Anionen. Das redoxschaltbare „Multiwellenlängen“-Sensorpaar [Dansyl-Ala-Fca-Ala-CH2-Naphthyl]0/+ ist in der Lage, insgesamt sieben Anionen aufgrund von sechs einfach zu erhaltenden optischen Messwerten eindeutig zu diskriminieren. Die Vorzugskonformation des neutralen Rezeptors mit intramolekularen Wasserstoffbrücken wird mittels X-Ray, NMR- und DFT-Methoden im Festkörper, in Lösung und in der Gasphase bestimmt. Die oligomeren Fca-Verbindungen SG-Fcan-HN-Fc (SG = Boc, Fmoc; n = 1, 2) und SG-Fca2-OMe (SG = Boc, Fmoc) werden mittels Peptidkupplung in Lösung hergestellt, Fmoc-Fca3-Gly-OMe, Fmoc-Fcan-OMe (n = 3-5) und Fmoc-Fca4-NH2 dagegen durch ein neu entwickeltes Festphasensynthese-Protokoll. Die amidverknüpften Verbindungen bilden eine „Zick-Zack“-Struktur mit 1,2’-Konformation der Fca-Einheiten und achtgliedrigen intramolekularen Wasserstoffbrücken-Ringen, wie durch X-Ray, 2D-NMR-, DFT-Methoden und Dipolmoment-Bestimmung gezeigt wird. Elektrochemische Experimente belegen eine elektronische Wechselwirkung der Eisenzentren. Die gemischt-valenten Verbindungen zeichnen sich durch IVCT-Banden im nahen Infrarot aus. Die elektronische Kopplungskonstante beträgt Hab ≈ 145-215 cm–1 für einen einzelnen FeII/FeIII-Übergang und belegt die Zugehörigkeit der Verbindungen zur Robin-Day-Klasse II. Im Festkörper sind die Valenzen gemäß Mößbauerspektren lokalisiert. Die vollständig oxidierten Verbindungen liegen nach DFT-Rechnungen nicht mehr in einer „Zick-Zack“-Struktur, sondern in einer gestreckten Konformation vor. Als Nebenprodukte bei der Amidkupplung werden die Anhydride SG-(Fca)2O (SG = Ac, Boc, Fmoc) isoliert. Diese zählen aufgrund des Fehlens einer IVCT-Bande zur Klasse I-II. Die ferrocenyloge Bfca wird in Form der N- und C-geschützten Bfca auf zwei Wegen synthetisiert. Schlüsselschritte stellen die Cu(II)-vermittelte Homokupplung bzw. die Pd-katalysierte Stille-Kupplung dar. Bfca und die amid- und harnstoffverknüpften Bis-Bfca-Verbindungen besitzen keine nachweisbare Vorzugskonformation in Lösung. Die gemischt-valenten Bfca-Kationen zeigen eine IVCT-Bande (Hab ≈ 300-600 cm–1) und gehören eher zur Klasse II-III. Die gemischt-valenten Verbindungen des als Nebenprodukt isolierten Tetraferrocenylstannans Sn[Fn(COOMe)4] (Fn = 1,1’-Ferrocenylen) mit einatomiger σ-Brücke zwischen den Ferroceneinheiten, zeigen IVCT-Banden im NIR-Spektrum und gehören somit zur Klasse II. Die elektronischen Kopplungen in Sn[Fn(COOMe)4]+/2+ betragen Hab ≈ 145 und 220 cm–1.

Nuovi complessi alchinil tetrazolici di iridio(III) e renio(I): Sintesi, reattività e proprietà fotofisiche.

In this experimental thesis, two luminescent Ir(III) and Re(I) complexes which have a terminal alkynyl group on the tetrazole ligand were prepared. The aim was to use them as building blocks, in order to synthesize more complex structures. We explored two simple reactions: the first one was a coupling, for the formation of Ir(III)/Au(III) and Re(I)/Au(III) hetero binuclear complexes, and the second was a 1,3-dipolar Cu(I)-catalyzed “Click” cycloaddition, between the terminal alkyne and azide. The synthesized products were characterized through photophysical analysis, evaluating how the photoemissive properties of these substrates were affected by the formation of more complex structures. In questo lavoro di tesi sperimentale sono stati preparati due complessi luminescenti di Ir(III) e Re(I) che presentano un alchino terminale sul legante tetrazolico. Lo scopo è stato quello di utilizzarli come building blocks per la sintesi di strutture più complesse. Sono state esplorate due semplici reazioni: la prima di coupling, per la formazione di complessi etero binucleari Ir(III)/Au(III) e Re(I)/Au(III), e la seconda di “click”, ossia una cicloaddizione 1,3-dipolare Cu(I) catalizzata tra l’alchino terminale e un’azide. I prodotti sintetizzati sono stati caratterizzati attraverso analisi fotofisiche, valutando come le proprietà fotoemissive di questi substrati siano influenzate in seguito alla formazione di strutture più complesse.

Sintesi e caratterizzazione di oligo e politiofeni per applicazioni in elettronica e biodiagnostica

Negli ultimi anni sono stati sintetizzati numerosi oligomeri e polimeri del tiofene che, grazie alle loro proprietà di semiconduttori, hanno trovano largo impiego in molti campi di interesse tecnologico come, ad esempio, transistor ad effetto di campo, diodi elettroluminescenti, dispositivi ottici non lineari e celle fotovoltaiche. Più recentemente, oligomeri tiofenici ossidati allo zolfo hanno trovato applicazione sia in campo elettronico, come materiali accettori in blenda con il poli(3-esiltiofene) (P3HT) usato come materiale donatore, in celle solari di tipo Bulk Hetero Junction (BHJ), ma anche in campo biologico come marcatori fluorescenti di proteine e oligonucleotidi. Tuttavia la sintesi di queste specie richiede condizioni di reazione spinte e al contempo rischiose dovute all’utilizzo in largo eccesso di agenti ossidanti molto forti. Uno degli obiettivi di questa tesi è stato lo sviluppo di metodi più versatili per la mono e di-ossidazione selettiva allo zolfo del tiofene di building-blocks dibromurati di diversa natura. Successivamente i building-blocks S-monossido e S,S-diossido derivati sono stati impiegati per la sintesi di oligomeri e polimeri tramite reazioni di cross-coupling Palladio catalizzate. I composti finali sono stati caratterizzati sia dal punto di vista spettroscopico UV-Vis che elettrochimico, mettendo in evidenza le relazioni che esistono fra gli andamenti dei dati sperimentali ottenuti con il diverso stato di ossidazione dei composti tiofenici diversamente sostituiti. Infine i composti finali sono stati testati sia in campo fotovoltaico che biologico.

Lipophilic nucleosides: studies toward self-assembled functional materials

Molecular self-assembly takes advantage of supramolecular non-covalent interactions (ionic, hydrophobic, van der Waals, hydrogen and coordination bonds) for the construction of organized and tunable systems. In this field, lipophilic guanosines can represent powerful building blocks thanks to their aggregation proprieties in organic solvents, which can be controlled by addition or removal of cations. For example, potassium ion can template the formation of piled G-quartets structures, while in its absence ribbon-like G aggregates are generated in solution. In this thesis we explored the possibility of using guanosines as scaffolds to direct the construction of ordered and self-assembled architectures, one of the main goals of bottom-up approach in nanotechnology. In Chapter III we will describe Langmuir-Blodgett films obtained from guanosines and other lipophilic nucleosides, revealing the “special” behavior of guanine in comparison with the other nucleobases. In Chapter IV we will report the synthesis of several thiophene-functionalized guanosines and the studies towards their possible use in organic electronics: the pre-programmed organization of terthiophene residues in ribbon aggregates could allow charge conduction through π-π stacked oligothiophene functionalities. The construction and the behavior of some simple electronic nanodevices based on these organized thiopehene-guanosine hybrids has been explored.

Silicon Photonics Integrated Circuits for Flexible Optical Systems

This dissertation deals with the design and the characterization of novel reconfigurable silicon-on-insulator (SOI) devices to filter and route optical signals on-chip. Design is carried out through circuit simulations based on basic circuit elements (Building Blocks, BBs) in order to prove the feasibility of an approach allowing to move the design of Photonic Integrated Circuits (PICs) toward the system level. CMOS compatibility and large integration scale make SOI one of the most promising material to realize PICs. The concepts of generic foundry and BB based circuit simulations for the design are emerging as a solution to reduce the costs and increase the circuit complexity. To validate the BB based approach, the development of some of the most important BBs is performed first. A novel tunable coupler is also presented and it is demonstrated to be a valuable alternative to the known solutions. Two novel multi-element PICs are then analysed: a narrow linewidth single mode resonator and a passband filter with widely tunable bandwidth. Extensive circuit simulations are carried out to determine their performance, taking into account fabrication tolerances. The first PIC is based on two Grating Assisted Couplers in a ring resonator (RR) configuration. It is shown that a trade-off between performance, resonance bandwidth and device footprint has to be performed. The device could be employed to realize reconfigurable add-drop de/multiplexers. Sensitivity with respect to fabrication tolerances and spurious effects is however observed. The second PIC is based on an unbalanced Mach-Zehnder interferometer loaded with two RRs. Overall good performance and robustness to fabrication tolerances and nonlinear effects have confirmed its applicability for the realization of flexible optical systems. Simulated and measured devices behaviour is shown to be in agreement thus demonstrating the viability of a BB based approach to the design of complex PICs.

Bioconjugation and synthetic approach towards enantioenriched gem-difluoromethylene compounds through carbenium ions

Bioconjugation of peptides and asymmetric synthesis of gem-difluoromethylene compounds are areas of the modern organic chemistry for which mild and selective methods continue to be developed. This thesis reports new methodologies for these two areas based on the use of stabilized carbenium ions. The reaction that makes the bioconjugation of peptides possible takes place via the direct nucleophilic substitution of alcohols and is driven by the spontaneous formation of stabilized carbenium ions in water. By reacting with the thiol group of cysteine in very mild conditions and with a high selectivity, these carbenium ions allow the site-specific ligation of polypeptides containing cysteine and their covalent derivatization with functionalized probes. The ligation of the indole ring of tryptophan, an emerging target in bioconjugation, is also shown and takes place in the same conditions. The second area investigated is the challenging access to optically active gem-difluoromethylene compounds. We describe a methodology relying on the synthesis of enantioenriched 1,3-benzodithioles intermediates that are shown to be precursors of the corresponding gem-difluoromethylene analogues by oxidative desulfurization-fluorination. This synthesis takes advantage of the highly enantioselective organocatalytic α-alkylation of aldehydes with the benzodithiolylium ion and of the wide possibilities of synthetic transformations offered by the 1,3-benzodithiole group. This approach allows the asymmetric access to complex gem-difluoromethylene compounds through a late-stage fluorination step, thus avoiding the use of fluorinated building blocks.

From large polycyclic aromatic hydrocarbons to extended aromate-rich networks

The common ground of this study is the development of novel synthetic strategies to extended one-, two- and three-dimensional aromate-rich systems for which a number of applications are envisaged. rnThe point of departure is the synthesis and characterization of highly symmetric macrocyclic PAHs (polycyclic aromatic hydrocarbons) for which various aspects of supramolecular chemistry will be investigated. The versatility of the Yamamoto macrocyclization will be demonstrated on the basis of a set of cyclic trimers that exhibit a rich supramolecular chemistry. 1,10-phenanthroline, triphenylene and ortho-terphenyl building blocks have been successfully assembled to the corresponding macrocycles following the newly developed synthetic route. Scanning-tunneling microscopy (STM) and two-dimensional wide-angle X-ray scattering (2D-WAXS) were used to study the two- and three-dimensional self-assembly, respectively.rnSecondly, the development of chemical approaches to highly shape-anisotropic graphene nanoribbons (GNRs) and related nanographene molecules shall be discussed. Aryl-aryl coupling was used for the bottom-up fabrication of dendronized monomers, polymers and model compounds. Subsequently, these structures were converted into the final graphene material using oxidative (Scholl-type) cyclodehydrogenation. The GNRs thus obtained are characterized by an unprecedented length and lateral extension. The relevance of structural tailoring in the field of well-defined graphene materials is discussed in detail as only the chemical approach provides full geometry control. rnLastly, novel pathways towards the synthesis of extended three-dimensional networks that are dominated by nitrogen-rich motifs will be presented. If porous, these materials hold a great potential in the fields of gas and energy storage as well as for applications in catalysis. Hence, poly(aminal) networks based on melamine as crosslinking unit were synthesized and characterized with respect to the applications mentioned above. As set of conjugated poly(azomethine) networks was investigated regarding their use as a novel class of organic semiconductors for photocatalytic water splitting. The network structures described in this chapter can also be subjected to a controlled pyrolysis yielding mesoporous, nitrogen-rich carbon materials that were evaluated as active component for supercapacitors.rn

Polyphenylendendrimere zur Gefahrstoffdetektion

Zusammenfassung: rnrn Die vorliegende Arbeit mit dem Thema „Polyphenylendendrimere zur Gefahrstoffdetektion“ ist hauptsächlich synthetisch orientiert und behandelt vor allem den Aufbau neuartiger innenfunktionalisierter Polyphenylendendrimer-Systeme durch die systematische Anwendung wiederholter Diels-Alder- bzw. Desilylierungs-Reaktionen. Diskutiert wird dabei die Synthese der dafür notwendigen Verzweigungsbausteine, die daraus hervorgehende Darstellung der verschiedenen Dendrimere sowie deren Charakterisierung. Als Referenz zu den monodispersen dendritischen Systemen werden parallel verschiedene hyperverzweigte Polymere mittels Diels-Alder-Reaktion bzw. Suzuki-Kupplung dargestellt und beide Makromolekül-Systeme im direkten Vergleich besprochen. Erstmals wird die Einbindung funktioneller Elemente, wie z.B. Triazol oder Pyren, synthetisch ermöglicht. Die dendritischen Systeme werden bis zur dritten Generation aufgebaut, im Fall des Ester-funktionalisierten Systems wird auch eine Darstellung der vierten Generation erreicht. Im Anschluss wird das supramolekulare Verhalten der erhaltenen dendritischen, wie auch polymeren Verbindungen mittels zweier unterschiedlicher Meßmethoden (QMB, ITC) gegenüber verschiedenen Lösungsmitteln und Gefahrstoffen untersucht. Dabei kann eine Diskrepanz im Einlagerungsverhalten der verschiedenen makromolekularen Strukturen gegenüber den verwendeten Gast-Molekülen beobachtet werden. Aufgrund der umfassenden systematischen Analyse aller getesteten Verbindungen wird ein tiefer greifendes Verständnis für die während des Einlagerungsprozesses verantwortlichen Wechselwirkungen aufgebaut. Dabei spielt die dreidimensionale Anordnung des dendritischen Gerüsts, resultierend aus der Polarität und dem sterischen Anspruch der eingebundenen funktionellen Gruppen eine entscheidende Rolle. Als Anwendungsbeispiel der dendritischen Strukturen wird die Verwendung eigens beschichteter Schwingquarze zur Detektion von Sprengstoffen, wie z. B. TATP, erläutert und eine daraus resultierende Steigerung der Sensibilität der Detektoren erklärt.rn

ALMASat-1, ALMASat-EO and beyond: evolution of structural concepts and technologies towards multifunctional structures for microsatellites

Multifunctional Structures (MFS) represent one of the most promising disruptive technologies in the space industry. The possibility to merge spacecraft primary and secondary structures as well as attitude control, power management and onboard computing functions is expected to allow for mass, volume and integration effort savings. Additionally, this will bring the modular construction of spacecraft to a whole new level, by making the development and integration of spacecraft modules, or building blocks, leaner, reducing lead times from commissioning to launch from the current 3-6 years down to the order of 10 months, as foreseen by the latest Operationally Responsive Space (ORS) initiatives. Several basic functionalities have been integrated and tested in specimens of various natures over the last two decades. However, a more integrated, system-level approach was yet to be developed. The activity reported in this thesis was focused on the system-level approach to multifunctional structures for spacecraft, namely in the context of nano- and micro-satellites. This thesis documents the work undertaken in the context of the MFS program promoted by the European Space Agency under the Technology Readiness Program (TRP): a feasibility study, including specimens manufacturing and testing. The work sequence covered a state of the art review, with particular attention to traditional modular architectures implemented in ALMASat-1 and ALMASat-EO satellites, and requirements definition, followed by the development of a modular multi-purpose nano-spacecraft concept, and finally by the design, integration and testing of integrated MFS specimens. The approach for the integration of several critical functionalities into nano-spacecraft modules was validated and the overall performance of the system was verified through relevant functional and environmental testing at University of Bologna and University of Southampton laboratories.

In-situ and real time scanning probe microscopy of organic ultra thin films

In recent decades, Organic Thin Film Transistors (OTFTs) have attracted lots of interest due to their low cost, large area and flexible properties which have brought them to be considered the building blocks of the future organic electronics. Experimentally, devices based on the same organic material deposited in different ways, i.e. by varying the deposition rate of the molecules, show different electrical performance. As predicted theoretically, this is due to the speed and rate by which charge carriers can be transported by hopping in organic thin films, transport that depends on the molecular arrangement of the molecules. This strongly suggests a correlation between the morphology of the organic semiconductor and the performance of the OTFT and hence motivated us to carry out an in-situ real time SPM study of organic semiconductor growth as an almost unprecedent experiment with the aim to fully describe the morphological evolution of the ultra-thin film and find the relevant morphological parameters affecting the OTFT electrical response. For the case of 6T on silicon oxide, we have shown that the growth mechanism is 2D+3D, with a roughening transition at the third layer and a rapid roughening. Relevant morphological parameters have been extracted by the AFM images. We also developed an original mathematical model to estimate theoretically and more accurately than before, the capacitance of an EFM tip in front of a metallic substrate. Finally, we obtained Ultra High Vacuum (UHV) AFM images of 6T at lying molecules layer both on silicon oxide and on top of 6T islands. Moreover, we performed ex-situ AFM imaging on a bilayer film composed of pentacene (a p-type semiconductor) and C60 (an n-type semiconductor).

Designer synthesis of monodisperse heterodimer and ferrite nanoparticles

The work presented in this doctoral thesis is a facile procedure, thermal decomposition, forrnthe synthesis of different types of monodisperse heterodimer M@iron oxide (M= Cu, Co, Nirnand Pt) and single ferrites, MFe2O4 (M= Cu and Co), nanoparticles. In the following chapter,rnwe study the synthesis of these monodiperse nanoparticles with the similar iron precursorrn(iron pentacarbonyl) and different transition metal precursors such as metalrnacetate/acetylacetonate/formate precursors in the presence of various surfactants and solvents.rnAccording to their decomposition temperatures and reducing condition, a specific and suitablernroute was designed for the formation of Metal@Metal oxide or MFe2O4 nanoparticlesrn(Metal/M=transition metal).rnOne of the key purposes in the formation of nanocrystals is the development of syntheticrnpathways for designing and controlling the composition, shape and size of predictedrnnanostructures. The ability to arrange different nanosized domains of metallic and magneticrnmaterials into a single heterodimer nanostructure offers an interesting direction to engineerrnthem with multiple functionalities or enhanced properties of one domain. The presence andrnrole of surfactants and solvents in these reactions result in a variety of nanocrystal shapes. Therncrystalline phase, the growth rate and the orientation of growth parameters along certainrndirections of these structures can be chemically modulated by using suitable surfactants. In allrnnovel reported heterodimer nanostructures in this thesis, initially metals were preformed andrnthen by the injection of iron precursor in appropriate temperature, iron oxide nanoparticlesrnwere started to nucleate on the top or over the surfaces of metal nanoparticles. Ternary phasesrnof spherical CuxFe3-xO4 and CoFe2O4 ferrites nanoparticles were designed to synthesis just byrnlittle difference in diffusion step with the formation of mentioned phase separated heterodimerrnnanoparticles. In order to use these magnetic nanoparticles in biomedical and catalysisrnapplications, they should be transferred into the water phase solution, therefore they werernfunctionalized by a multifunctional polymeric ligand. These functionalized nanoparticles werernstable against aggregation and precipitation in aqueous media for a long time. Magneticrnresonance imaging and catalytic reactivities are two promising applications which have beenrnutilized for these magnetic nanoparticles in this thesis.rnThis synthetic method explained in the following chapters can be extended to the synthesis ofrnother heterostructured nanomaterials such as Ni@MnO or M@M@iron oxide (M=transitionrnmetal) or to use these multidomain particles as building blocks for higher order structures.

Ortsgerichtete Modifikationen von Somatostatin-14 zur Darstellung von maßgeschneiderten Biohybridkonjugaten

Die hochspezifische Funktionalisierung von Proteinen und Peptiden kann durch milde reduktive Spaltung der lösungsmittelzugänglichen Disulfidbrücken und anschließende Rückverbrückung durch den Einbau sogenannter Linkermoleküle über einen konsekutiven Eliminierungs-Additionsprozess verwirklicht werden. Die Erweiterung des Linkerportfolios stellte in erster Instanz die Entwicklung von verschieden funktionalisierten Systemen dar, welche als hochflexible Kernbausteine für den Aufbau komplexer Architekturen dienten. Das Verständnis für die Reaktivität und Reversibilität der Thioladdition an die Mono-und Bissulfone in Abhängigkeit des Substituenten in p-Position konnte durch Variation von Parametern wie Lösungsmittel oder pH-Wert für intelligentes Produktdesign genutzt werden. Heterokonjugate zweier Biomoleküle mit ungepaartem Cystein wurden durch die Kombination von Maleinimid- und Bissulfonchemie innerhalb eines Linkermoleküls realisiert. Polymer-Peptid-Konjugate wurden einerseits über die grafting to Methode durch Modifizierung von Somatostatin mit PEGbissulfonen und anderseits durch grafting from unter Verwendung eines zuvor synthetisierten ATRP-Makroinitiators dargestellt. Multivalente Konjugate konnten durch die Synthese von hochsymmetrischen Tetra- sowie Hexasulfonen und anschließende Umsetzung mit Somatostatin erhalten werden. Die Polyinterkalatorpolymere, die durch lebende radikalische Polymerisation eines Bissulfidmonomers generiert wurden, wurden mit Glutathion umgesetzt. Durch die Interkalation von p-Ethinyl sowie p-Iodmonosulfon in die Disulfidbrücke von Somatostatin konnte erfolgreich gezeigt werden, dass die Rückverbrückung unter Rezyklisierung gelang. Die biologische Integrität wurde durch die Modifikation nicht beeinträchtigt und die erfolgreiche Aufnahme wurde nur bei den rezeptorpositiven Zellen (CAPAN-2) beobachtet. Das artifizielle Iodderivat im Vergleich zum nativen Somatostatin ein erhöhtes Potential zur Apoptoseinduktion. Die Somatostatinderivate präsentierten sich somit als attraktive potentielle Therapeutika.

Synthetic strategies of new spin-labelled supramolecular systems

Molecular recognition and self-assembly represent fundamental issues for the construction of supramolecular systems, structures in which the components are held together through non-covalent interactions. The study of host-guest complexes and mechanical interlocked molecules, important examples in this field, is necessary in order to characterize self-assembly processes, achieve more control over the molecular organization and develop sophisticated structures by using properly designed building blocks. The introduction of paramagnetic species, or spin labelling, represents an attractive opportunity that allows their detection and characterization by the Electron Spin Resonance spectroscopy, a valuable technique that provides additional information to those obtained by traditional methods. In this Thesis, recent progresses in the design and the synthesis of new paramagnetic host-guest complexes and rotaxanes characterized by the presence of nitroxide radicals and their investigation by ESR spectroscopy are reported. In Chapter 1 a brief overview of the principal concepts of supramolecular chemistry, the spin labelling approach and the development of ESR methods applied to paramagnetic systems are described. Chapter 2 and 3 are focused on the introduction of radicals in macrocycles as Cucurbiturils and Pillar[n]arenes, due to the interesting binding properties and the potential employment in rotaxanes, in order to investigate their structures and recognition properties. Chapter 4 deals with one of the most studied mechanical interlocked molecules, the bistable [2]rotaxane reported by Stoddart and Heath based on the ciclobis (paraquat-p-phenylene) CBPQT4+, that represents a well known example of molecular switch driven by external stimuli. The spin labelling of analogous architectures allows the monitoring by ESR spectroscopy of the switch mechanism involving the ring compound by tuning the spin exchange interaction. Finally, Chapter 5 contains the experimental procedures used for the synthesis of some of the compounds described in Chapter 2-4.

Synthese perfluoralkylierter mucinanaloger Glycolipopeptide zur multivalenten Antigenpräsentation

In dieser Dissertation konnten neuartige perfluoralkylierte Membranankersysteme basierend auf Tris(hydroxymehtyl)aminomethan (TRIS) dargestellt werden. Die perfluoralkylierte Ankersysteme mit C4F9-, C6F13- und C8F17-Ketten konnten in Glycolipopeptide des Mucins MUC1 eingebaut und immunologisch evaluiert werden. In allen untersuchten perfluoralkylierten Glycolipopeptiden konnten spezifische Wechselwirkungen mit Antikörpern nachgewiesen werden. Die Immunisierungen von Mäusen mit diesen nicht-natürlichen Verbindungen führten zur Bildung tumorspezifischer Antikörper. Insgesamt sind die Bindungsaffinitäten der gebildeten Antikörper noch zu gering in Bezug auf die Entwicklung effektiver anti-tumor Vakzine. Diese Bindungsaffinitäten könnte jedoch in künftigen Forschungsarbeiten durch die multivalente Präsentation der perfluoralkylierten Antigene in liposomalen Vakzinen verstärkt werden.rnrn