@phdthesis{Rehm2008, author = {Rehm, Thomas Helge}, title = {A Guide to Supramolecular Assemblies in Polar Solutions - From Nanometre-Sized Cyclic Dimers to Large Vesicular Structures}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-28359}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2008}, abstract = {This PhD thesis introduced several concepts for the construction of new supramolecular assem-blies in polar solvents. Although the building blocks differ in their binding mode and association strength they follow the same principle: one main driving force for the self-assembly in polar solutions in combination with one texturing force. The main self-assembly process is based on the mutual interaction of hydrogen-bond enforced ion pairs which deliver the association energy needed for stable, supramolecular structures even in polar solvents. The texturing force itself is represented by the linkers between the zwitterionic building blocks or parts of them. The different length and functionalization of the linkers have a tremendous influence on the mode of self-assembly leading to cyclic dimers, vesicles, layers or solid spheres. Hence, this principle is suitable for the construction of programmable monomers. Since the derivatisation of the main binding motive is rather simple it offers a great number of new and undoubtedly fascinating structures with potential applications in material and biomimetic science.}, subject = {Supramolekulare Chemie}, language = {en} } @phdthesis{Renner2021, author = {Renner, Rebecca}, title = {Aggregation, Chirality and Reduction of Nonplanar Polycyclic Aromatic Hydrocarbons}, doi = {10.25972/OPUS-24700}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-247000}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2021}, abstract = {Within this thesis the interactions between novel corannulene derivatives in solution as well as in the solid state by changing the imide residue of a literature known extended corannulene dicarboximide were investigated, in order to obtain a better understanding of the packing and possible charge transport in potential applications. Accordingly, the goal of the work was to synthesize and investigate an electron-poor corannulene bis(dicarboximide) based on previously published work but with higher solubility and less steric encumbrance in imide position to enable self-assembly in solution. To obtain further insights into the conformational stability, structure and chiroptical properties of heavily twisted PBIs another aim of this thesis was the design, synthesis, and optoelectronic investigation of various fourfold directly arylated PBIs by substitution in bay position with smaller hydrocarbons with different steric demand, i.e., benzene, naphthalene and pyrene, which should be separable by chiral high performance liquid chromatography (HPLC). As of yet, no concise study concerning the optical and electronic properties of differently core-substituted PBIs in the neutral as well as the mono- and dianionic state in solution is available, which also elucidates the origin of the different optical transitions observed in the absorption and emission spectra. Thus, in this thesis, the investigation of five PBI derivatives with different frontier energetic levels to produce a reference work of reduced PBIs was tackled.}, subject = {Corannulene}, language = {en} } @phdthesis{Sengupta2011, author = {Sengupta, Sanchita}, title = {Bio-inspired Zinc Chlorin Dye Assemblies for Supramolecular Electronics}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-66935}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2011}, abstract = {Chlorophylls are the most important pigments owing to their involvement in photosynthesis. They perform multiple functions that arise due to their optical and redox as well as packing properties. Semisynthetic zinc chlorins investigated in this thesis are the counterparts for the natural protein-free bacteriochlorophyll (BChl) c assemblies in light-harvesting (LH) systems in bacterial chlorosomes. The major advantage of the zinc chlorin model compounds over the native BChls lies in their facile semisynthetic accessibility from chlorophyll a (Chl a), their higher chemical stability and the possibility to influence their packing by suitable chemical modifications of peripheral side chains. Whilst the favorable excitonic properties and the suitability of ZnChl and natural BChl c dye aggregates for long distance exciton transport are well documented, charge transport properties of aggregates of semisynthetic ZnChls are hitherto unexplored. The present study involves structural elucidations of aggregates of a variety of semisynthetic zinc chlorin derivatives in solution, in solid state and on surfaces by combination of spectroscopic, crystallographic and microscopic techniques, followed by investigation of charge transport properties and conductivities of these aggregates. Chart 1 shows the different ZnChls synthesized in this work that are functionalized with hydroxy or methoxy substituents at 31 position and contain different substituents at the 172-position benzyl ester functional group. The self-assembly of these dyes is strongly dependent upon their chemical structures. While ZnChls 1a, 2a, 3, which are functionalized with 31-hydroxy group bearing dodecyl and oligoethylene glycol side chains form well-soluble rod aggregates, the corresponding 31-methoxy functionalized counterparts 1b, 2b form stacks in solution and on surfaces. These supramolecular polymers have been studied in detail in Chapter 3 by UV/Vis and circular dichroism (CD) spectroscopy and dynamic light scattering (DLS). These studies provided useful insights into the aggregation process of these two types of aggregates. Whereas 31-hydroxy functionalized ZnChl 1a self-assemble into rod aggregates via an isodesmic mechanism, corresponding stack aggregates of ZnChl 1b are formed by a cooperative nucleation-elongation pathway. Detailed electron microscopic studies such as transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) provided unequivocal evidence for hollow tubular nanostructures of water-soluble 31-hydroxy zinc chlorin 3 aggregates for the first time. The measured tube diameter of ~ 5-6 nm of these aggregates is in excellent agreement with electron microscopy data of BChl c rod aggregates in chlorosomes (Chloroflexus aurantiacus, diameter ~ 5-6 nm) and thus complied with the tubular model postulated by Holzwarth and Schaffner... In concord with their highly organized structures, micrometer-scale one dimensionality, robust nature and efficient charge transport capabilities, these self-assembled ZnChl nanotubular, stack and liquid crystalline assemblies are highly promising for supramolecular electronic applications. Research efforts in utilizing these assemblies for (opto)electronic device fabrication, for instance, in organic field effect transistors, should thus be rewarding in the future...}, subject = {Supramolekulare Chemie}, language = {en} } @phdthesis{PeethambaranNairSyamala2021, author = {Peethambaran Nair Syamala, Pradeep}, title = {Bolaamphiphilic Rylene Bisimides: Thermodynamics of Self-assembly and Stimuli-responsive Properties in Water}, doi = {10.25972/OPUS-21342}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-213424}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2021}, abstract = {The present thesis demonstrates how different thermodynamic aspects of self-assembly and stimuli-responsive properties in water can be encoded on the structure of π-amphiphiles, consisting of perylene or naphthalene bisimide cores. Initially, quantitative thermodynamic insights into the entropically-driven self-assembly was studied for a series of naphthalene bisimides with UV/Vis and ITC measurements, which demonstrated that their thermodynamic profile of aggregation is heavily influenced by the OEG side chains. Subsequently, a control over the bifurcated thermal response of entropically driven and commonly observed enthalpically driven self-assembly was achieved by the modulation of glycol chain orientation. Finally, Lower Critical Solution Temperature (LCST) phenomenon observed for these dyes was investigated as a precise control of this behavior is quintessential for self-assembly studies as well as to generate 'smart' materials. It could be shown that the onset of phase separation for these molecules can be encoded in their imide substituents, and they are primarily determined by the supramolecular packing, rather than the hydrophobicity of individual monomers.}, subject = {Supramolekulare Chemie}, language = {en} } @phdthesis{MezaChincha2021, author = {Meza Chincha, Ana Lucia}, title = {Catalytic Water Oxidation with Functionalized Ruthenium Macrocycles}, doi = {10.25972/OPUS-20962}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-209620}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2021}, abstract = {In light of the rapidly increasing global demand of energy and the negative effects of climate change, innovative solutions that allow an efficient transition to a carbon-neutral economy are urgently needed. In this context, artificial photosynthesis is emerging as a promising technology to enable the storage of the fluctuating energy of sunlight in chemical bonds of transportable "solar fuels". Thus, in recent years much efforts have been devoted to the development of robust water oxidation catalysts (WOCs) leading to the discovery of the highly reactive Ru(bda) (bda: 2,2'-bipyridine-6,6'-dicarboxylic acid) catalyst family. The aim of this thesis was the study of chemical and photocatalytic water oxidation with functionalized Ruthenium macrocycles to explore the impact of substituents on molecular properties and catalytic activities of trinuclear macrocyclic Ru(bda) catalysts. A further objective of this thesis comprises the elucidation of factors that influence the light-driven water oxidation process with this novel class of supramolecular WOCs.}, subject = {Rutheniumkomplexe}, language = {en} } @phdthesis{Munzert2018, author = {Munzert, Stefanie Martina}, title = {Coordination of dynamic metallosupramolecular polymers (MEPEs)}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-160650}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2018}, abstract = {Several transition metal ions, like Fe2+, Co2+, Ni2+, and Zn2+ complex to the ditopic ligand 1,4-bis(2,2':6',2''-terpyridin-4'-yl)benzene. Due to the high association constant, metal ion induced self-assembly of Fe2+, Co2+, and Ni2+ leads to extended, rigid-rod like metallo-supramolecular coordination polyelectrolytes (MEPEs) even in aqueous solution. Here, the kinetics of coordination and the kinetics of growth of MEPEs are presented. The species in solutions are analyzed by stopped-flow fluorescence spectroscopy, light scattering, viscometry and cryogenic transmission electron microscopy. At near-stoichiometric amounts of the reactants, high molar masses are obtained, which follow the order Ni-MEPE ~ Co-MEPE < Fe-MEPE. Furthermore, a way is presented to adjust the average molar mass, chain-length and viscosity of MEPEs using the monotopic chain stopper 4'-(phenyl)-2,2':6',2''-terpyridine.}, subject = {Supramolekulare Chemie}, language = {en} } @phdthesis{Shen2021, author = {Shen, Chia-An}, title = {Dicyanomethylene Squaraines: Aggregation and G-Quadruplex Complexation}, doi = {10.25972/OPUS-24359}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-243599}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2021}, abstract = {Squaraine dyes have attracted more attention in the past decade due to their strong and narrow absorption and fluorescence along with the easily functionalized molecular structure. One successful approach of core functionalization is to replace one oxygen of the squaric carbonyl group with a dicyanomethylene group, which shifts the absorption and emission into the near infrared (NIR) region and at the same time leads to a rigid, planar structure with C2v symmetry. However, such squaraines tend to aggregate cofacially in solution due to dispersion forces and dipole-dipole interactions, usually leading to H-type exciton coupling with undesired blue-shifted spectrum and quenched fluorescence. Therefore, the goal of my research was the design of dicyanomethylene-substituted squaraine dyes that self-assemble into extended aggregates in solution with J-type coupling, in order to retain or even enhance their outstanding optical properties. Toward this goal, bis(squaraine) dyes were envisioned with two squaraine units covalently linked to trigger a slip-stacked packing motif within the aggregates to enable J-type coupling. In my first project, bis(squaraine) dye BisSQ1 was synthesized, in which two dicyanomethylene squaraine chromophores are covalently linked. Concentration and temperature-dependent UV/Vis/NIR spectroscopy experiments reveal that BisSQ1 undergoes cooperative self-assembly resulting in J-type aggregates in a solvent mixture of toluene/1,1,2,2-tetrachloroethane (TCE) (98:2, v/v). The J type exciton coupling is evident from the significantly red shifted absorption maximum at 886 nm and the fluorescence peak at 904 nm. In conclusion, this was a first example to direct squaraine dye aggregation in solution to the more desired slip-stacked packing leading to J-type exciton coupling by simply connecting two dyes in a head-to-tail bis chromophore structure. Connecting two squaraine dyes with an additional phenylene spacer (BisSQ2) leads to two different polymorphs with very distinct absorption spectra upon cooling down a solution of BisSQ2 in a solvent mixture of toluene/TCE (98:2, v/v) with different rates. Accordingly, rapid cooling resulted in rigid helical nanorods with an absorption spectrum showing a panchromatic feature, while slow cooling led to a sheet-like structure with a significant bathochromic shift in the absorption spectrum. It was discovered that the conventional molecular exciton model failed to explain the panchromatic absorption features of the nanorods for the given packing arrangement, therefore more profound theoretical investigations based on the Essential States Model (ESM) were applied to unveil the importance of intermolecular charge transfer (ICT) to adequately describe the panchromatic absorption spectrum. Moreover, the red-shift observed in the spectrum for the sheet-like structure can be assigned to the interplay of Coulomb coupling and ICT-mediated coupling. Furthermore, the same bis-chromophore strategy was adopted for constructing an NIR-II emitter with a bathochromically-shifted spectrum. In chloroform, BisSQ3 exhibits an absorption maximum at 961 nm with a significant bathochromic shift (1020 cm-1) compared to the reference mono-squaraine SQ, indicating intramolecular J-type coupling via head-to-tail arrangement of two squaraine dyes. Moreover, BisSQ3 shows a fluorescence peak at 971 nm with a decent quantum yield of 0.33\%. In less polar toluene, BisSQ3 self-assembles into nanofibers with additional intermolecular J-type coupling, causing a pronounced bathochromic shift with absorption maximum at 1095 nm and a fluorescence peak at 1116 nm. Thus, connecting two quinoline-based squaraines in a head-to-tail fashion leads to not only intra-, but also intermolecular J-type exciton coupling, which serves as a promising strategy to shift the absorption and emission of organic fluorophores into the NIR-II window while retaining decent quantum yields. In conclusion, my research illustrates based on squaraine dyes how a simple modification of the molecular structure can significantly affect the aggregation behavior and further alter the optical properties of dye aggregates. Elongated supramolecular structures based on dicyanomethylene substituted squaraine dyes were successfully established by covalently linking two squaraine units to form a bis-chromophore structure. Then, a simple but efficient general approach was established to direct squaraine dye aggregation in solution to the more desired slip-stacked packing leading to J-type exciton coupling by directly connecting two squaraine dyes in a head-to-tail fashion without spacer units. Moreover, the additional spacer between the squaraine dyes in BisSQ2 allowed different molecular conformations, which leads to two different morphologies depending on the cooling rates for a hot solution. Hence, this is a promising strategy to realize supramolecular polymorphism. In general, it is expected that the concept of constructing J-aggregates by the bis-chromophore approach can be extended to entirely different classes of dyes since J-aggregates possess a variety of features such as spectral shifts into the NIR window, fluorescence enhancement, and light harvesting, which are commonly observed and utilized for numerous fundamental studies and applications. Moreover, the insights on short-range charge transfer coupling for squaraine dyes is considered of relevance for all materials based on alternating donor-acceptor π-systems. The panchromatic spectral feature is in particular crucial for acceptor-donor-acceptor (ADA) dyes, which are currently considered as very promising materials for the development of bulk heterojunction solar cells.}, subject = {Squaraine}, language = {en} } @phdthesis{Kaufmann2019, author = {Kaufmann, Christina}, title = {Discrete Supramolecular Architectures of Bay-linked Perylene Bisimide Dimers by Self-Assembly and Folding}, doi = {10.25972/OPUS-17300}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-173005}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2019}, abstract = {Supramolecular self-assembly of perylene bisimide (PBI) dyes via non-covalent forces gives rise to a high number of different PBI architectures with unique optical and functional properties. As these properties can be drastically influenced by only slightly structural changes of the formed supramolecular ensembles (Chapter 2.1) the controlled self-assembly of PBI dyes became a central point of current research to design innovative materials with a high potential for different applications as for example in the fields of organic electronics or photovoltaics. As PBI dyes show a strong tendency to form infinite aggregated structures (Chapter 2.2) the aim of this thesis was to precisely control their self-assembly to create small, structurally well-defined PBI assemblies in solution. Chapter 2.3 provides an overview on literature known strategies that were established to realize this aim. It could be demonstrated that especially backbone-directed intra- and intermolecular self-assembly of covalently linked Bis-PBI dyes evolved as one of the most used strategies to define the number of stacked PBI chromophores by using careful designed spacer units with regard to their length and flexibility. By using conventional spectroscopic methods like UV/Vis and fluorescence experiments in combination with NMR measurements an in-depth comparison of the molecular and optical properties in solution both in the non-stacked and aggregated state of the target compounds could be elucidated to reveal structure-property relationships of different PBI architectures. Thus, it could be demonstrated, that spacer units that pre-organize two PBI chromophores with an inter-planar distance of r < 7 {\AA} lead to an intramolecular folding, whereas linker moieties with a length between 7 to 11 {\AA} result in an intermolecular self-assembly of the respective Bis-PBIs dyes via dimerization to form well-defined quadruple PBI pi-stacks. Hence, if the used spacer units ensure an inter-planar distance r > 14 {\AA} larger oligomeric PBI pi-stacks are generated. In Chapter 4 a detailed analysis of the exciton coupling in a highly defined H-aggregate quadruple PBI pi-stack is presented. Therefore, bay-tethered PBI dye Bis-PBI 1 was investigated by concentration-dependent UV/Vis spectroscopy in THF and toluene as well as by 2D-DOSY-NMR spectroscopy, ESI mass spectrometry and AFM measurements confirming that Bis-PBI 1 self-assembles exclusively into dimers with four closely pi-stacked PBI chromophores. Furthermore, with the aid of broadband fluorescence upconversion spectroscopy (FLUPS) ensuring broadband detection range and ultrafast time resolution at once, ultrafast Frenkel exciton relaxation and excimer formation dynamics in the PBI quadruple pi-stack within 1 ps was successfully investigated in cooperation with the group of Dongho Kim. Thus, it was possible to gain for the first time insights into the exciton dynamics within a highly defined synthetic dye aggregate beyond dimers. By analysing the vibronic line shape in the early-time transient fluorescence spectra in detail, it could be demonstrated that the Frenkel exciton is entirely delocalized along the quadruple stack after photoexcitation and immediately loses its coherence followed by the formation of the excimer state. In Chapter 5 four well-defined Bis-PBI folda-dimers Bis-PBIs 2-4 were introduced, where linker units of different length (r < 7 {\AA}) and steric demand were used to gain distinct PBI dye assemblies in the folded state. Structural elucidation based on in-depth UV/Vis, CD and fluorescence experiments in combination with 1D and 2D NMR studies reveals a stacking of the two PBI chromophores upon folding, where geometry-optimized structures obtained from DFT calculations suggest only slightly different arrangements of the PBI units enforced by the distinct spacer moieties. With the resulting optical signatures of Bis-PBIs 2-4 ranging from conventional Hj-type to monomer like absorption features, the first experimental proof of a PBI-based "null-aggregate" could be presented, in which long- and short-range exciton coupling fully compensate each other. Hence, the insights of this chapter pinpoint the importance of charge-transfer mediated short-range exciton coupling that can significantly influence the properties of pi-stacked PBI chromophores In the last part of this thesis (Chapter 6), spacer-controlled self-assembly of four bay-linked Bis-PBI dyes Bis-PBIs 5-8 into well-defined supramolecular architectures was investigated, where the final aggregate structures are substantially defined by the nature of the used spacer units. By systematically extending the backbone length from 7 to 15 {\AA} defining the inter-planar distance between the tethered chromophores, different assemblies from defined quadruple PBI pi-stacks to larger oligomeric pi-stacks could be gained upon aggregation. In conclusion, the synthesis of nine covalently linked PBI dyes in combination with a detailed investigation of their spacer-mediated self-assembly behaviour in solution concerning structure-properties-relationships was presented within this thesis. The results confirm a strong exciton coupling in different types of Bis-PBI architectures e.g. folda-dimers or highly defined quadruple pi-stacks, which significantly influences their optical properties upon self-assembly.}, subject = {Supramolekulare Chemie}, language = {en} } @phdthesis{Neitz2024, author = {Neitz, Hermann}, title = {Hydrophobic recognition motifs in functionalized DNA}, doi = {10.25972/OPUS-34838}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-348382}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2024}, abstract = {In w{\"a}ssriger Umgebung spielen hydrophobe Wechselwirkungen eine wichtige Rolle f{\"u}r die DNA. Die Einf{\"u}hrung von Modifikationen, die auf hydrophoben aromatischen Einheiten basieren, kann die Erkennung und Reaktivit{\"a}t von funktionellen Gruppen in der DNA steuern. Modifikationen k{\"o}nnen durch ein k{\"u}nstliches R{\"u}ckgrat oder in Form einer Erweiterung der Nukleobasen eingebracht werden und so zu zus{\"a}tzlichen Eigenschaften der DNA f{\"u}hren. Diese Dissertation befasst sich mit der Verwendung von hydrophoben Einheiten zur Funktionalisierung von DNA. Im ersten Teil der Arbeit wurde das Tolanmotiv (Diphenylacetylen) in Kombination mit dem acyclischen R{\"u}ckgrat von GNA und BuNA verwendet, um Erkennungseinheiten im DNA-Kontext zu erzeugen. Die gezielte Fluorierung der aromatischen Ringe des Tolan-Bausteins bildete die Grundlage f{\"u}r eine supramolekulare Sprache, die auf Aren-Fluoroaren-Wechselwirkungen basiert. Die spezifische Erkennung wurde mittels thermodynamischer, kinetischer und NMR-spektroskopischer Methoden untersucht. Im zweiten Teil der Arbeit wurden Desoxyuridin-Derivate mit einer hydrophoben aromatischen Modifikation hergestellt und in die DNA-Doppelhelix eingebaut. Die Bestrahlung mit UV-Licht f{\"u}hrte zu einer [2+2]-Cycloaddition zwischen zwei modifizierten Nukleosiden in der DNA. Das Reaktionsprodukt wurde strukturell charakterisiert und die Reaktion in verschiedenen biochemischen und nanotechnologischen DNA-Anwendungen eingesetzt.}, subject = {Supramolekulare Chemie}, language = {en} } @phdthesis{Wich2009, author = {Wich, Peter Richard}, title = {Multifunctional Oligopeptides as an Artificial Toolkit for Molecular Recognition Events}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-38108}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2009}, abstract = {The main focus of this thesis was the synthesis and analysis of multifunctional oligopeptides. The study of their non-covalent interactions with various counterparts revealed interesting new results, leading to both methodological and application related progress. The first project of this thesis concentrated on the in-depth analysis of the peptide receptor CBS-Lys-Lys-Phe-NH2 to acquire a better understanding of its binding mode upon complexation with a substrate. In this context it was possible to develop—in cooperation with the group of Prof. Sebastian Schl{\"u}cker—a direct and label free spectroscopic detection of immobilized compounds which are often found in combinatorial libraries. This new screening method utilizes the advantages of the surface enhanced Raman spectroscopy and allowed for the first time a surface mapping of a single polystyrene bead for the identification of peptides in femtomolar concentrations. Hence, this method allows a very fast and sensitive detection of resin bound compounds. The development of this promising new approach set the starting point for future experiments to enable on-bead library screenings and to investigate the complex formation of immobilized compounds. After the comprehensive analysis of the basic structural features of small peptide receptors in the first part of this thesis, the second big block focused on its in vitro evaluation using biological relevant targets. Therefore, several different modifications of the initial peptide structures were synthesized. These modifications provided a molecular toolkit for the tailor made synthesis of structures individually designed for the respective target. The first tests addressed the interaction with Alzheimer's related amyloid fibrils. During these experiments, the successful SPPS syntheses of tri- and tetravalent systems were achieved. The comparison of the multivalent form with the corresponding monovalent version was then under special investigations. These concentrated mainly on the interaction with various bacteria strains, as well as with different parasites. To localize the compounds within the organisms, the synthesis of fluorescence labelled versions was achieved. In addition, several compounds were tested by the Institute for Molecular Infection Biology of the University of W{\"u}rzburg for their antibacterial activity. This thorough evaluation of the biological activity generated precious information about the influence of small structural changes in the peptide receptors. Especially the distinct influence of the multivalency effect and the acquired synthetic skills led to the development of an advanced non-covalent recognition event, as described in the final project of this thesis. The last part of this thesis discussed the development of a novel inhibitor for the serine protease beta-tryptase based on a tailor-made surface recognition event. It was possible to study and analyze the complex interaction with the unique structure of tryptase, that features a tetrameric frame and four catalytic cleavage sites buried deep inside of the hollow structure. However, the point of attack were not the four binding pockets, as mostly described in the literature, but rather the acidic areas around the cleavage sites and at the two circular openings. These should attract peptides with basic residues, which then can block the accessibility to the active sites. A combinatorial library of 216 tetravalent peptide compounds was synthesized to find the best structural composition for the non-covalent inhibition of beta-tryptase. For the screening of the library a new on-bead assay was applied. With this method a simultaneous readout of the total inhibition of all library members was possible, thus allowing a fast and direct investigation of the still resin bound inhibitors. Several additional experiments in solution unveiled the kinetics of the inhibition process. In conclusion, both mono- and multivalent inhibitors interact in a non-destructive and reversible way with the tryptase.}, subject = {Peptidsynthese}, language = {en} }