Inhalt des Abstactbandes

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3 Inhaltsverzeichnis Inhalt des Abstactbandes Grusswort Unterstützer Messestände Vortragende Appetithäppchen Abstracts der Teilnehmer Teilnehmerliste nach Fachbereichen aufgeschlüsselt Notizen Programm (Rückseite) Druck Copier-Center Haase, Würzburg Dieser Abstractband besitzt keine Seitenzahlen. Dafür sind jeweils am Rand die Posternummern eingetragen. In eben dieser Reihenfolge sind die Poster auch während der Posterpräsentation aufgestellt. Weitere Informationen können aus den Lageplänen entnommen werden.

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5 GRUSSWORT JCF Liebe Teilnehmer der Chem-SyStM 2016, sehr geehrte Gäste, vor ziemlich genau 10 Jahren hatten die damaligen, aktiven Mitglieder des JungChemikerForums Würzburg die Idee ein Symposium an unserer Fakultät ins Leben zu rufen und somit einen gewichtigen Beitrag zum wissenschaftlichen Austausch und zur Vernetzung der einzelnen Fachbereiche zu leisten. Tragende Säule dieser Veranstaltung sollte, damals wie heute, die Studentenschaft bilden und dadurch die Möglichkeit erhalten sich im familiären Umfeld erste oder weiterführende Fertigkeiten im wissenschaftlichen Präsentieren und Kommunizieren zu erlangen. Vor diesem Hintergrund und der Tatsache, dass sich dieses Symposium auch zur 6. Auflage weiterhin großer Beliebheit erfreut, ist es dem JCF-Würzburg ein besonderes Vergnügen Sie zur Chem-SyStM 2016 begrüßen zu dürfen. Unter dem Motto Großes vereint im Kleinsten bieten wir auch dieses Jahr wieder ein abwechslungsreiches Programm, darunter die bekannten Poster-Appetithäppchen und die Postersession, sowie einen Abendvortrag zum Thema Chemie der Pyrotechnik gehalten von Herrn Dr. Klein-Sommer. Darüber hinaus wird es erstmals bereits am Morgen einen Vortrag geben, Vortragsgast ist Herr Christian Lange vom VAA (Verband angestellter Akademiker und leitender Angestellter der Chemischen Industrie e.v.). Als abschließenden Höhepunkt dürfen wir uns alle auf ein Feuerwerk auf dem Campusgelände freuen, bevor ein hoffentlich ereignisreicher und wissenschaftlich ansprechender Tag bei geselliger Runde seinen gebührenden Ausklang findet und vielleicht dem/der einen oder anderen Teilnehmer/in ein zukünftiges Engagement im JungChemikerForum schmackhaft gemacht hat. Wir wünschen Ihnen viel Freude, gute Unterhaltung und einen interessanten Austausch bei der Chem-SyStM Euer Sprecher-Team des JCF-Würzburg Thomas Steffenhagen Sebastian Endres Domenik Schleier

6 GRUSSWORT OVV Liebe Studierende, Neugierde und Faszination sind gelebte Attribute, die uns in der Wissenschaft täglich Schritt für Schritt auf dem steinigen Weg von der Idee zur Erkenntnis vorantreiben. Von den Hochschulen werden Spitzenleistungen in Lehre und Forschung erwartet. Die Universität Würzburg, im Speziellen die Fakultät für Chemie und Pharmazie, stellt sich diesen Herausforderungen und forscht mit ihren Mitarbeitern und den Studierenden gemeinsam für eine umfassende Perspektive auf die großen Zukunftsfragen wie Nachhaltigkeit und Gesundheit oder neue Materialien und Bauelemente, führt aber auch wichtige Grundlagenforschung durch, deren Relevanz sich vielleicht erst viel später zeigen wird. Chemie Großes vereint im Kleinsten kann natürlich vieles heißen. Großes schaffen mit kleinen molekularen Einheiten. Es könnte aber auch bedeuten, die Ähnlichkeiten in großen Gebilden, seien es biologische Zellen oder auf neuen Materialien basierende Bauelemente, sind dadurch vereint, dass sie auf ähnlichen chemischen Prinzipien beruhen. Beides, das Große aber auch die gemeinsamen Prinzipien bringt eine Komplexität der Fragestellungen mit sich, die immer häufiger nur durch Netzwerke beantwortet werden können, an denen Wissenschaftler aus vormals abgegrenzten Bereichen kooperieren müssen. Zentral für den Erfolg solcher Netzwerke ist jedoch der kommunikative Austausch der einzelnen wissenschaftlichen Disziplinen. Das Chemie-Symposium der Studierenden Mainfrankens, kurz Chem-SyStM, die von dem JCF-Regionalforum Würzburg in guter Tradition zum sechsten Mal organisiert wird, ermöglicht eine solche Kommunikation, denn das grundlegende Ziel und die zentrale Aufgabe dieses Symposiums liegen in der Präsentation und regen Diskussion wissenschaftlicher Arbeiten von Studierenden sehr unterschiedlicher Fachrichtungen im familiären Umfeld der eigenen Universität. Ich freue mich auf interessante Forschungsarbeiten von Studierenden für Studierende und wünsche allen Teilnehmerinnen und Teilnehmern einen spannenden und erkenntnisreichen Tag. Prof. Dr. Bernd Engels Ortsverbandsvorsitzender OV Unterfranken

7 GRUSSWORT Dekan Liebe Mitglieder des Jungchemikerforums, liebe Kolleginnen und Kollegen, liebe Studierende, die ChemSyStM findet nun seit ihrer Etablierung im Jahre 2007 das sechste mal statt und hat sich somit einen festen Platz im akademischen Jahr unserer Fakultät erarbeitet. Auch dieses Jahr stehen wieder spannende Vorträge und eine Postersession an, in der junge Nachwuchswissenschaftler ihre Forschung und damit einen Einblick in die Forschung unserer Arbeitskreise vorstellen werden. Dies soll nicht nur dem wissenschaftlichen Austausch unter den Arbeitskreismitgliedern dienen, sondern auch den Studierenden, sich über Arbeitskreise, den dort bearbeiteten Forschungsschwerpunkten sowie über mögliche Bachelor- oder Masterarbeitsthemen zu erkundigen. Aufgrund der stark gewachsenen Anzahl an Arbeitskreisen haben wir und dieses Jahr dazu entschieden, die sonst übliche Präsentation der Arbeitskreise durch Ultrakurzvorträge von den Arbeitskreis-Chefs durch entsprechende informative Poster zu ersetzen. Es würde mich freuen, wenn wir von Seiten der Teilnehmer eine Rückmeldung über diese Vorgehensweise erhalten könnten, so dass wir Ihre Meinung bei künftigen Planungen berücksichtigen können. Für dieses Mal wünsche ich allen Teilnehmern eine spannende und nicht zuletzt auch unterhaltsame ChemSyStM 2016! Ihr Christoph Lambert Dekan

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9 UNTERSTÜTZER Bedanken möchten wir uns hiermit bei unseren finanziellen Unterstützern, den folgenden Unternehmen und Institutionen: Fakultät für Chemie und Pharmazie

10 MESSE In diesem Jahr mit einem Informationsstand vertreten sind die folgenden Unternehmen und Institutionen mit Ansprechpartnern:

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12 Appetithäppchen Appetithäppchen # Name Vorname Arbeitskreis Kategorie 16 Paul Ursula Radius Anorganische Chemie und Materialwissenschaften 22 Schmitt Hans- Physikalische und Theoretische Fischer Christian Chemie 29 Lombe Blaise Bringmann Biochemie und Organische Chemie 31 Schweeberg Sarah Krüger Biochemie und Organische Chemie 38 Pres Sebastian Brixner Physikalische und Theoretische Chemie 48 Warkentin Viktor Krüger Biochemie und Organische Chemie 53 Griesbeck Stefanie Marder Anorganische Chemie und Materialwissenschaften 66 Feizy Nilab Schatzschneider Anorganische Chemie und Materialsynthese 67 Soberats Bartolome Würthner Biochemie und Organische Chemie 72 Moustafa Ahmed Schatzschneider Anorganische Chemie und Materialwissenschaften 80 Merz Julia Marder Anorganische Chemie und Materialwissenschaften 83 Syamala Pradeep Würthner Biochemie und Organische Chemie 86 Leonhardt Viktoria Beuerle Biochemie und Organische Chemie 88 Wachtler Stefan Krüger Biochemie und Organische Chemie 89 Nowak-Król Agnieszka Würthner Biochemie und Organische Chemie

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15 ABSTRACTS ABSTRACTS

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17 Anorganische Chemie und Materialwissenschaften AK Prof. Müller-Buschbaum Hybrid Materials Introduction and Overview of our Research P1 T. Schäfer, T. Wehner, S. Zottnick, J. Stangl, F. Mühlbach, A. Sedykh, J. Sorg, K. Müller- Buschbaum Institut für Anorganische Chemie, JMU-Würzburg, Am Hubland, Würzburg, Germany The research of our workgroup is focused on inorganic-organic hybrid materials based on solid-state chemistry. This includes the field of coordination chemistry in particular complexes, coordination polymers (CPs) and metal-organic frameworks (MOFs) as well as the functionalization of other materials with our systems. For our syntheses, we employ various metal precursors and organic ligands such as amines, amides, heterocyclic systems, ionic liquids and borates. Besides ordinary Schlenktechniques, various synthesis strategies are used, such as solvent-free melt synthesis and mechanochemical synthesis, known from solid-state-chemistry. In addition, we are strongly interested in the properties of our compounds with the synthesis of luminescent MOFs as well as fine-tuning of their luminescence being one focus. The latter refers to maximize quantum-efficiencies as well as accurate color adjustments, which is, among other things, achieved by co-doping of host lattices with luminescent cations. By combination of MOFs with other functional materials, new multifunctional hybrid materials and composites with highly specialized properties can be obtained. Thus, we are interested in modification of various substrates by deposition of defined thin films of MOFs on their surface. Furthermore, the surface modification of luminescent or superparamagnetic micro- and nanoparticles with MOFs can lead to unprecedented multifunctional sensor-type materials that combine the properties of both materials. For the characterization of our materials, we use single crystal and powder X-Ray diffraction methods assisted by a wide range of spectroscopic methods (IR, RAMAN, NMR, UV-VIS-NIR, Photoluminescence spectroscopy and Fluorescence microscopy), elemental analysis methods like CHNS and EDX and many other additional analytical methods such as simultaneous DTA/TG and BET. For more information, please visit our website or contact us via k.mueller-buschbaum@uni-wuerzburg.de

18 P2 Physikalische und Theoretische Chemie AK Engel - höchst dynamisch! Unser Ansatz: Man nehme eine physikalisch-chemische Fragestellung und würze diese mit Mathematik, bis sich ein Modell ergibt. Anschließend muss der Ansatz programmiert werden und hoffentlich werden alle Bugs entfernt. Rechnungen mit Minuten oder Tagen an Rechenzeit liefern dann mehr oder weniger erfreuliche Ergebnisse. Es fehlt dann noch deren Interpretation, die eventuelle Modifizierung der Modelle und die publizierte Antwort auf alle Fragen. In diesem Sinne werden auf unserem AK-Poster die grundlegenden Konzepte der Quantendynamik und Auszüge aus der aktuellen Forschung vorgestellt.

19 Anorganische Chemie und Materialwissenschaften AK Mandel Complex nanostructured particles by design The Particle Technology Group (Karl Mandel) P3 Fraunhofer-Institut für Silicatforschung ISC Neunerplatz Würzburg Lehrstuhl Chemische Technologie der Materialsynthese an der Julius-Maximilians-Universität Würzburg, Röntgenring 11, Würzburg The Particle Technology Group focuses on the synthesis and processing of nano- and microparticles. The fundamental question is how complex, nanostructured particles can be synthesised and which novel properties can be obtained from these (inorganic) particles. In the recent years, the art of synthesising and tailoring nanoparticles with distinct properties has attracted tremendous interest and has been explored very well. The next step further is to consider these particles as nano-building blocks which shall be combined bottom-up to form again particles, but now complex, nanostructured particles. The aim is to achieve novel functional particles with interactive properties that can only be obtained from the smart assembly of nano-building blocks to combined entities. An example in the field of magnetic particles are nanocomposite particles which can be employed for water purification [1,2] or as magnetically collectable, optical sensors for target substances in fluids [3] or as unique hollow magnetic architectures. [4] Other nanoparticle building-blocks such as nano silica can be assembled to nanostructured micro-raspberry particles which act as mechanically reactive container structures, which can, for instance, be used in coatings with a refreshable surface functionality such as an anti-bacterial activity. [5] Beyond that, many more unique properties, and from that, new applications in the field of energy, environment or sustainability, can be targeted by building complex particle entities from nano-building-blocks. [1] ACS Applied Materials and Interfaces 2012, 4, [2] RSC Journal of Materials Chemistry A 2013, 1, [3] ACS Applied Materials and Interfaces 2016, 8, [4] ACS Nano, accepted, DOI: /acsnano.6b06063 [5] ACS Applied Materials and Interfaces 2015, 7,

20 P4/5 Anorganische Chemie und Materialwissenschaften AK Dembski Multifunctional Nanoparticles for Medical Applications S. Dembski, M. Straßer, C. Schneider, B. Christ, H. Walles Fraunhofer Institute for Silicate Research, Neunerplatz 2, Wuerzburg, Germany Translational Center Wuerzburg Regenerative therapies in oncology and musculoskelettal diseases and Department Tissue Engineering and Regenerative Medicine (TERM), University Hospital Wuerzburg, Roentgenring 11, Wuerzburg, Germany The main emphasis of the competence team Theranostics at the Fraunhofer Institute for Silicate Research ISC is, in cooperation with the Translational Center Würzburg Regenerative therapies in oncology and musculoskelettal diseases, on products enabling highly efficient and personalized therapy accompanying in vitro and in vivo diagnosis or even combine diagnosis and therapy in situ. Well-tailored multifunctional nanoparticles (NPs), which are in focus of our R&D work, are playing a major role in the development of future oriented advanced functional materials for life science applications e.g. contrast agents in medical imaging, in vitro and in vivo diagnostics, drug delivery as well as tissue engineering. Especially, inorganic-organic biohybrid NPs are considered to be important for the development of smart materials and novel technologies for medical applications. NPs can be prepared by wet-chemical methods: sol-gel, precipitation or hydrothermal synthesis. The main focus of our R&D work lies on inorganic and hybrid materials e.g. silicate based materials, calcium fluoride and phosphate, TiO 2 and iron oxide. To ensure multifunctionality different approaches can be applied e.g. labelling of NP matrix with organic dyes or lanthanoid ions as well as combination of various materials by core-shell NP design. The resulting NPs are subsequently modified with various chemical functionalities and biological moieties using conventional functionalization and bioconjugation methods. The great potential of new developed NPs as immunodetection assay labels, contrast agent for medical imaging or tool for tumor therapy is demonstrated by the different projects.

21 Organische Chemie und Biochemie AK Pöppler Investigation of Polymeric Drug Delivery by NMR P6 Improvement of the drug delivery and bio-availability of active pharmaceutical ingredients (APIs) is a huge and important field of research to which we would like to contribute on the basis of NMR experiments in the solid-state, in gels and in solution (Figure 1). For example, polymeric vehicles can reduce the toxicity of a drug by shielding it, transport poorly soluble molecules to the site of action or release molecules as response to an external stimulus. A variety of systems such as different polymeric architectures, microemulsions, liquid crystals or nanotubes can be applied for this purpose. [1] Synthetic approaches can yield tailored macromolecules with different functionalities [2] or attached to biological molecules. [3] The broad field of NMR Spectroscopy (Figure 2) provides a variety of tools to study intermolecular interactions of the drug molecules with each other as well as with the surrounding polymeric environment. The poster will give a first impression on three different steps, (i) the thorough analysis of the APIs by NMR in the solid-state and in solution, (ii) the characterization of polymer networks and hydrogels in general by anisotropic Figure 1: Schematic representation of the systems and NMR methods to study drug delivery mediated by polymeric systems. NMR and (iii) the study of the interactions between the API and the polymer environment as well as the drug release process (e.g. by diffusion, a stimulus, degradation, etc.). Furthermore, first NMR results from a recently started study of curcumin in collaboration with the work group of Prof. Luxenhofer will be shown. Figure 2: Orientation dependent and orientation independent NMR interactions in solids and in liquids: z = Zeemann, rf = radio frequency, D = diploar, CS = chemical shift, Q = quadrupolar and J = J coupling. [1] N. Kamaly, Z. Xiao, P. M. Valencia, A. F. Radovic-Moreno, O. C. Farokhzad, Chem. Soc. Rev. 2012, 41, [2] M. Danial, C. My-Nhi Tran, P. G. Young, S. Perrier, K. A. Jolliffe, Nat Commun 2013, 4. [3] I. Cobo, M. Li, B. S. Sumerlin, S. Perrier, Nat Mater 2015, 14,

22 P7 Organische Chemie und Biochemie AK Lambert Projekte für Bachelorarbeiten M. Moos 1, C. Lambert 1 1 Institute of Organic Chemistry, University of Würzburg, Am Hubland, Würzburg michael.moos@uni-wuerzburg.de, christoph.lambert@uni-wuerzburg.de Mehr Informationen erhalten Sie an Poster 7, wir freuen uns auf Ihr Kommen!

23 Pharmazie und Lebensmittelchemie Characterization of novel in-silico designed Hsp70 inhibitors P8 C. Plank 1,2, A. Hofmann 1, C. Grimm 2, C. Sotriffer 1 1 Institute of Pharmacy and Food Chemistry, University of Würzburg 2 Theodor Boveri Institute, Department of Biochemistry, University of Würzburg Heat-shock protein 70 (Hsp70) has been shown to play a crucial role in the development of Multiple Myeloma (MM), a neoplastic disease of terminally differentiated, antibody-producing B-cells. Although various Hsp70 inhibitors have already been reported, these were mostly directed against the nucleotide (ATP)-binding domain of Hsp70, rendering them likely to cause selectivity problems. Our work focusses on identifying inhibitors that bind to the domain interface of Hsp70, thus greatly enhancing their selectivity for Hsp70. Starting from structural information about the Hsp70 protein, virtual screening identified compounds that displayed low micromolar activities against MM cells. The most potent hit was expanded into a library of derivatives, which led to a series of compounds active against MM cells without toxicity on non-malignant peripheral blood mononuclear cells. The mode of action of these compounds is now being investigated by an approach combining functional assays and structural studies via X-ray crystallography. To this end, recombinantly purified truncated and double-mutated bovine heat-shock cognate 70 (bhsc70 ED 1-554) and endogenous native full-length Hsc70 from pig brain have been screened for crystallization with these inhibitors. In parallel, functional viability of the purified Hsc70 isoforms was ascertained with luciferase refolding assays, demonstrating 30-50% chaperone activity. Inhibition assays are now being conducted to quantify the potency of the inhibitors and characterize their inhibition mechanism. This might help to develop more potent and selective inhibitors of Hsp70, thus springing open interesting avenues in translational research for MM.

24 P9 Anorganische Chemie und Materialwissenschaften LÖSUNGEN VON BRØNSTED-SÄUREN UND MÜNZMETALLSALZEN IN NIEDRIG-VISKOSEN IONISCHEN FLÜSSIGKEITEN C. Kerpen 1, J. A. P. Sprenger 1, L. Herkert 1, T. Ribbeck 1, F. A. Brede 1, N. V. Ignat'ev 2, K. Müller-Buschbaum 1, M. Finze 1 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg; 2 Berater, Merck KGaA, Darmstadt/D jan.sprenger@uni-wuerzburg.de, christoph.kerpen@uni-wuerzburg.de Ionische Flüssigkeiten, basierend auf Cyanoborat-Anionen, z. B. [BH 4 n(cn) n] (n = 2 4), sind aufgrund ihrer hohen thermischen, elektrochemischen und chemischen Stabilität verbunden mit ihrer meist sehr niedrigen Viskosität vielseitig einsetzbar. [1] Gegenwärtig untersuchen wir ausgewählte physikalische und chemische Eigenschaften von Hauptgruppen- und Übergangsmetallsalzen mit Cyanoborat-Anionen und ihre Lösungen in ionischen Flüssigkeiten. Auf Cyanoborat-Anionen basierende Brønsted-Säuren stellen dabei zweckmäßige Startmaterialien für eine Vielzahl von verschiedenen Cyanoboraten dar. Bisher wurden allerdings erst wenige Protonen- und Oxonium-Salze mit Cyanoborat-Anionen beschrieben, beispielsweise H[B(CN) 4] [2] und (H 3O) 2[B 2(CN) 6]. [3] Vor kurzem haben wir eine effiziente Synthese zu der bisher unbekannten Brønsted-Säure H[BH 2(CN) 2] (Abb. 1) entwickelt, [4] die bisher beispiellose Eigenschaften in ihrem chemischen, elektrochemischen und thermischen Verhalten zeigt. H[BH 2(CN) 2] besitzt eine außergewöhnlich hohe Löslichkeit (ca. 35 Gew.% bei RT) in EMIm[BH 2(CN) 2]. [5] Dies macht die Säure zu einem ausgezeichneten Startmaterial für Synthesen, insbesonders von (Metall-)Salzen mit dem [BH 2(CN) 2] - Anion. Von großem Interesse sind die zu H + isolobalen Münzmetall(I)-Ionen, wodurch sie für Vergleiche mit Brønsted-Säuren interessant sind. Daher wurden die Ag + - und Cu + -Salze mit dem [BH 2(CN) 2] -Anion synthetisiert und ihre Eigenschaften mit denen des H + -Salzes verglichen. Abbildung 1: Ausschnitt aus den Ketten von 1 H[BH2(CN)2]} (links) and 1 Ag(bpy)[BH2(CN)2]} (rechts). [1] N. V. Ignat'ev, M. Finze, J. A. P. Sprenger, C. Kerpen, E. Bernhardt, H. Willner, J. Fluorine Chem. 2015, 177, [2] T. Küppers, E. Bernhardt, C. W. Lehmann, E. Willner, Z. Anorg. Allg. Chem. 2007, 633, [3] J. Landmann, J. A. P. Sprenger, M. Hailmann, V. Bernhardt-Pitchougina, H. Willner, N. Ignat'ev, E. Bernhardt, M. Finze, Angew. Chem. Int. Ed. 2015, 54, [4] M. Drisch, L. A. Bischoff, L. Herkert, J. A. P. Sprenger, M. Finze, N. Ignatyev, R. van Hal, Merck Patent GmbH, WO A1, [5] E. Bernhardt, V. Bernhardt-Pitchougina, H. Willner, N. Ignatyev, M. Schulte, Merck Patent GmbH, WO , 2012.

25 Physikalische und Theoretische Chemie Photodissociation reactions of the ortho- & para-xylyl radical: A Velocity Map Imaging study P10 K. Pachner 1, I. Fischer 1 1 Institut für Physikalische und Theoretische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland Süd, Würzburg, Deutschland Xylyl radicals can be found as intermediates in combustion processes. Their parent molecules, the xylenes, are used as additives in fuels to increase antiknock properties. The thermal decomposition of the xylyl radicals has been explored recently by Hemberger et al. in a synchrotron experiment. [1] Based on these studies, we investigated the photodissociation of the ortho- &para-xylyl radical using velocity map imaging. Xylyl radicals were formed via flash pyrolysis in a pulsed molecular beam using 2- respectively 4-methylphenethyl nitrite as a precursor. Irradiation of the xylyl radicals with UV light leads to a hydrogen atom loss forming para-xylylene for the para isomer, while either ortho-xylylene or benzocyclobutane could be the product for the ortho isomer. Generated hydrogen fragments are then ionized in a [1+1 ]-REMPI process via the 1s-2p transition and detected on a velocity map imaging detector. Afterwards the angular as well as the kinetic energy distribution of the abstracted hydrogen atoms are analyzed. [1] Hemberger et al., J. Phys. Chem. A 2014, 118,

26 P11 Organische Chemie und Biochemie Star-shaped oligo(phenylenevinylene) mesogens for segregated nanomaterials M. Dechant, M. Hügel, M. Lehmann Institut für Organische Chemie, Universität Würzburg, Am Hubland, Würzburg Star-shaped oligo(p-phenylenevinylene) compounds are nonconventional shape-persistent mesogens, which form liquid crystalline mesophases despite the large void space between their arms (Figure 1). [1] The four-armed phthalocyanine stars with terminal oligoethyleneoxy chains exhibit hexagonal columnar LC-phases over broad temperature ranges by nanosegregation of the rigid core and the long lateral chains. Phthalocyanines are highly interesting substances for the application in organic photovoltaic cells due to their strong absorption in the red- and infrared range and their flat and broad π-system, which allows efficient π-stacking along columnar assemblies. [2,3] Analogous to previous work [4] fullerenes are covalently linked via short spacers to the stilbene arms. This design should result in the segregation of fullerene and phthalocyanine/stilbene scaffolds and consequently in quadruple helical columnar self-assemblies. The highly ordered, liquid-crystalline structures are investigated by means of polarized optical microscopy, differential scanning calorimetry and comprehensive X-ray scattering. R = O(C 2 H 4 O) 3 C 2 H 5 X = H, n = 0,1,2 Free space 1 [1] M. Lehmann, B. Schartel, M. Hennecke, H. Meier, Tetrahedron 1999, 55, [2] R. F. Enes, J.-J. Cid, A. Hausmann, O. Trukhina, A. Gouloumis, P. Vázquez, J. A. S. Cavaleiro, A. C. Tomé, D. M. Guldi, T. Torres, Chemistry A European Journal 2012, 18, [3] P. Apostol, J. Eccher, M. E. R. Dotto, C. B. Costa, T. Cazati, E. A. Hillard, H. Bock, I. H. Bechtold, Physical Chemistry Chemical Physics 2015, 17, [4] M. Lehmann, M. Hügel, Angewandte Chemie International Edition 2015, 54,

27 Anorganische Chemie und Materialwissenschaften NHC-stabilisierte Derivate des Tricarbonylnitrosylkobalts P12 K. Lubitz, U. Radius* Institut für Anorganische Chemie der Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg, Durch die Umsetzung des Tricarbonylnitrosylkobalts [Co(CO) 3(NO)] mit N-Heterozyklischen Carbenen (NHC s) konnte eine Vielzahl einfach und zweifach substituierter Komplexe des Typs [Co(CO) 2(NO)(NHC)] bzw. [Co(CO)(NO)(NHC) 2] isoliert und charakterisiert werden (NHC: ipr 2Im, npr 2Im, Cy 2Im, Me 2Im, ipr 2ImMe, Me 2ImMe, MeiPr 2Im, MetBu 2Im; R 2Im = 1,3-di-alkyl-imidazolin-2- ylidene). [1] Die Verwendung sterisch anspruchsvoller NHC s führte dabei ausschließlich zu der Bildung der einfach substituierten Komplexe [Co(Dipp 2Im)(CO) 2(NO)], [Co(Mes 2Im)(CO) 2(NO)] sowie [Co(MecAAC)(CO) 2(NO)]. Für die Umsetzung mit tbu 2Im wurde eine abnormale Koordination über das Rückgrat beobachtet und der Komplex [Co(tBu 2aIm)(CO) 2(NO)] erhalten. Eine Untersuchung der thermischen Eigenschaften ergab, dass sich die Komplexe leicht in die Gasphase überführen lassen, sublimierbar sind und sich erst bei hohen Temperaturen zersetzen. Somit erfüllen sie die thermischen Ansprüche, um zum Beispiel in der chemischen Gasphasenabscheidung Anwendung zu finden. [2,3] [1] F. Hering, J. H. J. Bertel, Organometallics 2016, 35, [2] K. Gao, N. Yoshikai, Acc. Chem. Res. 2014, 47, [3] M. Leskalä, M. Ritala, Thin Solid Films 2002, 409,

28 P13 Anorganische Chemie und Materialwissenschaften Copper(I)-catalyzed Suzuki-Miyaura type cross-coupling reactions A. Eichhorn, U. Radius*, T. B. Marder* Prof. Dr. Todd B. Marder, Chair of Inorganic Chemistry, Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg We recently reported efficient systems for the borylation of arylhalides and alkylhalides using copper(i) and phosphines as ligands. [1,2] In addition, we are interested in developing other Cu-catalyzed B-C and C-C coupling processes, such as Suzuki-Miyaura type reactions. [3,4] Proposed catalytic cycle for Cu(I) catalyzed borylation. Discrete steps in Cu-catalyzed C-B and C-C coupling processes. In order to obtain insight into reaction mechanisms and rates, we have begun a study of stoichiometric reactions modelling discrete steps in likely catalytic pathways. To do this, we have prepared and characterized a wide variety of (NHC)-Cu(I)-Y complexes wherein Y = halides, alkoxide, acetate, alkyl, aryl and boryl. The synthesis and preliminary reactivity studies of such Cu(I) complexes will be presented. [1] C. Kleeberg, L. Dang, Z. Lin, T. B. Marder, Angew. Chem. Int. Ed. 2009, 48, [2] C.-T. Yang, Z.-Q. Zhang, H. Tajuddin, C.-C. Wu, J. Liang, J.-H. Liu, Y. Fu, M. Czyzewska, P. G. Steel, T. B. Marder, L. Liu, Angew. Chem. Int. Ed. 2012, 51, [3] Y. Zhou, W. You, K. B. Smith, M. K. Brown, Angew. Chem. Int. Ed. 2014, 53, [4] S. K. Gurung, S. Thapa, A. Kafle, D. A. Dickie, R. Giri, Org. Lett. 2014, 16,

29 Organische Chemie und Biochemie Living Supramolecular Polymerization of Dye Aggregates with H- and J-Type Exciton Coupling P14 W. Wagner, M. Wehner, O. Soichiro, V. Stepanenko, F. Würthner* Universität Würzburg, Center for Nanosystems Chemistry, Institut für Organische Chemie and Bavarian Polymer Institute, Universität Würzburg, Würzburg, Germany * Supramolecular polymerization of π conjugated has recently attracted attention in material science as a concept to create well-defined architectures with controlled properties and functions. [1] Although the thermodynamics of supramolecular polymerizations was studied in detail and analyzed by mathematical models,the knowledge about the kinetics of aggregation processes is still not well-known. Remarkably, kinetic effects in supramolecular systems are essential, playing an important role in the structure and functions of the self-assembled aggregates. One strategy to control the kinetics of an aggregation process is the seeded polymerization concept, which consists of the induction of supramolecular polymerization of kinetically trapped building blocks by addition of seeds (small aggregates acting as nuclei). [2] Figure 1: Visualization of the concept of seeded polymerization and molecular structure of MeO-PBI. In our previous studies we have successfully applied the concept of seeded supramolecular polymerization in perylene bisimide (PBI) dye aggregates. [3] In the present work, we demonstrate that this approach can be also employed to transform kinetically trapped non-fluorescent H-aggregates of a dimethoxy-substituted PBI dye (MeO-PBI) into highly emissive J-aggregates by an innovative living supramolecular polymerization mechanism. This is an unprecedented approach to control the kinetics of supramolecular polymerization and to obtain out-of-equilibrium polymers with low polydispersity, narrow size distribution and photofunctional properties. [1] (a) T. Aida, E. W. Meijer, S. I. Stupp, Science 2012, 335, 813. (b) D. van der Zwaag, T. F. A. de Greef, E. W. Meijer, Angew. Chem. Int. Ed. 2015, 54, [2] S. Ogi, K. Sugiyasu, S. Manna, S. Samitsu, M. Takeuchi, Nat. Chem. 2014, 6, 188. [3] (a) S. Ogi, V. Stepanenko, J. Thein, F. Würthner, J. Am. Chem. Soc. 2016, 138, 670. (b) S. Ogi, V. Stepanenko, K. Sugiyasu, M. Takeuchi, F. Würthner, J. Am. Chem. Soc. 2015, 137, 3300.

30 P15 Anorganische Chemie und Materialwissenschaften The Light at the End of the Cycle: Luminescent Rhodacyclopentadienes and Rhodium 2,2 Biphenyl Complexes C. Sieck 1, M. Guan Tay 2, M.-H. Thibault 2, A. Steffen 1,2, T. B. Marder 1,2 * 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg, Germany 2 Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK Reactions of [Rh(κ 2 -O,O-acac)(PMe3)2] (acac = acetylacetonato) and α,ω-bis- (arylbutadiynyl)alkanes afford two isomeric types of MC4 metallacycles with very different photophysical properties. As a result of a [2+2] reductive coupling at Rh, 2,5- bis(arylethynyl)rhodacyclopentadienes (A) are formed, which display intense fluorescence (Φ = , τ = ns) despite the presence of the heavy metal atom. Rhodium biphenyl complexes (B), which show exceptionally long-lived (hundreds of μs) phosphorescence (Φ = ) at room temperature in solution, have been isolated as a second isomer originating from an unusual [4+2] cycloaddition reaction and a subsequent β-h-shift. We attribute the different photophysical properties of isomers A and B to a higher excited state density and a less stabilized T1 state in the biphenyl complexes B, allowing for more efficient intersystemcrossing S1 Tn and T1 S0. Control of the isomer distribution is achieved by modification of the bis(diyne) linker length, providing a fundamentally new route to access photoactive metal biphenyl compounds. [1] [1] C. Sieck, M. G. Tay, M.-H. Thibault, R. M. Edkins, K. Costuas, J.-F. Halet, A. S. Batsanov, M. Haehnel, K. Edkins, A. Lorbach, A. Steffen, T. B. Marder, Chem. Eur. J. 2016, 22, 1052.

31 Anorganische Chemie und Materialwissenschaften Eigenschaften und Reaktivität von zyklischen Alkylaminocarbenen (CAACs) und deren Nickelcarbonylkomplexe P16 U. Paul, U. Radius * Institut für Anorganische Chemie der Julius-Maximilians-Universität Würzburg ursula.paul@uni-wuerzburg.de, u.radius@uni-wuerzburg.de Seit den bahnbrechenden Arbeiten von Arduengo et al. zur Synthese und Isolierung des stabilen 1,3- Diadamantylimidazolin-2-ylidens [1] vor 25 Jahren hat die Chemie von N-Heterozyklischen Carbenen (NHCs) enorme Beachtung erfahren, besonders durch deren Anwendung als Liganden in der Übergangsmetallchemie. [2] Ihre Effizienz ist auf einen sterisch anspruchsvollen Aufbau und starke σ- Donor-Eigenschaften zurückzuführen. [3] Durch Austausch eines der beiden elektronegativen Aminosubstituenten in direkter Nachbarschaft zum Carbenkohlenstoffatom durch Alkylgruppen werden sogenannte zyklische Alkylaminocarbene (CAACs) generiert. Diese sind folglich elektronenreicher und somit nukleophiler als die zugrundeliegenden NHCs. Gleichzeitig resultiert dieser Austausch auch in einer Absenkung des Carben π*-orbitals, was zudem eine höhere Elektrophilie der CAACs bedingt. [4] Im Fokus unserer Arbeiten standen CAAC-stabilisierte Nickelcarbonylkomplexe, welche primär dazu dienen sollten, einen Einblick in elektronische und sterische Parameter, die diese Carbenklasse auszeichnen, zu erlangen und sie mit denen der verwandten NHCs zu vergleichen. [5] Desweiteren wollten wir die Reaktivität dieser neuartigen heteroleptischen Nickelcarbenkomplexe mit Hauptaugenmerk auf CO-Substitution durch Neutralliganden und oxidativer Addition von Aryl- und Allylhalogeniden untersuchen. Im Rahmen dieses Beitrags wollen wir die entsprechenden Ergebnisse vorstellen und diskutieren. [1] A. J. Arduengo III, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113, [2] a) P. de Frémont, N. Marion, S. P. Nolan, Coord. Chem. Rev. 2009, 253, ; b) S. P. Nolan (Ed.), N-Heterocyclic Carbenes: Effective Tools for Organometallic Synthesis, Wiley-VCH, Weinheim, [3] C. M. Crudden, D. P. Allen, Coord. Chem. Rev. 2004, 248, [4] a) V. Lavallo, Y. Canac, C. Präsang, B. Donnadieu, G. Bertrand, Angew. Chem. Int. Ed. 2005, 44, ; Angew. Chem. 2005, 117, 5851; b) M. Soleilhavoup, G. Bertrand, Acc. Chem. Res. 2015, 48, [5] U. S. D. Paul, C. Sieck, M. Haehnel, K. Hammond, T. B. Marder, U. Radius, Chem. Eur. J. 2016, 22,

32 P17 Physikalische und Theoretische Chemie Study of the self-reaction products of o-benzyne radicals via IR/UV ion-dip-spectroscopy F. Hirsch, P. Constantinidis, I. Fischer, A. M. Rijs The self-reaction products of o-benzyne radicals produced by flash pyrolysis have been studied by ion-dipspectroscopy in a free jet. As recent studies suggest, these molecules might play an important role in the even numbered growth of polycyclic aromatic hydrocarbons (PAH s) and consequently soot, as they can serve as a source of acetylene and diacetylene in combustion processes. The spectroscopic method utilized in this study is capable of providing mass selective infrared spectra, which can be used for unambiguous identification of the formed molecules. The radicals have been generated by flash pyrolysis from the benzocyclobutendion precursor and ionized at fixed wavelengths at 265 and 275 nm. A tunable free electron laser provided infrared radiation in the range of cm -1. Subsequent analysis of the differences in ion signals, with and without infrared excitation, resulted in the sought after infrared spectra. Eventually comparison with theoretical and experimental data was performed for identification of the various reaction products. This poster will provide a fundamental overview of methodology and results of this study, executed at the Free Electron Laser for Infrared experiments (FELIX) (Nijmegen, Netherlands).

33 Organische Chemie und Biochemie Defined Electron-Poor Nanographenes: One-Pot Synthesis and Single Crystal Structure Analysis P18 S. Seifert, K. Shoyama, D. Bialas, D. Schmidt, F. Würthner* Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, Würzburg, Germany * Polycyclic aromatic hydrocarbons (PAHs) are an outstanding class of organic molecules that are characterized by extended carbon-rich sp 2 -hybridized scaffolds with high thermal stability and interesting electronic properties. Therefore, this type of compounds has attracted continuous interest during the last decades as promising candidates for applications in organic electronics and photovoltaics. The synthesis of electron rich PAHs is often realized by multistep procedures including C-C coupling reactions and oxidative dehydrogenations [1] while the synthetic access to electron-poor systems is generally underdeveloped presumably due to the instability of electron-deficient carbocations which are integral intermediates in oxidative dehydrogenation reactions. In our contribution we report the one-pot synthesis and full characterization of core extended pyrenes bearing multiple dicarboximide substituents that can be regarded as electron-poor nanographenes. [2] Figure 1: Solid-state molecular structure of an electron-poor nanographene (ellipsoids set at 50 % probability). We efficiently combined palladium catalyzed Suzuki-Miyaura cross coupling and dehydrohalogenation to synthesize large sized multiple imide containing chromophores with up to ten new C-C bonds formed in a single reaction. The molecular structures of these π-extended systems have been elucidated by single-crystal X-ray analysis confirming the formation of multiple C-C bonds and planar geometry of the scaffolds. Moreover, the optical and electrochemical properties of these electron-poor PAHs have been characterized and show their relevance for potential applications in (opto)electronic devices. [1] a) A. Narita, X.-Y. Wang, X. Feng, K. Müllen, Chem. Soc. Rev. 2015, 44, 6616; b) M. Grzybowski, K. Skonieczny, H. Butenschön, D. T. Gryko, Angew. Chem. Int. Ed. 2013, 52, [2] a) S. Seifert, K. Shoyama, D. Schmidt, F. Würthner, Angew. Chem. Int. Ed. 2016, 55, 6390; b) S. Seifert, D. Schmidt, F. Würthner, Org. Chem. Front. 2016, DOI: /c6qo00421k.

34 P19 Anorganische Chemie und Materialwissenschaften Bismuth-based Luminescent Materials J. R. Sorg, K. Müller-Buschbaum Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, Würzburg This research projects aims at the synthesis and characterisation of new coordination polymers (CPs) and metal-organic frameworks (MOFs) constructed from inorganic bismuth salts, such as bismuth halides, and organic, multidentate, aromatic N-donor ligands. Various synthetic pathways have already been established for the synthesis of such CPs, namely reactions in solution, in ligand- and salt-melts, under solvothermal conditions, as well as mechanochemical reactions. Bismuth-based CPs show extraordinary luminescence properties dominated by charge-transfer processes between inorganic building units, e.g. bismuth/halide-units, and the π-system of the organic linkers. [1] Additionally, Bi 3+ and trivalent lanthanide cations Ln 3+ prefer the same oxidation state +3 and exhibit similar ionic radii, hence bismuth-based CPs are predestined as host-lattices for Ln 3+ cations. [2] As lanthanides are well-known emission centres in luminescent materials, these host/guest compounds promise applicability in lighting and sensor technologies, as they combine the luminescence properties of the bismuth-based hostlattices and the Ln 3+ guests. Thus, colour-tunable emission by variation of the ratio of the different emission centres becomes availbale. [3] Furthermore, these co-doped materials could be used as ratiometric sensors, in which the emission of the host-lattice serves as internal standard to enable quantitative detection of small target molecules. The first examples of bismuth-based coordination polymers synthesised during this research project are the one-dimensional compounds α- and β- 1 [ Bi 2X 6(bipy) 2] (X: Cl, Br, I; bipy: 4,4 -Bipyridine), in which the bismuth cations are coordinated in distorted octahedra by four chlorido- and two 4,4 -bipyridine ligands. Interesting photoluminescence properties based on charge-transfer processes are observed for X = Cl and X = Br. Figure 1: Crystal structure along c (left) and photoluminescence spectra measured at 77 K (right) of β- [ 1 Bi 2Cl 6(bipy) 2]. [1] O. Toma, M. Allain, F. Meinardi, A. Forni, C. Botta, N. Mercier, Angewandte Chemie International Edition [2] J. Heine, T. Wehner, R. Bertermann, A. Steffen, K. Müller-Buschbaum, Inorg Chem 2014, 53, [3] P. R. Matthes, C. J. Hoeller, M. Mai, J. Heck, S. J. Sedlmaier, S. Schmiechen, C. Feldmann, W. Schnick, K. Müller-Buschbaum, J. Mater. Chem. 2012, 22,

35 Pharmazie und Lebensmittelchemie Isotopically labelled mass tags as in vivo diagnostics P20 K. Dodt 1, A. Schlosser 2, J. Vanselow 2, T. Lühmann 1, L. Meinel 1 1 Institute of Pharmacy and Food Chemistry, University of Würzburg, Am Hubland, Würzburg, Germany 2 Rudolf-Virchow-Zentrum für Experimentelle Biomedizin, University of Würzburg, Josef-Schneider- Str. 2, Würzburg, Germany Profiling enzymatic activity of inflamed tissues is essential for patient stratification. In one scenario, each patient is a priori categorized and directed to medicine one is going to respond to (personalized medicine). In spite of this promise, proper tools for patient stratification within the context of inflamed joints (rheumatoid arthritis - RA, osteoarthritis - OA) are yet to be found in the future. Therefore, we aim at developing proteasecleavable linkers (PCL) conjugated to mass encoded peptides that are cleaved by upregulated matrix metalloproteinases (MMP) in inflamed osteoarthritic joints, thereby reflecting the release of the drug in situ (Figure 1). MMP Mass tag ce Surfa PCL Drug Figure 1: Bioresponsive drug delivery system: protease-cleavable linkers are cleaved by up regulated MMP and released mass tags are analysed by LC-MS/MS in body fluids. To detect PCL cleavage by MMP activity in vivo, mass tags with isotopically labelled amino acids were designed, allowing quantification by tandem mass spectrometry. [1] In order to create a suitable mass tag that forms two major ion fragments, three amino acid sequences were synthesized by Fmoc based solid phase peptide synthesis (SPPS). After RP-HPLC purification the mass tags were analysed by LC-MS/MS resulting in the amino acid sequence SADGPGFR being the best fragmenting mass encoded peptide. Four different PCLs and the respective mass tags are currently prepared by SPPS and are conjugated to a biopolymer by conducting bio-orthogonal chemical reactions, such as copper-catalyzed azide alkyne cycloaddition (CuAAC). [2] Future steps include the demonstration of the in vivo efficacy in relevant animal systems of RA and OA. [1] G. A. Kwong, G. von Maltzahn, G. Murugappan, O. Abudayyeh, S. Mo, I. A. Papayannopoulos, D. Y. Sverdlov, S. B. Liu, A. D. Warren, Y. Popov, D. Schuppan, S. N. Bhatia, Nat. Biotechnol. 2013, 31, 63. [2] M. Gutmann, E. Memmel, A. C. Braun, J. Seibel, L. Meinel, T. Luhmann, Chembiochem 2016, 17, 866.

36 P21 Organische Chemie und Biochemie Kinetic control of supramolecular polymerization by ultrasonication M. Wehner, S. Ogi, W. Wagner, V. Stepanenko, F. Würthner* Universität Würzburg, Center for Nanosystems Chemistry, Institut für Organische Chemie, and Bavarian Polymer Institute, Universität Würzburg, Würzburg, Germany * Supramolecular polymerization has recently attracted particular attention for the development of welldefined functional architectures. [1] While the thermodynamics of supramolecular polymerizations were studied in detail by mathematical models, deep knowledge on the kinetics of aggregation processes is still lacking. Perylene bisimide (PBI) dyes are suitable to study these phenomena since they possess favorable aggregation behaviors and outstanding optical properties. [2] Recently, the kinetics of self-assembly processes of PBI derivatives have been studied by seeded supramolecular polymerization. [3] In the present work we achieved the kinetic control on the aggregation behavior of chiral (S,S)-PBI-C2* and studied the influence of ultrasonication by IR, UV/Vis and CD spectroscopy as well as AFM (Figure 1). Figure 1. Chemical structure of (S,S)-PBI-C2* (a); absorption spectra (b) and AFM height images (c) of the different aggregates of (S,S)-PBI-C2* and photographs of their colored solutions in MCH/Tol 5:4 (c T = 400 µm, 298 K). [1] T. Aida, E. W. Meijer, S. I. Stupp, Science 2012, 335, [2] F. Würthner, C. R. Saha-Möller, B. Fimmel, S. Ogi, P. Leowanawat, D. Schmidt, Chem. Rev. 2016, 116, [3] a) S. Ogi, V. Stepanenko, J. Thein, F. Würthner, J. Am. Chem. Soc. 2016, 138, 670; b) S. Ogi, V. Stepanenko, K. Sugiyasu, M. Takeuchi, F. Würthner, J. Am. Chem. Soc. 2015, 137,

37 Physikalische und Theoretische Chemie ps-zeitaufgelöste Photoionisation des S2(ππ*)-Zustands von Xanthon P22 M. Flock, H.-C. Schmitt, I. Fischer Die Dynamik angeregter Zustände von Heterozyklen, die auch Carbonylgruppen enthalten, hängt stark von der Konkurrenz der Desaktivierung über IC und ISC ab. Dies konnte bereits an den Molekülen 9-Fluorenon, [1] NDCA [2] und Naphthalimid [3] gezeigt werden. Ein weiterer Vertreter dieser Substanzklasse ist Xanthon. Mittels Photoinisations-Experimenten konnte die vibronische Struktur des S 2-Zustands aufgelöst und die Desaktivierung des Moleküls nach Anregung in diesen verfolgt werden. In einem gepulsten Molekularstrahlexperiment wurden die Moleküle mit einem nm Pump-Puls zunächst resonant in den S 2- Zustand angeregt. Anschließend erfolgte die Ionisation mit einem 351 nm Probe-Puls. Zwei Zeitkonstanten sowie ein anschließender Offset wurden im Experiment beobachtet. Während die erste Zeitkonstante unterhalb der zeitlichen Auflösung des Setups liegt, konnte für die zweite ein Wert von 24 ps ermittelt werden. Der Offset kommt durch die Population eines im Rahmen der Zeitskala des Experiments langlebigen Triplett-Zustands zustande, was in Einklang der literaturbekannten Phosphoreszenz steht. [4] Für die Relaxation aus dem S 2-Zustand können zwei verschiedene Modelle in Betracht gezogen werden. Es kann zum einen zunächst ein IC-Übergang in den S 1-Zustand und anschließend ein ISC-Prozess in die Triplett- Umgebung stattfinden (Modell A). Andererseits kann es auch zuerst zu einem ultraschnellen ISC-Prozess in die Triplett-Umgebung, gefolgt von anschließender Interner Konversion (IC) innerhalb dieser, kommen (Modell B). Um dies aufklären zu können, sollen in Zukunft zeitaufgelöste Photoelektronen-Imaging- Experimente durchgeführt werden. [1] T. Gerbich, J. Herterich, J. Köhler, I. Fischer, The Journal of Physical Chemistry A 2014, 118, [2] T. Gerbich, H.-C. Schmitt, I. Fischer, J. Petersen, J. Albert, R. Mitrić, The Journal of Physical Chemistry A 2015, 119, [3] T. Gerbich, H.-C. Schmitt, I. Fischer, R. Mitrić, J. Petersen, The Journal of Physical Chemistry A 2016, 120, [4] H. J. Pownall, J. R. Huber, Journal of the American Chemical Society 1971, 93,

38 P23 Organische Chemie und Biochemie MOLECULAR DESIGN OF METALLOSUPRAMOLECULAR RUTHENIUM CATALYSTS FOR WATER OXIDATION A. L. Meza, D. Schindler, V. Kunz, M. Schulze, F. Würthner Universität Würzburg, Institut für Organische Chemie, Am Hubland, Würzburg, Germany The development of new sustainable energy sources constitutes one of the most important challenges of our generation. In this regard, the light-induced splitting of water into its elements has attracted particular attention as both sunlight and water are widely available and inexpensive resources. The goal is to achieve a cycle of clean energy production by using the elemental hydrogen obtained from the catalytic splitting of water as an ecologically friendly fuel. Currently, our research has focused on the half reaction of the oxidation of water to oxygen which is considered to be the bottleneck of the entire water splitting process. So far we have been able to synthesize a robust metallosupramolecular ruthenium catalyst, which has an activity comparable to that of the oxygen evolving complex (OEC) of the photosystem II. Based on our mechanistic investigations on the catalytic water oxidation our next goal is to introduce different substituents into the catalyst s scaffold to tune its electronic properties to obtain even higher catalytic activities. Here we present the synthesis and characterization of novel molecularly designed metallo-supramolecular ruthenium catalysts that are equipped with electron withdrawing or donating substituents. Investigations regarding their activity toward chemical and light-induced water oxidation are currently being performed in our laboratories. [1] V. Balzani, A. Credi, M. Venturi, Chem. Sus. Chem. 2008, 1, [2] P. D. Frischmann, K. Mahata, F. Würthner, Chem. Soc. Rev. 2013, 42, [3] M. Schulze, V. Kunz, P. D. Frischmann, F. Würthner, Nat. Chem. 2016, 8,

39 Organische Chemie und Biochemie Synthesis of a novel Donor Sensitizer Acceptor Triad for the Investigation of Magnetic Field Effects P24 D. Mims, C. Schwarz, C. Lambert Triads with small B 1/2,hfc values, which are about one magnitude larger than the earth s magnetic field have already been investigated by Lambert et. al. [1] These triads comprise of triarylamine donors containing a nitrogen atom with a nuclear spin of I = 1. Since the magnetic field effect is dependent on the nuclear magnetic moment of the donor- and acceptor moiety, a substitution of these donors with the sulfur (I = 0) bearing building block tetrathiafulvalene should lead to a charge separated state with a decreased effective magnetic moment and thus should give rise to triads that are sensitive to the earth s magnetic field. Yet the synthesis of the desired complex proves to be difficult due to the electronrich tetrathiafulvalene building block. Hence detailed information on planed and already realized synthesis is given in this study. Figure 1: After absorption of visible light a charge separated state occurs. The triplet splitting of the cs-state and its kinetics are dependent on the external magnetic field. [1] [1] J. H. Klein, D. Schmidt, U. E. Steiner, C. Lambert, J. Am. Chem. Soc. 2015, 137,

40 P25 Organische Chemie und Biochemie Functionalised precursors for extended π-systems with a Tribenzotriquinacene core R. Buschmann, A. Krueger Institut für Organische Chemie, Am Hubland, Würzburg Tribenzotriquinacene (TBTQ, 1) is a bowl-shaped aromatic hydrocarbon, whose curved structure derives from the three fused five-membered rings at its centre. Theoretical studies have indicated that TBTQ can be considered as a defect centre in a distorted nanographene. [1] The aim is to functionalise 1 by bridging the bay regions (indicated in bold below) and thereby extend the carbon network to give PAH 2. TBTQ synthesis can be achieved either using the Kuck synthesis pathway [2] or the triple cyclisation method from Hopfet al., [3] which allows access to ortho-functionalised derivatives, by using suitably substituted starting materials. Examples of ortho-substituted TBTQ derivatives are limited, [4] due to increased steric strain experienced at this position. TBTQs 3, 4 and 5 are synthetic aims of this work and progress made towards their realisation will be presented and discussed. [1] J. Tellenbröker, D. Kuck, Angew. Chem. Int. Ed. 1999, 38, 919. [2] D. Kuck, Angew. Chem. Int. Ed. Engl. 1984, 23, 508. [3] H. Hopf, G. Markopoulos, L. Henneicke, J. Shen, Y. Okamoto, P. G. Jones, Angew. Chem. Int. Ed. 2012, 51, [4] Y. Kirchwehm, A. Damme, T. Kupfer, H. Braunschweig, A. Krueger, Chem. Comm. 2012, 48, 1502.

41 Physikalische und Theoretische Chemie Excitons and Polarons in Motion: Understanding Charge Generation Pathways at the Interfaces of Organic Solar Cells P26 C. Brückner, B. Engels Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Germany In view of the need to exploit alternative energy resources, organic solar cells based on small organic molecules were designed. While fullerene and derivatives are often employed as the n-type semiconductor, the structural diversity of p-type semiconductors is larger. For a selection of p-type molecular semiconductors in combination with fullerene C 60, we generated model structures of the organic-organic interfaces in organic solar cells using MM (molecular mechanics) techniques. Careful benchmarking (DFT, semiempiric and wave-function based methods) was performed in order to find quantum-mechanical methods that are both efficient and correct (to a reasonable extent) for the prediction of geometric and electronic properties of the p-type semiconductors. Energetic profiles of the bilayer interfaces were calculated using a dimer approach, electric fields and an effective epsilon. The calculation of both charged and excited transport bands yields polaronic and excitonic states in the vicinity of the organic-organic interface. From the energetic profiles of the interfaces, it can be concluded that particularly interfacial trap states, i.e., geminate electron-hole pairs which are significantly bound due to weakly shielded charge-charge interactions, could limit device efficiencies. In order to model the charge generation route in organic solar cells, kinetic Monte Carlo simulations were conducted. Resulting charge separation efficiencies highlighted the critical role of slow charge transport processes around the organic-organic interface.

42 P27 Pharmazie und Lebensmittelchemie Personalisierte Dosisfindung in der Psychiatrie A. Pospiech *1, M. Zilker *1, J. Scheiber 2, U. Holzgrabe 1, P. Högger 1 *zu gleichen Teilen beigetragen 1 Institut für Pharmazie und Lebensmittelchemie, Universität Würzburg 2 BioVariance GmbH, Waldsassen Einleitung Die patientenindividuelle pharmakogenetische Ausstattung bestimmt die Pharmakokinetik von in der Psychiatrie eingesetzten Arzneistoffen, weshalb Dosisanpassungen und Anwendungsbeschränkungen in der psychiatrischen Praxis an der Tagesordnung sind. Das Ziel ist die Entwicklung eines Algorithmus, der basierend auf Literaturdaten und einer experimentell angelegten Studie eine zuverlässige Aussage zur Dosisfindung von Psychopharmaka liefert und für die Umsetzung einer Smartphone App geeignet ist. Methoden Zuerst wurde für die Arzneistoffklasse der trizyklischen Antidepressiva eine umfassende Datenerhebung durchgeführt, da deren Metabolismus hochgradig von Polymorphismen beeinflusst wird. Parallel dazu wird eine Genotypisierungsstudie durch das Labor für Therapeutisches Drug Monitoring des Zentrums für psychische Gesundheit am Universitätsklinikum Würzburg organisiert. Die Literatursuche erfolgt nach einem Rechercheleitfaden, der eine umfassende und systematische Datensammlung und auswertung ermöglicht. Ergebnisse Für die trizyklischen Antidepressiva Amitriptylin, Nortriptylin, Clomipramin, Doxepin, Imipramin, Desipramin und Trimipramin wurden detaillierte Informationen zu Polymorphismen relevanter CYP-Enzyme, wie z.b. CYP 2D6 und CYP 2C19, Daten zur Pharmakokinetik sowie Häufigkeiten unerwünschter Arzneimittelwirkungen in Abhängigkeit von CYP-Genvarianten gesammelt. Jede Quelle wurde mit Hilfe eines Scoring Systems hinsichtlich ihrer Methodik und analytischen Qualität geprüft bevor die Daten aufbereitet und strukturiert in die Datenbank eingetragen wurden. Fazit Am Ende soll ein Algorithmus etabliert werden, um eine intuitiv leicht bedienbare Datenbank zu entwickeln, die alle Antidepressiva und Antipsychotika enthält. Dabei soll die Suche nach der optimalen Dosierung basierend auf individuellen genetischen Daten ermöglicht und dadurch die Therapiesicherheit erhöht werden.

43 Anorganische Chemie und Materialwissenschaften Conjugated Triarylborane Dendrimers P28 F. Rauch 1, L. Ji 1, T. B. Marder 1 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Würzburg, Germany florian.rauch@uni-wuerzburg.de Triarylboranes are interesting acceptor moieties in the synthesis of π-conjugated materials and find application in OLEDs, nonlinear optical materials and anion sensors as well as two-photon absorption (TPA) materials. [1] Conjugated dendrimers also show promising properties for applications in OLEDs, TPA materials and photovoltaics. [2] Herein, we report the development of a new reaction sequence by which triarylboranes can be synthesized using bench stable potassium trifluoroborate salts as precursors. Furthermore, we applied this reaction sequence in the synthesis of a novel first generation borane dendrimer which exhibits a considerable amount of conjugation throughout the π-system. [1] For reviews see: a) C. D. Entwistle, T. B. Marder, Angew. Chem. Int. Ed. 2002, 41, ; b) C. D. Entwistle, T. B. Marder, Chem. Mater. 2004, 16, [2] For reviews see: a) D. Astruc, C. Ornelas, J. Ruiz, Acc. Chem. Res. 2008, 41, ; b) R. Hourani, A. Kakkar, Macromol. Rapid Commun. 2010, 31,

44 P29 Organische Chemie und Biochemie Absolute Stereostructures and Possible Biosynthetic Origins of the Novel Cage-like Naphthylisoquinoline Alkaloid Dimers Cyclo-Mbandakamines A1 and A2 B. K. Lombe 1,2, T. Bruhn 1, D. Feineis 1, V. Mudogo 2, G. Bringmann 1 1 Institute of Organic Chemistry, University of Würzburg, Am Hubland, D Würzburg, Germany 2 Faculté des Sciences, Université de Kinshasa, B.P. 202, Kinshasa XI, Democratic Republic of the Congo Naphthylisoquinoline alkaloids constitute a unique class of natural products, found so far only in the Ancistrocladaceae and Dioncophyllaceae plant families. [1] They consist of two polyketide-derived molecular portions, a naphthalene and an isoquinoline moiety, connected by a biaryl axis, which is, in most cases, rotationally hindered. Besides this element of axial chirality, these alkaloids carry one or two stereogenic centers in the isoquinoline part, hence making them stereochemically thrilling. [1] Even more stimulating are the dimeric naphthylisoquinoline alkaloids, since some of them, depending on the individual structures, have shown pronounced bioactivities [2,3] and a total number of seven stereogenic elements. [3,4] From the leaves of a botanically yet undescribed Congolese Ancistrocladus species, [5] we have discovered the very first oxygen-bridged naphthylisoquinoline alkaloids dimers, named cyclo-mbandakamines A 1 (1) and A 2 (2). Their cage-like structures, displaying an unprecedented dihydrofuran-cyclohexenone-pyrane sequence, reveal eight elements of chirality the highest total number for all naphthyl isoquinoline alkaloids known so far. In addition, one of their C,O-bonds (highlighted in yellow in the figure), arises presumably from a phenol oxidation, thus making them the first representatives to result from four phenol-oxidative steps (three C,C- and one C,O-bonds highlighted in the figure). Our poster will provide more details on the structural elucidation of 1 and 2 and will also present the proposed biosynthetic pathway leading to these unprecedented quateraryls. [1] G. Bringmann, F. Pokorny, In The Alkaloids (Cordell, G. A., Ed.) 1995, 46, [2] M. R. Boyd et al., J. Med. Chem. 1991, 34, [3] G. Bringmann et al., Chem. Eur. J. 2013, 19, [4] G. Bringmann et al., Org. Lett. 2013, 15, [5] F. Turini et al., Taxon 2014, 63,

45 Anorganische Chemie und Materialwissenschaften Reversible Oxidative Addition of Highly Polar Bonds to a Transition Metal P30 J. Müssig, H. Braunschweig* jonas.muessig@uni-wuerzburg.de Department of Inorganic Chemistry, Julius-MaximiliansUniversitaetWuerzburg, Wuerzburg, Germany The reactivity of group 13 halides towards the well established metal Lewis base [Pt(PCy 3) 2] has been studied in our group in the past years. We found that AlX 3 (X = Cl, Br, I) and GaCl 3 form unsupported metal-only Lewis pairs (MOLPs) with [Pt(PCy 3) 2], whereas the reaction with BX 3 (X = Cl, Br, I), GaBr 3 and GaI 3 results in oxidative addition (OA) products: trans-(halo)(gally) and trans- (halo)(boryl) complexes. [1-4] In the case of gallium halides the substitution of the halide plays an important role to vary the reaction pathway. To gain better understanding of dative bonds between two metals our current investigations are concentrated on the reactivity of InX 3 (X = Cl, Br, I) towards platinum(0) Lewis bases. The indium-platinum systems show well-defined equilibrium mixtures between the products of oxidative additions of the highly polar In-X bonds ( EN = ) and their MOLP counterparts (reductive elimination products).the results mark the first observation of an equilibrium between MOLPs and OA isomers, as well as the most polar bond ever observed to undergo reversible oxidative addition to a metal complex. [1] H. Braunschweig, K. Gruss, K. Radacki, Angew. Chem. Int. Ed. 2007, 46, [2] H. Braunschweig, K. Gruss, K. Radacki, Inorg. Chem. 2008, 47, [3] H. Braunschweig, P. Brenner, A. Müller, K. Radacki, D. Rais, K. Uttinger, Chem. Eur. J. 2007, 13, [4] H. Braunschweig, K. Radacki, K. Uttinger, Inorganic Chemistry 2007, 46,

46 P31 Organische Chemie und Biochemie Dispersability of Nanodiamonds in Physiological Media S. Schweeberg 1, S. Suliman 2, M. Popa 3, K. Mustafa 2, A. Krueger 1 1 Institut für Organische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg 2 Department of Clinical Dentistry, Center for Clinical Dental Research, University of Bergen, Norway 3 KinN Therapeutics, Bergen, Norway Nanotechnology is gaining increasing interest for a wide community of medical, chemical and physical scientists. [1] Nanodiamond in particular has unique properties such as inertness, chemical reactivity if surface functionalization is involved, hardness and biocompatibility. [2] Nanodiamond particles tend to agglomerate in solutions with a high salt concentration so that physiological media like PBS buffer are not suitable for the preparation of nanodiamond for biomedical applications. Figure 1: Nanodiamond without dispersion and with dispersion in glucose solution. Physiological glucose solution was used as an alternative for the preparation of stable, fully dispersed colloids, and even after 20 days at room temperature the particles do not agglomerate, which is a very positive indication of its suitability as a suitable, fully dispersed nanodiamond formulation. With the nanodiamond solution in water, agglomeration takes places immediately just as the proteins of the serum get in contact with the particles (figure 1). Due to the strong precipitation and agglomeration DLS measurements were not successful. In glucose solution, no agglomeration takes place upon adding serum to the nanodiamond solution. Funding by Volkswagenstiftung (grant number: 88393) is gratefully acknowledged. [1] V. N. Mochalin, Y. Gogotsi, Nat Nano 2012, 7, [2] A. M. Schrand, L. Dai, J. Phys. Chem. B 2007, 111, 2-7.

47 Organische Chemie und Biochemie A Supramolecular Cage linked by Boron Nitrogen Dative Bond and Synthesis of a New Apically Functionalized Tribenzotriquinacene Building Block P32 A. Dhara, F. Beuerle* Universität Würzburg, Institut für Organische Chemie & Center for Nanosystems Chemistry, Am Hubland, Würzburg, Germany * florian.beuerle@uni-wuerzburg.de Precise control of supramolecular self-assembly processes is fundamental requirement to construct a welldefined architecture from a set of molecular building blocks by utilizing non-covalent interactions. Although hydrogen bond, metal coordination and hydrophobic interactions are well-explored to form a number of supramolecular structures [1] the bond strengths of these interactions are not so easy to tune systematically to have the desired thermodynamic and kinetic stabilities of the self-assembled systems. In this respect B N dative bonds which are formed by Lewis acid/base interactions between electrophilic boron center and nitrogen nucleophiles can act as a suitable motif for supramolecular self-assembly. [2] Here we present a bipyramidal [2+3] assembly formed by B N dative bond. [3] Thermodynamic equilibria of cage formation were studied by isothermal titration calorimetry (ITC) and reversible cage opening/reassembly was investigated by variable temperature 1 H-NMR spectroscopy. Also we report on the facile synthesis of a new tribenzotriquinacene (TBTQ) molecule possessing a terminal alkyne group at the apical position which can be modified by the azide alkyne Huisgen cyclo addition and Sonogashira cross-coupling reaction to attach different functional groups as needed. [4] This can lead to facile exohedral functionalization of organic cages formed by TBTQ building units. Also we describe a mild and practically useful protocol to deprotect methoxy- groups in presence of terminal alkyne. [1] M. Yoshizawa, J. K. Klosterman, M. Fujita, Angew. Chem. Int. Ed. 2009, 48, [2] K. Severin, Dalton Trans. 2009, [3] A. Dhara, F. Beuerle, Chem. Eur. J. 2015, 21, [4] A. Dhara, J. Weinmann, A-M. Krause, F. Beuerle, Chem. Eur. J. 2016, 22,

48 P33 Pharmazie und Lebensmittelchemie Site-directed conjugation and bioresponsive delivery of IGF-I A. Braun 1, M. Gutmann 1, R. Ebert 2, F. Jakob 2, T. Lühmann 1, L. Meinel. 1 1 Institute for Pharmacy and Food Chemistry, University of Würzburg, Germany 2 Orthopedic Center for Musculoskeletal Research, Würzburg, Germany Human Insulin-like Growth Factor-I (IGF-I) is a 7.6 kda peptide hormone with an anabolic function e.g. in muscle growth and regeneration, therefore discussed as a potential treatment option for muscular atrophy. [1] In this study we aimed at developing IGF-I delivery systems with superior safe and efficacy profiles by directing the hormone s release to inflamed muscle tissue and minimizing off-target activity. [1,2] To this end, IGF-I was conjugated at position 68 to a protease-cleavable linker (PCL) responding to pathophysiologically elevated matrix metalloproteinase (MMP)-9 as representative for the inflamed muscle. [3] In the next step, this PCL-IGF-I conjugate was site-specifically coupled to DBCO-reactive PEG 10kDa and characterized before and after exposition to MMPs. [4] Characterization of the coupled IGF-I variants was performed by MALDI-MS, HPLC and tricine gel electrophoresis. Bioactivity was determined by MG-63 cell proliferation in comparison to wild type IGF-I. Scheme 1: Principle of bioresponsive IGF-I release triggered by MMP-9 secretion of diseased tissue. Site-directed conjugation of the PCL to IGF-I as well as response to MMP-9 was confirmed by HPLC and MALDI-MS analysis. The PCL-IGF-I conjugate demonstrated comparable bioactivity as the wild type analogue. The conjugate was successfully immobilized onto DBCO-functionalized agarose particles using SPAAC click chemistry and labelled with monoclonal IGF-I antibody and Alexa 488 conjugated secondary antibody. The soluble conjugate with PEG 10kDa also responded to MMP-9 and is now profiled for systemic delivery, thereby featuring site-directed conjugation of IGF-I to biomaterials as a promising approach for an improved safety profile of anabolic growth factor delivery targeting muscle regeneration. Acknowledgments: The financial support from the Bavarian Research Foundation (grant # AZ FORMOsA ) is gratefully acknowledged. [1] I. Schultz, J. Wurzel, L. Meinel, European Journal of Pharmaceutics and Biopharmaceutics 2015, 97, Part B, [2] T. Lühmann, L. Meinel, Current Opinion in Biotechnology 2016, 39, [3] A. C. Braun, M. Gutmann, R. Ebert, F. Jakob, H. Gieseler, T. Lühmann, L. Meinel, Pharmaceutical Research 2016, [4] O. Germershaus, T. Lühmann, J. C. Rybak, J. Ritzer, L. Meinel, International Materials Reviews 2015, 60,

49 Pharmazie und Lebensmittelchemie Site-directed functionalization of cell derived matrices by metabolic glycol-engineering and click chemistry P34 M. Gutmann 1, A. Braun 1, E. Memmel 2, J. Seibel 2, L. Meinel 1, T. Lühmann 1 1 Institute for Pharmacy and Food Chemistry, University of Würzburg, Germany ²Institute for Organic Chemistry,University of Würzburg, Germany The extracellular matrix (ECM) is a complex and 3D-network that is secreted by various cell types. The ECM has different essential roles in regulating the function, development and homeostasis of eukaryotic cells. It provides mechanical support, regulates the abundance of signaling molecules (e.g. growth factors) and receptors as well as ph and hydration status. Cell derived matrices (CDM) have been recently attracted attention as biocompatible scaffold material for skeletal tissue engineering and cardiovascular/vascular tissue engineering. [1] This study aims at modification of glyco-engineered ECM scaffolds derived from fibroblasts (NIH3T3) by site directed chemistry deploying bioorthogonal azide-alkyne cycloadditions (CuAAC/SPAAC). For the synthesis of glycoengineered CDMs, NIH3T3 fibroblasts were incubated with N-azido acetyl glucosamine [2] and stimulated with 50 µg/ml ascorbic acid and decellularized as previously described. [3,4] To analyze the presentation of the azide-modified glycoproteins embedded in the CDM, we applied alkyne-azide click reactions using opposed fluorescent dyes (Sulfo- Cy5-alkyne; DBCO-Sulfo-Cy5) in line with an anti-fibronectin antibody and a fluorescent-labeled second antibody for ECM structure visualization. Site-directed immobilization of the fluorophor was investigated by confocal laser scanning microscopy (CLSM) after different time points, displaying ECM like structures, which colocalized with the fibronectin counterstaining (Figure 1). Figure 1: Isolated modified ECM after 9 days. (A) Azido-sugar treated ECM stained with Sulfo-Cy5-Alkyne (1) and Anti-Fibronectin-Alexa 488 (2). (B) Untreated ECM stained with Sulfo-Cy5-Alkyne (1) and Anti-Fibronectin-Alexa 488. Ongoing experiments focus on the modification of glycoengineered material with respect to protein modification [5] and on the characterization of the cell-derived material by western blotting procedures. We successfully developed protocols enabling both CDM formation and the integration of functionalizable sugarmoieties by metabolic glycolengineering. Engineering CDMs with functional cues is a promising strategy for scaffold design allowing for high decoration versatility in tissue engineering applications. [1] L. E. Fitzpatrick et al., Biomater. Sci. 2015, [2] E. Memmel et al., Chemical communications 2013, 49, [3] M. Gutmann et al., Chembiochem : a European journal of chemical biology 2016, 17, [4] R. Castello-Cros et al., Methods in molecular biology 2009, 522, [5] G. Wandrey et al., Journal of biological engineering 2016, 10, 11.

50 P35 Organische Chemie und Biochemie PBI-Cyclophane Chromophormakrozyklen für die Wirt/Gast-Chemie M. Sapotta, A. Sieblist, P. Spenst, F. Würthner* Universität Würzburg, Center for Nanosystems Chemistry, Institut für Organische Chemie, Universität Würzburg, Würzburg, Germany * Seitdem die Entdeckung der Kronenether und deren Kationen-komplexierende Eigenschaft durch Pedersen [1] in den 60er Jahren den Weg für die Supramolekulare Chemie ebnete, haben makrozyklische Moleküle die Wissenschaft fasziniert. Eine ihrer bekanntesten Eigenschaften ist hierbei die Fähigkeit zur Aufnahme von Gästen in ihrem Innenraum. [2] Eine besonders interessante Verbindungsklasse stellen makrozyklische Verbände aus Chromophoren dar, in denen sich die optischen Eigenschaften des Molekülverbands durch Aufnahme von Gastmolekülen verändern. [3] Das kürzlich in unserem Arbeitskreis synthetisierte Cyclophan 1 illustriert dies in beeindruckender Weise. [3] Durch die rigide Xylylenbrückeneinheit werden die Chromophore in einem Abstand von 6.5 Å fixiert, der zwar noch schwache Wechselwirkungen zwischen den Chromophoren erlaubt, aber eine vollständige Aggregation verhindert. Gleichzeitig wird eine Kavität aufgespannt, in der über π-π- Wechselwirkungen eine Vielzahl aromatischer Kohlenwasserstoffe wie Naphthalin, Fluorenon oder Perylen gebunden werden können. Bemerkenswert ist, dass hierbei die elektronische Situation des Gastes Einfluss auf die Emissionseigenschaften des Cyclophans in Chloroform nimmt (Abbildung 1). Bei Komplexierung eines elektronenreicheren Gastmoleküls kommt es zur Fluoreszenzlöschung des Wirts, wohingegen die Einlagerung elektronenärmerer Gäste eine Fluoreszenzverstärkung hervorruft. Dadurch wird 1 gleichzeitig sowohl zu einem turn on- als auch einem turn off-fluoreszenzsensor für polycyclische Aromaten. Abbildung 1: Struktur des Perylenbisimidcyclophans 1 und schematische Darstellung der bei der Komplexierung von Gästen auftretenden Fluoreszenzverstärkung (links) oder Fluoreszenzlöschung (rechts). [1] a) C. J. Pedersen, J. Am. Chem. Soc. 1967, 89, ; b) C. J. Pedersen, J. Am. Chem. Soc. 1967, ; c) C. J. Pedersen, Angew. Chem. Int. Ed. Engl. 1988, 27, [2] D. J. Cram, J. M. Cram, Science 1974, 183, [3] a) P. Spenst, F. Würthner, Angew. Chem. Int. Ed. 2015, 54, ; b) P. Spenst, R. M. Young, M. R. Wasielewski, F. Würthner, Chem. Sci. 2016, 7,

51 Organische Chemie und Biochemie PHOTOPHYSICS AND SPIN-CHEMISTRY IN DONOR-ACCEPTOR- SUBSTITUTED DIPYRRINATO-METAL-COMPLEXES P36 S. Riese 1, U. E. Steiner 2, C. Lambert 1 1 University of Würzburg, Am Hubland, Würzburg 2 University of Konstanz, Konstanz Magnetic field dependent transient absorption measurements of Triarylamine-iridium(III)-dipyrrinnaphthalene diimide triads could show for the first time a biphasic magnetic field effect which can be assigned to the transition from coherent to incoherent spin-motion at about 10 mt. [1] In this study we focus on the influence of the central, metal containing chromophor on the lifetime and spin-chemistry of the charge separated states. Therefore we synthesized the Pt(II)-analogue of the Ir(III)-triad. The complexes were characterized by steady-state UV/vis-spectroscopy, cyclic voltammetry and magnetic field dependent transient absorption spectroscopy in the nanosecond time-regime at fields between 0 mt and 1800 mt. The analysis of the experimental data show that the central complex does indeed influence both the photophysics and the spin-chemistry of the triads. For example the magnetic field effect rises from a 6 timesincrease in lifetime for Ir to a 27 times-increase for Pt while the characteristic magnetic field-strenghts remain relativly unchanged as shown in Fig Pt triad (THF) Ir triad (MeCN) 10 7 Fit (Ir triad ) Fit (Pt triad ) k / s B / mt Figure 1: Plot of the relaxation-constant against the magnetic field strength [1] J. H. Klein, D. Schmidt, U. E. Steiner, C. Lambert, J. Am. Chem. Soc. 2015, 137,

52 P37 Pharmazie und Lebensmittelchemie Diagnostic chewing gums targeting the tongue as 24/7 available detector T. Miesler 1, J. Ritzer 1, C. Rode 2, M. C. Amstalden 1, M. Pein 3, T. Lühmann 1, L. Meinel 1 1 Institute for Pharmacy and Food Chemistry, University of Würzburg, Germany 2 INNOVENT e.v., Technology Development Jena, Germany 3 Institute of Pharmaceutics and Biopharmaceutics, Heinrich-Heine-University Düsseldorf, Germany Sore throat is a well perceptible symptom, but a lot of diseases have to be considered as the trigger. [1] On the other hand, some infections are noted too late, because of a lack of specific symptoms, for example the early stages of caries. [2] To this end, we (1) designed and synthesized specific systems reacting to the presence of a respective pathogen by releasing a flavor (Fig. 1) and (2) formulated these systems into a chewing gum to make use of the human tongue as a 24/7 detector. Figure 1: The peptide bond of the system is cleaved by proteases from macrophages or bacteria, so the flavor (F) is released from the nanoparticle (NP). The basic concept consists of an optimized peptide sequence linking a flavor with a nanoparticle. Denatonium was used as flavor component. Taste intensity was measured using an electronic tongue setup. Systems were originally designed, reacting to aureolysin from staphylococcus aureus and human matrix metalloproteinases 1, 8, 9 and 13. Numerous peptide sequences were synthesized and analyzed for their cleavage rate and selectivity towards the named proteases. Several systems were formulated into a chewing gum to examine the release of our compounds. With the information gathered, we are now addressing caries by detection of the decay-causing bacterium streptococcus mutans. First systems are now established, enabling the specific detection of certain pathogens by their unique enzymatic properties. The development and closer investigation of such systems could lead to new forms of diagnostics. [1] B. Renner, C. A. Mueller, A. Shephard, Inflamm Res. 2012, 61, [2] B. Nyvad, Caries Res. 2004, 38,

53 Physikalische und Theoretische Chemie A coherent two-dimensional nanoscopy setup P38 S. Pres 1, T. Brixner 1, L. Dietrich 1, M. Hensen 1, B. Huber 1, V. Lisinetskii 1, J. Lüttig 1 1 Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Am Hubland, Würzburg, Germany How do energy transport processes between individual molecules or inside large heterogeneous structures like light harvesting complexes occur? Is the transport dominated by step-by-step hopping of excitation or do the individual molecules form a strongly coupled system in which the excitation is delocalized over all constituents (quantum mechanical entanglement). How are these transport phenomena influenced by interactions with the substrate, the environment and external light sources? Is it possible to control the outcome of chemical reactions by nanostructuring the environment of molecules? To investigate these questions the measurement signal of the prepared system has to be retrieved with high temporal (femtosecond regime) and spatial resolution far below the optical diffraction limit (several nanometers). Therefore, we bring ultra-fast optical 2D spectroscopy, which is usually used to investigate resonances and couplings of molecular systems, to the nanoscale: Instead of detecting optical-diffraction limited light fields, we measure non-optical observables, i.e. photoemitted electrons which allow a resolution down to 1 nm at 1 ev kinetic energy. [1] The optical excitation is generated by a noncollinear optical parametric amplifier (NOPA) featuring wide spectral tuneability from the NIR to the UV range. The excited state population can then be probed as photoemitted electrons which are detected with high spatial resolution (<10 nm) using an aberration corrected photoemission electron microscope (AC-PEEM). This setup offers many possibilities for thesis projects in the fields of (an)organic synthesis, sample preparation and characterisation as well as electron microscopy and laser spectroscopy. [1] M. Aeschlimann et al., Science 2011, 333,

54 P39 Physikalische und Theoretische Chemie Theoretical Studies On The Water Oxidation Mechanism in Ruthenium Macrocyclic Systems J. Lindner, M. I. S. Röhr, R. Mitric We used the QM/MM approach to simulate the spectroelectrochemistry of Ruthenium water oxidation catalysts by calculating UV/VIS spectra in different catalyst oxidation states. As absorption spectra are highly dependent on structural changes, averaged ensemble spectra were identified to be an appropriate model. Furthermore, molecular dynamics simulations were used in order to give insights on the reaction mechanism with priority to the outstanding turnover frequency of the macrocycle compared to the corresponding monomer. [1] We found different reasons for the enhanced activity, including H-bonding networks between the three catalytic moieties of the macrocycle. Figure 1: H-bonding networks promoting the water nucleophilic attack of a water molecule to the Ru(V)=O species. [1] M. Schulze, V. Kunz, P. D. Frischmann, F. Würthner, Nat. Chem. 2016, 8, 576.

55 Pharmazie und Lebensmittelchemie Targeting Structural Differences in MIP Proteins and FKBPs P40 M. A. Kuhn 1*, C. A. Sotriffer 1 1 Institute of Pharmacy and Food Chemistry, University of Würzburg, Würzburg, 97074, Germany *maximilian.kuhn@uni-wuerzburg.de Bacterial Macrophage Infectivity Potentiator (MIP) proteins and human FK506-binding proteins (FKBPs) both belong to the class of peptidyl-prolyl-isomerases and exhibit a highly conserved binding pocket. The MIP proteins of Burkholderia pseudomallei and Legionella pneumophila are important for replication and full virulence, rendering them potential targets for antimicrobial substances. Human FKBPs play miscellaneous roles, as for example in the regulation of steroid hormone receptor function and the immune response. Several small-molecule pipecolic acid derivatives are capable of binding to MIP proteins of B. pseudomallei, [1,2] L. pneumophila [1,3] and other bacterial species as well as to human FKBPs. Analysing and comparing the structure-activity relationships for these complexes is crucial for the development of new MIP inhibitors with sufficient selectivity. The impact of structural differences in two loops (called 50's and 80's loop in FKBP12) adjacent to the binding pocket was investigated via molecular dynamics simulations. Substitutions at the phenyl ring of a reference ligand (CJ168) positioned close to the 80's loop lead to differential effects on the ligand orientation depending on the loop composition of the isoenzyme, thus modulating interaction pattern and binding affinity. Furthermore, differences in the 50's loop between FKBPs and several MIP proteins should allow to preferentially address the latter by modifying the ligand with an additional hydrogen bond acceptor. [1] F. Seufert, M. Kuhn, M. Hein, M. Weiwad, M. Vivoli, I. Norville, M. Sarkar-Tyson, L. Marshall, H. Bruhn, N. Harmer, C. Sotriffer, U. Holzgrabe, Bioorg. Med. Chem. 2016, 24, [2] D. Begley, D. Fox III, D. Jenner, C. Juli, P. Pierce, J. Abendroth, M. Muruthi, K. Safford, V. Anderson, K. Atkins, S. Barnes, S. Moen, A. Raymond, R. Stacy, P. Myler, B. Staker, N. Harmer, I. Norville, U. Holzgrabe, M. Sarkar-Tyson, T. Edwards, D. Lorimer, Antimicrob. Agents Chemother. 2014, 58, [3] C. Juli, M. Sippel, J. Jäger, A. Thiele, M. Weiwad, K. Schweimer, P. Rösch, M. Steinert, C. Sotriffer, U. Holzgrabe, J. Med. Chem. 2011, 54,

56 P41 Anorganische Chemie und Materialwissenschaften Multifunctional soft materials based on borate-containing ionic liquids and lanthanides S. H. Zottnick, J. A. P. Sprenger, T. Ribbeck, M. Finze, K. Müller-Buschbaum Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, D Würzburg The focus of our joint research project is the synthesis of novel functional materials by a combination of borate containing ionic liquids and salts with lanthanide metal ions. Therefore, the anions of ionic liquids (ILs) are utilized as linkers for the formation of lanthanide based coordination compounds, thereby combining relevant properties of lanthanide hybrid materials e. g. luminescence with the hydrophilic/hydrophobic character of ionic liquids. As especially metal-organic frameworks (MOFs) and coordination polymers (CPs) with boron-based linkers are hardly known, despite remarkable properties, boron-based ILs and salts are particularly attractive. For spiro-borates, the structural variability of the bis(salicylato)borate anion (BSB ) ranges from complexes via one-dimensional strand-like coordination polymers 1 [Ln(BSB) 3(py) 2], Ln = Y, La Nd, Sm to twodimensional structures 2 [Ln(BSB) 3(py)], Ln = Tb, Er, exhibiting strong luminescence of the constituting units (Fig. 1). Reactions utilize salts and ionic liquids and are carried out at the junction of ionothermal and solvothermal reaction conditions. [1] For cyanoborates, the one-dimensional coordination polymers 1 [La(NO 3) 2(H 2O) 4B(CN) 4] and 1 {[EMIM][La(NO 3)(H 2O) 3{B(CN) 4} 3] (EMIM= 1-ethyl-3-methylimidazolium) as well as 3 [La{C 2F 5B(CN) 3} 3] show the variability of possible products, all obtained from ILs without further solvents. Figure 1: Crystal structure of 2 [Tb(BSB) 3(py)] along the c-axis as well as excitation and emission spectra (right). [1] S. H. Zottnick, J. R. Sorg, J. A. P. Sprenger, M. Finze, K. Müller-Buschbaum, Z. Anorg. Allg. Chem. 2015, 641,

57 Pharmazie und Lebensmittelchemie Prevention of colitis by controlled oral release of carbon monoxide P42 C. Hermann 1, C. Steiger 1, L. Meinel 1 1 Institute for Pharmacy and Food Chemistry, University of Würzburg, Germany Carbon monoxide (CO) has been recognized as an endogenous signal transmitter for several years. CO is produced endogenously by the enzyme heme oxygenase (HO) which catalyses the degradation of heme to billiverdin, ferrous iron and CO. This signal transmitter triggers various physiological processes including gastrointestinal (GI) homeostasis. Although CO has been described as potential therapeutic, addressing inflammatory gastrointestinal (GI) disorder, translation of these findings into clinical practise is currently challenged by inappropriate drug delivery approaches. We recently described a micro scale Oral Carbon Monoxide Release System (M-OCORS) for controlled oral delivery of CO in rodent animal models and reported on promising pharmacokinetic (PK) / pharmacodynamic (PD) characteristics of this system. [1] A major challenge limiting therapeutic use of this approach, however, is the exposure of the GI tract with potentially toxic transition metals (e.g. Ruthenium). We hence modified the release system by translating the concept into a membrane based release system (Membrane based Carbon Monoxide Release System MCRS). MCRS comprises the CO releasing as well as CO release triggering compounds of M-OCORS in a gas permeable silicone membrane. On top, it comprises a water cartridge initiating CO release upon breakage (see Figure 1A). In conclusion, the novel release system was designed to deliver CO to GI tissue and on top prevent leakage of transition metals from the system exposing the GI tract addressing the challenges of our previous delivery concepts. Figure 1: (A) Schematic drawing detailling the Membrane based Carbon Monoxide Release System (MCRS). A sealed straw (yellow) containing water is disrupted upon manual activation, dissolving coated Sodium sulfite particles wich releases carbon monoxide (CO) from CORM-2. Generated CO thereafter is released via the silicone membrane in a highly tailorable fashion allowing controlled GI delivery. In contrast to other approaches, potentially challenging transition metals are retained within the capsule. (B) CO release pattern of the MCRS. [1] C. Steiger, K. Uchiyama, T. Takagi, K. Mizushima, Y. Higashimura, M. Gutmann, C. Hermann, S. Botov, H. G. Schmalz, Y. Naito, L. Meinel, J. Control. Release, 2016, 239,

58 P43 Physikalische und Theoretische Chemie Investigations on covalent-reversible inhibitors using QM and QM/MM approaches A. Heilos, T. A. Le, W. Waigel, B. Engels Most drugs consist of ligands which interact with their target non-covalently. They have the advantage that they are so unreactive that unintended reactions with DNA or proteins do not take place. However, they have the drawback that their free energy of binding do generally not exceed 15 kcal/mol. Higher binding affinities can only be achieved with ligands which form a covalent bond with their target. Despite famous examples as Penicillin or Aspirin in the past the industry hesitated to develop new covalent drugs because they fear unintended side reactions resulting from the reactivity of ligands. Since about 2005 covalent ligands undergo an intensive renaissance in academia and industry, because various very selective drugs were detected in the last few years. As for example covalent reversible protease inhibitors based on nitriles or a number of reversible and irreversible kinase inhibitors. [1-4] In this work, several systems have been investigated in regard of possible covalent inhibitors and inhibition mechanisms. Also calculations concerning the protonation state of active site cysteine and histidine has been performed (Figure 1). CYS? HIS19 Figure 1: surface: CathB, crystal structure 1HUC; ball and stick: active site amino acids CYS29 and HIS199. [1] Gütschow and Co-work., ChemMedChem 2013, 8, [2] Schirmeister and Co-work., ChemMedChem 2013, 8, 967. [3] Kwak et al., Proc. Natl. Acad. Sci. USA 2005, 102, [4] Taunton and Co-work., J. Am. Chem. Soc. 2013, 135, 5298.

59 Organische Chemie und Biochemie Controlling the Superstructure in Polymeric Squaraine Dyes P44 M. H. Schreck 1, C. Lambert 2 1,2 Institut für Organische Chemie & Center for Nanosystems Chemistry, Universität Würzburg Am Hubland Würzburg, Germany christoph.lambert@uni-wuerzburg.de We recently prepared a polymer P1 based on a dicyanovinylene-substituted cis-indolenine squaraine dye M1 via Ni-mediated Yamamoto homocoupling reaction.this homopolymer displays a bathochromic shift of the absorption maximum but also a weaker band at higher energies. This observation can be explained by a mixture of H- and J-type alignment of chromophores, which then exhibit hypsochromic (H) and bathochromic (J) shifts. In this context, the solvent itself is significantly involved in the sort of superstructure (helical or zigzag-structures) formed by the polymer in solution. The ongoing goal is to control the superstructure and the optical properties involved, and rule out the superior role of the solvent by structurally modifying the parent squaraine monomer M1 which was realized via two attempts: (1) Introducing bulky substituents into the indolenine moiety and (2) partially stiffening the polymer backbone. Both new polymers P2 and P3 show a red-shifted absorption in comparison to their corresponding monomers M2 and M3, respectively, indicating J-aggregate behavior and no dependence on the solvent. Consequently, the polymers exclusively form zig-zag structures irrespective of the chosen solvent.

60 P45 Anorganische Chemie und Materialwissenschaften Ungewöhnlich effiziente struktur dirigierte Phosphoreszenz in Silber(I)-Clustern realisiert mit Carba-closo-dodecaboranylethinyl-Liganden M. Hailmann, N. Wolf, B. Hupp, A. Steffen, M. Finze * Universität Würzburg, Institut für Anorganische Chemie michael.hailmann@uni-wuerzburg.de Silber(I)-alkinyle zeigen eine vielseitige Chemie und sind für eine Vielzahl (potentieller) Anwendungen von Interesse. Beispielsweise sind sie Startmaterialien in der Synthesechemie und werden aufgrund ihrer Eigenschaften, wie z. B. Lumineszenz, im Bereich der Materialwissenschaften untersucht. [1] Ihre Strukturchemie ist aufgrund der Bildung von Ag I -Clustern äußerst vielfältig. Im Gegensatz zu Silber(I)-alkinylen, die oft schwierig zu charakterisierende Koordinationspolymere sind, sind Silber(I)-alkinyle mit weiteren Liganden, wie z.b. Pyridin, Silber(I)-Doppelsalze oder mit Templaten in der Regel einfacher zugänglich. Die Selbstorganisation zu Koordinationspolymeren oder Ag I -Clustern beruht vor allem auf (i) der flexiblen Koordination der Ag I -Ionen an mehrere Alkinylliganden, (ii) verbrückenden Alkinylliganden und (iii) argentophilen Wechselwirkungen. Diese Wechselwirkungen sind häufig auch der Grund für Lumineszenz. Carba-closododecaboranylethinyl-Liganden zeigen ein ungewöhnliches Koordinationsverhalten, [2] das maßgeblich durch die negative Ladung des Borkäfigs und die B CC-Bindung bestimmt wird. Cs[12-HC C-closo-1-CB 11H 11] [3] reagiert mit AgNO 3 in wässriger Lösung zu {Ag 2(12-C C-closo-1-CB 11H 11)} n (1), das in exzellenter Ausbeute als mikrokristalliner Feststoff isoliert wird. [4] Die Reaktion von 1 mit Pyridin, 4-Me-Pyridin, 4-tBu-Pyridin und 3,5-Lutidin führt zu Ag I -Clustern mit sieben bis acht Ag I -Ionen, vier Carba-closo-dodecaboranylliganden und zehn bis 12 der jeweiligen Pyridinmoleküle (2 5). [4] Mit 4-CF 3-Pyridin werden temperaturabhängig unterschiedliche Cluster gebildet: [Ag 16(12-C C-closo-1-CB 11H 11) 8(4-CF 3Py) 10{(CH 3) 2CO} 2] (6) bei Raumtemperatur und [Ag(4-CF 3Py) 2] 2[Ag 14(12-C C-closo-1-CB 11H 11) 8(4-CF 3Py) 12] (7) bei 30 C. Alle Ag I - Cluster zeigen bei Raumtemperatur Phosphoreszenz mit Lebensdauern im Bereich von s und im Falle des verzerrt pentagonal-bipyramidalen Clusters, der ausgehend von 1 und 3,5-Lutidin gebildet wird, wird eine für Ag I -Cluster präzedenzlose Quantenausbeute von 0.76 beobachtet. [1] H. Schmidbaur, A. Schier, Angew. Chem. Int. Ed. 2015, 54, ; Q.-W. Wang, Y.-M. Lin, K.-G. Liu, Acc. Chem. Res. 2015, 48, ; N. J. Long, C. K. Williams, Angew. Chem. Int. Ed. 2003, 42, ; R. Buschbeck, P. J. Low, H. Lang, Coord. Chem. Rev. 2011, 255, ; U. Halbes- Letinois, J.-M. Weibel, P. Pale, Chem. Soc. Rev. 2007, 36, [2] A. Himmelspach, M. Finze, S. Raub, Angew. Chem. Int. Ed. 2011, 50, [3] A. Himmelspach, G. J. Reiss, M. Finze, Inorg. Chem. 2012, 51, ; A. Himmelspach, M. Finze, J. Organomet. Chem. 2010, 695, [4] M. Hailmann, N. Wolf, R. Renner, T. C. Schäfer, B. Hupp, A. Steffen, M. Finze, Angew. Chem. 2016, 128,

61 Physikalische und Theoretische Chemie Ultrafast Coherent Multidimensional Spectroscopy with Shot-to-Shot Scanning P46 S. Roeding 1, S. Draeger 1, T. Brixner 1 1 Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Am Hubland, Würzburg, Germany Coherent two-dimensional (2D) femtosecond spectroscopy, the optical analogue of 2D NMR, is a powerful technique to investigate the temporal evolution of complex quantum systems, such as natural and artificial light-harvesting multichromophores, on an ultrafast timescale. [1] In intuitive and readily understandable 2D spectra it is possible to look into the dynamics of quantum states and especially to resolve couplings between the states. First, we implement liquid-phase 2D spectroscopy with collinear four-pulse excitation and fluorescence detection (see Fig. 1). Pulse-sequence parameters are varied on a shot-to-shot basis using a fast pulse shaper. A complete set of all third-order signals (photon echo, double-quantum coherence, etc.) is acquired via 27-fold phase cycling [2,3] in just 6 s plus averaging. Second, we introduce as a new technique coherent two-dimensional (2D) spectroscopy on molecular beams, combining mass-resolved ion detection and ultrafast pulse shaping in the visible regime. This provides2d spectra of isolated molecules in the gas phase with ion selectivity. For demonstration we investigate the photodissociation of highly-excited NO 2. Figure 1: (a) Experimental setup. The pulse sequence is varied on a shot-to-shot basis using an acousto-optic programmable dispersive filter (AOPDF). (b) Absorptive spectra in collinear fluorescence (top) and noncollinear geometry (bottom). The different signs result from different numbers of interactions with the ket side of the Feynman diagram. (c) Off-diagonal signals from regions marked in (b) as a function of population time in collinear (red) and noncollinear geometry (green) reveal an oscillatory behavior due to vibrational coherence. With both implementations at hand we can in principle study the same sample in different environments and investigate the role of the environment in the decoherence of photophysical phenomena. [1] T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R. E. Blankenship, G. R. Fleming, Nature 2005, 434, [2] P. Tian, D. Keusters, Y. Suzaki, and W. Warren, Science 2003, 300, [3] H. Tan, J. Chem. Phys. 2008, 129,

62 P47 Pharmazie und Lebensmittelchemie Fluorine Walk: The Role of Fluorine in Quinolone amides active against T. b. brucei M. Berninger 1, A. Fuß 2, E. Al-Momani 3, I. Israel 3, P. Guentzel 1, M. Raschig 1, S. Samnick 3, U. Holzgrabe 1 1 Institute of Pharmacy and Food Chemistry, University of Würzburg, Am Hubland, Würzburg, Germany 2 Medical Mission Institute Würzburg, Hermann-Schell-St. 7, Würzburg, Germany 3 Institute of Nuclear Medicine, University Hospital of Würzburg, Josef-Schneider-Str. 2, Würzburg, Germany Human African Trypanosomiasis (HAT) is caused by an infection with Trypanosoma brucei, a vectorborne parasite, which is transmitted by the bite of infected tsetse flies. Two clinically relevant stages can be differentiated, i.e. stage I which is characterized by unspecific headache, fever and joint pains, and stage II in which the parasites cross the blood brain barrier (BBB) and affect the central nervous system. [1] Previous investigations identified novel 4-quinolone-3-carboxamides as a promising scaffold having a submicromolar activity [2] and a confirmed in vivo efficacy against T. b. brucei. [3] As the ability of the quinolone amides to pass the BBB should be investigated, 18 F-labeled derivative of our most potent substance was synthesized and subjected to autoradiography studies. Experiments using murine brain confirmed the ability of the respective derivative 1 to pass the BBB 60 min after p.i. application. Besides utilizing fluorine for PET, we explored its impact on toxicity, pharmacokinetic and pharmaco dynamics properties when being added in different position of the quinolone scaffold. This fluorine walk led to structure 2 with an improved selectivity index >2000 due to lower cytotoxicity and consistent activity against T. b. brucei. [1] WHO, fact sheet N 259; February 2016 [2] G. Hiltensperger et al., J. Med. Chem. 2012, 55, [3] G. Hiltensperger et al., Antimicrob Agents Chemother 2016, 60,

63 Organische Chemie und Biochemie A Zwitterion a Day Keeps the Proteins Away P48 V. Warkentin, A. Krueger Institut für Organische Chemie, Universität Würzburg, Am Hubland, D Würzburg krueger@chemie.uni-wuerzburg.de Surface functionalization of nanoparticles (NPs) is an essential tool for the control of chemical, physical and physiological behavior of these materials. Especially nanodiamond s (ND s) surface can easily be modified by using their broad variety of functional moieties. [1] In addition, NDs have low to non-existing toxicity, reliable production and chemical inertness which makes them attractive for biomedical applications. [2] When NDs are exposed to bio-fluids, such as serum, proteins adsorb on the surface of the particles and form in situ a protein corona. This corona masks all the desired functionalities on the surface and changes the interaction with the surrounding fluid. Both, the colloidal stability and the physiological properties are not controllable anymore. [3] Here, we report zwitterionic moieties in combination with tetraethylene glycol (TEG) to improve the colloidal dispersion in physiological media with strong ion background and the prevention of non-specific interactions with proteins. [4] Figure 1: Schematic illustration of a functionalized ND with zwitterionic head of a TEG chain. [5] These properties play a central role for the bioapplication of nanomaterials since only a precise surface functionalization leads to controlled behavior in biomedical application. This project has received funding from the Volkswagenstiftung under Grant Agreement no [1] A. Krueger, D. Lang, Adv. Funct. Mater. 2012, 22, 890. [2] A. Krueger, Chem. Eur. J. 2008, 14, [3] W. C. W. Chan, C. D. Walkey, J. Am. Chem. Soc. 2012, 134, [4] V. M. Rotello, D. F. Mayano, ACS Nano 2014, 8, [5] S. Heywood, R. Adams, mabs 2016, 8, 1336.

64 P49 Organische Chemie und Biochemie Coupled Chromophores for Studying Energy Transfer N. A. Schopf, C. Lambert * Institut für Organische Chemie & Wilhelm Conrad Röntgen Research Center for Complex Material Systems, Universität Würzburg, Am Hubland, Würzburg * christoph.lambert@uni-wuerzburg.de Energy transfer is a highly researched topic as it is not only a fundamental process in the photosynthesis of plants and bacteria but also finds application in organic photovoltaics. [1] Suitable model systems to study energy transfer processes indepth are needed. In such systems a donor is excited and transfers energy to an acceptor, which then can fluoresce. [2] To get a better understanding of the dependency of the energy transfer on the photophysical properties, different trimers were synthesised by choosing from a pool of four different chromophores. With these chromophores a broad spectral range of absorption and fluorescence wavelength can be covered. By varying the types of chromophores, the amount of different chromophores, and the sequence several trimers can be synthesised. The energy transfer properties are investigated through steady-state absorption, fluorescence spectroscopy and transient absorption spectroscopy. [1] R. Ziessel, G. Ulrich, A. Haefele, A. Harriman, J. Am. Chem. Soc. 2013, 135, [2] G.-S. Jiao et al., Tetrahedron 2003, 59,

65 Anorganische Chemie und Materialwissenschaften Superparamagnetic Luminescent Composite Particles P50 T. Wehner 1, K. Mandel 2, M. Schneider 2, G. Sextl 2, K. Müller-Buschbaum 1 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität, Am Hubland, Würzburg, Deutschland 2 Fraunhofer-Institut für Silicatforschung ISC, Neunerplatz 2, Würzburg, Deutschland Herein, we present the generation of multifunctional composite materials consisting of superparamagnetic Fe 3O 4/SiO 2 microparticles and different luminescent lanthanide-containing metal-organic frameworks (MOFs). The modification could be achieved by various reaction conditions including mechanochemistry. The resulting composites are core-shell materials with the microparticle as core and a MOF-containing shell and combine the properties of both constituents: superparamagnetism and luminescence. If the magnetite particles are functionalized with the 2D-MOF 2 [Eu2Cl6(Bipy)3] 2Bipy (Bipy = 4,4 -bipyridine), the hybrid material can be used as potential water detector in fluids since the MOF luminescence is quenched by contact with low amounts of water. Exploiting the magnetic properties of the composite, the signal can be augmented by gathering the particles in one spot. Figure 1: Detection of water and magnetic signal augmentation of the composite particles [Eu2Cl6(Bipy)3] 2Bipy@Fe3O4/SiO2 (top) and principle of the water detector system (bottom). 2 2 A color mixture of red Eu 3+ and green Tb 3+ centers can be achieved via the composite [EuxTb2-xCl6(Bipy)3] 2Bipy@Fe3O4/SiO2, which can therefore be used for color tuning and is potentially suitable as ratiometric luminescent detector. The modification of Fe 3O 4/SiO 2 with other MOF systems like 3 [Eu(Im)2] (Im = imidazolate) and 3 [Eu2(BDC)3] 2DMF 2H2O (BDC = 1,4-benzendicarboxylate) leads to further variation of the luminescence color and other properties of the composite. Instead of spherical Fe 3O 4/SiO 2 particles, magnetite microrods can be prepared, which exhibit intensive light reflection in dependence of their orientation in an external magnetic field as additional property. Modification of the microrods with 3 [Eu2(BDC)3] 2DMF 2H2O leads to a hybrid material, which combines the isotropic reflection properties of the microparticles with the anisotropic luminescence of the MOF. Switching between both properties is possible by variation of the excitation wavelength. [1] T. Wehner, K. Mandel, M. Schneider, G. Sextl, K. Müller-Buschbaum, ACS Appl. Mater. Interfaces 2016, 8, [2] K. Mandel, F. Hutter, C. Gellermann, G. Sextl, ACS Appl. Mater. Interfaces 2012, 4, [3] C. J. Höller, M. Mai, C. Feldmann, K. Müller-Buschbaum, Dalton Trans. 2010, 39, 461. [4] P. R. Matthes, C. J. Höller, M. Mai, J. Heck, S. J. Sedlmaier, S. Schmiechen, C. Feldmann, W. Schnick, K. Müller-Buschbaum, J. Mater. Chem. 2012, 22, [5] A. Zurawski, M. Mai, D. Baumann, C. Feldmann, K. Müller-Buschbaum, Chem. Commun. 2011, 47, 496. [6] Z.-H. Zhang, S.-Y. Wan, T.-a. Okamura, W.-Y. Sun, N. Ueyama, Z. Anorg. Allg. Chem. 2006, 632, 679.

66 P51 Pharmazie und Lebensmittelchemie Bioresponsive interleukin-4 delivery system deploying silk-elastinlike proteins for the treatment of osteoarthritis V. Spieler 1, C. Karavasili 2, T. Lühmann 1, L. Meinel 1* 1 Institute for Pharmacy and Food Chemistry, University of Würzburg, Am Hubland, Würzburg, Germany 2 Department of Pharmaceutical Technology, Aristotle University, Thessaloniki GR 54124, Greece * Corresponding Author: Lorenz Meinel, lorenz.meinel@uni-wuerzburg.de Controlling macrophage polarization using a bioresponsive drug delivery system for rhil-4 in osteoarthritis holds potential in meeting challenges with the systemic administration of this antiinflammatory cytokine. [1,2] In this study, the silk-elastin-like protein (SELP) S2E8C, a genetically engineered biomaterial, is used for immobilization of IL-4. SELPs consist of repeating units of silk and elastin blocks and self-assemble into small micellar-like particles at body temperature. [3] S2E8C features twelve cysteines allowing for bioorthogonal conjugation reactions. IL-4 modified with an unnatural amino acid containing a functionality for copper(i)-catalyzed azide alkyne cycloaddition (CuAAC) at position 42 [4] and a protease cleavable linker (PCL) responding to proteases up regulated during inflammation [5] modified with a sulfhydryl-reactive iodoacetyl group were used to decorate S2E8C. Following intra articular injection, the system is designed to remain within the osteoarthritic joint, where it deploys its sensory function for constant surveilling of the disease status only to respond to flare by releasing IL-4, hence preventing disease progression and initiating tissue repair. A new S2E8C version with thrombin cleavable His-tag was cloned and expressed in E. coli. Purification was performed by precipitation at high temperature and low ph with subsequent resolubilization in water, thereby removing the potential need of a potentially immunogenic His-tag. Conjugation of S2E8C to the PCL was with a succinimidyl iodo acetate crosslinker. CuAAC linking S2E8C-PCL and IL-4 is currently under investigation. S2E8C as a biomaterial for site-directed immobilization of IL-4 allows for creating a biocompatible and injectable drug delivery system for targeting inflammation by controlling macrophage plasticity in a timely and spatially regulated manner. [6] [1] D. M. Mosser, J. P. Edwards, Nat. Rev. Immunol. 2008, 8, [2] T. Lühmann, L. Meinel, Curr. Opin. Biotechnol. 2016, 39, [3] X. X. Xia, Q. Xu, X. Hu, G. Qin, D. L. Kaplan, Biomacromolecules 2011, 12, [4] T. Lühmann, V. Spieler, V. Werner, M.-G. Ludwig, J. Fiebig, T. Müller, L. Meinel, Chembiochem [5] A. C. Braun, M. Gutmann, R. Ebert, F. Jakob, H. Gieseler, T. Lühmann, L. Meinel, Pharm. Res. 2016, [6] W. Huang, A. Rollett, D. L. Kaplan, Expert Opin. Drug Deliv. 2015, 12,

67 Anorganische Chemie und Materialwissenschaften Reactivity of the Vicinal Biscarbenoid Bis(piperidyl)acetylene P52 H. Braunschweig 1, S. Kachel 1, H. Kelch 1 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität, Am Hubland, Würzburg, Deutschland We present the reactivity of the diaminoacetylene Pip C C Pip which exhibits strong biscarbenoid behavior based on the extraordinarily high electron density of the acetylenic moiety. [1] The molecule displays extensive bond activation chemistry beyond that of commonly employed monofunctional carbenes. Treatment with moderately Lewis acidic and/or polar substrates leads to clean activation of B B, B C and B N bonds under ambient conditions. [2] The resulting products feature intriguing structural and electronical properties as exemplified in the first transition-metal-free synthesis of 1,4- azaborinines highly sought-after benzene analogs with potential applications in medicinal and material science. [3] Cyclodimerization of Pip C C Pip with the aid of group XIV metals leads to the formation of cyclobutadiene derivatives displaying a unique mode of stabilization based on charge separation and Lewis pair formation. [4] [1] A. R. Petrov, T. Bannenberg, C. G. Daniliuc, P. G. Jones, M. Tamm, Dalton Trans. 2011, a 40, [2] H. Kelch, S. Kachel, M. A. Celik, M. Schäfer, B. Wennemann, K. Radacki, A. R. Petrov, M. Tamm, H. Braunschweig, Chem. Eur. J. 2016, 22, [3] H. Lee, M. Fischer, B. K. Shoichet, S.-Y. Liu, J. Am. Chem. Soc. 2016, 138, [4] R. Bertermann, H. Braunschweig, M. A. Celik, T. Dellermann, H. Kelch, Chem. Commun., DOI: /C6CC07741B.

68 P53 Anorganische Chemie und Materialwissenschaften Water-Soluble 3-Coordinate Boron Chromophores for One- and Two-Photon Excited Fluorescence Imaging of Mitochondria in Cells S. Griesbeck 1, Z. Zhang 1, M. Gutmann 2, T. Lühmann 2, R. M. Edkins 1, G. Clermont 3, A. N. Lazar 3, M. Blanchard-Desce 3, L. Meinel 2, T. B. Marder 1 stefanie.griesbeck@uni-wuerzburg.de 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Würzburg, Germany 2 Institut für Lebensmittelchemie und Pharmazie, Julius-Maximilians-Universität Würzburg, Würzburg, Germany 3 Institut de Sciences Moléculaires, Université de Bordeaux, Bordeaux, France Triarylboranes have attracted a huge amount of interest due to their application in many different fields such as anion sensing, OLEDs and non-linear optical materials. [1] Over the last few years, we have studied the use of dimesitylboron-based -acceptors (A) in two-photon absorption (TPA) chromophores. We designed dipolar, quadrupolar and octupolar compounds with exceptional TPA cross sections and high fluorescence quantum yields. [2] Furthermore, we reported structure-tpa cross section relationships for our quadrupolar A- -A compounds. [3] Recently, we synthesized oligothiophene-bmes 2 chromophores, with significantly enhanced TPA cross sections of up to 1930 GM in the near-infrared region, the biological transparent window. [4] We present herein the further functionalization of such chromophores with ammonium groups, an approach pioneered by Gabbaï, [5] in order to achieve hydrophilicity and biocompatibility, and our initial results of both one- and two-photon excited fluorescence (TPEF) microscopy allowing the imaging of mitochondria in cells with our chromophore. [1] (a) C. D. Entwistle, T. B. Marder, Angew. Chem. Int. Ed. Engl. 2002, 41, (b) C. D. Entwistle, T. B. Marder, Chem. Mater. 2004, 16, [2] J. C. Collings, C. Katan, A. Beeby, D. Kaufmann, W.-Y. Wong, M. Blanchard-Desce, T. B. Marder et al., Chem. Eur. J. 2009, 15, [3] (a) M. Charlot, L. Porrès, C. D. Entwistle, A. Beeby, T. B. Marder, M. Blanchard-Desce, Phys. Chem. Chem. Phys. 2005, 7, (b) C. D. Entwistle, J. C. Collings, A. Steffen, A. Beeby, A. S. Batsanov, J. A. K. Howard, W.-Y. Wong, A. Boucekkine, J.-F. Halet, T. B. Marder et al., J. Mater. Chem. 2009, 19, [4] L. Ji, R. M. Edkins, A. Beeby, A. S. Batsanov, J. A. K. Howard, A. Boucekkine, Z. Liu, J.-F. Halet, C. Katan, T. B. Marder et al., Chem. Eur. J. 2014, 20, [5] C.-W. Chiu, Y. Kim, F. P. Gabbaï, J. Am. Chem. Soc. 2009, 131,

69 Anorganische Chemie und Materialwissenschaften Experimentelle und theoretische Untersuchungen sterischer und elektronischer Parameter NHC-stabilisierter Nickel-Carbonylkomplexe P54 J. Berthel, U. Radius * Julius-Maximilians-Universität Würzburg/Institut für Anorganische Chemie johannes.berthel@uni-wuerzburg.de, u.radius@uni-wuerzburg.de Freie NHCs finden seit ihrer erstmaligen Synthese und Isolierung [1] breitgefächerte Anwendung in der Übergangsmetallchemie. [2-4] Dies gründet neben ihren starken σ-donor- und schwachen π- Akzeptoreigenschaften auch auf ihren mannigfaltigen Synthesemöglichkeiten bei struktureller Variabilität und sterischer Flexibilität. [5-8] Mithilfe des sterischen Anspruchs und der elektronischen Eigenschaftender NHCs kann dabei deren Einfluss auf die Struktur von Übergangsmetallkomplexen bestimmt werden. [9] Vorgestellt wird die Synthese neuer NHC-stabilisierter Nickel-Carbonylkomplexe und die Untersuchungen bezüglich ihrer sterischen und elektronischen Eigenschaften. Zur Unterstützung der Ergebnisse wurden quantenmechanische Berechnungen angefertigt und die Bindungsbildungs- und Bindungsdissoziationsenergien ΔG der Komplexe abgeschätzt. [1] A. J. Arduengo III, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113, 361. [2] N-Heterocyclic Carbenes in Synthesis, S. P. Nolan (Hrsg.), Wiley-VCH, Weinheim, [3] N-Heterocyclic Carbenes in Transition Metal Catalysis, F. Glorius (Hrsg.), Top. Organomet. Chem., Vol. 21, [4] N-Heterocyclic Carbenes: From Laboratory Curiosities to Efficient Synthetic Tools, S. Díez- González (Hrsg.), Catalysis Series No. 6, RSC, Cambridge, [5] N. M. Scott, S. P. Nolan, Eur. J. Inorg. Chem. 2005, [6] V. Lavallo, Y. Canac, A. DeHope, B. Donnadieu, G. Bertrand, Angew. Chem. 2005, 117, 7402; Angew. Chem. Int. Ed. 2005, 44, [7] E. Peris, R. H. Crabtree, Coord. Chem. Rev. 2004, 248, [8] C. M. Crudden, D. P. Allen, Coord. Chem. Rev. 2004, 248, [9] U. S. D. Paul, C. Sieck, M. Haehnel, K. Hammond, T. B. Marder, U. Radius, Chem. Eur. J. 2016, 22,

70 P55 Anorganische Chemie und Materialwisenschaften iclick -Reaktionen von Ru- und Rh-Azid-Komplexen mit elektronenarmen Alkinen: Regioselektivität, Stabilität und Kinetik L. Waag-Hiersch 1, S. Eilbacher 1, M. Voelkel 1, J. Mößeler 1, U. Schatzschneider 1, * 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg Am Hubland, D Würzburg (Germany) Luisa.Hiersch@uni-wuerzburg.de Anorganische Click-Reaktionen (engl. inorganic click, iclick ) [1-2] zwischen Metall-Azid- Komplexen und elektronenarmen Alkinen stellen einen schnellen Zugang zu strukturell vielfältigen Triazolatkomplexen dar. Die iclick -Reaktion von Ruthenium-Azid-Komplexen der allgemeinen Formel [Ru(N 3)(aren)(L-L)] + mit bidentaten Stickstoffliganden sowie Rhodium-Azid-Komplexen der allgemeinen Formel [Rh(Cp * )(N 3)(bpy R,R )] + mit unterschiedlich substituierten 2,2 -Bipyridin- Coliganden und elektronenarmen Alkinen wie Dimethylacetylendicaboxylat (DMAD) und 4,4,4- Trifluorobut-2-insäureethylester wurde untersucht. Inbesondere wurde die Geschwindigkeit der iclick -Reaktion von Ruthenium-Azid-Komplexen in Abhängigkeit von funktionellen Gruppen in 4- und 4 -Position am Bipyridin-Ligand sowie Variation des Aren-Liganden (Hexamethylbenzol vs. p- Cymol) bestimmt und dafür verschiedene analytische Methoden (HPLC, IR-Spektroskopie in Lösung und 19 F NMR-Spektroskopie) verwendet. Da Triazolate prinzipiell über die N1-, N2- oder N3- Stickstoffatome an ein Metallzentrum binden können, wurde ein besonderes Augenmerk auch auf die Untersuchung der Regioselektivität gerichtet. Des Weiteren wurde die Stabilität der resultierenden Verbindungen unter biorelevanten Bedingungen untersucht. Neben der Stabilität in saurem und schwach basischem Milieu ist dabei insbesondere der mögliche Ligandenaustausch mit funktionellen Gruppen in Aminosäureseitenketten von Bedeutung. [1] T. J. D. Castillo, S. Sarkar, K. A. Abboud, A. S. Veige, Dalton Trans. 2011, 40, [2] L. Henry, C. Schneider, B. Mützel, P. V. Simpson, C. Nagel, K. Fucke, U. Schatzschneider, Chem. Commun. 2014, 50,

71 Anorganische Chemie und Materialwissenschaften Photocatalytic water splitting with [FeFe]-hydrogenase mimic in aqueous micellar solution P56 M. Roos 1, C. Lambert 1, R. Luxenhofer 2 1 Institute of Organic Chemistry, University of Würzburg, Am Hubland, Würzburg 2 Chair of chemical technology of material synthesis, University of Würzburg, Röntgenring 11, Würzburg Because of the continual growth of worldwide energy demand and against the background of the climate change the interest in an environmental friendly energy carrier generation becomes more and more important. One possible method is the photocatalytic water splitting, in which hydrogen is generated due to sunlight irradiation. As catalyst a [FeFe]-hydrogenase mimic is used, which gets reduced during the process by a light-excited photosensitizer. In order to archive a thermodynamic favored electron cascade the redoxpotentials of the concerned components has to be adjusted to each other. [1] Besides transition metal organic complexes like Tris(bipyridine)ruthenium(II) chloride also pure organic compounds like the Xanthene dye Eosin Y could be use as photosensitizer. [1,2] As electron source a sacrificial donor like triethylamine or the Vitamin C containing ascorbic acid is used. [1] To perform the photocatalysis in pure water, the [FeFe]-catalyst, as a water insoluble compound, is solubilized with poly(2-oxazoline) micelles. [3] Due to the dynamic character of the micelle formation the exchange between the ambient solution and the [FeFe]-catalyst within the micelle is possible, so the requirements for the photocatalytic activity of the three component system are fulfilled. We synthesised in our group a series of [FeFe]-catalysts with different dithiolate bridging ligands and characterised their photocatalytic properties. Thereby a maximum turnover number of 144 was archived with the system shown above. [1] M. Wang, L. Chen, X. Lia, L. Sun, Dalton Trans. 2011, 40, [2] C. Orain, F. Quentel, F. Gloaguen, ChemSusChem. 2014, 7, [3] Y. Han, Z. He, A. Schulz, T. K. Bronich, R. Jordan, R. Luxenhofer, A. V. Kabanov, Mol. Pharm. 2012, 9,

72 P57 Organische Chemie und Biochemie Functionalised Diamond Particles for the Photocatalytic Conversion of CO2 B. Kiendl, J. Fink, C. Heinz, A. Krueger 1 1 Institut für Organische Chemie, Universität Würzburg, Am Hubland, D Würzburg krueger@chemie.uni-wuerzburg.de Carbon dioxide, one of the most alarming greenhouse gases, is usually reduced by transition metals and their corresponding oxides. [1] Recently, synthetic diamond materials have been used to convert carbon dioxide to carbon monoxide or even formaldehyde, either photocatalytically or electrochemically. [2,3] Therefore, diamond based materials provide a cheap, antrophogenic and safe alternative for the selective reduction of carbon dioxide. Concerning diamond catalysed reduction processes, solvated electrons play an important role as powerful reducing agent. In order to generate those electrons, boron-doped diamond materials have been irradiated so far using high-energy UV light. [2] However, the electronic structure of diamond can not only be influenced by dopants, but also by different surface terminations and functionalizations. Figure 1: Immobilisation of transition metal complexes (TMC) by linker molecules. In this work we present the synthesis of a bifunctionalised linker molecule and its subsequent grafting onto diamond nanoparticles. Furthermore, the immobilisation of transition metal complexes on this linker using the concept of click-chemistry is reported. The ability of these conjugates to reduce carbon dioxide will be investigated in the context of photocatalysis. This project has received funding from the European Unions s Horizon 2020 Programme under Grant Agreement no (DIACAT). [1] J. L. White, M. F. Baruch, J. E. Pander III, Y. Hu, I. C. Fortmeyer, J. E. Park, T. Zhang, K. Liao, J. Gu, Y. Yan, T. W. Shaw, E. Abelev, A. B. Bocarsly, Chem. Rev. 2015, 115, [2] L. Zhang, D. Zhu, G. M. Nathanson, R. J. Hamers, Angew. Chem., Int. Ed. 2014, 53, [3] K. Nakata, T. Ozaki, C. Terashima, A. Fujishima, Y. Einaga, Angew. Chem, Int. Ed. 2014, 53,

73 Organische Chemie und Biochemie Synthesis and Characterization of Bay-tether-connected Perylene Bisimide Dimers P58 C. Kaufmann, A. Nowak-Król, F. Würthner* Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, Würzburg, Germany * Perylenebisimides (PBI) form remarkable self-assembled structures induced by stacking of monomeric units, yielding fascinating optical and electronic properties. [1] The aggregation behavior of such organic dyes is often governed by a solvent, concentration and temperature dependence. This selfassembly of perylenebisimide (PBI) dyes has been a subject of extensive investigations over more than a decade. By developing a foldable system where single monomers are covalently fixed in a rigid framework, the resulting PBI aggregate with defined geometry may shed light on the structure-property relationship of this class of dyes. [2] Hence, we paid attention to covalent scaffolds that preorganize PBI dyes in a suitable way with regard to intramolecular folding into specific three-dimensional architectures. Therefore we present the synthesis and characterization of new covalently linked bisperylene-bisimids which were investigated by UV/Vis-, Fluorescence- and NMR-Spectroscopy to determine their individual aggregation behavior intermolecular aggregation into defined dye stacks vs. self-assembly into larger aggregates. Scheme 1: Synthetic route and molecular structures of bis-pbis 1-3 (left) and structural model of bis- PBI 1 dimers (right). [1] a) X. Zhang, S. Rehm, M. M. Safont-Sempere, F. Würthner, Nature Chem. 2009, 1, ; b) Z. Chen, V. Stepanenko, V. Dehm, P. Prins, L. D. A. Siebbeles, J. Seibt, P. Marquetand, V. Engel, F. Würthner, Chem. Eur. J. 2007, 13, [2] B. Fimmel, M. Son, Y. M. Sung, M. Grüne, B. Engels, D. Kim, F. Würthner, Chem. Eur. J. 2015, 21,

74 P59 Anorganische Chemie und Materialwissenschaften Rare earth metal coordination polymers with pyrene-2,7- dicarboxylate linkers A. E. Sedykh, J. Merz, L. Ji, T. B. Marder, K. Müller-Buschbaum Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Würzburg, Germany A coordination polymer (CP) is a coordination compound with repeating coordination entities extending in 1, 2, or 3 dimensions. [1] Rare earth metals (RE) are outstanding functional metal centers due to their coordination behavior [2] and luminescent properties. [3] The architecture of their coordination polymers is directly connected with the linker structure. [4] Pyrene-2,7-dicarboxylic acid (H 2PDC) is a linear rigid molecule, and usage of it as a linker source might lead to the formation of coordination polymers with potential voids metal-organic frameworks (MOFs). Till now only a few examples of CPs with pyrene-2,7-dicarboxylate are known, almost all of them with transition metals, [5,6] but one with rare earth metal terbium. [6] Reaction between pyrene-2,7-dicarboxylic acid and rare earth metal chloridesleads to the formation of desired products. Several different structures were obtained, determined by infrared spectroscopy and powder X-ray diffraction, still yet only for one of them a single crystal was successfully acquired and studied. Interesting results await in the luminescence properties studies: a combination of luminescent lanthanides and linker leads to the complete absence of luminescence. This is most likely the result of radiationless decay instead of emission from corresponding lanthanide and ligand energy levels. Nonetheless, products of non-luminescent metals show ligand-based emission. Wherein, the ligand emission band is shifted hypsochromically by 50 nm as result of deprotonation and coordination to the metal. In addition, the intensity of some processes is increasing upon cooling. [1] S. R. Batten, N. R. Champness, X.-M. Chen, J. Garcia-Martinez, S. Kitagawa, L. Öhrström, M. O Keeffe, M. P. Suh, J. Reedijk, Pure Appl. Chem. 2013, 85, [2] S. A. Cotton, J. M. Harrowfield, Lanthanides: Coordination Chemistry. Encyclopedia of Inorganic and Bioinorganic Chemistry, [3] G. F. de Sa, O. L. Malta, C. de Mello Donega, A. M. Simas, R. L. Longo, P. A. Santa-Cruz, E. F. da Silva Jr., Coord. Chem. Rev. 2000, 196, 165. [4] G. Zhu, Coord. Chem. Rev. 2009, 253, [5] M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O Keeffe, O.M. Yaghi, Science 2002, 295, 469. [6] N. L. Rosi, J. Kim, M. Eddaoudi, B. Chen, M. O Keeffe, O. M. Yaghi, J. Am. Chem. Soc. 2005, 127, 1504.

75 Pharmazie und Lebensmittelchemie Site-directed incorporation of propargyl-l-lysine into insulin-like growth factor- I (IGF-I) for site specific decoration P60 F. Wu, J. Ritzer, T. Lühmann, L. Meinel Institute for Pharmacy and Food Chemistry, University of Wuerzburg, Am Hubland, 97074, Wuerzburg, Germany Current decoration approaches, which typically follow random coupling strategies to present lysines or cysteines on the protein-surface, have led to heterogeneous pharmaceutical products. [1] This impacts their activity and challenges homogenous product outcome. Here we pursue a highly attractive strategy for the controlled insulin-like growth factor- I (IGF-I) conjugates delivery. We genetically engineered IGF-I variants (TrxplkIGF-I) containing a N-terminal thioredoxin [2] (Trx) His 6 [3] tag-thrombin cleavage site and a non-natural amino acid, propargyl-protected lysine derivative (plk) incorporated at position 3 of IGF-I, thereby allowing targeted, specific decoration of IGF-I with other molecules. The expression of the TrxplkIGF-I fusion protein was compared in four different Escherichia coli hosts (BL21 (DE3), shuffle T7, Rosetta DE3, and C321 dela.exp). Additionally, the effects of different expression conditions (induction temperature, isopropyl β-d-1- thiogalactopyranoside (IPTG) concentration, plk amount) were systematically investigated. Figure 1: Expression of plkigf-i. The propargyl-l-lysine (plk) is incorporated at the site of an amber stop codon (UAG) of IGF-I by using the orthogonal pair PylRS/tRNAPyl from M. barkeri. The TrxplkIGF-I fusion protein was expressed in all these four strains with different expression levels, whereas shuffle T7 showed the highest soluble TrxplkIGF-I production. Furthermore, TrxplkIGF-I production was correlated to plk concentrations and induction parameters including time and IPTG amount. Purified plkigf-i was successfully demonstrated by Western Blot. In conclusion, we maximize the risk-benefit ratio of our IGF-I conjugate by directing these anabolic therapeutic to local sites in need while minimizing systemic exposure. [1] K. S. Masters, Macromolecular Bioscience 2011, 11, [2] D. Zhang, P. Wei, L. Fan, J. Lian, L. Huang, J. Cai, Z. Xu, Process Biochemistry 2010, 45, [3] E. Hochuli, W. Bannwarth, H. Dobeli, R. Gentz, D. Stuber, Nat Biotech 1988, 6,

76 P61 Pharmazie und Lebensmittelchemie The use of capillary blood to estimate the kidney function of diabetic patients M. Scherf-Clavel, P. Högger Institut für Pharmazie und Lebensmittelchemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg, Deutschland In therapy with renally eliminated drugs, for example metformin or sitagliptin, it is important to monitor the kidney function. Typically, the renal function is estimated with the help of serum creatinine based equations, for example the Cockcroft-Gault equation. [1] Therefore, a venous blood sampling has to be performed and in patients serum the creatinine concentration is quantified with the Jaffé reaction, which is affected by many other compounds. [2] To simplify the control of the therapy, a method to quantify metformin, sitagliptin and creatinine out of dried capillary blood samples was recently developed by our group. [3] The quantification of creatinine is very selective, the sampling of capillary blood is much easier and more comfortable for the patient than the venous blood sampling. [3] Due to the use of the Cockcroft-Gault formula, a correlation factor to convert the capillary blood concentration of creatinine into serum concentration had to be evaluated. Figure 1: Illustration how to handle with dried blood spot analytics. A drop of capillary blood is sampled by finger prick and spotted on a filter paper. After drying the sample is extracted and the analytes are quantified. Therefore, a clinical study was conducted in cooperation with a physician specialized in diabetology. The study was approved by the Ethics Committee of the medical department of the University of Würzburg. After patients informed consent capillary blood samples from 70 patients were collected. After analyzing the samples a factor to convert the creatinine concentration in capillary blood into the serum concentration was established and verified. With these results it is possible to use a drop of capillary blood to estimate the renal function. [1] J. L. Steffl, W. Bennett, A. J. Olyaei, J Clin Pharmacol 2012, 52,(1 Suppl), 63S-71S. [2] E. Mohabbati-Kalejahi et al., Talanta 2012, 97, 1-8. [3] M. Scherf-Clavel, P. Högger, J Chromatogr B Analyt Technol Biomed Life Sci 2015, 997,

77 Physikalische und Theoretische Chemie The CAST program A tool for specialized potential energy surface investigations P62 D. Weber 1, D. Bellinger 1, D. Kaiser 1, M. Prem 1, S. Sauer 1, S. Wirsing 1, B. Engels 1 1 Julius-Maximilians-Universität, Institut für Physikalische und Theoretische Chemie, Emil-Fischer-Straße 42, D Würzburg, Germany The CAST (Conformational Analysis and Search Tool) [1] program is a computational chemist s toolkit which enables users to investigate ground state chemistry problems like sampling, global optimization and analysis in a sophisticated manner. The program-package is founded on the principle to be independent of the underlying potential energy description. In this way, all implemented methods can be performed via classical force field calculations as well as DFT or semi empirical methods. CAST offers the Tabu-Search approach for finding the global minimum for a given system, e.g. an optimal solvation shell. Multiple specially designed algorithms for the treatment of the solvation problem are available, enhancing the speed and quality of optimizations of water shells. CAST is capable to deal with complex chemical reactions through the use of the Pathopt [2] algorithm, as well as various doubly nudged elastic band (NEB) [3] methods. Within the framework of sampling of systems such as protein-inhibitor complexes CAST offers the possibility to simulate changes in terms of free energy (FEP [4], modified FEP, Umbrella Sampling [5] ). A further but no less important issue is the analysis of data obtained from molecular simulations. Within CAST this may be addressed through novel principal component analysis(pca) [6] based approaches. Acknowledgments: We are grateful to the Deutsche Forschungsgemeinschaft (GRK 1221, FOR 1809, SPP 1355) for financial support. [1] C. Grebner, J. Becker, D. Weber, D. Bellinger, M. Tafipolski, C. Brückner, B. Engels, J. Comp. Chem. 2014, 35, [2] D. Weber, D. Bellinger, B. Engels, Methods in Enzymology 2016, 578, [3] G. Henkelman, B. P. Uberuaga, H. Jonsson, J. Chem. Phys. 2000, 113, [4] C. Chipot, A. Pohorille, Free energy calculations. Springer-Verlag Berlin, Heidelberg, [5] G. M. Torrie, J. P. Valleau, J. Comp. Phys. 1977, 23, [6] H. Abdi, L. J. Williams, Wiley Interdisciplinary Reviews: Computational Statistics 2010, 2,

78 P63 Anorganische Chemie und Materialwissenschaften Seltenerdmetallkomplexe mit dem Perfluorethyltricyanoborat-Anion T. Ribbeck 1, S. Zottnick 1, N. V. Ignat'ev 2, K. Müller-Buschbaum 1, M. Finze 1 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg 2 Berater, Merck KGaA, Darmstadt/D maik.finze@uni-wuerzburg.de Perfluorierte Alkyltricyanoboratanionen [1] [R F B(CN) 3] (R F = Perfluoralkyl) sind ausgehend von Salzen mit dem entsprechenden Perfluoralkyltrifluoroborat-Anion und Trimethylsilylcyanid gut zugänglich. [1,2] Ausgehend von der Säure des Pentafluorethyltricyanoborat-Anions (H 3O)[C 2F 5B(CN) 3] und den Chloriden der Seltenerdmetalle MCl 3 nh 2O (M = Eu, La, Ho) konnten erstmals die Komplexe M[C 2F 5B(CN) 3] 3 nh 2O synthetisiert und charakterisiert werden. Freie Koordinationsstellen am Metallzentrum werden im Kristall durch Wassermoleküle besetzt, die jedoch im Vakuum entfernt werden können. Die wasserfreien Salze M[C 2F 5B(CN) 3] 3 wurden u.a. NMR-, IR- und Ramanspektroskopisch charakterisiert und das Lumineszenzverhalten des Europium-Salzes wurde untersucht. Des Weiterengelang die strukturelle Charakterisierung der Verbindungen Eu[C 2F 5B(CN) 3] 3 3H 2O und La[C 2F 5B(CN) 3] 3 an Einkristallen. Die Kristallisation von Eu[C 2F 5B(CN) 3] 3 3H 2O erfolgte aus wässriger Lösung über konzentrierter Schwefelsäure. Einkristalle von wasserfreiem La[C 2F 5B(CN) 3] 3 wurden dagegen ausgehend von mikrokristallinem Material in der Ionischen Flüssigkeit Ethylmethylimidazolium-Perfluorethyltricyanoborat EMIm[C 2F 5B(CN) 3] unter Erwärmen erhalten. Eine nennenswerte Löslichkeit der wasserfreien Salze in EMIm[C 2F 5B(CN) 3] war allerdings nicht festzustellen. Die Strukturaufklärung der wasserfreien Salze Eu und Ho[C 2F 5B(CN) 3] 3 erfolgte anhand pulverdiffraktometrischer Daten. Eu[C 2F 5B(CN) 3] 3 3H 2O La[C 2F 5B(CN) 3] 3 [1] J. Sprenger, Dissertation, Heinrich-Heine-Universität Düsseldorf. [2] N. Ignatyev, M. Schulte, J. Sprenger, M. Finze, W. Frank, WO 2011/ A1, Merck Patent GmbH, Darmstadt, Germany.

79 Pharmazie und Lebensmittelchemie Charakterisierung der Pharmakokinetik von intranasal appliziertem Fluticasonpropionat (FP) und Azelastin-HCl (AZ) P64 A. Pospiech, P. Högger Institut für Pharmazie und Lebensmittelchemie, Universität Würzburg Mit dem Kombinationspräparat Dymista (Nasenspraysuspension, Wirksame Bestandteile: FP und AZ) steht seit 2013 eine neue Therapieoption zur lokalen Behandlung der Allergischen Rhinitis zur Verfügung, deren klinische Wirksamkeit bereits gezeigt werden konnte. [1] Im Rahmen einer klinischen Studie wird die Aufnahme von FP in die Nasenschleimhaut aus einem FP-Monopräparat und aus Dymista untersucht und verglichen werden. Als Spezimen werden Abstriche und Gewebeproben der Nasenschleimhaut der Probanden verwendet. Ziel ist die Entwicklung geeigneter Extraktions- und empfindlicher Analytikmethoden zur Quantifizierung von FP und AZ in beiden Spezimen. Da menschliches Nasensekret und menschliche Nasenschleimhaut für die Methodenentwicklung nicht verfügbar waren, bestand die Herausforderung darin, geeignete Probenmatrices festzulegen. Weiterhin sollten effektive Extraktionsmethoden etabliert werden. Für die Methodenentwicklung der Extraktion von FP und AZ aus Sinustamponaden wurde künstliches Nasensekret verwendet und mittels Flüssig-Flüssig-Extraktion aufgearbeitet. Die Methodenentwicklung der Gewebeextraktion erfolgte mit porciner Nasenschleimhaut, wobei nach enzymatischem Verdau mit Hilfe von Kollagenase eine Festphasenextraktion durchgeführt wurde. Abbildung: Beispielchromatogramm für die Extraktion von FP und AZ aus Sinustamponaden. Die beiden Analyten und ihre internen Standards (Clomipramin und Amcinonid) können mit der entwickelten Methode (Laufzeit 10 Minuten) basisliniengetrennt und simultan bei 254 nm detektiert werden. Zur Quantifizierung der Analyten wurden für die Extraktion aus den Sinustamponaden eine HPLC- UV/VIS-Methode und für die Gewebeextraktion eine LC/MS-MS-Methode entwickelt. Die Optimierung der Extraktionsmethoden sowie die Entwicklung und Validierung der analytischen Methoden werden präsentiert. [1] E. Meltzer et al., Int Arch Allergy Immunol 2013, 161,

80 P65 Pharmazie und Lebensmittelchemie Bacterial protease responsive antibiotic delivery M. C. Amstalden 1, A. A. Fayad 2, R. Müller 2, T. Lühmann 1, L. Meinel 1 1 Institute of pharmacy and food chemistry, University of Würzburg, Am Hubland Würzburg 2 Helmholtz-Institute for Pharmaceutical Research Saarland, Saarland University, Saarbrücken One cause driving antibiotic resistance is untargeted systemic circulation, leading to higher doses as well as impacting the commensal, desirable bacterial flora. In this study, we aimed at developing a bioresponsive drug delivery system (DDS) responding to virulent Staphylococcus aureus (S. aureus) with antibiotic discharge, thereby homing antibiotic activity to sites in need while minimizing off target activity. The DDI comprises a polymer, a peptide cleavable linker (PCL) and the antibiotic which is covalently attached to the peptide s C terminus. The PCL responds to the protease aureolysin, which is a virulence factor of S. aureus strains, [1] while the remaining amino acids attached to the antibiotic are cleaved by human aminopeptidases (Figure 1). Figure 1: Schematic representation of the protease dependent DDS. The dual-gated mechanism comprise cleavage of the index protease aureolysin followed by the human aminopeptidase, present in human plasma, and release of the active drug compound at target sites PCL prototypes were synthesized by Fmoc based solid phase peptide synthesis. [2] The PCLs were analyzed for sensitivity towards aureolysin (1.4 µg/ml) and human proteases. The conjugation of the PCL to the antibiotic was performed via EDC/NHS reaction. [3] Resulting peptide fragments after aureolysin cleavage were further analyzed for aminopeptidase cleavage using a final concentration of 3.6 µg/ml. We identified two selective and sensitive PCLs for aureolysin. Aminopeptidase treatment of theaureolysin-cleaved peptide-drug fragment resulted in the release of the free compound within 20 minutes. Ongoing work focuses on the construction of the entire conjugate and analysis of antibacterial activity. [1] A. J. Laarman et al., J. Immunol. 2011, 186, [2] J. L. T. Ritzer et al., Journal of controlled release (submitted). [3] K. Sakurai, T. M. Snyder, D. R. Liu, J. Am. Chem. Soc. 2005, 127,

81 Anorganische Chemie und Materialwissenschaften iclick reactions of Pt-and Pd-azide complexes with electron-poor alkynes P66 N. Feizy 1, U. Schatzschneider 1, * 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D Würzburg (Germany) nilab.feizy@uni-wuerzburg.de The concept of "iclick" reactions was first introduced by Veige for the inorganic version of the 1,3-dipolar cycloaddition between a metal-coordinated azide such as triphenylphosphine gold(i) azide with triphenylphosphine gold(i) phenylacetylide to form dinuclear triazolate-bridged gold complexes. [1] Triazolates and their metal complexes are used in pharmaceutical and inorganic medicinal chemistry. [2] For example, the treatment of human breast cancer cells with triazolate-linked Au(I)-peptide conjugates led to a breakdown of essential cell functions and eventually cell death. [3] To extend the range of applications of the iclick reaction, [4] in the present work, the synthesis of platinum(ii) and palladium(ii) triazolate complexes through a [3+2]-cycloaddition of Pt or Pd azide complexes with dimethylacetylenedicarboxylate (DMAD) was investigated. Thus, an anionic tridentate N,N,N-chelating 1,3-bis(2-pyridylimino)isoindoline ligand was prepared and coordinated to a palladium(ii) unit to obtain a neutral complex. The initial chloride ligand was then replaced by reaction with sodium azide. Finally, the iclick reaction with DMAD lead to the desired triazolate product and thus opens up a new and easy access to square-planar metal(ii)triazolate complexes. As an alternative pathway to cationic complexes of a similar core structure, substituted terpyridine derivatives are currently explored and the corresponding platinum(ii) compounds are also under preparation. [1] T. J. Del Castillo, S. Sarkar, K. A. Abboud, A. S. Veige, Dalton Trans. 2011, 40, [2] T. M. Klapötke, J. Stierstorfer, J. Am. Chem. Soc. 2009, 131, [3] S. D. Köster, S. Can, I. Kitanovic, S. Wolfl, R. Rubbiani, I. Ott, P. Riesterer, A. Prokop, K. Merz, N. Metzler-Notle, Chem. Sci. 2012, 3, [4] L. Henry, C. Schneider, B. Mützel, P. V. Simpson, C. Nagel, K. Fucke, U. Schatzschneider, Chem. Commun. 2014, 50,

82 P67 Organische Chemie und Biochemie Self-Assembled Bolamphiphilic Perylene Bisimides in Water B. Soberats, D. Görl, P. Syamala, F. Würthner* Universität Würzburg, Center for Nanosystems Chemistry, Institut für Organische Chemie, and Bavarian Polymer Institute, Universität Würzburg, Würzburg, Germany * Self-assembly of dyes in aqueous media has attracted a great deal of attention for the development of biocompatible sensors and stimuli responsive photoactive materials. [1] We recently focus on the fundamental understanding of the thermodynamic aspects of self-assembly in water of bolamphiphilic perylene bisimide (PBIs) dyes bearing oligoethylene glycol (OEG) groups (Figure 1a). [2] We found that the entropic release of water from the OEG chains overcomes the enthalpic contribution from π- π stacking interactions (Figure 1c), which has a determining influence on the thermodynamics of the aggregation process. [3] This leads to an inverse temperature response which induces lower critical solution temperature (LCST) phenomena, where the solution phase separates at a particular temperature upon heating. In the present study we show a novel supramolecular approach to control the LCST transitions in PBI 1/PBI 2 mixtures by adjusting their mixing ratio (Figure 1a). [4] Figure 1: a) Schematic representation of the supramolecular approach applied to control the LCST phase transition in bolamphiphilic PBI 1 and PBI 2 aggregates. b) Illustration of the LCST phase transition in PBI1/PB2 hydrogels. Furthermore, based on this concept, we prepared stimuli responsive hydrogels that undergo a remarkable color change triggered by the LCST phase transition between a hydrogel state and a lyotropic liquid-crystalline state (Figure 1b). [4] This study open new avenues to the development of photoactive biocompatible sensors based on aqueous soft matter systems. [1] E. Krieg, M. M. C. Bastings, P. Besenius, B. Rybtchinski, Chem. Rev. 2016, 116, [2] a) D. Görl, X. Zhang, V. Stepanenko, F. Würthner, Nat. Commun. 2015, 6, b) X. Zhang, D. Görl, V. Stepanenko, F. Würthner, Angew. Chem. Int. Ed. 2014, 53, [3] D. Görl, F. Würthner, Angew. Chem. Int. Ed. 2016, 55, [4] D. Görl, B. Soberats, S. Herbst, V. Stepanenko, F. Würthner, Chem. Sci. 2016, 7,

83 Anorganische Chemie und Materialwissenschaften Luminescent Ln-MOFs as Detector Systems for Water-Sensitive Pharmaceutical Products P68 J. Stangl 1, L. V. Meyer 1, K. Müller-Buschbaum 1, L. Meinel 2 1 Institut für Anorg. Chemie, Würzburg, Germany; 2 Institut für Phamazie u. Lebensmittelchemie, Würzburg, Germany; Luminescent Metal-organic frameworks (MOFs) have attracted attention for sensing/detection functions. [1,2] Based on the microporosity of the framework, chemical species such as gas, volatile molecules and ions can be adsorbed/detected. The accompanying interaction with the MOF can influence luminescence processes and is either reversible or irreversible. Thereby, especially strong changes in the luminescence either in intensity ( turn-off or turn-on effects) or in the chromaticity are interesting, especially if the signal change is selective for a certain species. Figure 1: Partial loss of the luminescence properties due to the presence of humidity We can now present lanthanide containing Ln-MOFs with N-functionalized linkers that can be utilized as water detectors. [3] Suitable MOF candidates are presented that show a significant turn-off effect of the luminescence through humidity, which can be combined with water sensitive pharmaceutical products. Complete quenching of the luminescence is used as an easy observable, which can be used for a screening of the real status of a pharmaceutical product instead of fixed usability dates. An additional control becomes available upon integration of the Ln-MOFs into the package materials of a pharmaceutical product. We can show that the lanthanide metal-based luminescence of the MOFs is retained, if they are included into organic polymers. Correlating border concentrations/sensitivities of Ln-MOF and pharmaceutical products enables a real status analysis. Different from other MOF sensors, this process is irreversible and can`t be falsified by a re-drying process. [1] K. Müller-Buschbaum, F. Beuerle, C. Feldmann, Microporous and Mesoporous Materials 2015, 216, [2] L. V. Meyer, F. Schönfeld, K. Müller-Buschbaum, Chem. Commun. 2014, 50, [3] L.V. Meyer, F. Schönfeld, A. Zurawski, M. Mai, C. Feldmann, K. Müller-Buschbaum, Dalton Trans. 2015, 44,

84 P69 Organische Chemie und Biochemie Total Synthesis of the Antimalarial Naphthylisoquinolines Dioncophylline C, 5-epi-Dioncophylline C and Dioncophylline F W. Shamburger, R. Seupel, S. K. Bischof, G. Bringmann Institute of Organic Chemistry, University of Würzburg, Am Hubland, D Würzburg Dioncophylline C (3a), a 5,1 -coupled naphthylisoquinoline alkaloid isolated from the West African liana Triphyophyllum peltatum, was found to show remarkable activity against Plasmodium falciparum in vitro and against P. berghei in vivo. [1,2] Therefore 3a represents an attractive synthetic target. This was further underlined by the outcome of Q(SAR) studies on structurally simplified analogs of 3a, such as molecules 4, 5, and 6, which were all found to display distinct weaker antiplasmodial activities compared to 3a. [3] Following a highly concise route, we now aim at the synthesis of compounds which differ from 3a only in one single structural parameter like e.g., 5-epi-dioncophylline C (3b). Key step is the Pd-catalyzed Suzuki-Miyaura cross-coupling of a naphthalene boronic acid ester (here 1) and an isoquinoline bromine (here 2). This approach furnished 3a and its atropisomer 3b in a good chemical yield and in stereochemically pure form after their resolution on a Symmetry-C18 column. This pathway has also been successfully applied to the total synthesis of the first, and so far only, 5,8 -coupled Dioncophyllaceae-type alkaloid dioncophylline F (7a and 7b), which is configurationally unstable at the biaryl axis. OH OMe OH OMe OiPr OMe BPin Me Br OiPr Me R R N Bn Me P 1' 5 OH Me Me N H Me + OH Me N H Me dioncophylline C ( 3a) 5-epi -dioncophylline C ( 3b) 1' 5 Me ipro OMe Cl MeO OMe OMe OMe OMe Me Me N H R N Me N Me Me Me P 8' 5 Me R S N H fast Me M 8' 5 Me R S N H OH OH Me OH OH Me OH Me dioncophylline F ( 7a + 7b) [1] G. Bringmann, Ann. Trop. Med. Parasitol. 1996, 90, [2] G. Bringmann, Antimicrob. Agents Chemother. 1997, 41, [3] G. Bringmann, Eur. J. Med. Chem. 2010, 45,

85 Anorganische Chemie und Materialwissenschaften Pseudo-polypeptides forming thermo responsive, biocompatible and injectable gels for multiple biomedical applications P70 T. Lorson 1, T. Jüngst 2, J. Groll 2, T. Lühmann 3, R. Luxenhofer 1 1 Functional Polymer Materials, Chair for Chemical Technology of Materials Synthesis, University of Würzburg, Röntgenring 11, Würzburg, Germany 2 Department for Functional Materials in Medicine and Dentistry, University of Würzburg, Pleicherwall 2, D Würzburg, Germany 3 Institute for Pharmacy and Food Chemistry, University of Würzburg, Am Hubland, Würzburg, Germany thomas.lorson@uni-wuerzburg.de Stimuli-responsive polymers that form physical or chemical hydrogels find great interest among engineers, scientist and clinicians. [1] With this development and the ever increasing visions on potential and actual applications, the need of suitable and adjustable hydrogels is rapidly developing and can be seen as a potential bottleneck. They have to meet various requirements like sufficient quantity, consistent quality and tunable biological and physical properties. [2] Having this in mind, natural polymers as well as synthetic polymers need to be taken into account. In the last decades poly(2-oxazoline)s, a prominent member of pseudo-polypeptides, have been intensely investigated, especially as thermo responsive materials [3] and for the usage as biomedical applications. [4] However, to the best of our knowledge no reports on thermogelling poly(2-oxazoline)s can be found through the literature. Here we report the synthesis of novel thermogelling pseudopolypeptides, their cytocompatibility and structure property relationships with respect to their rheological properties. 3D-printing experiments revealed potential applicability as BioInk. [1] T. Jüngst, W. Smolan, K. Schacht, T. Scheibel, J. Groll, Chem. Rev [2] S. Wang, J. M. Lee, W. Y. Yeong, Int. J. Bioprinting [3] C. Weber, R. Hoogenboom, U. S. Schubert, Progress in Polymer Science 2012, 37, 686. [4] R. Luxenhofer, Y. Han, A. Schulz, J. Tong, Z. He, A. V. Kabanov, R. Jordan, Macromolecular rapid communications 2012, 33, 1613.

86 P71 Anorganische Chemie und Materialwissenschaften Reaktivität N-heterocyclischer Carbene gegenüber Hauptgruppen- Element-Verbindungen der 14. und 15. Gruppe H. Schneider, D. Schmidt, U. Radius * Institut für Anorganische Chemie der Julius-Maximilians-Universität Würzburg heidi.schneider@uni-wuerzburg.de, u.radius@uni-wuerzburg.de In den letzten Jahren wurde durch verschiedenste Beispiele gezeigt, dass sich die Verwendung N- heterocyclischer Carbene nicht nur auf den Einsatz als Coliganden in Übergangsmetall-Komplexen beschränkt. Neuartige subvalente Hauptgruppen-Element-Verbindungen wie auch Verbindungen mit Element-Element-Bindungen konnten durch die guten σ-donor-eigenschaften dieser Singulett-Carbene stabilisiert werden. Überraschender Weise zeigte sich, dass NHCs neben der Rolle als unschuldige σ- Donoren, ebenfalls zur Element-Element- bzw. Element-Wasserstoff-Bindungsaktivierung unter milden Bedingungen fähig sind. [1] Weitere Untersuchungen belegten, dass die Addukte von NHCs mit Lewissauren Verbindungen bzw. Bindungsaktivierungsprodukte gegebenenfalls bei höheren Temperaturen eine Ringerweiterungsreaktion (RER) eingehen. Durch Umsetzung diverser NHCs mit Phenylsilanen konnten wir zeigen, das eine Insertion der Silyl-Einheit in den fünfgliedrigen Heterocyclus des NHCs stattfindet und durch Migration der zuvor an das Silan gebundenen Wasserstoffatome bzw. Reste die entsprechende Diazasilinane gebildet werden. [2] Ähnliche Reaktivitäten wurden von Hill [3], Rivard [4], Inoue [5], Stephan [6] und unserer Gruppe [7-8] für Beryllium- wie auch Borhydridverbindungen beobachtet und es konnte damit veranschaulicht werden, dass es ein gänzlich unbekanntes Feld der Reaktivität N- heterocyclischer Carbene zu entdecken gilt. Da sich die Untersuchungen der Reaktivität bis dato mit wenigen Ausnahmen auf die Element-Hydrid-Verbindungen der 13. und 14. Gruppe konzentrieren, präsentieren wir hier unsere Ergebnisse zur Reaktivität von NHCs gegenüber Phenylchlorsilanen [9] sowie den deutlich Lewis-basischeren Arylphosphanen [10]. [1] G. D. Frey, J. D. Masuda, B. Donnadieu, G. Bertrand, Angew. Chem. Int. Ed. 2010, 49, [2] D. Schmidt, J. H. J. Berthel, S. Pietsch, U. Radius, Angew. Chem. Int. Ed. 2012, 51, [3] M. Arrowsmith, M. S. Hill, G. Kociok-Köhn, D. J. MacDougall, M. F. Mahon, Angew. Chem. Int. Ed. 2012, 51, [4] S. M. I. Al-Rafia, R. McDonald, M. J. Ferguson, E. Rivard, Chem. Eur. J. 2012, 18, [5] D. Franz, S. Inoue, Chem. Asian J. 2014, 9, [6] T. Wang, D. W. Stephan, Chem. Eur. J. 2014, 20, [7] S. Pietsch, U. Paul, I. A. Cade, M. J. Ingleson, U. Radius, T. B. Marder, Chem. Eur. J. 2015, 21, [8] S. Würtemberger-Pietsch, H. Schneider, T. B. Marder, U. Radius, Chem. Eur. J. 2016, 22, [9] H. Schneider, D. Schmidt, U. Radius, Chem. Eur. J. 2015, 21, [10] H. Schneider, D. Schmidt, U. Radius, Chem. Commun. 2015, 51,

87 Anorganische Chemie und Materialwissenschaften Blue-light induced CO release from manganese(i) tricarbonyls containing benzimidazole ligands P72 A. M. Mansour 1,2*, U. Schatzschneider 1* 1 Institut für Anorganische Chemie der Julius-Maximilians-Universität Würzburg 2 Department of Chemistry, Faculty of Science, Cairo University, Gamma Street, Egypt mansour@sci.cu.edu.eg The development of carbon monoxide-releasing molecules (CORMs) as pro-drugs for the delivery of CO to cells and tissues in vivo is significant of interest to biology, since this method of application is an attractive and safe alternative to inhalation. Photo-activated CO release enables a well-defined control of the location and the timing of the CO release as well as its dosage. [1] Although the benzimidazole motif is a crucial pharmacophore in drug discovery with interesting biological properties including antiviral, antitumor,antihistaminic, and antimicrobial activity, [2] it has not been explored in the context of CORMs.So far a series of eight photoactivatable CORMs of the general formula [MnBr(CO) 3(N-N)] incorporating chelating 1H-benzimidazol-2-ylmethyl-(N-aryl)amine ligands was synthesized, and characterized using several analytical and spectral methods.the influence of the type and position of the substituent in the aniline ring on the photophysical properties of the studied compounds was systematically explored. Photo-activation profiles were examined by UV/Vis and solution IR studies. Illumination at 468 nm with a LED array resulted in fast release of two equivalents of carbon monoxide, while stepwise liberation of two CO takes place upon excitation at 412 nm.therefore, the CO release from the investigated compounds could be switched on and off by time control and choosing the suitable light source. OC OC Br Mn CO N N H R NH 9, R = H (50%) 10, R = 4-CH 3 (73%) 11, R = 4-OCH 3 (64%) 12, R = 4-Cl (70%) 13, R = 4-COOCH 3 (72%) 14, R = 4-NO 2 (30%) 15, R = 2-COOCH 3 (66%) 16, R = 3-COOCH 3 (68%) Absorbance Wavelength / nm 0 min 1 min 2 min 3 min 4 min 5 min 10 min 15 min 20 min 25 min [1] U. Schatzschneider, Brit. J. Pharmacol. 2015, 172, [2] N. T. Abdel-Ghani, A. M. Mansour, Eur. J. Med. Chem. 2012, 47,

88 P73 Pharmazie und Lebensmittelchemie Affinity Prediction of Protein-Ligand Complexes with Scoring Functions Based on Clustered Linear Regression L. P. Pason 1*, C. A. Sotriffer 1 1 Institute of Pharmacy and Food Chemistry, University of Würzburg, Würzburg, 97074, Germany lukas.pason@uni-wuerzburg.de The accurate prediction of binding affinities for protein-ligand complexes is a major challenge in drug design. [1] For routine application in docking and virtual screening, methods like free energy perturbation or thermodynamic integration are computationally still too demanding. Approximate but much more rapid access to the desired quantity is provided by empirical scoring functions, which are derived by relating structural features of protein-ligand complexes to the corresponding affinity values. Classical linear regression techniques or machine leaning methods are applied for this purpose. The circumvention of modelling assumptions in machine learning scoring functions has led to improved performance in many cases, [2] but at the cost of reduced interpretability. In this study, approaches of clustered linear regression [3] and clustered partial linear regression [4] were followed to derive a set of new scoring functions based on the SFCscore descriptors and subsets of the PDBbind refined set v2007 as training data. [5] The functions were tested against standard benchmarks divided into subsets in a similar way as the training data. Comparing the performance to a machine learning scoring function trained with the same experimental data and descriptors showed that the clustered linear regression procedure approaches the predictive quality of the machine learning function while maintaining full interpretability of the scoring functions. [1] L. P. Pason, C. A. Sotriffer, Mol. Inf. 2016, DOI: /minf [2] Q. U. Ain, A. Aleksandrowa, F. D. Roessler, P. J. Ballester, Wires Comput Mol Sci 2015, 5, [3] B. Ari, H. A. Güvenir, Knowl-Based Syst 2002, 15, [4] L. Torgo, J. P. Da Costa, Mach Learn 2003, 50, [5] T. Cheng, X. Li, Y. Li, Z. Liu, R. Wang, J Chem Inf Model 2009, 49,

89 Organische Chemie und Biochemie Entwicklung neuer Biokatalysatoren zur Synthese von Oligosacchariden und Saccharose-Analoga P74 C. Possiel, M. E. Ortiz-Soto, M. Timm, J. Görl, J. Seibel Institut für Organische Chemie, Universität Würzburg, Am Hubland, Würzburg, Deutschland Die Levansucrase von B. megaterium ist eine bakterielle Fruktosyltransferase und gehört zu der Enzymfamilie der Glykosidhydrolasen 68 (GH 68). Dieses Enzym katalysiert hauptsächlich die Hydrolyse von Saccharose in die Monomer-Bausteine Glukose und Fruktose (90% Hydrolyse- Aktivität), aber auch den Fruktosyl-Transfer auf weitere Zucker-Moleküle (Saccharose), was zur Bildung von kurz- und langkettigen β(2 6)-verknüpften Fructanen (Levan) [1] sowie in Gegenwart eines Glykosid-Akzeptors zu (1 2)-glykosidisch verknüpften Saccharose-Analoga führt. [2] Durch die geringe Spezifizität entsteht in Gegenwart von Saccharose oder Saccharose-Analoga jedoch eine große Bandbreite von verschiedenen Oligo- und Polysacchariden. Aus diesem Grund sollen durch gezielte Mutagenese effizientere Biokatalysatoren für die Synthese der einzelnen Zucker- Verbindungen entwickelt werden, die spezifisch (durch Verminderung des Produktspektrums oder höherer Fruktosyl-Transferrate) kurzkettige Di- bzw. Oligosaccharide wie z. B. Blastose, 1-Kestose, 6-Kestose und Neokestose produzieren können. Des Weiteren liegt der Fokus auf der Optimierung der Saccharose-Analoga-Synthese. Im Rahmen eines EU-Projektes werden neue Varianten der Levansucrase entwickelt und so Biokatalysatoren für die Synthese maßgeschneidert, um möglichst selektiv neuartige (1 2)-glykosidisch verknüpfte Saccharose-Analoga herzustellen. Die erhaltenen Saccharose-Analoga können durch die Anwendung zweier weiterer Enzyme gespalten, aktiviert und auf Aglykone (nicht-zucker-komponenten wie z. B. Wirkstoffe) übertragen werden, wodurch u. a. die Löslichkeit sowie die biologische Aktivität der Verbindungen erhöht werden können. [3,4] [1] G. Meng, K. Fütterer, Nat. Struct. Biol. 2003, 10, [2] A. Homann, J. Seibel, Appl. Microbiol. Biotechnol. 2009, 83, [3] S. G. Withers et al., Annu. Rev. Biochem. 2008, 77, [4] Y. Zheng et al., J. Biol. Chem. 2011, 286,

90 P75 Anorganische Chemie und Materialwissenschaften Nickel-Catalyzed Borylation of Polyfluoroarenes via C-F Bond Cleavage M. W. Kuntze-Fechner 1, U. Radius 1 maximilian.kuntze-fechner@uni-wuerzburg.de, u.radius@uni-wuerzburg.de 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg. The selective synthesis of fluoroarene compounds has become a subject of growing interest due to the prominent role such species play in many modern pharmaceuticals, agrochemicals and other industrially important products. [1] An attractive route for the selective substitution of fluoroarenes is based on the functionalization of activated aromatic C F bonds derived from readily available perfluoroarenes. The presentation covers the synthesis and reactivity of NHC-stabilized nickel complexes, which transfer the complex fragments [Ni(R 2Im) 2] (R 2Im = 1,3-Di(organyl)imidazole-2-ylidene) in stoichiometric and catalytic reactions under mild conditions, and their use in the functionalization to polyfluorinated arenes. [2] We are currently developing convenient methodologies to generate and use suitable, partially fluorinated organic precursors. These strategies employ, for example, (i) C-F functionalization of polyfluoroaromatics or (ii) use of the polyfluoroaromatics or fluoroaryl boronic ester in subsequent Suzuki-Miyaura coupling reactions. A smart way to achieve this goal would employ fluoroaromatic boronic acids or boronate esters. Arylboronic acid esters are versatile reagents in organic synthesis, especially in substituent conversions or in the widely employed Suzuki-Miyaura cross-coupling reaction. Transition-metal-catalyzed direct C-H borylation of arenes [3] and borylation of aryl halides [4] has emerged as one of the most important mild and attractive routes for the synthesis of aryl boronates in recent years. The conversion of fluoroaromatics into arylboronic esters via C-F bond activation, however, is relatively unexplored and was restricted to noble metal catalysts until recently. A focus of the contribution will be thus on the use of NHC nickel complexes in carbon fluorine activation and the use of these processes in catalytic borylation. [5] This work was supported in part by Deutsche Forschungsgemeinschaft (DFG) and the Julius-Maximilians- Universität Würzburg. [1] (a) H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119; (b) A. D. Sun, J. A. Love, Dalton Trans. 2010, 39, 10362; (c) T. Braun, D. Lenz, Angew. Chem. Int. Ed. 2013, 52, 3328; (d) T. Ahrens, J. Kohlmann, M. Ahrens, T. Braun, Chem. Rev. 2015, 115, 931. [2] (a) T. Schaub, U. Radius, Chem. Eur. J. 2005, 11, 5024; (b) T. Schaub, M. Backes, U. Radius, J. Am. Chem. Soc. 2006, 128, 15964; (c) T. Schaub, M. Backes, U. Radius, Eur. J. Inorg. Chem. 2008, 2680; (d) T. Schaub, P. Fischer, A. Steffen, T. Braun, U. Radius, A. Mix, J. Am. Chem. Soc. 2008, 130, 9304; (e) T. Schaub, P. Fischer, T. Meins, U. Radius, Eur. J. Inorg. Chem. 2011, 3122; (f) T. Zell, M. Feierabend, B. Halfter, U. Radius, J. Organomet. Chem. 2011, 696, 1380; (g) P. Fischer, K. Götz, A. Eichhorn, U. Radius, Organometallics 2012, 31, [3] (a) I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy, J. F. Hartwig, Chem. Rev. 2009, 110, 890; (b) A. Ros, R. Fernandez, J. M. Lassaletta, Chem. Soc. Rev. 2014, 43, [4] (a) M. Murata, Heterocycles 2012, 85, 1795; (b) W. K. Chow, O. Y. Yuen, P. Y. Choy, C. M. So, C. P. Lau, W. T. Wong, F. Y. Kwong, RSC Advances 2013, 3, [5] J. Zhou, M. W. Kuntze-Fechner, R. Bertermann, U. S. D. Paul, J. H. J. Berthel, A. Friedrich, Z. Du, T. B. Marder, U. Radius, J. Am. Chem. Soc. 2016, 138,

91 Anorganische Chemie und Materialwissenschaften iclick reactions for a modular access to Pt/Pd- complexes with high anticancer activity P76 K. Peng 1, P. Simpson 2, U. Schatzschneider 1 * 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D Würzburg (Germany) 2 Nanochemistry Research Institute Department of Chemistry, Curtin University Kent Street, Bentley 6102 WA(Australia) kun.peng@uni-wuerzburg.de Along with the widespread success of cisplatin in the clinical treatment of various types of malignancies, the chemistry of metal-based drugs has received enormous attention over the last few decades. [1] However, the effectiveness of these metal-based compounds as antitumor agents is often hampered by their poor solubility, low bioavailability, and lack of target specificity. Therefore, synthetic technology which quickly generates high molecular diversity and has great reaction efficiency is required to optimize compounds for specific biological properties and activities. Taking this perspective into consideration, inorganic Click (iclick) reactions, which will allow to easily tune the bioavailability and ADMET (absorption, distribution, metabolism, excretion, toxicity) properties of the novel compounds for bioactivity studies, were applied for a modular access to quickly generate molecular diversity in the synthesis of transition metal complexes with high antitumor activity based on novel structural motifs. [2] Consequently, two Pt/Pd- triazole complexes were synthesized by this approach (Scheme 1). Scheme 1: Synthetic routes to (a) Pt complexes and (b) Pd complexes by iclick reactions. With a certain amount of pure Pt/Pd- iclick products at hand, we are now trying to investigate their cytotoxicities, and their speciation and interaction with bio(macro)molecules such as amino acids, DNA nucleobases, and double-stranded DNA to deeply understand antitumor activities of the two compounds. [1] C. Santini, M. Pellei, V. Gandin, M. Porchia, F. Tisato, C. Marzano, Chem. Rev. 2014, 114, 815. [2] L. Herny, C. Schneider, B. Mützel, P. Simpson, C. Negal, K. Fucke, U.Schatzschneider, Chem. Commun. 2014, 50,

92 P77 Anorganische Chemie und Materialwissenschaften Luminescent MOF-mixed-matrix membranes F. Mühlbach 1, J. Dechnik 2, D. Dietrich 2, T. Wehner 1, M. Gutmann 3, T. Lühmann 3, L. Meinel 3, C. Janiak 2, K. Müller-Buschbaum 1 1 Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, D Würzburg 2 Institut für Anorganische Chemie und Strukturchemie, Universität Düsseldorf, Universitätsstraße 1, D Düsseldorf 3 Institut für Pharmazie und Lebensmittelchemie, Universität Würzburg, Am Hubland, D Würzburg, Luminescent metal-organic frameworks (MOFs) have a high potential for sensing/detection applications. The microporous character of MOFs allows them to adsorb/bind guest molecules, which can have significant influence on the luminescence behavior of the MOF, e.g. enhance or quench the luminescence intensity. Due to this impact of the guest molecules on the luminescence of the MOF, the latter can act as a sensor. [1] For industrial applications, the used MOFs have to be processed for example as thin films, pressed into tablets or used as part of a composite material. Some of the already established MOF composite materials are MOFmixed-matrix membranes (MMMs) for gas-separations. [2] Our main aim in this research projectis to produce the first example of luminescent MOF-MMMs. Therefore, we tried to embed 3 [Sr0.9Eu0.1(Im)2] (Im = imidazolate) and 2 [Tb2Cl6(bipy)3] 2bipy(bipy = 4,4 -bipyridine) in the mechanically stable polymers polysulfone and matrimid. For 3 [Sr0.9Eu0.1(Im)2], we could produce membranes with polysulfone and matrimid, whereby for 2 [Tb2Cl6(bipy)3] 2bipy embedding was only successful for polysulfone. The membranes were characterized via photoluminescence spectroscopy, powder X-ray diffraction, fluorescence microscopy and SEM-EDX. Investigations of the photoluminescence properties of the membranes showed that the luminescence of the pure MOFs is maintained in the membranes. In sum, our first examples of luminescent MOF-MMMs show that the application of MOF-MMMs for gas-separation can be expanded to potential sensor applications. [3] Figure 1: Normalized emission spectra of 3 [Sr0.9Eu0.1(Im)2] and 3 [Sr0.9Eu0.1(Im)2]@polysulfone. [1] L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van Duyne, J. T. Hupp, Chem. Rev. 2012, 112, [2] K. Hunger, N. Schmeling, H. B. T. Jeazet, C. Janiak, C. Staudt, K. Kleinermanns, Membranes 2012, 2, [3] J. Dechnik, F. Mühlbach, D. Dietrich, T. Wehner, M. Gutmann, T. Lühmann, L. Meinel, C. Janiak, K. Müller-Buschbaum, Eur. J. Inorg. Chem. 2016,

93 Organische Chemie und Biochemie FULLERENE-MEROCYANINE DYADS FOR SINGLE COMPONENT ORGANIC SOLAR CELLS P78 R. Hecht, D. Bialas, M. Stolte, F. Würthner* Institut für Organische Chemie & Center for Nanosystems Chemistry, Universität Würzburg, Am Hubland, Würzburg, Germany, * R. Wagener: Dyads of fullerene and donor molecules are interesting components for organic photovoltaics, because the fabrication of the cells is simplified and the morphology within the solar cell is more stable compared to bulk heterojunction (BHJ) solar cells. Additionally, the light absorption and the charge separation take place within the same molecule, so that short exciton diffusion length should not be a limiting factor. [1] A set of new dyad molecules was synthesized (Figure 1a). The dyads consist of a phenyl-c 61- propionic acid (PC 61PM), which is covalently bound to three different merocyanine dyes. We prepared solar cells from solution of these dyads (Figure 1b) and succeeded with first optimization experiments, reaching power conversion efficiencies (PCE) of up to 0.53 % in air. For comparison we investigated BHJ solar cells, using the merocyanines MD302, HB366 [2] and CS254 as donor and PC 61BM as acceptor in a molar ratio of 1:1. To these reference systems we added dyad molecules as mediator, to stabilize the donor-acceptor interface. The cells were characterized by measuring current-voltage characteristics, UV/Vis absorption, EQE and AFM. Figure 1: New dyad molecules and corresponding merocyanine dyes (a), studied in single component solar cells in the following device architecture (b). [1] J. Roncali, Advanced Energy Materials 2011, 1, [2] H. Bürckstümmer, E. V. Tulyakova, M. Deppisch, M. R. Lenze, N. M. Kronenberg, M. Gsänger, M. Stolte, K. Meerholz, F. Würthner, Angewandte Chemie International Edition 2011, 50,

94 P79 Anorganische Chemie und Materialwissenschaften Microbubbles loaded with platinum complexes for ultrasoundmediated treatment of brain cancer V. Mawamba 1, C. Hagemann 2, M. Löhr 2, V. Sturm 2, U. Schatzschneider 1 1 Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, D Würzburg 2 Tumor biologisches Labor, Neurochirugische Klinik und Polyklinik, Universitätsklinikum Würzburg, Joseph-Schneider Str.11/B1, D Würzburg viviane.mawamba-kemo@uni-wuerzburg.de Tumors of the central nervous system are among the most disabling and lethal types of cancer. [1] Because of their depth and location in functional inoperable areas, some brain cancers are surgically unreachable. Therefore, only standard treatment such as radio- and chemotherapy or a combination of both are possible. Chemotherapy has gained a lot of attention in the past two decades. Anti-cancer drugs are designed to kill malignant cells, but when administrated, only a small fraction of the injected dose reaches the target site, with the rest circulating through healthy tissue, resulting in dose-limiting side efffets. Encapsulation of drugs within microbubbles combined with local release triggered by focused ultrasound is thought to increase the local concentration of a chemotherapeutic agent at the site of disease while minimizing side effects on healthy tissue. [2,3] Figure 1: Fluorescence microscopy picture of octafluoropropane-filled lipid microbubbles stained with 1,1 -dioctadecyl-3,3,3,3 -tetramethylindocarbocyanine perchlorate (left) and general structure of membrane-affine cytotoxic platinum complex (right). Microbubbles are gas-filled colloidal particles with a size range between 1-8 µm. In medicine, they are well-known as ultrasound contrast agents for imaging and diagnosis. [4] Our current work to be presented here is focused on the encapsulation of different platinum-based drug candidates within microbubbles, the study of their stability, and payload delivery in vitro under application of ultrasound as an external stimulus. [1] S. A. Khuder, A. B. Mutgi, E. A. Schaub, Am. J. Ind. Med. 1998, 34, [2] Y. Liu, H. Miyoshi, M. Nakamura, J. Control. Release 2006, 114, [3] R. Deckers, C. T. W. Moonen, J. Control. Release 2010, 148, [4] S. Tinkov, R. Bekeredjian, G. Winter, C. Coester, J. Pharm. Sci. 2009, 98,

95 Anorganische Chemie und Materialwissenschaften Pyrene MO Shuffle Adjusting the HOMO-LUMO gap by changing the frontier MO ordering J. Merz, L. Ji, J. Fink, A. Friedrich, I. Krummenacher, H. Al Mamari, S. Lorenzen, M. Hähnel, A. Eichhorn, T. B. Marder* Institut für Anorganische Chemie, Julius-Maximilians Universität Würzburg Pyrene is a polycyclic aromatic hydrocarbon (PAH) that has very interesting photophysical properties which makes it suitable for a broad range of applications. [1] The 2,7-positions of pyrene are situated on nodal planes in both the HOMO and LUMO. Hence, electrophilic reactions take place at the 1-, 3-, 6-, and 8-positions. We developed a selective method to substitute directly the 2,7-positions by an iridium-catalyzed C-H borylation. [2] First investigations demonstrated that pyrene derivatives functionalized at the 2-position have different photophysical properties compared to the traditional functionalized pyrenes at the 1-position. [3] We report a series of new donor-acceptor and donor-donor pyrene systems with remarkable properties. Donors can raise HOMO-1 above the pyrene HOMO whereas acceptors can lower LUMO+1 below the pyrene LUMO which facilitates strong communication through the pyrene bridge. Further we could demonstrate the effectiveness of our pyrene bridge in comparison with biphenyl by photophysical and electrochemical measurements that are supported by DFT calculations and contrast with previous reports. P80 Figure 1: General numbering of pyrene (left) and our three target molecules (right). [1] T. M. Figueira-Duarte, K. Mullen, Chem. Rev. 2011, 111, 7260 [2] A. G. Crawford, Z. Liu, I. A. I. Mkhalid, M.-H. Thibault, N. Schwarz, G. Alcaraz, A. Steffen, J. C. Collings, A. S. Batsanov, J. A. K. Howard, T. B. Marder, Chem. Eur. J. 2012, 18, [3] A. G. Crawford, A. D. Dwyer, Z. Liu, A. Steffen, A. Beeby, L.-O. Pålsson, D. J. Tozer, T. B. Marder, J. Am. Chem. Soc. 2011, 133,

96 P81 Anorganische Chemie und Materialwissenschaften Formulation of extremely hydrophobic drugs using amphiphilic pseudo-polypeptide block copolymers M. Lübtow 1, B. Christ 2, S. Dembski 3, L. Persano 4, R. Luxenhofer 1 1 Functional Polymer Materials, Chair for Chemical Technology of Material Synthesis, University of Würzburg, Röntgenring 11, Würzburg (Germany) 2 Translational Center Regenerative therapies in oncology and musculoskeletal diseases, Fraunhofer IGB, Röntgenring 11, Würzburg (Germany) 3 Fraunhofer Institute for Silicate Research ISC, Neunerplatz 2, Würzburg (Germany) 4 National Nanotechnology Laboratory of InstitutoNanoscienze-CNR, Università del Salento, via Arnosano, I Leece (Italy) Michael.Luebtow@uni-wuerzburg.de Modern techniques like high-throughput combinatorial screenings [1] can quickly assay the biological or biochemical activity of a large number of potential drugs, but when it comes to formulation, one major issue remains. More than 40% of all NCEs (new chemical entities) developed in the pharmaceutical industry are practically insoluble in water. [2] Taking into account, that 90% of all compounds in today s drug delivery pipelines are reported to be poorly water-soluble, this poses a major challenge for the pharmaceutical industry. [3] The demand for excipients, which increase the water solubility without influencing the bioactivity of such hydrophobic drugs is enormous. Motivated by the high drug loadings of poly(2- oxazoline)spox based micelles for paclitaxel (PTX) of up to 45 wt%, [4] this work presents a preliminary study on the structure property relationships of pseudo-polypeptide based amphiphiles on the solubilization capacity for the non-water soluble compound curcumin (CUR).The extraordinary large loading capacity for CUR of more than 50 wt% active drug as well as high water solubility of the resulting formulation emphasize the use of these drug-loaded polymeric micelles for detailed in vitro and in vivo studies with regard of their anticancer and anti-inflammatory potential. Besides the formulation in aqueous solution, core-shell fibers comprised of a drug-loaded polymeric micelles core encapsulated in a biodegradable polycaprolactone (PCL) shell [5] as well as silica fibers loaded with polymeric micelles were prepared to enable a more sustained drug-release. Amphiphilic Block-Copolymers Extremely hydrophobic drugs Figure 1: Solubilization of extremely hydrophobic drugs with amphiphilic poly(2-oxazoline) (POx) based block-copolymers. [1] A. Persidis, Nat. Biotech. 1998, 16, [2] E. M. Merisko-Liversidge, G. G. Liversidge, Toxicologic Pathology 2008, 36, [3] V. A. V. Vharti, A. Munde, A. Birajdar, S. Bais, JIPBS 2015, 2, [4] a) R. Luxenhofer, A. Schulz, C. Roques, S. Li, T. K. Bronich, E. V. Batrakova, R. Jordan, A. V. Kabanov, Biomaterials 2010, 31, ; b) A. Schulz, S. Jaksch, R. Schubel, E. Wegener, Z. Di, Y. Han, A. Meister, J. Kressler, A. V. Kabanov, R. Luxenhofer, C. M. Papadakis, R. Jordan, ACS Nano 2014, 8, ; c) Y. Seo, A. Schulz, Y. Han, Z. He, H. Bludau, X. Wan, J. Tong, T. K. Bronich, M. Sokolsky, R. Luxenhofer, R. Jordan, A. V. Kabanov, Polymers for Advanced Technologies 2015, 26, ; d) Z. He, X. Wan, A. Schulz, H. Bludau, M. A. Dobrovolskaia, S. T. Stern, S. A. Montgomery, H. Yuan, Z. Li, D. Alakhova, M. Sokolsky, D. B. Darr, C. M. Perou, R. Jordan, R. Luxenhofer, A. V. Kabanov, Biomaterials 2016, 101, [5] L. Romano, A. Camposeo, R. Manco, M. Moffa, D. Pisignano, Molecular Pharmaceutics 2016, 13,

97 Pharmazie und Lebensmittelchemie Chemistry Meets Cancer Immunotherapy: Synthesis of Hapten-like Compounds to Redirect the Specificity of Programmable Antibodies and T Cells P82 P. A. Nagl 1, L. Wallstabe 2, M. Hudecek 2, U. Holzgrabe 1 1 University of Würzburg, Institute of Pharmacy and Food Chemistry, Am Hubland, Würzburg, Germany 2 Universitätsklinikum Würzburg, Medizinische Klinik und Poliklinik II, Oberdürrbacherstraße 6, Würzburg, Germany Immunotherapies are evolving as highly promising strategies for the treatment of cancer. An essential component of these approaches are reactive, tumor-specific T lymphocytes, which are rare for many malignancies and are difficult to isolate. However, they can be generated by genetic modification using genes encoding chimeric antigen receptors (CARs) or T cell receptors (TCRs). CAR-modified T cells are endowed with the specificity of tumor-specific antibodies. [1] Chemical programming of the used single-chain variable fragment (scfv) should be possible in the same way as performed by chemically programmed antibodies (cpabs). [2] With this approach, the scope of potential tumor-specific targets could be enlarged vastly while the production of effective T lymphocytes could be simplified. The aim of this work is to contribute to the development of chemically programmed T cells for cancer immunotherapy. Therefore, different hapten-like compounds should be synthesized. All of these compounds have reactive groups, which selectively bind to the lysine residue of the antigen receptor, and ether a targeting or labeling module (see figure 1). [3] Figure 1: Different reactions for reprogramming monoclonal antibodies or CAR T cells. The test results of the first molecules, equipped with biotin as labeling module, proofed the concept by showing that the compounds are not binding to reactive groups on the cell surface, but selectively react with the lysine residue of the receptor. Current work includes the synthesis of an Arg-Gly-Asp (RGD) peptidomimetic motif as targeting module for integrin α vβ 3, which is overexpressed in solid tumor cells [4]. [1] C. J. Turtle, M. Hudecek, M. C. Jensen, S. R. Riddell, Curr. Opin. Immunol. 2012, 24, [2] C. Rader, Trends Biotechnol. 2014, 32, [3] J. I. Gavrilyuk, U. Wuellner, C. F. Barbas, Bioorg. Med. Chem. Lett. 2009, 19, [4] L. Li, C. Rader, M. Matsushita, S. Das, C. F. Barbas, R. a Lerner, S. C. Sinha, J. Med. Chem. 2004, 47,

98 P83 Organische Chemie und Biochemie Thermodynamic insights into the entropically driven self-assembly of rylene bisimide dyes in water P. Syamala, D. Görl, B. Soberats, F. Würthner* Universität Würzburg, Center for Nanosystems Chemistry (CNC), Institut für Organische Chemie, and Bavarian Polymer Institute (BPI), Universität Würzburg, Würzburg, Germany * A fundamental understanding of the thermodynamic aspects of self-assembly is quintessential to develop supramolecular polymers with desired properties. [1] This task is especially challenging in aqueous systems where supramolecular polymerization is principally determined by the intricate interplay between entropic contribution from solvation/dissolution of monomeric units and enthalpic contributions arising from the solvation of extended aggregates. [3] We recently reported on the self-assembly behavior of bolaamphiphilic perylene bisimide dyes appended with oligoethylene glycol (OEG), which show an entropically driven aggregation process in water, while the process is enthalpically driven in the presence of THF as a co-solvent (Figure 1a). [4] In the present study, a detailed thermodynamic profile of the self-assembly of various OEG based bolaamphiphilic rylene dyes is carried out in water at different temperatures, using isothermal titration calorimetry and UV/ Vis studies (Figure 1b). Figure 1: a) Chemical structures of PBI 1 and NDI 1 (top) and Gibbs free energy, ΔG of PBI 1 self-assembly in H2O/THF mixtures (bottom). b) Heat release per injection of an aqueous solution of PBI 1 (top) and NBI 1 (bottom) into pure water in an ITC dilution experiment showing enthalpic penalty associated with the selfassembly. c) Schematic representation of the proposed aggregation mechanism of PBI 1 in water. Remarkably, we found that the entropic release of water from the OEG chains overcomes the enthalpic contribution from π- π stacking interactions (Figure 1c), which has a determining influence on the thermodynamics of the aggregation process. This fundamental study sheds light on thermodynamics aspects of self-assembly in water, providing new elements to control the aggregation processes. [1] E. Krieg, M. M. C. Bastings, P. Besenius, B. Rybtchinski, Chem. Rev. 2016, 116, [2] J. N. Israelachvili, Intermolecular and Surface Forces (Third Edition), Academic Press: San Diego, [3] D. Gorl, X. Zhang, F. Würthner, Angew. Chem. Int. Ed. 2012, 51, [4] D. Görl, F. Würthner, Angew. Chem. Int. Ed. 2016, 55,

99 Anorganische Chemie und Materialwissenschaften Synthesis of Neutral Boron-Centered Lewis Bases Derived from Terminal Arylborylene-Complexes P84 M. Nutz, C. W. Tate, H. Braunschweig Julius-Maximilians-Universitaet-Wuerzburg, Department of Inorganic Chemistry, Wuerzburg, Germany A variety of neutral electron-rich monovalent boron compounds has been synthesized (1 3). [1] The synthetic strategy used liberation of a borylene ligand from a transition metal is broadly applicable, leading to a number of unprecedented monovalent boron species bearing different Lewis basic groups. [1,2] Depending on the steric demand of the base, homoleptic (1, 3) or heteroleptic (2) compounds are formed, which all show a trigonal planar geometry at the boron atom. Analysis of the frontier orbitals indicates that the HOMO level consists of a three-centered π-bonding interaction between the boron and the attached ligands. Further computational investigations show an extensive boron-to-ligand backbonding in these molecules [1] H. Braunschweig, R. D. Dewhurst, F. Hupp, M. Nutz, K. Radacki, C. W. Tate, A. Vergas, Q. Ye, Nature 2015, 522, [2] H. Braunschweig. R. D. Dewhurst, L. Pentecost, K. Radacki, A. Vargas, Q. Ye, Angew. Chem. Int. Ed. 2015, 54, 1-6.

100 P85 Anorganische Chemie und Materialwissenschaften Reactivity of N-heterocyclic Carbenes towards Chloro- and Hydrostannanes M. J. Krahfuß, H. Schneider, U. Radius Institut für Anorganische Chemie der Julius-Maximilians-Universität Würzburg, Since the isolation of the first N-heterocyclic carbene in 1991 through Arduengo [1] a multitude of novel NHC-metal-complexes had been synthesized and characterized. In main-group element chemistry these small organic molecules open up a variety of reaction pathways, which fundamentally differ from their use as ligands in the coordination sphere of metals. [2,3] Besides the deprotonation of Brønsted-acids using carbenes our group could observe reductive dehydrocoupling of primary and secondary phosphines. Carbenes are also capable of oxidative addition reactions with bond activation in e.g. boranes, silanes and phosphines. Furthermore, ring expansion reactions of E-H-substrates of the groups 2, 13 and 14, as well as adduct formation followed by rearrangement in silanes are known. [4] Considering the significantly different reaction patterns of silicon hydrides and chlorides with NHCs we were interested in their reactivity towards the heavier homologues of tin (RmSnHn/Xn). Studies of Wesemann et al. with the sterically demanding stannanes trip 2SnH 2 and trip 3SnH showed solely the formation of the distannanes via reductive dehydrocoupling. [5] On this account we studied tin compounds with more simple substituents like methyl and phenyl to investigate their behavior towards the NHCs ipr 2Im and ipr 2Im Me. [6] [1] A. J. Arduengo, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113, [2] H. Braunschweig, R. D. Dewhurst, K. Ferkinghoff, Chem. Commun. 2016, 52, [3] P. Ai, A. A. Danopoulos, P. Braunstein, Dalton Trans. 2016, 45, [4] a) D. Schmidt, J. H. J. Berthel, S. Pietsch, U. Radius, Angew. Chem. Int. Ed. 2012, 51, ; b) H. Schneider, D. Schmidt, U. Radius, Chem. Commun. 2015, 51, ; c) H. Schneider, D. Schmidt, U. Radius, Chem. Eur. J. 2015, 21, [5] a) C. P. Sindlinger, L. Wesemann, Chem. Sci. 2014, 5, ; b) C. P. Sindlinger, W. Grahneis, F. S. W. Aicher. L. Wesemann, Chem. Eur. J. 2016, 22, [6] H. Schneider, M. J. Krahfuß, U. Radius, Z. Anorg. Allg. Chem. 2016, ahead of print.

101 Organische Chemie und Biochemie Shape-controlled Synthesis of Covalent Organic Cage Compounds P86 V. Leonhardt, S. Klotzbach, F. Beuerle* Universität Würzburg, Institut für Organische Chemie & Center for Nanosystems Chemistry, Am Hubland, Würzburg, Germany * Porous functional materials are promising candidates for applications in the areas of heterogeneous catalysis, sensing, gas storage and separation, or membranes. [1] For example, organic cage compounds can be constructed via the concept of dynamic covalent chemistry. [2] Previously, we reported on the synthesis of molecular cubes, [3] tetrahedra and bipyramids by crosslinking the catechol units of tribenzotriquinacene (TBTQ) with various diboronic acids. Currently we elaborate on the self-assembly of planar, catechol functionalized hexahydroxytriphenylene (HHTP) with rigid diboronic acids possessing different bite angles into molecular cages. Thereby, the geometry of the diboronic acids is transferred to structure and shape of the self-assembled nanosized objects. Synthesis of the cage compounds can be monitored by 1 H-NMR spectroscopy and size and shape is analyzed by 2D-NMR as well as DOSY-NMR spectroscopy. [1] G. Férey, Chem Soc. Rev. 2008, 37, [2] M. Mastalerz, Chem. Eur. J. 2012, 18, [3] S. Klotzbach, T. Scherpf, F. Beuerle, Chem. Comm. 2014, 50,

102 P87 Physikalische und Theoretische Chemie Photoelectron Spectroscopy of the three Picolyl Radical Isomers E. Reusch, F. Holzmeier, P. Constantinidis, P. Hemberger, I. Fischer Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Am Hubland, Würzburg, Germany The picolyl radical (C 6H 6N), which is used as a model compound for heteroaromatic radicals, should be a key-intermediate in the combustion of bio fuels. Its structure is isoelectronic to benzyl C 7H 7, an important combustion intermediate. Therefore, the decomposition of picoline to picolyl in pyrolysis processes has been studied previously. [1-3] In contrast to benzyl, there are three different isomers for picolyl. The ring can be substituted in the ortho-, meta-, or para-position with respect to the nitrogen atom. Even though the ionization energies of the three radicals have already been determined by electron impact ionization, optimized values obtained by threshold photoelectron spectroscopy (TPES) will be reported. [4,5] Figure 1: Mass selective Threshold Photoelectron Spectra of the three Picolyl Radical Isomers To get new insights this study applies imaging Photoelectron Photoion Coincidence Spectroscopy (ipepico), which is able to supply mass selective TPES. This method has the advantage of assigning only one mass to the corresponding TPES-signal. Picolylamine has been selected as an excellent precursor for generating the picolyl radical. The radical was produced by flash pyrolysis and photoionized by tunable vacuum ultraviolet synchrotron radiation. This poster offers a fundamental overview of mass selective TPES and an improved value for the ionization energy of the three picolyl radicals, executed at the Swiss Light Source (SLS) for synchrotron radiation (Villigen, Switzerland). [1] A. Terentis, A. Doughty, J. C. Mackie, J. Phys. Chem. 1992, 96, [2] A. Doughty, J. C. Mackie, J. Phys. Chem. 1992, 96, [3] J. Jones, G. B. Bacskay, J. C. Mackie, Isr. J. Chem. 1996, 36, [4] J. A. Bray, E. R. Bernstein, J. Phys. Chem. A 1999, 103, [5] T. F. Palmer, F. P. Lossing, J. Am. Chem. Soc. 1963, 85,

103 Organische Chemie und Biochemie Sugar Coated Nanodiamonds P88 S. Wachtler 1, C. Fessele 2, V. Chandrasekaran 2, C. Stiller 1, T. K. Lindhorst 2, A. Krueger 1 1 Institut für Organische Chemie, Universität Würzburg, Am Hubland, D Würzburg krueger@chemie.uni-wuerzburg.de 2 Institut für Organische Chemie, Universität Kiel, Otto-Hahn-Platz 3 4, D Kiel, tklind@oc.uni-kiel.de Nanodiamonds have proven to be an interesting material for biological and biomedical applications because of their low toxicity. [1] Several studies have also shown promising results of saccharide functionalized nanodiamonds for detecting specific pathogens and creating antiadhesive surfaces. One of these pathogens is type 1 fimbriated E. Coli bacteria which possess lectin FimH on their surface and therefore show a specific binding to α-d-mannosides. [2] Figure 1: Functionalization of nanodiamond with saccharides using thiourea-bridging. In order to link the saccharides to the nanodiamond particles, a new binding method using the formation of thiourea from an amino group and an isothiocyanate has been developed. All three synthesized samples show affinity for bacterial lectin FimH and their binding strength is in accordance with the expected interaction between the mannose derivatives and the lectin FimH binding pocket. [3] This project has received funding from the European commision and the German Bundesministerium für Bildung und Forschung (BMBF) (contract NanoDiaMed grant number 13N12255 in EuroNanoMed). [1] A. Krueger, Chem. Eur. J. 2008, 14, [2] M. Hartmann, P. Betz, Y. Sun, S. N. Gorb, T. K. Lindhorst, A. Krüger, Chem. Eur. J. 2012, 18, [3] C. Fessele, S. Wachtler, V. Chandrasekaran, C. Stiller, T. K. Lindhorst, A. Krüger, Eur. J. Org. Chem. 2015, 25,

104 P89 Organische Chemie und Biochemie Synthesis and Properties of Methoxy-Bay-Substituted Perylene Bisimides A. Nowak-Król, P. Leowanawat, F. Würthner Universität Würzburg, Institut für Organische Chemie, Am Hubland, D Würzburg, Germany Universität Würzburg, Center for Nanosystems Chemistry (CNC) & Bavarian Polymer Institute (BPI), Theodor-Boveri-Weg, Würzburg, Germany Perylene bisimides (PBIs) feature high molar absorption coefficients and mirror image fluorescence with fluorescence quantum yields typically above 90% in a wide range of solvents. A combination of these favorable properties along with an exceptional thermal and photostability accounts for an extensive exploration of PBIs in a large variety of fields spanning from commercial colorant chemistry, supramolecular polymerization, liquid crystals to complex supramolecular architectures. [1] Core-non-substituted PBIs bearing a large variety of imide substituents and tetraphenoxy-pbis were commonly prepared and investigated within this group of compounds, whereas tetra-bay-substituted alkoxy-pbis were not accessible. Recently, we have developed an efficient protocol for the synthesis of tetra-methoxy-bay-substituted PBIs via copper-mediated cross-coupling of 1,6,7,12-tetrabromoperylene tetraester with sodium methoxide, which gave rise to the corresponding PBIs. [2] The introduction of four methoxy groups into bay positions of the PBI core entailed a significant modulation of the electronic band gap. This new class of compounds display interesting photophysical properties, such as bathochromically shifted absorption and emission (beyond 600 nm), and most notably high fluorescence quantum yields despite electron-donating bay substituents. We have also identified interesting features of the solid packing which have implications on the general understanding of dynamic processes occurring in bay-substituted perylene bisimides. These aspects as well as photophysical properties of the new class of compounds will be discussed and compared with the previously studied bay-substituted-pbis. [1] F. Würthner, C. R. Saha-Möller, B. Fimmel, S. Ogi, P. Leowanawat, D. Schmidt, Chem. Rev. 2016, 116, [2] P. Leowanawat, A. Nowak-Król, F. Würthner, Org. Chem. Front. 2016, 3,

105 Organische Chemie und Biochemie Anti-tumoral Naphthoquinones: Isolation from Plants and Total Synthesis P90 C. Froschgeiser 1, J. Maier 1, G. Zhang 1, A. Irmer 1, S. Rüdenauer 1, R. Bargou 2, M. Chatterjee 2, G. Bringmann 1 1 Institute of Organic Chemistry, University of Würzburg, Am Hubland, Würzburg, Germany 2 Department of Internal Medicine II, Comprehensive Cancer Center Mainfranken, Hospital of Würzburg, Versbacher Straße 5, Würzburg, Germany The West African liana Triphophyllum peltatum (Dioncophyllaceae) has proven to be a rich source of natural products. Besides the plant itself, callus cultures were also found to produce distinct amounts of secondary metabolites, in particular naphthoquinones like plumbagin and droserone. By solidification of the medium, these cell cultures were exposed to aerobic and thus oxidative conditions, which favored the formation of further, structurally related new naphthoquinones like dioncoquinones A (1) and B (2). These new compounds (especially 2) show excellent - and specific - antitumoral activities against the multiple-myeloma (MM) cell line INA-6 without any significant toxicity on normal blood cells. [1] An efficient total synthesis of dioncoquinone B (2) was established to provide this lead structure in sufficient amounts for a more-in-depth biological evaluation. A first series of structural analogs of dioncoquinone B (2) was obtained by semi and total synthesis for structure-activity relationship (SAR) studies hopefully leading to new agents with enhanced anti-mm activities and low cytotoxicities. [2] Moreover, a synthetic route to a dioncoquinone B derivative was developed, equipped with a probe (e.g., biotin like in 3) suited for affinity labeling experiments to investigate the interactions of 3 with its cellular target(s) and/or binding partner(s). [1] G. Bringmann et al., Phytochemistry 2008, 69, [2] G. Bringmann et al., Eur. J. Med. Chem. 2011, 46,

106 P91 Organische Chemie und Biochemie Quality of Antimalarial Drugs in Africa: Data on Artemisinin-Based Combination Therapy Products (Artemether-Lumefantrine) from the Democratic Republic of the Congo J. P. Mufusama 1,2, K. Ndjoko Ioset 1, U. Holzgrabe 3, G. Bringmann 1 1 Institute of Organic Chemistry, University of Würzburg, Am Hubland, Würzburg, Germany 2 Faculté des Sciences Pharmaceutiques, Université de Kinshasa, B.P. 212, Kinshasa XI, Democratic Republic of the Congo 3 Institute of Pharmacy and Food Chemistry, University of Würzburg, Am Hubland, Würzburg, Germany Malaria, with 90% of prevalence in Sub-Saharan Africa, is the most dangerous tropical disease with more than two million people dying each year. Nearly half of the world population is exposed to the disease; pregnant women and children under the age of five years are the main victims. [1] Combination therapies in which an artemisinin (1) derivative like artemether (2) is associated to another class of antimalarial drugs like lumefantrine (3), the so-called artemisinin-based combination therapies (ACT), are nowadays recommended by the World Health Organization (WHO) as first-line treatment for uncomplicated falciparum malaria. [2] The poster will address quality issues of these essential antimalarial medicines within the African continent including findings of a nationwide survey in the Democratic Republic of the Congo. Results were obtained based on packaging, thin-layer chromatography (TLC), and high-performance liquid chromatography (HPLC) analyses. [1] WHO (2015) World Malaria Report WHO, Geneva. [2] WHO (2015) Guidelines for the treatment of malaria, 3 rd Edition. WHO, Geneva.

107 Organische Chemie und Biochemie Korundamines and Mbandakamines, Unsymmetric NaphthylisoquinolineDimers from the Congolese Liana Ancistrocladus ealaensis P92 D. T. Tshitenge 1,2, D. Feineis 1, B. K. Lombe 1, G. Bringmann 1 1 Institute of Organic Chemistry, University of Würzburg, Am Hubland, Würzburg, Germany 2 Faculty of Pharmaceutical Sciences, University of Kinshasa, P.O. Box 212 Kinshasa XI, Democratic Republic of the Congo Naphthylisoquinoline alkaloids (NIQs) are thrilling natural products occurring in the two paleotropic plant families of Ancistrocladaceae and Dioncophyllaceae. [1] They are unique due to their unprecedented biosynthetic origin, their unusual structural features, and their high anti-infective activities. [1] Ancistrocladus ealaensis is a widespread Central African liana mainly located in the Northwestern part of the Democratic Republic of the Congo. [2] Most recent phytochemical studies have shown that the plant is a rich source of structurally intriguing, highly unsymmetric dimeric NIQs. More than twelve new dimers, among them new korundamine-type dimers, have of two mbandakamine-type dimers, [3] viz., 1-epi-mbandakamine A (2) and 1-epi-cyclombandakamine A (3). The korundamines are the first fully elucidated NIQ mixed dimers consisting of a 5,8 - and a 7,8 - linked monomeric halves, connected by a freely rotating central biaryl axis.the new dimer 2 combines in the highest known steric hindrance at the central chiral axis between the monomers, with the scarce cis-relative configuration in one molecular half. Most exciting is the fact that dimers like 2 can undergo further intramolecular cyclization reactions, due to the extreme steric constrains, leading to unprecedented cage-like dimers, like e.g. 3. The detection of dimers of a huge steric demand at the central axis, together with dimers possessing a freely rotating central axis indicates the unique synthetic potential of A. ealaensis. Moreover, these compounds exhibit remarkable antimalarial activities against Plasmodium falciparum. [1] G. Bringmann et al., Progress in the Chemistry of Organic Natural Products, Springer-Verlag, Wien, New York, 2001, 82, pp [2] J. Léonard, Bull. Soc. Bot. Belg. 1949, 82, [3] G. Bringmann et al., Org.Lett. 2013, 15,

108 Abstract Abendvortrag Dr. Klein-Sommer Dr. Günther Klein-Sommer Chemie der Pyrotechnik Theorie und Effektdemonstration Im Gegensatz zur Sprengtechnik werden in der Pyrotechnik die Explosionsstoffe für Vergnügungs- oder technische Zwecke eingesetzt. Unter Ausnutzung der nach der Zündung freigesetzten Energie können Licht-, Schall-, Rauch-, Nebel- oder Bewegungswirkungen erzeugt werden. Von besonderem Interesse, wie die Umsätze der Pyrotechnischen Industrie zum Jahresende zeigen, ist die Pyrotechnik im Zusammenhang mit der Feuerwerkerei. Im Rahmen des Vortrages wird einleitend die historische Entwicklung der Feuerwerkskunst vorgestellt. Aus der Erfahrung heraus resultiert die Entwicklung der heute verwendeten pyrotechnische Zubereitungen und pyrotechnischen Gegenstände Feuerwerkskörper die zur Erzeugung von Licht-, Schall-, und Raucheffekten oder von Bewegungswirkungen verwendet werden. Im Anschluss an den Vortrag erfolgt eine Demonstration von Effekten aus den Bereichen Bühnenpyrotechnik, Spezialeffekte und Feuerwerk.

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111 TEILNEHMER Anorganische Chemie/Materialwissenschaften # Name Vorname Arbeitskreis 54 Berthel Johannes Radius 13 Eichhorn Antonius Radius 66 Feizy Nilab Schatzschneider 53 Griesbeck Stefanie Marder 45 Hailmann Michael Finze 52 Kachel/ Kelch Stephanie u. Hauke Braunschweig 9 Kerpen Christoph Finze 85 Krahfuß Mirjam Radius 75 Kuntze-Fechner Maximilian Radius 70 Lorson Thomas Luxenhofer 12 Lubitz Katharina Radius 81 Lübtow Michael Luxenhofer 79 Mawamba Kemo Viviane Schatzschneider 80 Merz Julia Marder 72 Moustafa Mansour Ahmed Schatzschneider 77 Mühlbach Friedrich Müller-Buschbaum 30 Müssig Jonas Braunschweig 84 Nutz Marco Braunschweig 16 Paul Ursula Radius 76 Peng Kun Schatzschneider 28 Rauch Florian Marder 63 Ribbeck Tatjana Finze 71 Schneider Heidi Radius 59 Sedykh Alexander Müller-Buschbaum 15 Sieck Carolin Marder 19 Sorg Jens Müller-Buschbaum 68 Stangl Johannes Müller-Buschbaum 55 Waag-Hiersch Luisa Schatzschneider 50 Wehner Tobias Müller-Buschbaum 41 Zottnick Sven Müller-Buschbaum

112 TEILNEHMER Organische Chemie/Biochemie # Name Vorname Arbeitskreis 25 Buschmann Rachel Krüger 11 Dechant Moritz Lehmann 32 Dhara Ayan Beuerle 90 Froschgeiser Christina Bringmann 78 Hecht Reinhard Würthner 58 Kaufmann Christina Würthner 57 Kiendl Benjamin Krüger 86 Leonhardt Viktoria Beuerle 29 Lombe Blaise Kimbadi Bringmann 23 Meza Ana Lucia Würthner 24 Mims David Lambert 91 Mufusama Jean-Pierre Bringmann 89 Nowak- Król Agnieszka Würthner 74 Possiel Christian Seibel 36 Riese Stefan Lambert 56 Roos Markus Lambert 35 Sapotta Meike Würthner 49 Schopf Nina Lambert 44 Schreck Maximilian Lambert 31 Schweeberg Sarah Krüger 18 Seifert Sabine Würthner 69 Shamburger William Bringmann 67 Soberats Bartolome Würthner 83 Syamala Peethambaran Nair Würthner 92 Tshitenge Dieudonné Bringmann 88 Wachtler Stefan Krüger 14 Wagner Wolfgang Würthner 48 Warkentin Viktor Krüger 21 Wehner Marius Würthner

113 TEILNEHMER Pharmazie/Lebensmittelchemie # Name Vorname Arbeitskreis 65 Amstalde Cecilia Meinel 47 Berninger Michael Holzgrabe 33 Braun Alexandra Meinel 20 Dodt Katharina Meinel 34 Gutmann Marcus Meinel 42 Hermann Cornelius Meinel 40 Kuhn Maximilia Sotriffer 37 Miesler Tobias Meinel 82 Nagl Patrick Holzgrabe 73 Pason Lukas Sotriffer 8 Plank Christina Sotriffer 64 Pospiech Andreas Högger 27 Pospiech/Zilker Andreas u. Markus Högger/Holzgrabe 61 Scherf-Clavel Maike Högger 51 Spieler Valerie Meinel 60 Wu Fang Meinel

114 TEILNEHMER Physikalische Chemie/Theoretische Chemie # Name Vorname Arbeitskreis 62 Bellinger Daniel Engels 26 Brückner Charlotte Engels 22 Flock/Schmitt Marco u. Hans- Christian Fischer 17 Hirsch Florian Fischer 43 Le Thien Anh Engels 39 Lindner Joachim Mitric 10 Pachner Kai Fischer 38 Pres Sebastian Brixner 87 Reusch Engelbert Fischer 46 Roeding Sebastian Brixner

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118 Organisationskomitee Das Jungchemikerforum Würzburg im Februar 2016.

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120 JungChemikerForum Würzburg Programm ChemSyStM Begrüßung durch das JCF Würzburg und den GDCh Ortsverband (HS B) Gastvortrag des Verbandes angestellter Akademiker und leitender Angestellter (VAA) (HS A) Mittagspause Posterappetizer (HS A) Postersession Sektempfang Abendvortrag der Firma Sommer-Feuerwerk: Chemie der Pyrotechnik (HS A) Preisverleihung (HS A) Abschlussfeuerwerk im Freien (Sommer-Feuerwerk) gemütlicher Ausklang bei Abendessen und Bier