Book of Abstracts - Ruhr-Universität Bochum

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OP-31 ISBOMC `10 5.7 – 9.7. 2010 Ruhr-Universität Bochum Polypeptides Induced Self-Association and Emission Properties of Platinum(II) and Gold(I) Complexes Toshiyuki Moriuchi, *a Masahiro Yamada, a Kazuki Yoshii, a and Toshikazu Hirao a a Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada-oka, Suita, Osaka 565-0871, Japan. E-mail: moriuchi@chem.eng.osaka-u.ac.jp Highly-ordered molecular assemblies are constructed in bio-systems to fulfill unique functions as observed in enzymes, receptors, etc. Introduction of functional complexes into highly-ordered biomolecules is considered to be a convenient approach to novel biomaterials, bio-inspired systems, etc. Recently, the field of bioorganometallic chemistry has drawn great attention and undergone rapid development. Conjuction of organometallic compounds with biomolecules such as peptides and nucleobases is envisioned to afford such bioconjugates. The non-covalent bond is a powerful tool in the construction of architectural molecular assemblies. We have already demonstrated the chirality organization of ferrocene-peptide bioconjugates to induce highly-ordered molecular assemblies. 1 Poly-L-glutamic acid (P(Glu)) is known to exist in a �-helix form at around pH 4.3. The carboxyl groups of side chains are expected to assemble cationic metal complexes along the exterior of poly-Lglutamic acid through the electrostatic interactions. On the other hand, poly-L-Lysine (P(Lys)) exists as a random coil conformation at a neutral pH due to repulsion between positively charged side chains, and an �-helical conformation at above pH 10.6 due to the reduced charge on the side chains at a pH above the pKa (10.5). P(Lys) bearing multiple positively charged side chains is envisioned to serve as a polymeric spatially aligned scaffold for the aggregation of negatively charged metal complexes. From these points of view, we embarked upon the assembling and self-association of luminescent metal complexes spatially along the cationic or anionic polypeptides to form the luminescent aggregates. The cationic organoplatinum(II) complexes [Pt(trpy)C≡CR] + (trpy = 2,2',6',2''-terpyridine; R = Ph (PtH), PhC12H25 (PtC12)) were introduced into the anionic poly-L-glutamic acid (P(Glu)) through electrostatic interactions. An emission based on metal-metal-to-ligand charge transfer (MMLCT) transition was observed in the case of P(Glu)-PtC12. However, such synergistic effect was not observed in the case of P(Glu)-PtH. Poly-L- glutamic acid was found to serve as an efficient molecular scaffold, wherein the platinum(II) complexes might be accommodated. The assembling and self-association of anionic dicyanoaurate(I), [Au(CN)2] � , spatially around the cationic poly-L-Lysine (P(Lys)) through electrostatic interactions was also demonstrated to form the luminescent [Au(CN)2] � aggregates. References 1. (a) Chem. Commun. 1998, 1963. (b) J. Organomet. Chem. 1999, 589, 50. (c) J. Am. Chem. Soc. 2001, 123, 68. (d) Organometallics 2001, 20, 1008. (e) Organometallics 2001, 20, 3101. (f) J. Organomet. Chem. 2001, 637-639, 75. (g) Org. Lett. 2003, 5, 4285. (h) Org. Lett. 2005, 7, 5265. (i) Org. Lett. 2006, 8, 31-34. (j) Dalton Trans. 2009, 4286. 47 M M M M M M M M M M
OP-32 ISBOMC `10 5.7 – 9.7. 2010 Ruhr-Universität Bochum Homogeneous and Bio-Catalysis in Concert: Hybrids of ECE-pincer Organometallics and Lipases Gerard van Koten *a a Organic Chemistry and Catalysis, Faculty of Science, Utrecht University, The Netherlands g.vankoten@uu.nl Bis-ortho-chelated aryl-metal complexes, the socalled ECE-pincer metal complexes, exist in great varieties. Several novel strategies for anchoring these ECE-pincer metal complexes to soluble and insoluble supports have been developed. Novel synthetic routes have been developed for the direct introduction of functional para-substituents onto the pre-formed ECE-pincer metal complexes. 1 This allows, for example the introduction of anionic tethers which can non-covalently bind the ECE-pincer metal complex to the core of multicationic core-shell dendrimers. Recently, we concentrated on the covalent anchoring of ECE-pincer metal complexes to proteins. 2 This approach, involving the inhibitory activity of nitrophenyl phosphonate esters to the catalytic triad (serine, histidine and asparagine) of lipases, has great potential for future applications in the fields of protein structure elucidation (NMR, X-Ray, mass spectrometry), medicinal chemistry (biomarkers, MRI contrast agents, radiopharmaceuticals), biomaterials and catalysis (enantioselectivity, catalysis in aqueous media). Crystal structures of these novel ECE-pincer metal-lipase hybrids show in detail how the ECE-pincer metal unit is covalently attached to the enzyme. 3 The photophysical (biomarker), coordinative and catalytic (dynamic kinetic resolution) properties of these and related rutheniumlipase hybrid materials will be discussed. Fig 1. Structure in the solid state of the NCN-pincer platinum bromide-cutinase hybrid. References 1. M.Gagliardo, D.J.M. Snelders et al., Angew. Chem. 2007, 46, 8558. 2. C.A. Kruithof et al., Chem. Eur. J. 2005, 11, 6869. 3. B. Wieczorek et al., Chem. Eur. J. 2009, 15, 4270. 48
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Sergey Abramkin Universität Wien,
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Tensim Dallagi ENSCP, France t.dall
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Prof. Dr. Toshikazu Hirao Osaka Uni
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Obiora Augustine Orakwue Hyqid Nige
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