ISBN: 978-83-60043-10-3 - eurobic9

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Eurobic9, 2-6 September, 2008, Wrocław, Poland P177. 1-Deazapurine as a Potential Artificial Nucleobase for Metal- Mediated Base Pairing K. Seubert , J. Müller Inorganic Chemistry, TU Dortmund, Otto-Hahn-Str. 6, 44227, Dortmund, Germany e-mail: kristof.seubert@tu-dortmund.de The growing area of research of developing and analysing oligonucleotides containing artificial nucleobases provides a way towards the generation of functionalized nanoarchitectures. Metal-mediated base pairs are of special interest since one expects interesting magnetic or electric properties.[1, 2] We report the synthesis of the artificial 1-deazapurine nucleoside as well as the characterisation of its metal-ion binding properties in oligonucleotides. The addition of silver(I) ions results in a concentration-dependend melting behaviour with various oligonucleotides (d(X14A), d(X16A), d(X19A) (X = 1-deazapurine)). This can be explained by the formation of a double helix with up to 19 consecutive metal-mediated artificial base pairs (Scheme). References: [1] Müller, J., Eur. J. Inorg. Chem. 2008, in press (doi: 10.1002/ejic.200800301). [2] Carell, T., Clever, G.H.; Kaul, C., Angew. Chem. Int. Ed., 2007, 6226-6236. _____________________________________________________________________ 296
Eurobic9, 2-6 September, 2008, Wrocław, Poland P178. Reactivity for Isocyanide and Nitrile by Using Cobalt(III) Complexes Directed to an Active Site Model of Nitrile Hydratase T. Shibayama, T. Yano, Y. Funahashi, T. Ozawa, H. Masuda Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan, e-mail: 19415083@stn.nitech.ac.jp Nitrile Hydratase (NHase) is an enzyme which hydrates a nitrile compound to the corresponding amide. A noncorrin Co(III) or a non-heme Fe(III) ion is included in its active site. Crystal structural analyses of their proteins demonstrated that both metal centers were coordinated by two amide nitrogens from the peptide backbone and two oxidized cystein sulfurs (Cys-SO and Cys-SO2) in the equatorial plane and a cystein sulfur and H2O (Cotype) [1] or NO (Fe-type) [2] in the axial positions. (Fig. 1) Recently, Odaka and co-workers reported that Fetype NHase also hydrolyzed t-butyl isocyanide (tBuNC) to t-butyl amine (tBuNH2) [3]. In order to understand the reaction mechanism, we have prepared and characterized six Co(III) complexes with N2S2- [4] or N2S3-type ligands [5]; [Co III (L1)(tBuNC)2] - (1) (L1: N, N'-bis((2-mercapto-2-methyl)propioyl)-1, 3propanediamine) with two thiolate sulfurs, [Co III (L1(SO)2)(tBuNC)2] - (2) with two sulfenate sulfurs and [Co III (L1(SO2)2)(tBuNC)2]- (3) with two sulfinate sulfurs, [Co III (L2)] - (4) (L2: 3, 3'-bis(2-mercapto-2methylpropionylamino)-dipropylsulfide) with two thiolate sulfurs, [Co III (L2(SO)(SO2))] - (5) with a sulfenate sulfur and a sulfinate sulfur, and [Co III (L2(SO2)2)] - (6) with two sufinate sulfurs. In this study, we tried the hydrolysis reaction of tBuNC and acetonitrile using their complexes under of a large excess of the substrate concentrate. References: [1] A. Miyanaga, S. Fushinobu, K. Ito, T. Wakagi, Biochem. Biophys. Res. Commun., 288, 1169 (2001). [2] S. Nagashima, M. Nakasako, N. Dohmae, M. Tsujimura, K. Takio, M. Odaka, M. Yohda, N. Kamiya, I. Endo, Nat. Struct. Biol., 5, 347 (1998). [3] K. Hashimoto, M. Yohda, M. Odaka, 13th International Conference on Biological Inorganic Chemistry, Vienna, Austria, Abstr., P133 (July, 2007). [4] T. Yano, Y. Wasada-Tsutsui, H. Arii, S. Yamaguchi, Y. Funahashi, T. Ozawa, H. Masuda, Inorg. Chem., 46, 10345 (2007). [5] T. Yano, T. Ikeda, Y. Funanhashi, T. Ozawa, H. Masuda, Adv. Mater. Res., 11-12, 347 (2006). _____________________________________________________________________ 297
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ISBN: 978-83-60043-10-3 - eurobic9

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