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

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Eurobic9, 2-6 September, 2008, Wrocław, Poland P113. Labeling Thiele’s Acid and its Derivatives with [ 99m Tc(CO)3(H2O)3] + Through Retro-Diels-Alder Reaction in Aqueous Media Y. Liu, P. Schmutz, B. Spingler, R. Alberto Institute of Inorganic Chemistry, University of Zürich, Winterthurerstr. 190, CH-8057, Zürich, Switzerland e-mail: liuyu@aci.uzh.ch The amino acids coupled with tripodal Dap (Diamino propionic acid) has been introduced in our group to prepare Re(I)/Tc(I) tri-carbonyl complexes, which can be recognized and transported by LAT1 transporter[1]. Based upon this observation, Cp (Cyclopentadiene), with its smaller and more compact size than Dap, should be a good chelator candidate for Re(I)/Tc(I) tri-carbonyl chemistry. Contrary to the conventional view of moisture sensitive chemistry of Cp, C5H5COOH can react with Re(I)/Tc(I) triscarbonyl to produce (CO)3MC5H4COOH (M=Re(I), 99m Tc(I)) in aqueous media (Scheme). What is more, the Diels-Alder dimer of C5H5COOH, Thiele’s acid (C5H5COOH)2, reacting with Re(I)/Tc(I) triscarbonyl as well in aqueous media, results in the formation of (CO)3MC5H4COOH (Scheme), which gives a first example of retro-Diels-Alder complexation of triscarbonyl compound at low temperature (
Eurobic9, 2-6 September, 2008, Wrocław, Poland P114. Complexes of Copper(II) with Nicotinamide Adenine Dinucleotide (NAD + ) in Binary and Ternary Systems Including Spermine (Spm) L. Lomozik, A. Gasowska, K. Basinski Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland e-mail: basinski@amu.edu.pl Nicotinamide adenine dinucleotide (NAD + ) is a coenzyme found in all living cells which consists of two nucleotides linked through their phosphate groups. In metabolism, NAD + is involved in redox reactions of cellular respiration, carrying electrons from one reaction to another [1, 2]. The bioligand makes an interesting object of research because of its biochemical reactivity with the enzymes from the group of dehydrogenases [3]. Unfortunately not much literature on the coordination of NAD + through metals present in living organism has been published as yet [4]. Interaction of nicotinamide adenine dinucleotide with copper(II) ions in binary and ternary systems including spermine has been observed. Computer analysis of potentiometric titration data in the Cu(II)-NAD + system has shown the formation of CuH2(NAD + ), CuH(NAD + ), Cu(NAD + )(OH) and Cu(NAD + )(OH)2 complexes and in the ternary system including spermine (1, 12-diamino-4, 9-diazadodecane) – the formation of Cu(NAD + )H4(Spm) and Cu(NAD + )H5(Spm) complexes. To determine the coordination centres, Vis spectra of the complexes were made. For example, the λmax values obtained were 808.0, 793.7 and 665.0 nm for CuH2(NAD + ), CuH(NAD + ) and Cu(NAD + )(OH)2, respectively, which corresponds to the {O} type of metallation in CuH2(NAD + ) and CuH(NAD + ) and the {N, O} type of metallation in Cu(NAD + )(OH)2 complex [5]. Analysis of the 13 C and 31 P NMR spectra has confirmed these conclusions. Full recognition of the character of copper-NAD + and copper-NAD + -spermine interactions in model systems is expected to give information on their probable participation in biological processes, in which nicotinamide adenine dinucleotide takes part. The results of these observations should yield better insight into intracellular mechanisms and emphasise the role of metals in living organisms. References: [1] S. Sivaranam et al., Biochem., 42, 4406-4413 (2003) [2] J. M. Berg, J. L. Tymoczko, L. Stryer, Biochemistry, 465-514 (2005) [3] G. R. Stockwell, J. M. Thornton, J. Mol. Biol., 356, 928-944 (2006) [4] L. A. Herrero et al., J. Biol. Inorg. Chem., 7, 313-317 (2002) [5] A. Gasowska, J. Inorg. Biochem., 99, 1698-1707 (2005) _____________________________________________________________________ 233
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Author Index Eurobic9, 2-6 Septembe
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ISBN: 978-83-60043-10-3 - eurobic9

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