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

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Eurobic9, 2-6 September, 2008, Wrocław, Poland P77. A Novel Technique to Probe the Inorganic and Bioinorganic Chemistry of Lead: 204m Pb-PAC Spectroscopy L. Hemmingsen a , J. Vibenholt b , M. Magnussen b , M. Stachura a , M. J. Bjerrum a , P. W. Thulstrup a a Department of Natural Sciences, University of Copenhagen, Denmark e-mail: lhe@life.ku.dk b Department of Chemistry, University of Copenhagen, Denmark Perturbed angular correlation of γ-rays (PAC) spectroscopy has been applied routinely in solid state physics over the past 5 decades, and to a lesser extent in coordination chemistry and biochemistry using a variety of PAC probes, providing information on the molecular and electronic structure in the vicinity of the PAC probe [1]. 204m Pb-PAC spectroscopy was first applied in 1973 by Haas and Shirley [2], in investigations of inorganic compounds such as PbCl2, PbFCl, PbI2, PbO, PbSO4, PbCrO4, PbC2O4, and Pb(SCN)2. Only recently the technique was “revived” in an effort by the PAC-group in Leipzig, Germany, and the ISOLDE collaboration at CERN [3], where additional inorganic compounds (PbCO3, Pb2O(CO3), Pb3(PO4)2, Pb(CN)2, PbO, Pb3O4, Pb(IO3)2, PbBr2, PbTiO3) were investigated. No applications to coordination compounds nor applications in biochemistry have been published yet in peer reviewed journals, although a convincing attempt to determine the NQI in Pb(II)-substituted azurin was carried out in the Ph.D. work by Frank Heinrich [4]. In this work [5] we present the first application of 204m Pb-PAC spectroscopy to a coordination compound, in the sense that it possesses a full molecular entity in the unit cell, see Figure 1, rather than the periodic crystalline structure of the inorganic compounds investigated previously. Figure 1 Left: The structure of [Pb(II) iso-maleonitriledithiolate] 4- ([6], counterions not shown). Right: the Fourier tranform of the perturbation function recorded by 204m Pb-PAC spectroscopy (Thin line: data; boldfaced line: fit). Acknowledgements: The Danish Natural Science Research Council is acknowledged for funding, and ISOLDE/CERN for beam time References: [1] Hemmingsen L., Sas K.N., Danielsen E. Chem. Rev. 2004, 104, 4027. [2] Haas H., Shirley D. J. Chem. Phys. 1973, 58, 3339. [3] Tröger W., Dietrich M., Araujo J.P., Correia J.G., Haas H., and the ISOLDE collaboration Z. Naturforsch. 2002, 57A, 586. [4] Heinrich F., Ph.D. thesis, 2005, Faculty of Physics and Geosciences, University of Leipzig, Germany [5] Vibenholt J., Magnussen M., Stachura M., Bjerrum M.J., Thulstrup P.W. and Hemmingsen L. in prep. [6] Magyar J.S., Weng, T.-C., Stern C.M., Dye D.F., Rous B.W., Payne J.C., Bridgewater B.M., Mijovilovich A., Parkin G., Zaleski J.M., Penner-Hahn J.E., and Godwin H.A. J. Am. Chem. Soc. 2005, 127, 9495 _____________________________________________________________________ 196
Eurobic9, 2-6 September, 2008, Wrocław, Poland P78. Structural Studies of the Intermediates in the Reaction Between Myoglobin and Peroxides H. P. Hersleth a , Y. W. Hsiao b , C. H. Görbitz c , U. Ryde b , K.K. Andersson a a Department of Molecular Biosciences, University of Oslo, P.O.Box 1041 Blindern, N-0316, Oslo, Norway e-mail: h.p.hersleth@imbv.uio.no b Department of Theoretical Chemistry, Lund Univeristy, P.O.Box 124, S-221 00, Lund, Sweden c Department of Chemistry, University of Oslo, P.O.Box 1033 Blindern, N-0315, Oslo, Norway The intermediates generated in the reaction between myoglobin and peroxides mimic the intermediates found in many peroxidases, oxygenases and catalases [1, 2]. These myoglobin intermediates are also relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress. We have in this study combined crystallography and single-crystal light absorption spectroscopy (microspectrophotometry). Radiation-induced changes of the different intermediates in this reaction cycle have been observed and followed by microspectrophotometry [2, 3, 4] . We have been able by cryoradiolytic reduction of an oxymyoglobin equivalent (compound III) to generate and trap the so-called peroxymyoglobin intermediate, a Fe(II)-superoxide form indicated by quantum refinement analysis [2, 4]. By annealing of this compound the oxygen-oxygen bond is broken and the reaction propagates to the compound II intermediate [3, 4]. The structures have further been refined with quantum refinement [3, 4, 5]. References: [1] Hersleth, H.-P., Ryde, U., Rydberg, P., Görbitz, C.H. & Andersson, K.K. (2006). J. Inorg. Biochem. 100, 460-476. [2] Hersleth, H.-P. Varnier, A., Harbitz, E, Røhr, Å. K., Schmidt, P. P., Sørlie, , M., Cederkvist, F. H., Marchal, S., Gorren, A. C. F., Mayer, B., Uchida, T., Schünemann, V., Kitagawa, T., Trautwein, A. X., Shimizu, T., Lange, R., Görbitz, C. H. & Andersson, K. K. (2008) Reactive Complexes in Myoglobin and Nitric Oxide Synthase. Inorg. Chim. Acta 361, 831-843. [3] Hersleth, H.-P., Uchida, T., Røhr, Å.K., Teschner, T., Schünemann, V., Kitagawa, T., Trautwein, A.X., Görbitz, C.H. & Andersson, K.K. (2007) Crystallographic and spectroscopical studies of peroxide-derived myoglobin compound II and Occurence of protonated FeIV-O. J. Biol. Chem. 282, 23372-23386. [4] Hersleth, H.-P., Hsiao, Y.-W., Ryde, U., Görbitz, C.H. & Andersson, K.K. (2008) The crystal structure of peroxymyoglobin generated through cryoradiolytic reduction of myoglobin compound III during data collection. Biochem. J. 412, 257-264. [5] Nilsson, K., Hersleth, H.-P., Rod, T.H., Andersson, K.K. & Ryde, U. (2004) The Protonation Status of Compound II in Myoglobin, Studied by a Combination of Experimental Data and Quantum Chemical Calculations: Quantum Refinement. Biophys. J. 87, 3437-3447. _____________________________________________________________________ 197
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Author Index Eurobic9, 2-6 Septembe
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Bursakov ..........................
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Smirnova...........................
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ISBN: 978-83-60043-10-3 - eurobic9

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