Bioinorganic Chemistry: Zn & its Toxic Congeners Deborah C. Bebout Chemistry Department The College of William & Mary.

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Bioinorganic Chemistry: Zn & its Toxic Congeners Deborah C. Bebout Chemistry Department The College of William & Mary

Zn Cd Hg Essential to all known life forms Thalassiosira weissflogii produces Cd(II)-dependent carbonic anhydrase in Zn(II) limiting conditions …or not IIB …but generally considered toxic to all known life forms Broad toxicity of Hg(II) likely precludes any physiologically beneficial role …LD 50 (ZnCl 2 ) 350 mg/kg, rat (oral)

L Coordination number variability Coordination geometry flexibility Rapid exchange M MM L 2 LLLL 3 LL 45678

New Insight NMR X-Ray ESI-MS >60 new complexes Slow exchange J( 199 Hg 1 H) J( 111/113 Cd 1 H)

Zn Cd Hg Spectroscopically silent …or not to see 12.3% 113 Cd spin & 12.8% 111 Cd with spin I = ½ 16.8% 199 Hg with spin I = ½

Julie A. Viehweg, Sarah M. Stamps, Jennifer J. Dertinger, Robert L. Green, Katherine E. Harris, Raymond J. Butcher, ‡ Erica J. Andriole, J.C. Poutsma, Steven M. Berry, Deborah C. Bebout* “A Synthetic Model of Hg(II) Sequestration” Dalton Transactions 2010, 39, 3174.

W. Lai, S.M. Berry, A. Q. A. Tran, W. P. Kaplan, M. S. Hain, J.C. Poutsma, R. J. Butcher, R. D. Pike and D. C. Bebout “Carbonate-templated self- assembly of an alkylthiolate-bridged cadmium macrocycle” Inorg. Chem. 2013, 52, Y. Xu, L. Feng, P.D. Jeffrey, Y. Shi, F. M. M. Morel Nature 2008, 452, 56.

 Organic synthesis  Purification  Coordination Chem  Routine NMR  IR, UV/Vis, etc.  Multinuclear NMR  ESI-MS  X-ray Crystallography  Scientific writing  Scientific presentations

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