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Bioinorganic Chemistry: Zn & its Toxic Congeners. Deborah C. Bebout Chemistry Department The College of William & Mary. …or not IIB. IIB. Essential to all known life forms. …LD 50 (ZnCl 2 ) 350 mg/kg, rat (oral). Thalassiosira weissflogii produces Cd(II)-dependent
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Bioinorganic Chemistry:Zn & its Toxic Congeners • Deborah C. Bebout • Chemistry Department • The College of William & Mary
…or not IIB IIB Essential to all known life forms …LD50 (ZnCl2) 350 mg/kg, rat (oral) Thalassiosira weissflogii produces Cd(II)-dependent carbonic anhydrase in Zn(II) limiting conditions …but generally considered toxic to all known life forms Broad toxicity of Hg(II) likely precludes any physiologically beneficial role
Bring order to chaos! M L M Rapid exchange M L 2 7 8 3 4 5 6 L L L L L L Coordination number variability Coordination geometry flexibility
Multi-faceted Approach ESI-MS New Insight NMR X-Ray Slow exchange J(199Hg1H) J(111/113Cd1H) >60 new complexes
…or not to see IIC Spectroscopically silent 12.3% 113Cd spin & 12.8% 111Cd with spin I = ½ 16.8% 199Hg with spin I = ½
Metallothionein Model 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 Transactions2010, 39, 3174.
Cd-Carbonic Anhydrase Model 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, 52,2286-2288. Y. Xu, L. Feng, P.D. Jeffrey, Y. Shi, F. M. M. Morel Nature2008, 452, 56.
Student Involvement • Organic synthesis • Purification • Coordination Chem • Routine NMR • IR, UV/Vis, etc. • Multinuclear NMR • ESI-MS • X-ray Crystallography • Scientific writing • Scientific presentations
Are you a heavy metal fan? I’M A HEAVY METAL FAN. ME TOO! • Recruiting Underclassmen • Please come talk to me if interested! • dcbebo@wm.edu ISC 2039 & 2028