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Comparison of Cysteine and Penicillamine Ligands in a Co(II) Maquette
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文摘
L-Penicillamine (Pen) has been investigated as a ligand formetalloprotein design by examining the binding of Co(II) to thesequence NH2-KL(Pen)EGG·(Pen)IG(Pen)GA(Pen)·GGW-CONH2.For comparison, we have studied Co(II) binding to the analogoussequence with Cys ligands, the ferredoxin maquette ligand IGAthat was originally designed to bind a [4Fe-4S] cluster. The Co(II)affinity and UV-vis spectroscopic properties of IGA indicateformation of a pseudotetrahedral tetrathiolate ligated Co(II). Incontrast, IGA-Pen showed formation of a pseudotetrahedralcomplex with Co(II) bound by three Pen ligands and an exogenousH2O. EXAFS data on both Co(II) complexes confirms not only theproposed primary coordination spheres but also shows six Co(II)-C methyl group distances in Co(II)-IGA-Pen. These resultsdemonstrate that ligand sterics in simple peptides can be designedto provide asymmetric coordination spheres such as thosecommonly observed in natural metalloproteins.

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