Cu(I) recognition via cation-pi and methionine interactions in CusF |
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Authors: | Xue Yi Davis Anna V Balakrishnan Gurusamy Stasser Jay P Staehlin Benjamin M Focia Pamela Spiro Thomas G Penner-Hahn James E O'Halloran Thomas V |
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Institution: | Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA. |
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Abstract: | Methionine-rich motifs have an important role in copper trafficking factors, including the CusF protein. Here we show that CusF uses a new metal recognition site wherein Cu(I) is tetragonally displaced from a Met2His ligand plane toward a conserved tryptophan. Spectroscopic studies demonstrate that both thioether ligation and strong cation-pi interactions with tryptophan stabilize metal binding. This novel active site chemistry affords mechanisms for control of adventitious metal redox and substitution chemistry. |
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