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Chem Soc Rev. 2013 Nov 7;42(21):8360-75. doi: 10.1039/c3cs60162e. Epub 2013 Jul 24.

Insights into metalloenzyme microenvironments: biomimetic metal complexes with a functional second coordination sphere.

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  • 1MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.


Non-covalent interactions in the second coordination sphere of metalloenzymes play a significant role in determining activity and selectivity. The importance of these interactions is reflected in the increasing number of reports on model complexes with a functional second coordination sphere. These hybrid mimics were developed according to the strategies of modification with functional groups, combination with supramolecular hosts and coupling with polymers, to shed light on the role of non-covalent interactions in metalloenzyme catalysis. This review provides an overview of recent progress in this area. An introduction to native metalloenzymes with an emphasis on the second coordination sphere is also given.

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