期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 24, 期 40, 页码 10099-10108出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201802052
关键词
co-crystallization; density functional calculations; dielectric distribution; polyoxometalates; protein-assisted dissociation
资金
- Research Foundation-Flanders (FWO Flanders)
- FWO
- FWO [G074616N, G0E4717N]
- Flemish Government-department EWI
The effect of the protein environment on the formation and stabilization of an elusive catalytically active polyoxometalate (POM) species, K-6[Hf((2)-P2W17O61)] (1), is reported. In the co-crystal of hen egg-white lysozyme (HEWL) with 1, the catalytically active monomeric species is observed, originating from the dimeric 1:2 POM form, while it is intrinsically unstable under physiological pH conditions. The protein-assisted dissociation of the dimeric POM was rationalized by means of DFT calculations. The dissociation process is unfavorable in bulk water, but becomes favorable in the protein-POM complex due to the low dielectric response at the protein surface. The crystal structure shows that the monomeric form is stabilized by electrostatic and water-mediated hydrogen bonding interactions with the protein. It interacts at three distinct sites, close to the aspartate-containing hydrolysis sites, demonstrating high selectivity towards peptide bonds containing this residue.
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