Vandebroek, Laurens, De Zitter, Elke, Hong, Giang Thi Ly, Conic, Dragan, Mihaylov, Tzvetan, Sap, Annelies, Proost, Paul, Pierloot, Kristine, Van Meervelt, Luc 
ORCID: 0000-0003-2186-5209 and Parac-Vogt, Tatjana N
(2018)
Protein-Assisted Formation and Stabilization of Catalytically Active Polyoxometalate Species.
CHEMISTRY-A EUROPEAN JOURNAL, 24 (40).
pp. 10099-10108.
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Abstract
The effect of the protein environment on the formation and stabilization of an elusive catalytically active polyoxometalate (POM) species, K<sub>6</sub> [Hf(α<sub>2</sub> -P<sub>2</sub> W<sub>17</sub> O<sub>61</sub> )] (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.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | co-crystallization, density functional calculations, dielectric distribution, polyoxometalates, protein-assisted dissociation |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 04 Jun 2019 08:28 |
| Last Modified: | 25 Jan 2023 17:03 |
| DOI: | 10.1002/chem.201802052 |
| Related URLs: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3043314 |
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