Volume 136, Issue 31 e202406669
Zuschrift

Non-Covalent and Covalent Binding of New Mixed-Valence Cage-like Polyoxidovanadate Clusters to Lysozyme

Gabriella Tito

Gabriella Tito

Department of Chemical Sciences, University of Naples Federico II, Complesso Universitario di Monte Sant'Angelo, Via Cintia, I-80126 Napoli, Italy

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Dr. Giarita Ferraro

Dr. Giarita Ferraro

Department of Chemical Sciences, University of Naples Federico II, Complesso Universitario di Monte Sant'Angelo, Via Cintia, I-80126 Napoli, Italy

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Federico Pisanu

Federico Pisanu

Dipartimento di Medicina, Chirurgia e Farmacia, Università di Sassari, Viale San Pietro, I-07100 Sassari, Italy

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Prof. Eugenio Garribba

Corresponding Author

Prof. Eugenio Garribba

Dipartimento di Medicina, Chirurgia e Farmacia, Università di Sassari, Viale San Pietro, I-07100 Sassari, Italy

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Prof. Antonello Merlino

Corresponding Author

Prof. Antonello Merlino

Department of Chemical Sciences, University of Naples Federico II, Complesso Universitario di Monte Sant'Angelo, Via Cintia, I-80126 Napoli, Italy

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First published: 06 June 2024

Abstract

The high-resolution X-ray structures of the model protein lysozyme in the presence of the potential drug [VIVO(acetylacetonato)2] from crystals grown in 1.1 M NaCl, 0.1 M sodium acetate at pH 4.0 reveal the binding to the protein of different and unexpected mixed-valence cage-like polyoxidovanadates (POVs): [V15O36(OH2)]5−, which non-covalently interacts with the lysozyme surface, [V15O33(OH2)]+ and [V20O51(OH2)]n− (this latter based on an unusual {V18O43} cage) which covalently bind the protein. EPR spectroscopy confirms the partial oxidation of VIV to VV and the formation of mixed-valence species. The results indicate that the interaction with proteins can stabilize the structure of unexpected – both for dimension and architecture – POVs, not observed in aqueous solution.

Data Availability Statement

The data that support the findings of this study are available in the Supporting Information. Coordinates and structure factors were deposited in the Protein Data Bank under the accession codes 9EX0, 9EX1, and 9EX2.

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