Supramolecular Self‐Assembly of Proteins Promoted by Hybrid Polyoxometalates

Abstract Controlling the formation of supramolecular protein assemblies and endowing them with new properties that can lead to novel functional materials is an important but challenging task. In this work, a new hybrid polyoxometalate is designed to induce controlled intermolecular bridging between biotin‐binding proteins. Such bridging interactions lead to the formation of supramolecular protein assemblies incorporating metal‐oxo clusters that go from several nanometers in diameter up to the micron range. Insights into the self‐assembly process and the nature of the resulting biohybrid materials are obtained by a combination of Small Angle X‐ray Scattering (SAXS), Transmission Electron Microscopy (TEM), and Dynamic Light Scattering (DLS), along with fluorescence, UV–vis, and Circular Dichroism (CD) spectroscopy. The formation of hybrid supramolecular assemblies is determined to be driven by biotin binding to the protein and electrostatic interactions between the anionic metal‐oxo cluster and the protein, both of which also influence the stability of the resulting assemblies. As a result, the rate of formation, size, and stability of the supramolecular assemblies can be tuned by controlling the electrostatic interactions between the cluster and the protein (e.g., through varying the ionic strength of the solution), thereby paving the way toward biomaterials with tunable assembly and disassembly properties.