Engineered Metal‐Loaded Biohybrids to Promote the Attachment and Electron‐Shuttling between Enzymes and Carbon Electrodes.

The inorganic content and the catalytic performance pose metal‐loaded enzyme nanoflowers as promising candidates for developing bioelectrodes capable of functioning without the external addition of a redox mediator. However, these protein‐inorganic hybrids have yet to be successfully applied in combination with electrode materials. Herein, the synthesis procedure of these bionanomaterials is reproposed to precisely control the morphology, composition, and performance of this particular protein‐mineral hybrid, formed by glucose oxidase and cobalt phosphate. This approach aims to enhance the adherence and electron mobility between the enzyme and a carbon electrode. The strategy relies on dressing the protein in a tailored thin nanogel with multivalent chemical motifs. The functional groups of the polymer facilitate the fast protein sequence‐independent biomineralization. Furthermore, the engineered enzymes enable the fabrication of robust cobalt‐loaded enzyme inorganic hybrids with exceptional protein loads, exceeding 90% immobilization yields. Notably, these engineered biohybrids can be readily deposited onto flat electrode surfaces without requiring chemical pre‐treatment. The resulting bioelectrodes are robust and exhibit electrochemical responses even without the addition of a redox mediator, suggesting that cobalt complexes promote electron wiring between the active site of the enzyme and the electrode. [ABSTRACT FROM AUTHOR]