We report on artificial metalloenzymes that incorporate a biotinylated dirhodium core embedded within engineered streptavidin (Sav hereafter) variants. The resulting biohybrid catalyzes the carbene insertion in C-H bonds and olefins. Chemical- and genetic optimization allows to modulate the catalytic activity of the artificial metalloenzymes that are shown to be active in the periplasm of E. coli (up to 20 turnovers).
