Artificial metalloenzymes, constructed by incorporating a synthetic catalyst into the internal spaces of a protein scaffold, can perform noncanonical chemical transformations that are not possible using natural enzymes. The addition of cell-permeable modules to artificial metalloenzymes allows for noncanonical catalysis to be implemented as a function of mammalian cells. In this chapter, we describe a protocol for controlling cellular function through a cascade consisting of an artificial metalloenzyme and a gene-circuit engineered via synthetic biology.
Keywords: Allylic dealkylation; Artificial metalloenzyme; Cell-penetrating polydisulfides; Gene switch; Intracellular catalysis; Ruthenium complex; Streptavidin; Thyroid hormone.