Stimulus‐Responsive Regulation of Enzyme Activity for One‐Step and Multi‐Step Syntheses

Multi‐step biocatalytic reactions have gained increasing importance in recent years because the combination of different enzymes enables the synthesis of a broad variety of industrially relevant products. However, the more enzymes combined, the more crucial it is to avoid cross‐reactivity in these cascade reactions and thus achieve high product yields and high purities. The selective control of enzyme activity, i.e., remote on‐/off‐switching of enzymes, might be a suitable tool to avoid the formation of unwanted by‐products in multi‐enzyme reactions. This review compiles a range of methods that are known to modulate enzyme activity in a stimulus‐responsive manner. It focuses predominantly on in vitro systems and is subdivided into reversible and irreversible enzyme activity control. Furthermore, a discussion section provides indications as to which factors should be considered when designing and choosing activity control systems for biocatalysis. Finally, an outlook is given regarding the future prospects of the field. [Image: see text]