Catalytic chemical transformations with conformationally dynamic catalytic systems

Proteins, RNA, and other functional biomacromolecules are sophisticated chemical entities that have evolved over billions of years. Their catalytic, constitutional, and communicating functions are intimately related to their three-dimensional molecular architecture and are exquisitely regulated in a spatiotemporal manner by conformational changes through allosteric regulators and a myriad of reversible and unidirectional posttranslational modifications. Their organized functional diversity is the key to the orderly and timely progression of complicated biological events. The main focus in the development of artificial catalysts is to accelerate a specific chemical transformation of interest, and extensive efforts have been devoted to fine-tuning catalytic activity. Here, we review recent developments of multistate catalysts able to perform distinct catalytic functions, with emphasis on the tight link between the structural modification of the conformationally flexible catalysts and the functional change. Although this field is still in its infancy with a simple output, continued advances will allow us to create intriguing systems with organized multitask output in an intricate molecular ensemble. © The Royal Society of Chemistry 2013.