Biomimics of Metalloenzymes via Imprinting

Metals have a vital role in catalysis, and their ability specifically to coordinate molecular structures has been exploited by nature with the development of metalloenzymes. Inspired by nature, chemists have been extensively using metals to catalyze a broad range of difficult transformations. The imprinting approach for the preparation of biomimics of metalloenzymes gives highly selective and robust catalysts applicable to molecular recognition processes with challenging conditions (e.g., high temperatures and pressures, extreme pHs, and organic solvents). Imprinted metal-containing catalysts can also be designed for reactions that are not catalyzed by natural enzymes, such as degradation of soil and water contaminants or hydrogen production. Imprinted biomimics of metalloenzymes are categorized and discussed based on templates, metal ions, polymerization techniques, imprinting approaches, and catalytic reactions. Initial studies focusing on proof-of-concepts in mimicking natural enzymes as well as state-of-the-art catalytic devices including nanogels, nanoreactors, and biosensors are discussed. Rational design methodologies and statistical designs of experiments are expected to assist the screening of matrices for their catalytic performance and consequently accelerate further development of the field.