Abstract
Artificial metalloenzymes (ArMs) comprise a synthetic metal complex in a protein scaffold. ArMs display performances combining those of both homogeneous catalysts and biocatalysts. Specifically, ArMs selectively catalyze non-natural reactions and reactions inspired by nature in water under mild conditions. In the past few years, the construction of ArMs that possess a genetically incorporated unnatural amino acid and the directed evolution of ArMs have become of great interest in the field. Additionally, biochemical applications of ArMs have steadily increased, owing to the fact that compartmentalization within a protein scaffold allows the synthetic metal complex to remain functional in a sea of inactivating biomolecules. In this review, we present updates on: (1) the newly reported ArMs, according to their type of reaction, and (2) the unique biochemical applications of ArMs, including chemoenzymatic cascades and intracellular/in vivo catalysis. We believe that ArMs have great potential as catalysts for organic synthesis and as chemical biology tools for pharmaceutical applications.
Highlights
A catalyst is defined as a material that accelerates the rate of a chemical reaction without being consumed by the reaction
Fujieda et al developed a protein-based Artificial metalloenzymes (ArMs) for this transformation
Even though only a few years passed since the last comprehensive review of ArMs by Ward et al, several dozen articles have been have passed since the last comprehensive review of ArMs by Ward et al, several dozen articles have published [7]
Summary
A catalyst is defined as a material that accelerates the rate of a chemical reaction without being consumed by the reaction. An ArM comprises a synthetic metal complex in a protein scaffold. A genetic code reprogramming technique has enabled the incorporation of unnatural amino acids, which can be a ligand for a metal complex or a catalytically active small molecule, into a protein upon its expression. This genetic incorporation of unnatural amino acids is considered as a fifth method for ArM construction [23]. High reaction selectivity can be achieved by ArMs because the protein scaffold provides a highly defined second coordination sphere for the metal complex, which is difficult to implement through synthetic chemistry. ArMs according to the type of reaction they catalyze and discuss the unique applications of ArMs that have been reported in the past few years
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