A Hydroxyquinoline‐Based Unnatural Amino Acid for the Design of Novel Artificial Metalloenzymes
Ivana Drienovská, Remkes A. Scheele, Cora Gutiérrez de Souza, Gérard Roelfes
Abstract
Abstract We have examined the potential of the noncanonical amino acid (8‐hydroxyquinolin‐3‐yl)alanine (HQAla) for the design of artificial metalloenzymes. HQAla, a versatile chelator of late transition metals, was introduced into the lactococcal multidrug‐resistance regulator (LmrR) by stop codon suppression methodology. LmrR_HQAla was shown to complex efficiently with three different metal ions, Cu II , Zn II and Rh III to form unique artificial metalloenzymes. The catalytic potential of the Cu II ‐bound LmrR_HQAla enzyme was shown through its ability to catalyse asymmetric Friedel‐Craft alkylation and water addition, whereas the Zn II ‐coupled enzyme was shown to mimic natural Zn hydrolase activity.