Some hemoproteins have the structural robustness to withstand extraction of the heme cofactor and replacement with a heme analog. Recent reports have reignited interest and exploration in this field by demonstrating the versatility of these systems. Heme binding proteins can be utilized as protein scaffolds to support heme analogs that can facilitate new reactivity by noncovalent bonding at the heme-binding site utilizing the proximal ligand for support. These substituted hemoproteins have the capability to enhance catalytic reactivity and functionality comparatively to their native forms. This review will focus on progress and recent advances of artificially engineered hemoproteins utilized as a new target for the development of biocatalysts.
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