Dated back to 1956, the first protein modified transition metal catalyst was documented. The Palladium(II) salt was absorbed onto silk fibroin fiber, reduced by hydrogen to get the first reported ArM, which can catalyze asymmetric hydrogenation.
First attempt to anchor an abiotic metal center onto a protein was reported by Whitesides using biotin-avidin interaction, making an artificial hydrogenase. The presence of avidin can significantly increase the catalytic capacity of Rhodium(I) cofactor in aqueous phosphate buffer.